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Leslie, Kathryn. "Naphthalimide-based fluorescent sensing." Thesis, The University of Sydney, 2018. http://hdl.handle.net/2123/19790.
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Fluorescent sensors are indispensable tools for studying the chemical environment of cells and furthering our understanding of the processes behind health and disease. The design of fluorescent sensors which can sensitively and selectively respond to specific analytes is of vital importance to biological research. A thorough understanding of the photophysical properties of fluorescent materials is essential for their successful development into fluorescent sensors. 4-Amino-1,8-naphthalimides are a commonly-used class of fluorophore, with many advantageous properties for sensing. However, their mechanism of fluorescence is not well understood, and this means in turn that their incorporation into fluorescent sensors is not very varied. The first part of this work describes the synthesis, photophysical characterisation and biological behaviour of a set of di-substituted 1,8-Naphthalimide dyes. The effect of different electron-withdrawing and -donating substituents and their position of substitution on the naphthalimide core is assessed, giving rise to some structure-property relationships and an understanding of how the internal charge transfer mechanism of fluorescence could be manipulated for this dye. The understanding gained in the first part of this project led to the design of sensors for hypoxia and nitric oxide using the naphthalimide scaffold. This was achieved by incorporation of sensing groups that manipulate the internal charge transfer fluorescence mechanism through their changing electronic nature in response to an analyte. A range of sensors for hypoxia incorporating nitro and nicotinamide sensing groups were synthesised and assessed for their suitability as intracellular hypoxia sensors. Work towards a naphthalimide-based nitric oxide sensor with improved emission properties and higher water solubility is also presented, as well as the development of an assay for nitric oxide in tear samples.
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Dana, Bogden Hariton, and n/a. "Pyridylacetylenes and their cobalt clusters; novel naphthalimide monomers and polymers." University of Otago. Chemistry Department, 2005. http://adt.otago.ac.nz./public/adt-NZDU20060707.142806.
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A series of 2,6- and 3,5-ethynylpyridyl compounds and their cobalt clusters have been prepared and analysed in Chapter 2, in order to study through-space and through-bond interactions between the ethynyl arms. Bidentate N- donor ligands, such as bipyridine and o-phenanthroline with alkyne functionality have been used extensively as building blocks for a wide range of molecular materials, but monodentate ethynylpyridyls have received less attention.
The results showed that while there is no orbital restriction on a RC[triple bond]C-n-[pi]�cc-C[triple bond]CR through-bond interaction in 2,6-ethynylpyridyls, no significant interaction exists. Nevertheless, there are intramolecular interactions as manifested in the distortions which occur in the solid state structure of the compounds and the lability of the diphenylphosphine methane (dppm) moieties in the oxidised Co₂(CO)₄dppm species.
Polymerisation by Sonogashira coupling between dibromo pyridines or diiodo ferrocene and ethynyl pyridines resulted in only oligomeric fractions that could be separated.
The thesis also reports the synthesis and characterization of some novel naphthalimide monomers with acrylic and allyl headgroups. The naphthalimide moiety is substituted in the 4-position with various functionalities. This is presented in detail in Chapter 3 of the thesis. The monomers� structure is the following: [illustration omitted] wherein: A may be a polymerizable group (methacrylate or allyl), which includes a spacer entity (aliphatic or aromatic); B is selected from an ethenyl or ethynyl linked organometallic group, a halogen and/or an amine (i.e. bromo, ethynylferrocene, ethenylferrocene, trimethylsilylethynyl, nitro, piperidine and ethenylpiperidine).
The acrylic monomers were synthesized by coupling 4-bromo-1,8-naphthalic anhydride with an amino alcohol to give an imide, which then was coupled with methacryloyl chloride to provide the methacrylate.
Functionalization in the 4-position of the naphthalimide moieties was achieved by Sonogashira and Heck coupling reactions with for example ethynylferrocene, trimethylsilyl acetylene, vinylferrocene.
For the allyl monomers synthesis, a reaction between allyl amine and 4-Bromo-naphthalic anhydride provided 4-bromo-naphthalimido allyl, which was then functionalized by further Sonogashira and Heck coupling reactions.
The monomers were polymerised and copolymerised with other widely used comonomers, such as methyl methacrylate, methyl acrylate, styrene, vinyl carbazole and acrylonitrile. The polymerisation processes and the full analyses of the (co)polymers are described in Chapter 4.
Free radical polymerisation, FRP, initiated by azo bisisobutyronitrile, AIBN at elevated temperature was the main technique employed for making the (co)polymers.
Atom Transfer Radical Polymerisation, ATRP was conducted for some monomers although the results were inconclusive (the yields were low, under 50%, but the molecular weight distributions were quite narrow, PDI�s <1.7).
Heck coupling polymerisation was performed for the bromo- substituted methacrylic and allyl monomers and supplied colorful, well-defined polymeric materials, with low polymerisation degrees.
All polymers were analyzed by HPLC, NMR, UV-VIS, IR, electrochemistry and fluorescence. The (co)polymers made by FRP had various molecular masses (Mn = 3000- 90.000), whereas the polydispersities were PDI = 1.4- 4.6.
Most of the (co)polymers were fluorescent and had good thermal and electrochemical properties. Potential applications of the polymers have been suggested and relevant literature background in the field is provided in both Chapters 1 and 4.
The monomers/ polymers are stable compounds (no special storage conditions required) and can act as good candidates for potential applications in light emitting devices, as resins/ binders for coating materials, in the dyes and pigment industry and also for manufacturing of conducting polymers and/or composite materials.
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Jin, Terry David. "Fluorogenic 1,8-naphthalimide derivatives for the detection of pathogenic bacteria." Thesis, The University of Sydney, 2015. http://hdl.handle.net/2123/14156.
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Novel fluorogenic enzyme substrates were synthesized by the coupling of 6-hydrazinobenz[de]isoquinoline-1,3-diones with β-alanine for the detection of β-alanyl aminopeptidase-producing Pseudomonas aeruginosa. A secondary reaction was also utilized involving the condensation of the 6-hydrazinobenz[de]isoquinoline-1,3-diones with a range of aryl aldehydes to give the corresponding hydrazones as a means for obtaining more favourable fluorescence properties. The photophysical properties of the synthesized hydrazines and their hydrazide and hydrazone derivatives, were examined and they were also incorporated into Columbia agar in order to determine their potential for the detection of pathogenic bacteria. The synthesized hydrazides and coupled derivatives displayed good fluorescence properties, with an average Stokes’ shift of 67 nm. Incorporation of a secondary reaction with aldehydes enhanced the fluorescence properties, with the exception of hydrazones containing the 4-dimethylamino substituent. Hydrazones prepared from benzaldehyde and 4-chlorobenzaldehyde displayed greatly increased fluorescence intensity, with no bathochromic shift, while the hydrazones from cinnamaldehyde and p-anisealdehyde displayed a favourable bathochromic shift along with a slight increase in fluorescence intensity. Incorporation of the synthesized compounds into Columbia agar, however, did not have the expected effects, as the majority of observed fluorescence was seen to be due to the substrate, and not the fluorophore. A high degree of localization of fluorescence within bacterial cells was, however, observed, although longer chain N-substituents appeared to have bactericidal effects on the microorganisms tested.
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Graziotto, Marcus Edward. "Chemical tools for understanding the biological activity of platinum anticancer agents." Thesis, University of Sydney, 2021. https://hdl.handle.net/2123/24492.
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Platinum-based chemotherapeutics are widely used for chemotherapy, but their continued use is restricted by patient side effects and resistance. To maximise efficacy and minimise side effects, there is a need to personalise the treatment to the patient and their cancer, which requires a better understanding of the biological interactions of platinum complexes. This thesis has investigated these interactions through new strategies and techniques.
Novel monofunctional platinum complexes were investigated in order to distinguish how these complexes differ from clinical agents. Two members of the series had a dramatic divergence in cytotoxicity which was ascribed to their cellular accumulation. Their protein binding profiles were characterised by SEC-ICP-MS for the first time, indicating that the monofunctional complexes react with unique intracellular protein targets.
Fluorogenic probes were recognised as tools that would help to unravel further information on biological platinum interactions. With no fluorogenic naphthalimide tetrazines reported to date, a novel series of compounds were synthesised. These compounds exhibited a strong fluorogenic response in vitro and in vivo. Their versatility was demonstrated by labelling of insulin fibrils for high-resolution imaging. Based on this scaffold, probes that monitor organelle health were developed. The first probe reported on the distribution of lysosomes within cells. The second probe had a fluorescent response that was sensitive to the mitochondrial membrane potential, which is an indicator of cellular health. Both probes were used in preliminary studies with platinum complexes, revealing that the mitochondria are disrupted and that the lysosomes do not change after 1 h of treatment.
The tools developed in this work have revealed insights about how platinum complexes interact with cells. It highlights the importance of studying these interactions and their translation to the clinic to improve patient outcomes.
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Jahandar, Kojouri Kimia. "Single Molecule Magnet and Luminescence Properties of Lanthanide and Transition Metal Complexes Using Tetrazine and Naphthalimide Based Ligands." Thesis, Université d'Ottawa / University of Ottawa, 2018. http://hdl.handle.net/10393/38384.
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This thesis examined two distinct characteristics of lanthanide and transition metal complexes: Magnetism and Luminescence. In chapter two, synthesis, characterization, magnetic and luminescence investigations of mononuclear lanthanide complexes using Schiff-base tetrazine based ligand were performed. Six novel lanthanide complexes, [LaIIICl3(Htzpy)2], [TbIIICl2(Htzpy)2(MeOH)]Cl, [HoIIICl2(Htzpy)2(MeOH)]Cl, [DyIIICl2(Htzpy)2(MeOH)]Cl, [ErIIICl2(Htzpy)2(MeOH)]Cl and [YbIIICl2(Htzpy)2]Cl have been synthesized successfully and the studies were performed with the application of single crystal X-ray diffractometry, SQUID magnetometry, UV-Vis-NIR spectrometry and custom-built hyperspectral microscope (for luminescence spectroscopy). Chapter three is mainly about the luminescence properties of CoII and CuII complexes using a naphthalimide based ligand. Two complexes, [CoIICl2(Pynap)2] and [CuIIBr2(Pynap)2] were synthesized successfully and characterized using single crystal X-ray diffractometry, UV-Vis spectrometry and hyperspectral microscope (for luminescence spectroscopy). In order to have information about the electrochemical properties of CoII and CuII complexes, their redox activity was monitored by cyclic voltammetry (CV) and compared with the parent ligand. In addition, a rational design to synthesize a new ligand (dipicnap) which consists of both naphthalimide and dipicolinic acid moieties is presented.
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Wagner, Ricarda [Verfasser], Börje [Akademischer Betreuer] Sellergren, and Bernhard [Gutachter] Lippert. "Imprinted fluorogenic receptors composed of a polymerisable naphthalimide-based oxyanion probe / Ricarda Wagner. Betreuer: Börje Sellergren. Gutachter: Bernhard Lippert." Dortmund : Universitätsbibliothek Dortmund, 2013. http://d-nb.info/1103588001/34.
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Loving, Galen. "New tools derived from the solvatochromic 4-N,N-dimethylamino-1,8-naphthalimide fluorophore for the detection of biomolecular interactions." Thesis, Massachusetts Institute of Technology, 2009. http://hdl.handle.net/1721.1/55092.
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Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2009.Cataloged from PDF version of thesis. Vita.
Includes bibliographical references.
The concept that complex cellular behavior is driven by an intricate network of biomolecular interactions, which emerged through billions of years of evolution, is one of the great wonders of nature. Living cells must constantly assimilate vital information from the surrounding environment and respond appropriately. Such responses include growth, proliferation, migration, and even death. Much of this activity is tightly regulated through elaborately integrated signal transduction pathways - sometimes involving hundreds of cellular components. In order to further our understanding of the basic molecular machinery responsible for coordinating life processes at the cellular level, new tools are required. Fluorescence methods have formed a cornerstone of modern cell biology and have allowed researchers to interrogate the dynamics of many biomolecular events in real-time. However, the criteria for a good fluorescent probe are often numerous and demanding, particularly when considering applications in complex chemical environments like that of a living cell. Tradeoffs often exist between variables such as good extinction coefficients, suitable wavelengths of excitation and emission, thermal and photochemical stability, size, and others. Here in, we report a new series of fluorescent tools based on the solvatochromic 4-N,Ndimethylamino- 1,8-naphthalimide (4-DMN) fluorophore for the study of biomolecular interactions. This fluorophore is distinctive in that it yields very few compromises by combining many of the key elements required of a good fluorescent tool.
(cont.) It can be excited in the visible spectrum (400-450 nm), thus minimizing the damaging effects of high-energy UV light; derivatives of the dye can be prepared in few synthetic steps for facile incorporation into peptides and proteins; it is highly stable to a wide range of chemical conditions; and it possesses extremely sensitive switch-like fluorescent properties capable of responding to subtle changes in the local solvent environment. This thesis chronicles the design and validation of a new fluorescent amino acid of the 4-DMN dye as well as. a series of thiol-modifying agents for application in protein and peptide studies. The power of these new tools is demonstrated using the calcium binding protein calmodulin as a model system. Ongoing work to develop a sensitive sensor of Cdc42 activity is also described.
by Galen Loving.
Ph.D.
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Al, Souki Eyad. "Investigation of new TADF material derivatives of 1,3,5-triazine and 1,8-naphthalimide molecules and study of the fluorine impact." Electronic Thesis or Diss., Université de Lille (2022-....), 2023. http://www.theses.fr/2023ULILR055.
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Les propriétés de fluorescence à retardement activée thermiquement (TADF), qui permettent de capter la lumière à partir des excitons singulet et triplet sans recourir à des métaux lourds nobles, suscitent un vif intérêt dans un large éventail d'applications, notamment les diodes électroluminescentes organiques (OLED). Dans le cadre de cette étude, une nouvelle série de molécules TADF a été synthétisée, présentant la 2,4,6-tris(4-fluorophényl)-1,3,5-triazine en tant qu'unité acceptrice combinée à de multiples unités donneuses (mono-, di-, ou tri-substitutions). Le processus de synthèse visait à être simple et économique, mais il s'est avéré insuffisant pour l'accès à des quantités suffisantes de composés, des quantités importantes étant nécessaires aux processus de sublimation et de fabrication de dispositifs OLED. En guise de solution, une méthode de synthèse alternative a été mise en œuvre, impliquant des réactions de couplage oxydant catalysées par le cuivre. De plus, une autre série de composés fluorés possédant le motif 1,8-naphtalimide en tant qu'unité acceptrice a été synthétisée à l'aide de réactions de couplage croisé catalysées par le palladium. Une analyse thermique complète de ces deux séries de composés a démontré l'influence favorable de l'incorporation de fluor, notamment lorsque le nombre d'atomes de fluor est le plus élevéThermally activated delayed fluorescence (TADF) properties, which enable the harvesting of light from both singlet and triplet excitons without the use of any noble heavy metals, are of interest for a wide range of applications, including organic light-emitting diodes. In this study, a novel series of TADF molecules featuring 2,4,6-tris(4-fluorophenyl)-1,3,5-triazine as an acceptor unit decorated with multiple donor units in mono-, di-, or tri-substituted configurations was synthesized using a simple nucleophilic aromatic substitution reaction. Scaling up the synthesis of these molecules was essential for the sublimation experiments and device fabrication processes. Since this synthetic pathway was not suitable for the synthesis of larger amounts of molecules, an alternative synthesis method was used by performing copper-catalyzed oxidative coupling reactions. Furthermore, another new fluorinated series based on 1,8-naphthalimide as an acceptor unit and several donor units were synthesized through palladium-catalyzed cross-coupling reactions. The thermal characteristics of these two series of compounds were studied, which showed the positive impact of fluorine incorporation, specifically for the highest fluorine contents
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Angelo, Ulisses Fiorin. "Imidas naftálicas e piromelíticas dissubstituídas como ligantes para complexos de metais de transição \'\'d\'\' com potencial aplicação em redes de coordenação metal-orgânicas." Universidade de São Paulo, 2017. http://www.teses.usp.br/teses/disponiveis/59/59138/tde-10062017-153532/.
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As imidas naftálicas (INs) compõe uma classe de moléculas orgânicas aromáticas derivadas, geralmente, de um anidrido naftálico e uma amina primária. São de grande interesse na área de materiais devido a uma série de propriedades físicas e químicas, mas principalmente devido à suas propriedades fotofísicas. Derivados de INs são compostos fluorescentes com propriedades fotofísicas interessantes como fotoestabilidade, emissão de fluorescência variável (dependendo dos ligantes, pH, temperatura e solvente), solvatocromismo e halocomismo. O estudo de compostos de coordenação formados por imidas naftálicas e metais de transição abre um leque interessante no que tange a pesquisa e desenvolvimento de novos materiais. Esta tese descreve a síntese da imida 4-amino-N-piridina-1,8-naftalimida (NF2), da diimida N,N\'-Bis-(4-piridil)piromelítica (DI1), a determinação dos valores de pKa (2,75 e 3,49), absortividade molar (3537 L.mol-1.cm-1), efeito solvatocrômico (positivo) e rendimento quântico (0,27) de NF2; absortividade molar (18246 L.mol-1.cm-1) e solvatocromismo negativo para DI1. Foram sintetizados compostos de coordenação entre o ligante DI1 e os íons Fe3+; Ru3+ e Co2+, porém a formação de complexos com o ligante NF2 não foi observada por meio das técnicas aplicadasNaphthalic imides (INs) comprise a class of aromatic organic molecules generally derived from a naphthalic anhydride and primary amine. They are of great interest in the field of materials chemistry due to a number of physical and chemical properties, but mainly to their photophysical properties. Derivatives of INs are fluorescent compounds with several interesting photophysical properties such as photostability, variable fluorescence emission (depending on ligands, pH, temperature and solvent), solvatochromism and halochromism. The study of coordination compounds formed between naphthalic imides and transition metals opens up an interesting range of research and development of new materials. This thesis describes the synthesis of 4-amine-N-pyridine-1,8-naphthalimide (NF2) and N, N\'-Bis- (4-pyridyl) pyromellitic diimide (DI1) , measurement of pKa values (2.75 and 3.49), molar absorptivity (3537 L:mol1:cm1), solvatochromic e_ect (positive) and quantum yield (0.27) of NF2; Molar absorptivity (18246 L.mol-1.cm-1) and solvatochromic efect (negative) for DI1. Coordination compounds with DI1 and Fe3+; Ru3+ and Co2+ ions were synthesized; but complexes with NF2 was not observed by the applied techniques
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CORREIA, RIBEIRO Gustavo. "PHOTOINDUCED ENERGY AND ELECTRON TRANSFER PROCESSES AT LIQUID-LIQUID INTERFACES." Doctoral thesis, Università degli Studi di Trieste, 2021. http://hdl.handle.net/11368/2988356.
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This project focus on a electron transfer reaction and its integration in a liquid-liquid interface. To do so we studied the synthesis of different dyes such as the Perylene, Perixanthene xanthene and the Naphthalimides. We then aplied these dyes in an interface between two liquids, either the complex emulsion of hexane/fluorohexane/water or a water/micellar interface. We finished with a study of a electron transfer model reaction in the interface using the dyes as photocatalysts.
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Klider, Karine Cristina Carrilho Weber dos Santos. "PREPARAÇÃO DE COMPOSTOS ORGÂNICOS COM POTENCIAL APLICAÇÃO EM DISPOSITIVOS FOTOVOLTAICOS: AVALIAÇÃO DE PROPRIEDADES FOTO-FÍSICAS E ELETROQUÍMICAS." UNIVERSIDADE ESTADUAL DE PONTA GROSSA, 2016. http://tede2.uepg.br/jspui/handle/prefix/11.
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In this study, we evaluated the optical and electrochemical properties of organic compounds of different types in order to analyze their potential for application active layer in photovoltaic devices. The work was divided into three parts. The first discloses the preparation and characterization of a derivative of 1,8-naphthalimide chromophore prepared from the reaction with a benzonitrile unit (also synthesized and characterized in this work). The BID-NB compound showed optical and electrochemical properties equivalent of the chromophore with optical and electrochemical band gap of 3.41 eV and 2.19 eV. Photovoltaic devices using bilayer architecture, constructed with the compound as the active layer, reached 0.9% of power conversion efficiency (PCE) and a current density at short circuit of 5.68 mA cm-2 by using the C70 fullerene as electron acceptor layer, and 1,8-diiodoocthane as additive in the solution for active layer deposition. The second part the work described the preparation of conjugated molecules (with electron donor acceptor characteristics) from the indigo dye modification by addiction of thiophene units. It was found that increasing number of thiophene units resulted in better opto-electrochemical properties. The molecule that showed the best behavior, DHT-IND, presented optical and electrochemical band gap of 1.64 and 1.45 eV respectively. Despite the low band gap value, the bulk heterojunction (BHJ) solar cell constructed with a 1: 3 mixture of DHT-IND and PC71BM as active layer, showed PCE of 0.7% and current density at short circuit of -4.59 mA cm-2. The fill factor (FF) was 26%. In the third part of this work we evaluated the photocurrent generation by the copolymer PPV/DCN-PPV formed by DCN-PPV chains attached to PPV chain. The evaluation performed as film deposited on a glass substrate containing ITO coated, which has exposed to a LED ilumination. After irradiation the copolymer generated current of A cm-2 (unstable), and -2 A cm-2 (stable).
Neste trabalho foram avaliadas as propriedades ópticas e eletroquímicas de deferentes compostos orgânicos, e analisar suas potencialidades para aplicação como camada ativa em dispositivos fotovoltaicos. Dividiu-se o trabalho em três partes. A primeira revelou a preparação e caracterização de um derivado do cromóforo 1,8-naftalimida, preparado a partir da reação com uma unidade de benzonitrila previamente preparada e caracterizada. O composto 4-(2-(1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-il)etoxi)-2,5-dimetilbenzonitrila, ou BID-NB, apresentou propriedades ópticas e eletroquímicas equivalentes às do cromóforo, com band gap óptico de 3,41 eV e eletroquímico de 2,19 eV. Dispositivos fotovoltaicos de bicamada foram construídos com o composto BID-NB como camada ativa, sendo que a eficiência máxima de conversão foi de 0,9% com uma densidade de corrente de curto circuito de -5,68 mA cm-2. O dispositivo que auferiu tais resultados foi construído com o fulereno elétron-aceptor C70, e com o auxilio do aditivo 1,8-diiodooctano na deposição da camada ativa. A segunda parte do trabalho consistiu da preparação de moléculas conjugadas do tipo doador/aceptor de elétrons, a partir da modificação do corante índigo com unidades de tiofenos. Constatou-se que o aumento da quantidade de unidades de tiofenos nas moléculas favoreceu suas propriedades opto-eletroquímicas. O composto 7,14-bis(3``,4`-diexil-[2,2`:5`,2``-tertiofen]-5-il)diindolo[3,2,1-de:3`,2`,1`-il][1,5]naftiridina-6,13-diona, ou DHT-IND, foi o que apresentou os menores valores de band gap óptico e eletroquímico, nos valores de 1,64 e 1,45 eV respectivamente. O dispositivo fotovoltaico de heterojunção, construído a partir da mistura 1:3 de DHT-IND e PC71BM como camada ativa, apresentou eficiência de conversão de 0,7% e densidade de corrente de -4,59 mA cm-2. Na terceira parte deste trabalho avaliou-se geração de fotocorrente em um copolímero formado por blocos de PPV ligados a blocos de DCN-PPV (PPV/DCN-PPV). A avaliação foi efetuada na forma de filme sobre um substrato de vidro contendo ITO, o qual foi exposto a iluminação de LED. O copolímero gerou corrente de até -4 A cm-2 (instável), e de -2 A cm-2 (estável) após iluminação.
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Yuan, Dongwu. "The synthesis and fluorescence properties of some substituted naphthalimides." Thesis, University of Central Lancashire, 1994. http://clok.uclan.ac.uk/20016/.
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A number of known and novel naphthalimide derivatives have been synthesised. For many of the known compounds, improvements in their syntheses have been achieved in terms of higher yield and/or milder reaction conditions. Some of the novel compounds have been prepared with the aim of improving the water-solubility of the system by the introduction of substituents containing polar terminal groups and by sulfonation on the naphthalene ring. The sulfonated compounds exhibit quite good watersolubility and the others also show some improvement. Chloroacetyl and maleimido functions have been introduced into naphthalimides as reactive groups for attachment to biological molecules. Some brominated naphthalimides have been prepared for a study of their photochemical properties. The absorption and fluorescence properties of the synthesised naphthalimides have been studied. The maximum absorption wavelengths and extinction coefficients of their ultraviolet/visible spectra and their fluorescence spectra together with quantum yields and lifetimes have been measured for the naphthalimide compounds. The effects of the substituents on the photophysical properties were studied. The fluorescence properties of 4-(n-butylamino)-9-(n-butyl)-1,8-naphthalimide were investigated in a range of organic solvents including binary solvent mixtures and aqueous solution containing sodium dodecyl sulfate. The environment-dependence of the fluorescence properties indicates a potential for the naphthalimides to be used as fluorescent probes and labels. The heavy atom quenching effect in the fluorescence quantum yields and lifetimes of the 3-bromonaphthalimides have been observed in the selected organic solvents. The fluorescence properties of some naphthalimides have been studied in ethanol and water. Specific solvent effects on the naphthalimide emission properties have been observed. The photophysical behaviour of a series of 4-amino-9-aminoalkyl-1,8-naphthalimides in water were studied as a function of pH. Changes in the absorption and fluorescence properties of the compounds due to the protonation of the 4-amino group were observed and used for calculation of the pKa5 and fluorescence quenching constants of the naphthalimides.
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Kucheryavy, Pavel Vladimirovich. "Proton-Coupled Electron Transfer for Long-Lived Charge Separation and Photocatalytic Water Splitting." Bowling Green State University / OhioLINK, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1285314331.
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Vollmer, Moritz [Verfasser]. "Neue hocheffiziente Phthalimid- und Naphthalimid-basierte Fluoreszenzfarbstoffe: Synthese, photophysikalische Charakterisierung und Einsatz als optische Aufheller / Moritz Vollmer." München : Verlag Dr. Hut, 2019. http://d-nb.info/1198542691/34.
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Guerta, Adelsimara Ceballos. "Propriedades fotoquímicas e fotofísicas de novos materiais derivados quinolinas e di naftalimidas." Universidade de São Paulo, 2007. http://www.teses.usp.br/teses/disponiveis/46/46135/tde-28052008-093225/.
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Um dos temas modernos em fotoquímica em soluções aquosas é a observação de prototropismo de estados eletrônicos excitados. Resumidamente, moléculas orgânicas contendo grupamentos ácido-base quando excitadas, e cujo tempo de vida do estado excitado seja longo o suficiente, reações competitivas de transferência de prótons com as do processo de relaxação poderão ocorrer. No caso de aumento de acidez os compostos são denominados fotoácidos e no contrário fotobases. Este fenômeno é atribuído a um estado isoeletrônico da molécula no estado fundamental tendo sido descritos variações de até sete unidades de pKa. Do ponto de vista da investigação Físico-Química o estudo da circunvizinhança, na qual as espécies excitadas percorrem uma superfície de potencial seja na direção da reassociação seja na da ionização com posterior solvatação das mesmas, fornece uma importante ferramenta de análise de propriedades de micro ambiente. Esta possibilidade advém das excelentes propriedades espectrais dos grupos cromofóricos desta classe de compostos o que facilita o monitoramento das espécies transientes adicionado ao estágio técnico atual de medidas ultra-rápidas. Neste estudo enfocamos o estudo de derivados de quinolina (fotobase), contendo grupos passíveis de reação de polimerização. Os derivados 3-alil-2-metilquinolin-4-ol (HIQ) e 3-alil-4-cloro-2-metilquinolina (CLQ) foram preparados e as propriedades fotoprototrópicas determinadas. O primeiro monômero comporta-se como fotobase ou fotoácido dependendo do pH do meio que este se encontra e o CLQ como fotobase. Na seqüência tentamos obter polímeros do HIQ e CLQ, porém não se obteve um resultado positivo devido a dificuldade da polimerização de grupos alil inclusive por via eletroquímica. Em seqüência prosseguimos à determinação das propriedades fotoquímicas e fotofísicas de derivados de di-naftalimidas, devido às inúmeras aplicações destes compostos em novos materiais. Propriedades destas ftalimidas são em geral devidas à conjugação dos elétrons do grupo imida aos do anel naftalênico. Esta conjugação confere uma alto grau de planaridade aos derivados, de forma que a solvatação é dificultada. Observa-se via de regra espectros tanto de absorção como de emissão de fluorescência com alta resolução vibrônica seja nas transições S0-S1 ou S0-S2. Os efeitos espectroscópicos esperados de solventes devem ser função das cadeias laterais nos grupos imidas. Neste contexto foram preparados vários derivados para uso como sondas. Foram estudados sete compostos: N,N\'-n-butil-1,4,5,8-di-naftalimida (BUNDI); N,N\'-(2-cloro-etileno)-1,4,5,8-di-naftalimida (CLNDI); N,N\'-(2-bromo-etileno)-1,4,5,8-di-naftalimida (BRNDI); N,N\'-2-hidroxietileno-1,4,5,8-di-naftalimida (OHNDI); N,N\'-(N,N\'-dimetiletilenodiamina)-1,4,5,8-di-naftalimida (DMNDI); N,N\'-amino-1,4,5,8-di-naftalimida(DANDI) e N,N\'-1,4,5,8-di-naftalimida (NDI). Os derivados aqui estudados responderam de forma excelente às expectativas levando seja à formação de dímeros e agregados seja a alterações nas intensidades e relações das bandas vibrônicas (excitação e emissão) das transições S0-S1. Demonstra-se aqui a excelente qualidade destes compostos como repórteres do próprio estado de suas moléculas como do meio circunvizinho.Excited state proto transfer reactions in aqueous media is among current themes in photochemistry research. Shortly, organic molecules having acid or basic groups and presenting excited state lifetimes long enough, competitive prototropic reactions can occur. This phenomenon is attributed to an isoelectronic state of the ground state molecule and up to seven units of pKa changes have been described. From the Physical Chemistry investigation viewpoint the study of the neighborhood where the excited species have a potential surface to describe either for the re association reaction or for the ionization followed by solvation, presents an important tool for the analysis of the microenvironment. This feature arises from the optimal spectral properties of the chromophoric groups of this class of compounds, which facilitates monitoring transient species as well by the current technology standards. In this work focused a photobase derivative from quinoline having a suitable polymerizable group. The 3-allyl-2-methylquinolin-4-ol (HIQ) and the 3-allyl-4-chloro-2-methylquinoline (CLQ) were synthesized and their photoprotrtopic behavior determined. The first compound shows both photoacid and photobase character as a function of the solution pH whereas CLQ is a photobase. Following attempts to obtain polymers were unsuccessful either using electrochemical routes. Given the several applications of di-naphthalimides as new materials, photochemical and photophysical of some derivatives were determined. The properties of these phthalimides arise from the conjugation of the imide electrons with vicinal naphthalic ring. This conjugation confers a high planarity degree and hindering the chromophore solvation. Accordingly high vibronic resolution is observed in both excitation and emission spectra either in the S0-S1 or S0-S2 transitions. Expected solvent spectroscopic effects are thus due to the radical N-imide groups. In this subject several di-imides derivatives were prepared for the use as medium probes. Seven compounds were investigated: N,N\'-n-butyl-1,4,5,8-di-naphthalimide (BUNDI; N,N\'-(2-chloroethylene)-1,4,5,8-di-naphthalimide (CLNDI); N,N\'-(2-bromoethylene) )-1,4,5,8-di-naphthalimide (BRNDI), N,N\'-2-hydroxiethylene-1,4,5,8-di-naphthalimide (OHNDI); N,N\'-(N,N\'-dimethylethylenodiamine)-1,4,5,8-di-naphthtalimide (DMNDI); N,N\'-amine-1,4,5,8-di-naphthalimide (DANDI) and N,N\'-1,4,5,8-di-naphthalimide (NDI). The derivatives studied fully satisfied the expectations leading to either a dimer and aggregate formation or to changes in the intensities or in the vibronic bands intensities relationships (excitation and emission) of the S0-S1 transitions. Here it is shown the excellent quality of these molecules as self and microenvironment probes.
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張庭瑞. "Synthesis of Phthal-, and Naphthalimide Disperse Dyes." Thesis, 1995. http://ndltd.ncl.edu.tw/handle/76069968395261008145.
Full textAbstract:
碩士國立臺灣科技大學
纖維及高分子工程技術研究所
83
Azo dyes were synthesized by the coupling reaction of diazotized aromatic primary amine with various aromatic amino compounds. A series of phthal-, and naphthalimide disperse azo dyes were obtained by dehydration of phthalic or naphthalic anhydride and azo dyes. Their chemical structure were confirmed by IR, UV, Mass, 1H-NMR spectrum. These dyes were applied to polyester fabrics and shown yellow hues. The sublimation fastness (200℃) of these dyes on polyester fabrics are range 3~5 grade. The lightfastness of these dyes on fabrics are range 2~6 grade. The photofading of dyes in ethyl acetate was studied in the present and absence of air. The results shown that the kinetic order of photofading are IV and V grade respectively. The photofading of dye 9f shows a phototreduction mechanism in the absence of air. The photofading of dyes and the pruity of colour on polyester fabrics were studied. The results shown Ⅱ,Ⅲand Ⅳ order respectively.
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Liu, Jen-Wei, and 劉任偉. "Synthesis of Highly Efficiency Fluorescent 1,8-Naphthalimide Derivatives." Thesis, 2014. http://ndltd.ncl.edu.tw/handle/9gctyu.
Full textAbstract:
碩士淡江大學
化學學系碩士班
102
1, 8 - Naphthalimides derivatives have strong fluorescence characters and their synthesis have been widely studied. They have been commonly used as fluorescent probes, anticancer agents, fluorescent cellular imaging agents and fluorescent dyes. They possess planar scaffold and stable conjugated system to lead to more photochemical stability, large Stokes shift and multiple fluorescence properties. Because 1, 8 - Naphthalimides derivatives have various application, therefore we want to explane a facile synthesis of derivatives to expect higher fluorescence efficiency. The first part is synthesis of nitrogen 1, 8 - Naphthalimides derivatives. These compounds can be complex with metal ion through lone pairs to lead to chelating structure. The fluorescence properties would be changed that can be used the metal ion probe in the future. Furthermore we can test its structure – activity relationship (SAR) studies as anticancer agents. The second part is synthesis of extended 1, 8 - Naphthalimides planarity derivatives. Arylation of azoles is mediated by Pd – Cu system. We can change the resulting adducts from weaker blue - violet fluorescence to stronger conjugated system with yellow-green fluorescence. It can be novel fluorescent labeling agents or fluorescent dyes. Low concentrations, these different functional 1, 8 - Naphthalimides derivative to produce intense fluorescence properties. They can be more widely used in various aspects.
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Huang, Ching-Ting, and 黃敬婷. "Biofunctional Nanofibers and Supramolecular Hydrogels of Naphthalimide-based Peptides." Thesis, 2014. http://ndltd.ncl.edu.tw/handle/jqjq6a.
Full textAbstract:
碩士國立交通大學
材料科學與工程學系所
103
Adhesive peptide sequences within many ECM proteins have been discovered via competitive adhesion assays and mutagenesis experiment. In our laboratory, Novel hydrogels based on Naphthalimide with peptide sequences DGEA, IKVAV, GFF, and FFG have been synthesized. This thesis has three-fold. In the first part, DGEA-containing peptides hydrogelators based on naphthalimide are developed. The DGEA tetra-peptide sequence is the shortest collagen type I-derived motif recognized by the collagen-binding integrin 21. Also, the materials have significant differences in their fluorescence intensity because of the capping group, 1,8-Naphthalimide-N-acetic acid and 4-Nitro-1,8-Naphthalimide-N-acetic acid. In the second part, small molecule hydrogels containing IKVAV polypeptide induced self-assembly to form nanofiber gel was synthesized. The IKVAV peptide sequence is located in the α-1 chain of laminin responsible for cell adhesion and neurite outgrowth. We reduce the molecular weight of IKVAV-containing hydrogelator and toward a better material that fits the Atomic economy and Green chemistry. In the last one, we capped peptide sequences, GFF and FFG with aromatic group, naphthalimide, and compared the cell viability of NI-GFF and NI-FFG. We also tested the cell viability of 4-Nitro-1,8-naphthalimide, NO2-FDGEA and NO2-FIKVAV to know whether if the cytotoxicity of the materials can be improved by conjugating the peptide sequences.
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Kao, Wei –. Ting, and 高維廷. "Synthesis of 1,8 - Naphthalimide derivatives for potential anticancer drugs." Thesis, 2018. http://ndltd.ncl.edu.tw/handle/ayfx9g.
Full textAbstract:
碩士淡江大學
化學學系碩士班
106
The 1,8 - Naphthalimide derivatives are widely used in the synthesis of anticancer drugs. The activity of these compounds embed in DNA has been tested and the results are very good. In recent years, many scientists have devoted themselves to the study of new synthetic methods of synthesizing of 1,8 - Naphthalimide derivatives. It has been found that these compounds embedded in breast cancer cells, colorectal cancer cells, and lung cancer cells very well. We designed two series of derivatives and hope to further study their applications in the future.
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Chen, Min-hung, and 陳明鴻. "Synthesis and Property of Polyhedral Silsesquioxanes Modified with Naphthalimide Dyes." Thesis, 2006. http://ndltd.ncl.edu.tw/handle/92954125137752196710.
Full textAbstract:
碩士國立中正大學
化學所
94
Reported in this manuscript, we synthesized ND and NDS successfully. Then ND and NDS handled with varies of metal ions, and can be characterized by NMR, MS, IR, TEM, NPA, UV and FL.
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Lin, Jhong-Hua, and 林仲驊. "Tunable Gelation and Fluorescence Properties of Naphthalimide-based Dipeptide Derivitives." Thesis, 2018. http://ndltd.ncl.edu.tw/handle/7mvjx9.
Full textAbstract:
碩士國立交通大學
材料科學與工程學系所
106
A systematic study of the synthesis and characterization of self-assembly naphthalimide-dipeptide hydrogels is described in this thesis. Four hydrogelators, NI-FG, NI-FA, NI-FV, and NI-FI were designed and synthesized. The hydrophobicity of the hydrogelators was regulated by changing the peptide sequence with amino acids containing alkyl side chains, i.e., glycine, alanine, valine, and isoleucine, which led to the differences in the gelation and fluorescence properties. The condition of hydrogel transition under neutral pH environment is verified. Formation of self-assembled nanotubes was examined under the transmission electron microscope. The fluorescence spectra showed an internal charge transfer band in basic solutions. And a chemical modification on the naphthalimide fluorophore using piperazine was introduced to adjust the color and to allow photoinduced electron transfer to enhance possible applications. Based on the above results, naphthalimide-dipeptide materials open up remarkable potential in biomedical electronic applications, such as bioimaging, drug delivery, pH sensing, and etc. This research provides a promising strategy in molecular designing of the fluorescent aqueous self-assembling small molecules.
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Hsu, Ling-Huang, and 徐令皇. "Organic π-Conjugated Nanomaterials from Self-assembled Naphthalene Diimide and Naphthalimide." Thesis, 2014. http://ndltd.ncl.edu.tw/handle/5ek6yq.
Full textAbstract:
碩士國立交通大學
材料科學與工程學系所
103
In this study, the conjugated systems are modified by attaching peptide sequences to improve functionality for applications. This thesis has two different parts. In the first part, we study the rheological properties of peptide hydrogels. Incorporation of a Naphthalene Diimide (NDI) and a single amino acid in the imide position, we found that different amino acid derivatives can determine the strength and gelation properties of this self-assembled hydrogels. The four compounds are presented in the study (C8NDI-S, C8NDI-D, C8NDI-E and C8NDI-K) which forms stable hydrogel in a wide range of pH conditions. The use of S or E can form hydrogels under acidic condition. The presence of K can facilitate the formation of the hydrogel in basic condition. The usage of D can gel water in neutral condition. This work illustrates the importance of the structure-property relationship on the development of new nanoscience and self-assembly nanomaterials. It also suggests that Naphthalene Diimide is an efficient hydrophobic component in the formation of hydrogels. In the second part, we study the properties of aggregation-induced emission (AIE) of the chromophores. Piperidine was used as electron-donating group to modify the 1, 8-naphthalimide (ppNI). Importantly, the ppNI series exhibit AIE properties. We further extend this study to multiple amino acids where the combination of ppNI and phenylalanine (Phe) or aspartic acid (Asp) was conducted. The materials have significant differences in their fluorescence intensity, which have a higher emission peak at acidic conditions. The number of aspartic acid can alter the hydrophilicity of hydrogels and the properties of AIE. Through this study, we found a simple strategy to construct the one-dimensional (1-D) nano- and micro-structures in relatively large scale.
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Unnikrishnan, Anagha K. "Design, Synthesis and Optical Characterization of 1,8-Naphthalimide based D-pi-A System." Thesis, 2021. https://etd.iisc.ac.in/handle/2005/5095.
Full textAbstract:
Design, Synthesis and Optical Characterization of 1,8-Naphthalimide based D-pi-A System
Luminescent materials find a lot of application in the field of OLEDs and bio-medical applications [1-2]. Our group has recently developed a series of 1,8-naphthilimide (NPI) based Donor-Acceptor (D-A) system [2], and we were able to fine-tune optical properties of 1,8-naphthilimide by changing donor strength judiciously. Furthermore, the PL features of 1,8-naphthilimide derivatives were sensitive to triplet oxygen, and these molecules were explored for differential imaging of hypoxia and normoxia live cancer cells. In the present study, we aim to extend the scope of available naphthalimide dyes by extending the system's conjugation by placing pi-spacer to obtain emission in near IR and utilize them for bio-imaging. In our earlier reports, the cyclic amine donors were directly connected with NPI acceptor through nitrogen on the amine moieties. In this study, we intended to connect the donor moiety via the carbon center of the amine donor moiety through a π-conjugated spacer with anticipation that the conjugated spacer may enhance the electronic conjugation length and reduce the bandgap; consequently, NIR emission may be realized. Accordingly, we designed two D-pi-A and D-pi-A-pi-D systems where donor phenothiazine is linked to accepter NPI through the vinyl pacer. The newly synthesized molecules show emission in the NIR region and the results are summerised in this thesis.
1. Salehi, A.; Fu, X.; Shin, D.; So, F. Adv. Funct. Mater 2019, 1808803, 1–21.
2. Liu, J.; Guo, X.; Hu, R.; Liu, X.; Wang, S.; Li, S.; Li, Y.; Yang, G.. Anal. Chem.2016, 88 , 1052–1057.
3. Jena, S.; Dhanalakshmi, P.; Bano, G.; Thilagar, P. J. Phys. Chem. B 2020, 124, 5393–5406.
4. Monici, M. Biotechnology annual review, 2005, 11, 227-256.
5. Pansare, V.J.; Hejazi, S.; Faenza, W. J.; Prud’homme, R. K. Chemistry of materials, 2012, 24, 812-827.
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Huang, Y.-Jing, and 黃怡菁. "Stimuli-Responsive Fluorescence in Supramolecular [2]Pseudo-Rotaxane Containing Naphthalimide Host and Spiropyran Guest." Thesis, 2019. http://ndltd.ncl.edu.tw/handle/vcj2j2.
Full textAbstract:
碩士國立交通大學
材料科學與工程學系所
108
A [2]pseudo-rotaxane supramolecular polymer containing pillararene- and naphthalimide-based host and spiropyran-based guest. Upon UV exposure, the closed form of spiropyran unit changed reversibly to the open form of merocyanine unit, which could be utitlized as a metal ion sensor. Owing to the combination of the naphthalimide host as an energy donor and the merocyanine guest as an energy acceptor, the construction of [2]pseudo-rotaxane produces a more efficient Förster resonance energy transfer (FRET) to induce higher fluorescence, so the optical sensor responses of supramolecular polymer towards various metal ions can be further amplified. The optical switchable supramolecular polymer possessing selective fluorescence response towards various metal ions can open an new avenue to the chemo- and bio-sensor applications of [2]pseudo-rotaxane supramolecular polymer.
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Palhares, David Rodrigues. "Synthesis and biological evaluation of mono and bis-naphthalimide derivatives against SH-SY5Y, human brain cancer cells." Master's thesis, 2015. http://hdl.handle.net/1822/41134.
Full textAbstract:
Dissertação de mestrado em Medicinal ChemistryNaphthalimides (1H-benzo[de]isoquinoline-1,3-(2H)-diones) consists of a flat, generally π-deficient aromatic or heteroaromatic system and show strong hydrophobicity. These types of compounds with this moiety demonstrate inherent fluorescence and biological properties such as anticancer, antimicrobial, antitrypanosomal, analgesic, antioxidative and antiviral properties. The naphthalimide compounds are also known to be very good DNA intercalators, since the planar naphthalimido moiety binds by perpendicular insertion between the base pairs of the double helix of DNA. Previous work had already shown that mono and bis naphthalimido derivatives exhibit strong activity against different cancer cell lines. Here in this work will be demonstrate that the alkyl chain, i.e. the linker between the naphthalimido groups or the substituent attached at the end of the linker chain, do have an impact on the biological and DNA binding properties. Therefore the synthesis of a series of new mono-naphthalimide derivatives were prepared in moderate to good yields by reaction of aminonaphthalimides containing different alkyl chain length with carious aromatic aldehydes. The new bisnaphthalimides were prepared by an N-alkylation reaction of different linkers with the corresponding O-tosyl alkylnaphthalimides. The biological activity of the newly synthesized compounds includes their ability to bind DNA, their toxicity against SH-SY5Y human brain cancer cells in vitro, cell morphology and cellular uptake were tested. As expected the bis-naphthalimide derivatives gave better results when compared to the mono-naphthalimides in all tests. For the mono naphthalimides, longer the length of the alkyl chain, better are the results; also the nature of the aromatic aldehyde interfere with the results. For the bis-naphthalimides the type of linker has influence on biological activity and binding studies. It has been shown when the linker has more flexibility, the biological activity and binding studies gave better results.
As naftalimidas (1H-benzo[de]isoquinoline-1,3-(2H)-dionas) consistem num sistema planar aromático ou heteroaromático deficiente em electrões π e mostram forte hidrofobicidade. Estes tipos de compostos apresentam fluorescência e propriedades biológicas como anticancerígenos, antimicrobianos, antitrypanosomal, analgésica, antioxidante e antiviral. Os compostos de naftalimida também são conhecidos como intercalantes do ADN, pois o seu núcleo naftalimido planar liga-se através de inserção perpendicular entre os pares de bases da dupla hélice do ADN. Em trabalhos anteriores mostraram que os derivados mono e bis naftalimidas exibiram forte atividade contra diferentes linhas celulares cancerígenas. Neste trabalho foi possível demonstrar que a cadeia alquílica, por exemplo a cadeia ligando, tem ou não impacto nas propriedades quer biológicas quer na ligação do ADN. A síntese de novos derivados de naftalimida foram preparados com rendimentos de moderados a bons através da reação de aminonaftalimidas contendo diferentes tamanhos de cadeia alquílica com aldeídos aromáticos. As novas bis naftalimidas foram preparados por uma reação de N-alquilação com diferentes ligandos com os correspondentes O-tosil alquilnaftalimidas. A atividade biológica dos novos compostos sintetizados incluindo a capacidade de ligação ao ADN, sua toxicidade in vitro contra células humanas do cancro do cérebro, SH-SY5Y, a morfologia celular e a absorção celular foram testadas. Como esperado os derivados de bis-naftalimida apresentaram melhores resultados quando comparadas com as mono-naftalimidas em todos os testes efetuados. Para as mono-naftalimidas, os resultados mostraram que o aumento da cadeia alquílica, tal como a natureza do aldeído aromático influenciam os resultados na atividade biológica e nos estudos de ligação ao ADN. Para as bis-naftalimidas, o tipo de flexibilidade do ligando tem influência nos resultados de atividade biológica e nos estudos de ligação ao ADN.
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Jang, Ya-Chi, and 張雅琪. "Synthesis and evaluation of a novel naphthalimide-derived chromogenic sensor for Hg(II) and Cr(III) ions." Thesis, 2012. http://ndltd.ncl.edu.tw/handle/81210820392695866725.
Full textAbstract:
碩士東海大學
環境科學與工程學系
100
In this thesis, the design and synthesis issued by the cooperative effect of ion sensors, research framework to 1,8-naphthalimide photoluminescence emission corporation, as a recognition unit selection; dithiodioxomonoaza as the capture metal ion recognition unit. In addition to design a control group to explore and to confirm the capture of the location of the metal ions for nitrogen, oxygen, sulfur crown ether, rather than the other locations. Crown ether molecules with the fluorophore binding conjugate, resulting from charge transfer, so there will be color change effects available to the naked eye can quickly detect metal ions arrested grasp. Therefore, the structure of the compounds to determine the correctness of the structure through NMR spectroscopy, UV-vis-NIR and fluorescence spectroscopy to the determination of the chemical sensor performance, but also to the naked eye identification method to detect the effect of its The detection limit of 1 × 10-5 M. This chapter, namely the results of the two fluorescent probes designed and synthesized for our show: UV-vis-NIR absorption spectra and color change, as well as changes in the fluorescence emission spectra, compound (I) added to the specific metal ions under observation in line with our the desired results, and will not participate in any ion binding. Compound (II), via titration with the metal ion competition experiments can be learned fluorescent probes for mercury ion and chromium ion binding capacity and selectivity, and sensitivity to achieve the ppb level, and compounds with mercury ion reaction is only 18 seconds. Therefore, our compounds have the advantage of dual recognition ion capacity, and by different pH values the initial screening of the two ions, thus proving that this sensor has a fast screening and compliance with high economic efficiency of the chemical sensors.
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Vidal, Rita Isabel Henriques Sério. "Antitumor activity of liposomal formulations oof bis-naphthalimide derivatives and erlotinib, in vitro study in pancreatic cancer cell lines." Master's thesis, 2013. https://repositorio-aberto.up.pt/handle/10216/83145.
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Hunag, Wei-Ting, and 黃偉婷. "Synthesis, Structures, and Fluorescence Sensing of Small Organic Compounds of Cadmium Coordination Polymers Containing 1,8-Naphthalimide-Based Bispyridyl Ligand." Thesis, 2018. http://ndltd.ncl.edu.tw/handle/cez5ed.
Full textAbstract:
碩士國立暨南國際大學
應用化學系
107
A series of fluorescent metal–organic frameworks (MOFs) based on Cd(II) and N-(pyridin-3-ylmethyl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-mbpy-34) and different aromatic dicarboxylates were synthesized. Compound [Cd(NO3)2(NI-mbpy-34)] (1) is a 1D ribbon-like chain structure; compound [Cd(1,4-bdc)〖"(NI-mbpy-34)" 〗_"2" ] (2, 1,4-bdc = benzene-1,4-dicarboxylate) is a 2D layer network；compound [Cd(1,4-ndc)(NI-mbpy-34)2] (3, 1,4-ndc = naphthalene-1,4-dicarboxylate) is a 3D pillared-layer framework. Compounds 1－3 exhibit strong solid-state fluorescence emissions, which would be applied in dectection of volatile organic and nitro compounds through vapor-sensing. Unfortunately, no significant fluorescence quenching was observed. Nevetheless, the toluene suspensions of 1 and 2 and the DMF suspension of 3 could be used as fluorescence sensors to dectect aromatic nitro compounds, such as nitrobenzene, 1,4-dinitrobenzene, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 4-nitrotoluene and 2,4-dinitrotoluene through obvious fluorescence quenching. On the other hand, nitromethane and 2,3-dimethyl-2,3-dinitrobutane are found to significantly enhance the fluorescence intensity of the DMF suspension of 3. Compounds 1－3 were found to adsorb iodine molecules, causing fluorescence quenching of 89%, 88% and 52%, respectively. Further, the color of the crystals of 1 and 2 is obviously changed from light yellow to brown. After dipping I2-loaded compounds 1－3 in methanol, I2 molecules were released into the solution, causing 63%, 68% and 100% recovery in fluorescence intensity for 1－3, respectively, making them reusable.
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Vidal, Rita Isabel Henriques Sério. "Antitumor activity of liposomal formulations oof bis-naphthalimide derivatives and erlotinib, in vitro study in pancreatic cancer cell lines." Dissertação, 2013. https://repositorio-aberto.up.pt/handle/10216/83145.
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Chen, Ya-Yin, and 陳雅音. "SYNTHESIS AND PROPERTIES OF NOVEL POLY(ETHER IMIDE)S CONTAINING TRIFLUOROMETHYL GROUPS AND POLY(ETHER NAPHTHALIMIDE)S CONTAINING PHTHALIDE GROUPS." Thesis, 2006. http://ndltd.ncl.edu.tw/handle/16795728160082047558.
Full textAbstract:
碩士大同大學
化學工程學系(所)
94
Part 1: A series of novel fluorinated poly(ether imide)s (IV) having inherent viscosities of 0.70-1.08 dL/g were prepared from 1,1-bis[4-(3,4-dicarboxyphenoxy)phenyl]cyclohexane dianhydride (I) and various trifluoromethyl (CF3)-substituted aromatic bis(ether amine)s II¬¬a-g by a standard two-step process with thermal and chemical imidization of poly(amic acid) precursors. These poly(ether imide)s showed excellent solubility in many organic solvents and could be solution-cast into transparent, flexible, and tough films. These films were essentially colorless, with an ultraviolet-visible absorption edge of 375-380 nm and a very low b* value (a yellowness index) of 5.5 to 7.3. They also showed good thermal stability with glass-transition temperatures of 207-269 oC, 10% weight loss temperatures in excess of 474 oC, and char yields at 800 oC in nitrogen more than 62%. In comparison with analogous V series poly(ether imide)s without the -CF3 substituents, the IV series polymers showed better solubility, lower color intensity, and lower dielectric constants. Part 2: A series of organosoluble and colorless fluorinated poly(ether imide)s (4a-g) were prepared from 3,6-bis(3,4-dicarboxyphenoxy) benzonorbornane dianhydride (1) and various trifluoromethyl (CF3)-substituted aromatic bis(ether amine)s 2a-g by a standard two-step process with thermal and chemical imidization of poly(amic acid) precursors. These poly(ether imide)s had inherent viscosities of 1.19-1.78 dL/g and showed excellent solubility in many organic solvents. They could be solution-cast into transparent, flexible, and tough films with good mechanical properties. These films were virtually colorless, with an ultraviolet-visible absorption edge of 372-379 nm and a very low b* value (a yellowness index) of 10.8 to 14.1. The glass-transition temperatures (Tg) and softening temperatures (Ts) were recorded between 216-292 oC and 209-285oC, respectively. The decomposition temperature for 10% weight loss all occurred above 479 oC in nitrogen and 467 oC in air, and the char yields at 800 oC in nitrogen were more than 51%. They also showed low dielectric constants of 2.84-3.58 (1 MHz) and moisture absorptions in the range of 0.05-0.19%. In comparison with analogous 5 series poly(ether imide)s without the -CF3 substituents, the 4 series ones showed better solubility, lower color intensity, and lower dielectric constants. Part 3: A series of organic-soluble polynaphthalimides (PNI) bearing flexible ether links and phthalide cardo group were synthesized from 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) with 3,3-bis[4-(4-aminophenoxy)-3-methylphenyl]phthalide (BAMP) and its mixtures with other dietheramines (6b-g) by high-temperature solution polycondensation in m-cresol. The PNIs had moderate to high inherent viscosities in the range of 1.24-2.25 dL/g and could afford flexible and tough films with tensile strengths of 97-138 MPa by casting their m-cresol solutions. These PNIs exhibited high thermal stability, with glass-transition temperature of 291-321 °C, 10% weight-loss temperatures above 542 °C, and char yields at 800 °C in nitrogen higher than 56%. In comparison with PNIs without the BAMP component, these BAMP-modified PNIs revealed an enhanced solubility and film-forming capability.
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馬瑞奇. "Synthesis of Naphthalimide Derivative and Diketopyrrolopyrrole (DPP)-Based [2]Rotaxane/Polyrotaxane as Novel Chemosensor Materials and a Controllable Hierarchical Nano Self-Assembled Structure from Polyrotaxane." Thesis, 2013. http://ndltd.ncl.edu.tw/handle/07354602595689667348.
Full textAbstract:
博士國立交通大學
材料科學與工程學系所
102
I Abstract Synthesis of Naphthalimide Derivative and Diketopyrrolopyrrole (DPP)-Based [2]Rotaxane/Polyrotaxane as Novel Chemosensor Materials and a Controllable Hierarchical Nano Self-Assembled Structure from Polyrotaxane Student: M. V. P. S. K. R. Raju Advisor: Hong-Cheu, Lin The pivotal objective of this dissertation is to construct novel orthogonally H-bonded mechanically interlocked molecular/polyrotaxane architectures with an asymmetric (Diketopyrrolopyrrole) stopper and to study their molecular shuttling process under solvent, anion, and acid-base stimuli control along with their controllable hierarchical nanostructure formations plugged with positive cooperativity non-covalent interactions. In the introduction of this doctoral thesis we have introduced brief early synthetic attempts to create mechanically interlocked molecules (MIMs) such as rotaxanes and catenanes as well as their polymeric counterparts. Moreover novel templating methodologies to build MIMs and some latest examples of MIMs based molecular shuttles under various stimuli control were also introduced. Fundamentally, underplayed chemo sensing mechanisms in these systems were presented. Meanwhile, we have developed a novel and facile fluorescent ratiometric chemodosimeter for grisly toxic hydrazine via mild Ing-Manske phthalimide deprotection method in this doctoral thesis as well. In chapter two, a novel [2]rotaxane based on an orthogonal H-bonded motif and 3,6-di(thiophenyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP) with controlled topicity was successfully constructed, displaying excellent stimulated responses toward anion and solvent polarity. The extensive 1H &; 19F NMR titrations were lucidly revealed the binding site and the mode binding interaction as well. The preorganized host selectively recognized F- with high optical sensitivity and reversibility via enhanced positive cooperativity and noncovalent interaction by evidence of a shorter fluorescence lifetime. Therefore we developed a first prototype [2]rotaxane molecular shuttle for selective recognition of F- with high optical outputs. II In chapter three, four analogous polymers were systematically synthesized by copolymerization of a 9-alkylidene-9H-fluorene monomer with various monomers, which contained a diketopyrrolopyrrole unit tethered with a dumbbell unit, a metalated [2]rotaxane, a demetalated orthogonal H-bonded [2]rotaxane, and a simple alkyl chain, to furnish P1, P2, P3, and P4, respectively, to investigate the supramolecular interactions of the mechanically interlocked rotaxane pendants and conjugated polymer backbones. Prevailing 1H NMR and UV-vis to NIR titration profiles indicated that the novel polyrotaxane P3 showed a sensitive and reversible acid-base molecular switch capability via supramolecular interactions in contrast to the other polymers (P1, P2, and P3). Compared with the other polymers, P3 possessed a narrower bandgap, which was also confirmed by the computational study. Prominently, the monitoring of a controllable nano-self-assembly process of P3 was obtained by reversible acid-base molecular switch approaches. The orthogonal H-bonded pendant [2]rotaxane unit and the steric demand of P3 judiciously allowed to morph into a hierarchical nanostructure via interconvertible H-bonds, anion-π and π-π stackings, as well as hydrophobic interactions. In chapter four, A facile and sensitive fluorescent probe for hydrazine based on phthalimide appended hydrophilic naphthalimide was successfully constructed, displaying excellent colorimetric and ratiometric responses towards hydrazine via Ing-Manske phthalimide deprotection conditions in semi-aqueous buffer solution. The estimated detection limit was as low as 4.2 nM (hydrazine content = 1 ppb) far below than the threshhold limit value (TLV) of 10 ppb according to the U. S. Environmental Protection Agency (EPA). Prevailing detection of hydrazine in living cells of the current probe is demonstrated. Thus in conclusion, a novel archetype DPP based highly fluorescent [2]rotaxane was developed. The remarkable stimulated responses towards solvent polarity and fluoride ion were discussed. Moreover, the extended efforts of this current design into polyrotaxane architectures along with their acid-base controllable hierarchical nanostructure formations via reversible optical molecular switch approaches coupled with various non-covalent interactions were discussed. Furthermore a novel fluorescent ratiometric chemodosimeter for hydrazine based on Ing-Manske phthalimide deprotection was presented in detail.
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Shih, Yen-Cheng, and 施衍丞. "Cobalt－Organic Frameworks Based on N-(Pyridin-4-yl)-4-(pyridin-4-yl)-1,8-naphthalimide and Aromatic Dicarboxylic Acids : Synthesis, Structures, CO2 Uptake, and Dye Adsorption." Thesis, 2017. http://ndltd.ncl.edu.tw/handle/6gsn52.
Full textAbstract:
碩士國立暨南國際大學
應用化學系
105
Abstract Through solvothermal reactions, four cobalt–organic frameworks, [{Co3(bpdc)3(NI-bipy-44)(DMF)}{Co3(bpdc)3(NI-bipy-44)(H2O)}] (1), [Co2(bpdc)2(NI-bipy-44)] (2), [Co2(1,4-bdc-Br)2(NI-bipy-44)2] (3), and [Co2(1,4-bdc-NO2)2(NI-bipy-44)2] (4) were constructed from Co(NO3)2∙3H2O, N-(pyridin-4-yl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-bipy-44), and aromatic dicarboxylic acids (biphenyl-4,4′-dicarboxylic acid, H2bpdc; 2-bromoterephthalic acid, 1,4-H2bdc-Br; nitroterephthalic acid, 1,4-H2bdc-NO2). Compounds 1 and 2 have a two-fold interpenetrated 3D pillared-layer structure with 43.2 and 62.3% porosities, respectively; compounds 3 and 4 have similar structure suiting a 3D non-interpenetrated pillared-layer structure with 56.1% and 49.9% porosities, respectively. Compound 2 showed gas adsorption ability for CO2, while compound 3 does not.Furthermore, dye adsorption studies showed that compounds 1 and 2 can adsorb methyl orange (MO), methylene blue (MB), methyl blue, malachite green chloride (MG), acid orange 7 (AO7) and rhodamine B (RhB), while compounds 3 and 4 can adsorb MO, MB, methyl blue, AO7, RhB and MR.
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LI, JR-YU, and 李志郁. "Zinc-Organic Networks based on N-(Pyridin-3-yl)-4-(pyridin-4-yl)-1,8-naphthalimide and Multicarboxylic Acids: Synthesis, Structures, Properties and Sensing of Nitro Compounds." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/c2z67b.
Full textAbstract:
碩士國立暨南國際大學
應用化學系
104
Reactions of N-(pyridin-3-yl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-bipy-34), Zn(NO3)2·6H2O and multicarboxylic acids (2,6-naphthalenedicarboxylic acid, 2,6-H2ndc; 1,4-benzenedicarboxylic acid, 1,4-H2bdc; 5-aminoisophthalic acid, 5-NH2-1,3-H2bdc; 1,3,5-benzenetricarboxylic acid, 1,3,5-H3btc) in N,N-dimethylformamide (DMF)-H2O media under hydro(solvo)thermal conditions afforded zinc–organic networks, {[Zn2(2,6-ndc)(2,6-Hndc)2(NI-bipy-34)]2·H2O}n (1), [Zn(2,6-ndc)(H2O)]n (2), [Zn(1,4-Hbdc)(1,4-bdc)0.5(NI-bipy-34)]n (3), [Zn(5-NH2-1,3-bdc)(H2O)]n (4), {[Zn(1,3,5-Hbtc)(NI-bipy-34)(H2O)]·H2O}n (5). Compound 1 has a three-fold interpenetrated 2D layered structure; compound 2 has a 3D structure; compound 3 has a 1D ladder structure; compound 4 has a 2D honeycomb structure; compound 5 has a 2D square grid structure. Compounds 1-5 exhibit intense photoluminescence with λmax of 400-550 nm, making them useful for detecting nitro compounds. Experimental results of nitro compound detection have shown that nitrobenzene would cause significant (60-80%) fluorescence quenching in the cases of compounds 1, 3 and 5, whereas 1,4-dinitrobenzene showed 30-50% fluorescence quenching in the cases of compounds 2, 3 and 5. Cation-exchange experiments showed that Zn2+ ions in compounds 2 and 5 would be partially exchange by Cu2+ ions, through post-synthetic modification (PSM), resulting in isomorphous compounds 2-Cu and 5-Cu, respectively. Otherwise, Co2+-exchanged experiments showed that Zn2+ ions in compound 2 would be exchanged, resulting compound 2-Co in a one-dimensional chain structure. Dye adsorption experiments of compounds 1-5, 2-Cu and 5-Cu have shown that there are no adsorptive behaviors between designed coordination polymer materials and part of these dye (AO7, MO, MB). In longer time of soak(1 to 3 days), methyl blue would be adsorbed by compounds 1, 2, 4, 5-Cu and MG would be adsorbed by compounds 1, 4 respectively.
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SU, CHUN-HAO, and 蘇雋皓. "Zinc－Organic Frameworks Based on N-(Pyridin-4-yl)-4-(pyridin-4-yl)1,8-naphthalimide and Multicarboxylic Acids : Synthesis, Structures, CO2 Adsorption, and Nitro Compounds Sensing." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/j76r8t.
Full textAbstract:
碩士國立暨南國際大學
應用化學系
104
A series of fluorescent metal－organic frameworks (MOFs) based on zinc metal and different aromatic dicarboxylate ligands were designed and synthesized. [Zn2(1,4 bdc)2(NI-bipy-44)] (1), [Zn2(2,6-ndc)2(NI-bipy-44)] (2), [Zn2(bpdc)2(NI-bipy-44)] (3), [Zn2(1,4-bdc-NH2)2(NI-bipy-44)] (4), [Zn2(1,3-bdc-NH2)2(NI-bipy-44)] (5), and [Zn3.5(1,3,5-btc)2(DMF)(H2O)1.5] (6) were constructed from the hydro(solvo)thermal reactions of zinc nitrate, N-(pyridin-4-yl)-4-(pydrin-4-yl)-1,8naphthalimide (NI-bipy 44), a well-designed dipyridyl bridging ligand, and dicarboxylic acids (1,4 benzenedicarboxylic acid, 1,4-H2bdc; 2,6-naphthalene dicarboxylic acid, 2,6-H2ndc; 4,4′-biphenyldicarboxylic acid, H2bpdc; 2-amino-1,4-benzenedicarboxylic acid, 1,4 H2bdc-NH2; 5-amino-1,3-benzenedicarboxylic acid, 1,3-H2bdc-NH2 and 1,3,5 benzenetricarboxylic acid, H3btc). Elongating ligand length and functionalized with amino group would adjust the resulted open-frameworks in different pore size or pore environment. Compounds 1-4 have similar structures suiting a 3D pillared-layer structure, and overall 2-fold interpenetration, while compound 5 has a 2D double-walled honeycomb structure and compound 6 has a 3D unique structure. IV The zinc MOFs can be used for detection of nitro-compounds. Through π–π stacking or hydrogen bonding between the main-framework and nitro compounds, a election transfer process would occur from MOFs to nitro compounds, resulting in fluorescence quenching. In addition, compounds 1, 2, 4 and 5 has shown gas adsorption abilities for CO2, and the isosteric heat of adsorption (Qst) has also be determined. We have studied adsorption abilities of zinc MOFs for organic dyes, the results demonstrate that the zinc MOFs did not show obvious intermolecular forces with organic dyes, so they do not have adsorption abilities for organic dyes.
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Shumilova, Tatiana A. "New synthetic hosts for sulfate and nucleoside triphosphates: understanding non-covalent interactions." 2017. https://monarch.qucosa.de/id/qucosa%3A20879.
Full textAbstract:
The present work describes new aspects of organic and supramolecular chemistry. The scientific contribution consists of two parts, which focus on the development of receptors for the sulfate anion and quantitative assessment of stacking interactions between an anthracene dye and nucleobases in an aqueous solution.
In Chapter 1, basic concepts concerning supramolecular chemistry and recognition of cations and anions are discussed, as well as modern methods for the determination of binding constants. Particular attention is paid to fluorescence sensing of ions and underlying mechanisms of binding-induced fluorescence responses. Chapter 2 is dedicated to the design and synthesis of new fluorescent sulfate receptors functioning in aqueous solution. After a short review of the most effective sulfate receptors/probes created so far, a new design of PET probes for sulfate sensing is presented. The syntheses and anion binding properties of new compounds are described. The experimental data obtained for the receptors are discussed in detail to reveal the origin of high selectivity towards sulfate. Chapter 3 explores the importance of nucleobase–arene stacking interactions in recognition of nucleotides by synthetic receptors. Various experimental and theoretical approaches are presented to assess dispersion interactions between aromatic rings and nucleobases in the receptor–nucleotide complexes.
36
WANG, WEI-KAI, and 王韋凱. "Zinc-Organic Frameworks Based on N-(Pyridin-4-yl)-4-(pyridin-4-yl)-1,8-naphthalimide and Dicarboxylic Acids: Synthesis, Structures, CO2 Adsorption, and Detection of Nitro Compounds." Thesis, 2017. http://ndltd.ncl.edu.tw/handle/r6t23j.
Full textAbstract:
碩士國立暨南國際大學
應用化學系
105
Fluorescent metal－organic frameworks (MOFs) [Zn3(1,4-chdc)3(NI-bipy-44)] (1), [Zn2(1,4-BDC-Br)2(NI-bipy-44)] (2), [Zn3(bpdc)3(NI-bipy-44)] (3) and [Zn3(bpdc)2(NI-bipy-44)] (4), were constructed from the hydro(solvo)thermal reactions of zinc nitrate, N-(pyridin-4-yl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-bipy-44), a well-designed dipyridyl bridging ligand, and dicarboxylic acids (1,4-H2chdc = trans-1,4-cyclohexanedicarboxylic acid, 1,4-H2bdc-Br = 2-bromoterephthalic acid, H2bpdc = biphenyl-4,4′-dicarboxylic acid). Compounds 2 and 4 have similar structures suiting a 3D pillared-layer structure, and overall 2-fold interpenetration, while compounds 1 and 3 have a 3D triangular prism structure. Compounds 1、2 and 4 exhibit intense solid-state photoluminescence with λmax of ~424 nm, making them useful for sensing nitro compounds and sensing of the nitro analytes were carried out in the vapor phase. In addition, compounds 1-4 have shown gas adsorption abilities for CO2
37
LIAO, KUO-SHUN, and 廖國舜. "Metal–Organic Frameworks Constructed from 1,8-Naphthalimide-Based Bispyridyl Ligand and Aromatic Dicarboxylic Acids: Synthesis, Structures, Gas Adsorption, and Fluorescence Sensing of Nitro Compounds, Anions, and Cations." Thesis, 2019. http://ndltd.ncl.edu.tw/handle/t8mx28.
Full textAbstract:
碩士國立暨南國際大學
應用化學系
107
Metal-organic frameworks [Zn(Br-1,3-bdc)(NI-mbpy-34)] (1), [Cd(Br-1,3-bdc) (NI-mbpy-34)(H2O)]·2H2O (2) and [Cd((OH)2)-1,4-bdc)(NI-mbpy-34)2] (3) are constructed from imide-based bispyridyl ligand N-(pyridin-3-ylmethyl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-mbpy-34) with different metal ions and aromatic dicarboxylic acids in DMF-water media under hydrothermal reactions. Compound 1 crystallizes in monoclinic space group C2/c; the Zn(II) centers are connected by the NI-mbpy-34 and Br-1,3-bdc to form a 3D condense network having no porosity. Compound 2 crystallizes in triclinic space group P1 ̅; the Cd(II) centers are connected by the NI-mbpy-34 and Br-1,3-bdc to form a 2D grid-like structure with porosity of 9.8%. Compound 3 crystallizes in triclinic space group P1 ̅; the Cd(II) centers are connected by the NI-mbpy-34 and (OH)2-1,4-bdc to form a 2D grid-like structure having no porosity. Compounds 1-3 in solvent suspensions all exhibit strong fluorescence emissions, which are potentially applied in the detection of nitro compounds, cations, and anions. In the detection of nitro compounds, compounds 1-3 exhibit remarkable fluorescence quenching with addition of aromatic nitro compounds, while insufficient fluorescence quenching toward aliphatic nitro compounds. In the detection of anions, compounds 1-3 exhibit remarkable fluorescence quenching with addition of dichromate (Cr2O72-) and chromate (CrO42-), even in the presence of interfering ions, meaning that compounds 1-3 are great materials for detection of dichromate and chromate. In the detection of cations, compound 1 shows remarkable fluorescence enhancement with addition of Fe3+, even in the presence of interfering ions. Compounds 2 and 3 exhibit remarkable fluorescence enhancement with addition of Al3+, Cr3+ and Fe3+. The anti-interference measurements show that with the exception of 3 towards Fe3+, other cases all display good anti-interference ability. We also try to determine the limit of detection (LOD) of compounds 1-3 for sensing ions. The results show that compounds 1-3 have low LODs of about 1-4 μM for cations and 5-50 μM for dichromate and chromate.
38
CHEN, TANG-CHING, and 陳堂慶. "Cadmium-Organic Frameworks Based on N-(Pyridin-4-yl)-4-(pyridin-4-yl)-1,8-naphthalimide and Aromatic Dicarboxylic Acids: Synthesis, Structures, CO2 Adsorption, and Detection of Nitro Compounds." Thesis, 2017. http://ndltd.ncl.edu.tw/handle/7hxx66.
Full textAbstract:
碩士國立暨南國際大學
應用化學系
105
A series of fluorescent metal-organic frameworks (MOFs) based on Cd(II) and N-(pyridin-4-yl)-4-(pydrin-4-yl)-1,8-naphthalimide (NI-bipy-44) with different aromatic dicarboxylates were synthesized. [Cd2(1,4-bdc)2(NI-bipy-44)2] (1, 1,4-H2bdc = 1,4-benzenedicarboxylic acid), [Cd2(1,4-bdc-Br)2(NI-bipy-44)2] (2, 1,4-H2bdc-Br = 2-bromoterephthalic acid), [Cd2(1,4-bdc-NO2)2(NI-bipy-44)2] (3, 1,4-H2bdc-NO2 = 2-nitroterephthalic acid), and [Cd2(BPDC)2(NI-bipy-44)2] (4, H2BPDC = biphenyl-4,4′-dicarboxylic acid) have similar structures suiting a 3D pillared-layer framework with porosity of 58.4%, 51.4%, 51.5%, and 41.4%, respectively. Of note, compound 4 is 2-fold interpenetration, while compounds 1-3 are non-interpenetration. Compounds 1-4 exhibit intense solid-state photoluminescence with λmax of 450 ± 5 nm, making them useful for detecting small organic molecules and nitro compounds. When compounds 1 and 2 were soaked in H2O and DMSO, there was a significant fluorescence quenching. On the other hand, compounds 4 soaked with o-xylene and p-xylene would result in fluorescence enhancement. After immersing compounds 1-4 in DMF solutions of nitro compounds, their luminescence could be efficiently and selectively quenched by a series of nitroaromatics, especially 2-nitrophenol (2-NP), 3-nitrophenol (3-NP), 4-nitrophenol (4-NP), and 1,4-dinitrobenzene (1,4-DNB), but not by aliphatic nitro analytes, such as nitromethane (NM) and 2,3-dimethyl-2,3-dinitrobutane (DMNB). On the other hand, when the photoluminescence sensing studies of the nitro analytes were carried out in the vapor phase, it was observed that nitrobenzene (NB), 2-NP, and 4-NP are effective quenchers. The quenching efficiency is approximately consistence with the vapor pressure of analytes. Studies on adsorption of iodine vapor showed that compounds 1-4 can adsorb iodine molecules, resulting in more than 90% fluorescence quenching and significant crystal color-changing from colorless to brown. In particular, compound 2 exhibits the ability to rapidly detect iodine molecules with fluorescence quenching up to 90% after 10 minutes of adsorption. Finally, compounds 1-4 display very poor carbon dioxide uptake ability even though they are high porosity.
39
PAI, HSIANG-YU, and 柏相宇. "Zinc－Organic Frameworks Constructed from a 1,8-Naphthalimide-Based Bispyridyl Ligand and 2-Substituted Benzene-1,4-dicarboxylic Acids: Synthesis, Structures, Gas Adsorption, and Detection of Volatile Organic Compounds and Nitro Compounds." Thesis, 2018. http://ndltd.ncl.edu.tw/handle/4chq73.
Full textAbstract:
碩士國立暨南國際大學
應用化學系
106
A series of fluorescent metal－organic frameworks (MOFs) [Zn2(1,4-bdc)2(NI-mbpy-34)] (1, 1,4-H2bdc = benzene-1,4-dicarboxylic acid)、[Zn2(NH2-1,4-bdc)2(NI-mbpy-34)] (2, NH2-1,4-H2bdc = 2-aminobenzene-1,4-dicarboxylic acid)、[Zn(NO2-1,4-bdc)(NI-mbpy-34)] (3, NO2-1,4-H2bdc = 2-nitrobenzene-1,4-dicarboxylic acid) consisting of Zn(II), N-(pyridin-3-ylmethyl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-mbpy-34), and dicarboxylates were synthesized. Compound 1 is a 2D layer structure of trigonal prismatic cages with porosity of 24.8%. Compound 2 is a 3D primitive cubic type pillared-layer framework with porosity of 27.0%, which is 2-fold interpenetration. Compound 3 is a 3D nonporous primitive cubic type pillared-layer framework. Compounds 1 and 2 have shown moderate CO2 adsorption abilities, with values of 69.5 cm3/g and 94.4 cm3/g, respectively, at 195 K and P/P0 = 1, but poor N2 uptakes, with values of 24.7 cm3/g and 9.5 cm3/g, respectively, at 77 K and P/P0 = 1. After adding nitro compounds to methanol suspensions of 1 and 3, their luminescence emissions would be efficiently quenched by a series of nitroaromatics, involving 2-nitrophenol (2-NP), 3-nitrophenol (3-NP), 4-nitrophenol (4-NP), 4-nitrotoluene (4-NT), 2,4-dinitrotoluene (2,4-DNT) and 1,4-dinitrobenzene (1,4-DNB), but not by nitrobenzene (NB) and aliphatic nitro compounds, such as nitromethane (NM) and 2,3-dimethyl-2,3-dinitrobutane (DMNB). We have further studied on vapor-sensing of 1 and 3 toward volatile nitro and organic compounds. The results show that the emissions of zinc MOFs did not effectively affected by both series of analytes, leading to inefficient detection for volatile nitro and organic compounds. Studies on adsorption of volatile iodine showed that 1 can adsorb iodine molecules, resulting in significant crystal color change from colorless to brown and more than 50% fluorescence quenching.
40
LU, XIAO-MIN, and 呂曉旻. "Cadmium－Organic Frameworks Constructed from a 1,8-Naphthalimide-Based Bispyridyl Ligand and 2-Substituted Benzene-1,4-Dicarboxylic Acids: Synthesis, Structures, Gas Adsorption, and Detection of Volatile Organic Compounds and Nitro Compounds." Thesis, 2018. http://ndltd.ncl.edu.tw/handle/g5bye5.
Full textAbstract:
碩士國立暨南國際大學
應用化學系
106
This work reports three cadmium-based fluorescent metal－organic frameworks (MOFs) constructed from imide-based bispyridyl ligand, N-(pyridin-4-ylmethyl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-mbpy-44), and aromatic dicarboxylate ligands. Compounds [Cd(Br-1,4-bdc)(NI-mbpy-44)]•H2O (1, Br-1,4-bdc = 2-bromobenzene-1,4-dicarboxylate), [Cd(NO2-1,4-bdc)(NI-mbpy-44)]•H2O (2, NO2-1,4-bdc = 2-nitrobenzene-1,4-dicarboxylate), and [Cd(NH2-1,4-bdc)(NI-mbpy-44)]•H2O (3, NH2-1,4-bdc = 2-aminobenzene-1,4-dicarboxylate) were synthesized from the hydro(solvo)thermal reactions of cadmium nitrate, NI-mbpy-44, and related 2-substituted benzene-1,4-dicarboxylic acids. Compounds 1 – 3 have similar crystal structures, which adopt a honeycomb-like 2D 63-layer structure, with two Cd2(NI-mbpy-44)2 (M2L2) macrocycles in the ortho positions of each hexagon of the layer structure. Two identical 2D layers interpenetrate each other in the way that the 2-substituted 1,4-bdc ligands thread through the M2L2 macrocycles to form a polyrotaxane-like 2D + 2D → 2D structures. Compounds 1 – 3 showed poor CO2 uptakes of 14.90, 18.12, and 14.58 cm3/g, respectively, at 195 K and p/po = 1, even if they are highly porous with porosities of 44.0, 44.9, and 47.5%, respectively. The toluene suspensions of compounds 1 and 2 exhibit strong fluorescence emissions, which would be quenched by different nitro compounds in different degrees. Among the chosen nitro compounds, aromatic nitro compounds exhibit remarkable fluorescence quenching (> 60%), especially 4-nitrophenol (4-NP) (> 99%). On the contrary, non-aromatic nitro compounds such as nitromethane (NM) and 2,3-dimethyl-2,3-dinitrobutane (DMNB) show only about 20–35% reduction in fluorescence intensity of the toluene suspensions. We have also examined the vapor-sensing ability of compounds 1 and 2 toward volatile nitro and organic compounds. The solid state fluorescence of compound 1 would be effectively reduced by 2-nitrophenol (2-NP), diethylamine (Et2NH), and aniline (C6H5NH2), while that of compound 2 would be quenched by 2-NP, 1,4-dinitrobenzene (1,4-DNB), NM, Et2NH, and C6H5NH2 significantly. Compounds 1 and 2 could be used to uptake volatile iodine (I2) molecules. After adsorbing iodine, the solid state fluorescence intensity of both compounds are reduced more than 80% in ten minutes, and the crystal color is also changed from yellow to brown. After releasing I2 molecules, compounds 1 and 2 can be reused to capture and detect volatile iodine as they exhibit 50% and 70% recovery, respectively, in fluorescence intensity.
41
謝緯勳. "Synthesis of The Chemical Sensor Based on 2-hydroxy-1-naphthalimine and the Studies of Their Ion-Sensing Properties." Thesis, 2012. http://ndltd.ncl.edu.tw/handle/01114358443315542745.
Full textAbstract:
碩士國立彰化師範大學
化學系
100
We design two simple and water-soluble Schiff base receptors B and C that are composed of two naphthalene fluorophores and aminoethylene linker. They were synthesized by a simple one step reaction. In addition, we also interested in investigated the metal ion and anion sensing properties of the purchased compound A. Their metal ion and anion sensing properties were investigated in 95% alcohol. All of the synthesis and the use of solvent are in compliance with the Green Chemistry. Compound A exhibits a turn-on type response and highly selective fluorescence behavior for CN(I) ion. The observed enhance efficiency were nearly 110%. In addition, it also show the selectivity toward Cu(II) ion. The observed quenching efficiency were nearly 95%. Compound B exhibits a turn-on type response and highly selective fluorescence behavior for Zn(II) ion and HSO4(I) ion. The observed enhancement efficiency were nearly 17000% and 90% for Zn(II) ion and HSO4(I) ion, respectively. Compound C exhibits a turn-on type response and highly selective fluorescence behavior for Zn (II) ion. The observed enhance efficiency were nearly 9500%.
42
Sudhakar, Pagidi. "Rational Design Facile Synthesis of Boryl Anilines : Intriguing Aggregation Induced Emission and External Stimuli Responsive Properties." Thesis, 2015. http://etd.iisc.ac.in/handle/2005/3884.
Full textAbstract:
The main thrust of this thesis is the development of facile synthetic routes for simple boryl anilines and study their structure-property correlations in both solid and solution states and to utilize this information to design functional materials with desired properties such as aggregation induced emission, mechanofluorochromism, and thiol sensors. This thesis contains eight chapters and the contents of each chapter are described below.
Chapter 1
The first chapter is an introduction to the theme of the thesis and presents a general review on the present work with emphasis on photophysics of triarylboron based donor-acceptor systems and their applications in various fields. In addition, advances in boron chemistry in the new frontier areas such as aggregation induced emission and mechanochromism are discussed in brief.
Chapter 2
The second chapter deals with the general experimental techniques and synthetic procedures utilized in this work.
Chapter 3
This chapter describes the rational design and synthesis of triarylborane bearing Unsubstituted amines, namely borylanilines (3.1-3.5). Compounds 3.1-3.4have similar donor and acceptor centres but differ their molecular conformations and also differ in the relative positions of amine moiety (para and meta). Compounds 3.1-3.4 contain one amine group while 3.5 contains two amine moieties. These compounds exhibit fascinating electrostatic intermolecular interactions, N −H- - -π in the crystal structure of 3.1, 3.2 and 3.4 and N −H--N interactions in crystal structure of 3.5. The solution state optical properties of 3.1-3.5 are typical of donor-acceptor (D-A) systems. Interestingly, compounds 3.3 and 3.5 showed unprecedented mechanochromic luminescent properties. Upon grinding, compound 3.3 showed color changes from blue to cyan blue and 3.5 showed intriguing color changes from blue to green and these color changes were found to be reversible. Single crystal X-ray diffraction analysis of 3.5BP (blue emission color crystal) and 3.5GP (green emission color crystal) clearly show that the color changes are due to the difference in their solid state packing.
Chapter 4
In chapter 4, the design and facile synthesis of boron based donor-acceptor (D-A) systems such as borylanilines 4.4-4.9 (D= -NH2 for 4.4-4.6 and -NMe2 for compounds 4.7-4.9) are reported. Compounds 4.4, 4.5 and 4.6 contain one, two or three -NH2 moiety(ies), respectively. Compounds 4.7, 4.8 and 4.9 contain one, two or three –NMe2 moiety(ies), respectively. A systematic investigation has been carried out to rationalize the effect of donor-acceptor ratio on the ICT process in borylanilines 4.4-4.9. The aryl spacer between donor amine and acceptor boron is kept the same in all the compounds to avoid the electronic effect of spacer on the ICT characteristics of these compounds. In the case of compounds 4.4-4.6, the increase in the number of donor -NH2 moieties does not affect their absorption profile, while in the case of compounds 4.7-4.9, the absorption spectra are shifted bathochromically with an increase in the number of donor-NMe2 moieties. Photoluminescence (PL) of 4.4-4.6 is significantly blue shifted with an increase in number of –NH2 moieties, while the PL of 4.7-4.9 was slightly blue shifted. The absorption and PL features of 4.4-4.6 are sensitive to the polarity of the solvent medium. In contrast, absorption profiles of 4.7-4.9 are not sensitive to the polarity of the solvent medium. The PL of these compounds is affected by the polarity of the solvent medium.
Chapter 5
This chapter deals with triarylboron based fluorescent probes (5.1-5.4) for the selective detection of thiophenols over aliphatic thiols. The probes were constructed by conjugating luminescent borylanilinies with luminescent quencher 2,4-dinitrobenzene sulfonyl (DNBS) moiety. In compound 5.1 and 5.2 the DNBS moiety is positioned at the para position with respect to the triarylborane moiety, while in 5.3 and 5.4 the DNBS moiety(ies) is(are) at the meta position(s). Probes 5.1-5.4 showed selective turn-on fluorescence response towards thiophenol. The fluorescence “off-on” switching mechanism of 5.1-5.4 against thiophenols was fully elucidated by theoretical calculations. Probes 5.1-5.4 are also capable of detecting thiophenols in the intra cellular environments.
Chapter 6
Design, facile synthesis and aggregation induced emission properties of a new series of novel triarylboron tethered N-aryl-1,8-naphthalimides (TAB-NPIs) 6.1-6.7 are described in this chapter. Systematic structural perturbation has been used for fine-tuning the optical and morphological properties of TAB- NPIs in both solid as well as in aggregated state. Compounds 6.1-6.7 are weekly luminescent in solutions. In contrast, all compounds (except compound 6.4) are strongly luminescent in the solid state and aggregated state in THF-H2O mixtures. The presence of sterically hindered boryl unit in 6.1-6.7 has endowed these molecules with unique AIE characteristics by preventing co-facial arrangements of NPI moieties. The propeller shape arrangement of TAB moiety in 6.1, 6.2, 6.5, 6.6 and 6.7 effectively prevents the aggregation induced emission quenching (AIEQ) and induce strong emission in the condensed state. In the solid state, compounds 6.1, 6.4, 6.5, and 6.6 generate an interesting supramolecular structure via intermolecular C-H--- and C-H---O interactions. No face to face intermolecular π---π interactions were found in the crystal structures of 6.1, 6.4, 6.5, and 6.6. This precludes the excimer formation which can be detrimental to the radiative process in these molecules. The scanning electron microscopy (SEM) images of as prepared samples of 6.1-6.7 clearly indicate that the morphology of these compounds strongly depends on the molecular conformations and number of naphthalimide moieties in the TAB-NPI conjugates.
Chapter 7
This chapter deals with design, synthesis and optical properties of novel dimesitylboryl appended perylenediimides. A simple synthetic strategy has been developed for the construction of novel TAB-PDIs conjugates. These conjugates can be conveniently synthesised by condensation of boryl anilines with perylene tetracarboxylic acid anhydride. The incorporation of TAB moiety enhanced the solubility of perylen bisimides in common organic solvents. The PL quantum yield of both 7.1 and 7.2 strongly depends on the excitation wavelength. Lower Pl efficiency observed for 7.1 and 7.2 upon excitation in the boryl dominated absorption region may be due to the photon induced electron transfer form mesityl units of boryl to perylene bisimide moiety. The morphology as well as emission colours of supramolecular architectures of both 7.1 and 7.2 can be modulated by controlling the concentrations of DCM solutions of these compounds. Both the compounds showed selective fluorogenic response for F-1 and CN-1
anions. The simple synthetic strategy reported in this chapter can be conveniently exploited for the construction of TAB conjugates of semiconducting organic anhydrides.
Chapter 8
Novel planar chiral Lewis acids 8.3(SP, SS), 1-phosphino-2-borylferrocenes 8.4(SP) and 2-phosphino-1-borylferrocenes 8.4(RP) have been synthesized from a readily accessible ferrocene sulphinate precursor. Adopting a simple synthetic approach and a single precursor, enantiomerically pure SP and RP isomers have been prepared. It would be worthwhile to investigate the catalytic properties of compounds 8.3(SS), 8.4(SP) and 8.4(RP). It would also be interesting to replace the mesityl groups on boron with other electron deficient groups like pentafluorophenyl and 1,3,5-trifluoromethylphenyl to fine tune the Lewis acidity of boron center and to set-up a general route to enantiomerically pure Planar Chiral Frustrated Lewis Pairs (PCFLP’s).
43
Sudhakar, Pagidi. "Rational Design Facile Synthesis of Boryl Anilines : Intriguing Aggregation Induced Emission and External Stimuli Responsive Properties." Thesis, 2015. http://etd.iisc.ernet.in/2005/3884.
Full textAbstract:
The main thrust of this thesis is the development of facile synthetic routes for simple boryl anilines and study their structure-property correlations in both solid and solution states and to utilize this information to design functional materials with desired properties such as aggregation induced emission, mechanofluorochromism, and thiol sensors. This thesis contains eight chapters and the contents of each chapter are described below.
Chapter 1
The first chapter is an introduction to the theme of the thesis and presents a general review on the present work with emphasis on photophysics of triarylboron based donor-acceptor systems and their applications in various fields. In addition, advances in boron chemistry in the new frontier areas such as aggregation induced emission and mechanochromism are discussed in brief.
Chapter 2
The second chapter deals with the general experimental techniques and synthetic procedures utilized in this work.
Chapter 3
This chapter describes the rational design and synthesis of triarylborane bearing Unsubstituted amines, namely borylanilines (3.1-3.5). Compounds 3.1-3.4have similar donor and acceptor centres but differ their molecular conformations and also differ in the relative positions of amine moiety (para and meta). Compounds 3.1-3.4 contain one amine group while 3.5 contains two amine moieties. These compounds exhibit fascinating electrostatic intermolecular interactions, N −H- - -π in the crystal structure of 3.1, 3.2 and 3.4 and N −H--N interactions in crystal structure of 3.5. The solution state optical properties of 3.1-3.5 are typical of donor-acceptor (D-A) systems. Interestingly, compounds 3.3 and 3.5 showed unprecedented mechanochromic luminescent properties. Upon grinding, compound 3.3 showed color changes from blue to cyan blue and 3.5 showed intriguing color changes from blue to green and these color changes were found to be reversible. Single crystal X-ray diffraction analysis of 3.5BP (blue emission color crystal) and 3.5GP (green emission color crystal) clearly show that the color changes are due to the difference in their solid state packing.
Chapter 4
In chapter 4, the design and facile synthesis of boron based donor-acceptor (D-A) systems such as borylanilines 4.4-4.9 (D= -NH2 for 4.4-4.6 and -NMe2 for compounds 4.7-4.9) are reported. Compounds 4.4, 4.5 and 4.6 contain one, two or three -NH2 moiety(ies), respectively. Compounds 4.7, 4.8 and 4.9 contain one, two or three –NMe2 moiety(ies), respectively. A systematic investigation has been carried out to rationalize the effect of donor-acceptor ratio on the ICT process in borylanilines 4.4-4.9. The aryl spacer between donor amine and acceptor boron is kept the same in all the compounds to avoid the electronic effect of spacer on the ICT characteristics of these compounds. In the case of compounds 4.4-4.6, the increase in the number of donor -NH2 moieties does not affect their absorption profile, while in the case of compounds 4.7-4.9, the absorption spectra are shifted bathochromically with an increase in the number of donor-NMe2 moieties. Photoluminescence (PL) of 4.4-4.6 is significantly blue shifted with an increase in number of –NH2 moieties, while the PL of 4.7-4.9 was slightly blue shifted. The absorption and PL features of 4.4-4.6 are sensitive to the polarity of the solvent medium. In contrast, absorption profiles of 4.7-4.9 are not sensitive to the polarity of the solvent medium. The PL of these compounds is affected by the polarity of the solvent medium.
Chapter 5
This chapter deals with triarylboron based fluorescent probes (5.1-5.4) for the selective detection of thiophenols over aliphatic thiols. The probes were constructed by conjugating luminescent borylanilinies with luminescent quencher 2,4-dinitrobenzene sulfonyl (DNBS) moiety. In compound 5.1 and 5.2 the DNBS moiety is positioned at the para position with respect to the triarylborane moiety, while in 5.3 and 5.4 the DNBS moiety(ies) is(are) at the meta position(s). Probes 5.1-5.4 showed selective turn-on fluorescence response towards thiophenol. The fluorescence “off-on” switching mechanism of 5.1-5.4 against thiophenols was fully elucidated by theoretical calculations. Probes 5.1-5.4 are also capable of detecting thiophenols in the intra cellular environments.
Chapter 6
Design, facile synthesis and aggregation induced emission properties of a new series of novel triarylboron tethered N-aryl-1,8-naphthalimides (TAB-NPIs) 6.1-6.7 are described in this chapter. Systematic structural perturbation has been used for fine-tuning the optical and morphological properties of TAB- NPIs in both solid as well as in aggregated state. Compounds 6.1-6.7 are weekly luminescent in solutions. In contrast, all compounds (except compound 6.4) are strongly luminescent in the solid state and aggregated state in THF-H2O mixtures. The presence of sterically hindered boryl unit in 6.1-6.7 has endowed these molecules with unique AIE characteristics by preventing co-facial arrangements of NPI moieties. The propeller shape arrangement of TAB moiety in 6.1, 6.2, 6.5, 6.6 and 6.7 effectively prevents the aggregation induced emission quenching (AIEQ) and induce strong emission in the condensed state. In the solid state, compounds 6.1, 6.4, 6.5, and 6.6 generate an interesting supramolecular structure via intermolecular C-H--- and C-H---O interactions. No face to face intermolecular π---π interactions were found in the crystal structures of 6.1, 6.4, 6.5, and 6.6. This precludes the excimer formation which can be detrimental to the radiative process in these molecules. The scanning electron microscopy (SEM) images of as prepared samples of 6.1-6.7 clearly indicate that the morphology of these compounds strongly depends on the molecular conformations and number of naphthalimide moieties in the TAB-NPI conjugates.
Chapter 7
This chapter deals with design, synthesis and optical properties of novel dimesitylboryl appended perylenediimides. A simple synthetic strategy has been developed for the construction of novel TAB-PDIs conjugates. These conjugates can be conveniently synthesised by condensation of boryl anilines with perylene tetracarboxylic acid anhydride. The incorporation of TAB moiety enhanced the solubility of perylen bisimides in common organic solvents. The PL quantum yield of both 7.1 and 7.2 strongly depends on the excitation wavelength. Lower Pl efficiency observed for 7.1 and 7.2 upon excitation in the boryl dominated absorption region may be due to the photon induced electron transfer form mesityl units of boryl to perylene bisimide moiety. The morphology as well as emission colours of supramolecular architectures of both 7.1 and 7.2 can be modulated by controlling the concentrations of DCM solutions of these compounds. Both the compounds showed selective fluorogenic response for F-1 and CN-1
anions. The simple synthetic strategy reported in this chapter can be conveniently exploited for the construction of TAB conjugates of semiconducting organic anhydrides.
Chapter 8
Novel planar chiral Lewis acids 8.3(SP, SS), 1-phosphino-2-borylferrocenes 8.4(SP) and 2-phosphino-1-borylferrocenes 8.4(RP) have been synthesized from a readily accessible ferrocene sulphinate precursor. Adopting a simple synthetic approach and a single precursor, enantiomerically pure SP and RP isomers have been prepared. It would be worthwhile to investigate the catalytic properties of compounds 8.3(SS), 8.4(SP) and 8.4(RP). It would also be interesting to replace the mesityl groups on boron with other electron deficient groups like pentafluorophenyl and 1,3,5-trifluoromethylphenyl to fine tune the Lewis acidity of boron center and to set-up a general route to enantiomerically pure Planar Chiral Frustrated Lewis Pairs (PCFLP’s).
44
Mukherjee, Sanjoy. "Investigations of Structure-Property Relationships in NPI and BODIPY Based Luminescent Material." Thesis, 2015. http://etd.iisc.ac.in/handle/2005/3933.
Full textAbstract:
Luminescent materials find numerous applications in recent times and have enriched human lives in several different ways. From display and lighting technologies to security, sensing and biological investigations, luminescent organic compounds have become indispensible and often preferred over their inorganic counterparts. The versatility of organic materials arises from their comparative low costs, ease of fine-tuning, low toxicity and the possibility to develop flexible devices. Even until very recent times, the investigations and usage of organic luminescent materials were mostly limited to solution-state properties. However, with progress of available characterisation techniques and parallel development of their usage in solid-state devices and other applications (e.g. security, forensics, sensing etc.), significantly greater attention has been paid to the development and investigations of solid-state emissive organic materials. In solid-state applications, apart from the molecular properties of any given material, their cumulative i.e. bulk physical properties are of even greater importance. Thus, investigations of structure-property relationships in organic luminescent compounds to understand their molecular and bulk properties are of fundamental interest. In this thesis, NPI (1,8-naphthalimide) and BODIPY (boron-dipyrromethene) dyes were investigated to provide a broad overview of their structure-property correlations. Among commonly encountered organic luminescent materials, NPIs and BODIPYs have emerged as two broad classes of luminescent organic compounds, finding applications as functional luminescent materials in various fields. However, lack of understanding for controlling the cumulative emissive properties of these compounds has limited their usage as active solid-state emitters in various applications. This thesis presents several new insights into the molecular and bulk emissive properties of these two classes of luminescent dyes (NPIs and BODIPYs). The contents of the six chapters contained in this thesis are summarised below.
Chapter 1 summarises the available understanding of the basic concepts of photoluminescence and the design strategies to develop solid-state luminescent and AIE (aggregation-induced emission) active materials. This chapter also emphasises in the basic nature of the NPI and BODIPY compounds, their substitution patterns and their inherent characteristics and touches upon the relatively unexplored properties of NPI and BODIPY based materials. The importance and scope of the work reported in the thesis is outlined at the end of the chapter.
Chapter 2 describes a detailed investigation of a series of seven (4-oxoaryl substituted) NPI compounds (1-7) providing an insight into the molecular and cumulative photophysical
behaviour of these compounds. The low ICT characteristics of the NPIs, coupled with the
twisted geometry, facilitated solid-state
luminescence in these materials. The solution and solid-state luminescent properties of these compounds can be directly correlated to their structural rigidity, nature of substituents and solid-state intermolecular interactions (e.g. π-π stacking, C-H•••O interactions etc.). The solid-state crystal structures of the NPI siblings are profoundly affected by the pendant substituents. All of the NPIs (1-7) show antiparallel dimeric π-π stacking interactions in the solid-state which can further extend in parallel, alternate, orthogonal or lateral fashion depending on the steric and electronic nature of the C-4′ substituents. Structural investigations including Hirsfeld surface analysis methods reveal that while strongly interacting systems show weak to moderate emission in their condensed states, weakly interacting systems show strong emission yields under the same conditions. The nature of packing and extended structures also affects the emission colors of the NPIs in the solid-state. DFT computational studies were utilized to understand the molecular and cumulative electronic behavior of the NPIs. Apart from the investigation of solid-state luminescence, other functional potentials of these NPIs were also explored. One of the compounds (i.e. 4) shows chemodosimetric response towards aqueous Hg(II) species with a ‘turn-on’ response. Also, depending on the molecular flexibility of the compounds, promising AIEE (aggregation-induced emission enhancement) features were observed in these NPIs. Later (in Chapter 3), we developed a systematic investigation in a series of purely organic NPIs, restricting various parameters, to attain a thorough understanding of such AIEE properties.
Chapter 3 describes a detailed experimental and computational study in order gain an insight into the AIE (aggregation-induced emission) and AIEE mechanisms in NPI compounds.
Systematic structural perturbation was used to fine tune the luminescence properties of three new 1,8-naphthalimides (8-10) in solution and as aggregates. The NPIs (8-10) show blue emission in solution state and the fluorescence quantum yields depend on their molecular rigidity. In concentrated solutions of the NPIs, intermolecular interactions were found to result in quenching of fluorescence. In contrast, upon aggregation (in THF:H2O mixtures), two of the NPIs show aggregation-induced-emission-enhancement (AIEE). The NPIs also show moderately high solid-state emission quantum yields (~10-12.7 %). The AIEE behaviors of the NPIs depend on their molecular rigidity and nature of intermolecular interactions. The NPIs (8-10) show different extents of intermolecular (π-π and C-H•••O) interactions in their solid-state structures depending on their substituents. Detailed photophysical, computational and structural investigations suggest that only an optimal balance of structural flexibility and intermolecular communication is the effective recipe for achieving AIEE characteristics in these NPIs.
Chapter 4 presents the design, synthesis and detailed investigations and potential applications of a series of NPI-BODIPY dyads (11-13). The NPI and BODIPY moieties in these dyads are electronically separated by oxoaryl bridges and the compounds only differ structurally with respect to methyl substitutions on the BODIPY fluorophore. The NPI and BODIPY moieties retain their optical features in these molecular dyads (11- 13). Dyads 11-13 show dual emission in solution state originating from the two separate fluorescent units. The variations of the dual emission in these compounds are controlled by the structural flexibility of the systems. The
dyads also show significant AIES (Aggregation-Induced-Emission Switching) features upon formation of nano-aggregates in THF-H2O mixtures with visual changes in emission from green to red color. Whereas the flexible and aggregation prone system (i.e. compound 11) shows aggregation-induced enhancement of emission, rigid systems with less favorable intermolecular interactions (i.e. compound 12-13) show aggregation-induced quenching of emission. The emission-intensity vs. the structural-flexibility correlations were found to be reverse in solution and aggregated states. Photophysical and structural investigations suggest that the intermolecular interactions (e.g. π-π stacking etc.) play major role in controlling emission of these compounds in aggregated states. Similar trends were also observed in the solid-state luminescence of these compounds. The applications of the luminescent dyads 11-13 as live-cell imaging dyes was also investigated.
Chapter 5 describes investigations of photophysical properties of a series of six BODIPY dyes (14-19) in which there is a systematic alteration of a common -C6H4Si(CH3)3 substituent. Inrelated constitutional isomers, the systematic increment of steric congestion and lowering of molecular symmetry around the BODIPY core result in a steady increment of
solution and solid- state fluorescence quantum yields. The increasing fluorescence quantum yields (solution, solid state) with increasing steric congestions show that the molecular free rotation and aggregation-induced fluorescence quenching of BODIPYs can be successfully suppressed by lowering the flexibility of the molecules. Photophysical and DFT investigations reveal that the electronic band gap in any set of these constitutional isomers remain almost similar. However, the crystal structures of the compounds reveal that the solid-state colour and quantum yields of the compounds in solid-state are also related to the nature of intermolecular interactions.
Chapter 6 demonstrates the use of DFT computational methods to understand the effect of alkyl groups in governing the basic structural and electronic aspects of BODIPY dyes. As demonstrated in Chapter 4 and Chapter 5, apparently electronically inactive alkyl groups can be of immense importance to control the overall photophysics of BODIPYs. In this context, a systematic strategy su was utilized considering all possible outcomes of constitutionally-isomeric molecules to understand the effects of alkyl groups on the BODIPY molecules. Four different computational methods were employed to ascertain the unanimity of the observed trends associated with the molecular properties. In line with experimental observations, it was found that alkyl substituents in BODIPY dyes situated at 3/5-positions effectively participate in stabilization as well as planarization of such molecules. Screening of all the possible isomeric molecular systems was used to understand the individual properties and overall effects of the typical alkyl substituents in controlling several basic properties of such BODIPY molecules.
45
Mukherjee, Sanjoy. "Investigations of Structure-Property Relationships in NPI and BODIPY Based Luminescent Material." Thesis, 2015. http://etd.iisc.ernet.in/2005/3933.
Full textAbstract:
Luminescent materials find numerous applications in recent times and have enriched human lives in several different ways. From display and lighting technologies to security, sensing and biological investigations, luminescent organic compounds have become indispensible and often preferred over their inorganic counterparts. The versatility of organic materials arises from their comparative low costs, ease of fine-tuning, low toxicity and the possibility to develop flexible devices. Even until very recent times, the investigations and usage of organic luminescent materials were mostly limited to solution-state properties. However, with progress of available characterisation techniques and parallel development of their usage in solid-state devices and other applications (e.g. security, forensics, sensing etc.), significantly greater attention has been paid to the development and investigations of solid-state emissive organic materials. In solid-state applications, apart from the molecular properties of any given material, their cumulative i.e. bulk physical properties are of even greater importance. Thus, investigations of structure-property relationships in organic luminescent compounds to understand their molecular and bulk properties are of fundamental interest. In this thesis, NPI (1,8-naphthalimide) and BODIPY (boron-dipyrromethene) dyes were investigated to provide a broad overview of their structure-property correlations. Among commonly encountered organic luminescent materials, NPIs and BODIPYs have emerged as two broad classes of luminescent organic compounds, finding applications as functional luminescent materials in various fields. However, lack of understanding for controlling the cumulative emissive properties of these compounds has limited their usage as active solid-state emitters in various applications. This thesis presents several new insights into the molecular and bulk emissive properties of these two classes of luminescent dyes (NPIs and BODIPYs). The contents of the six chapters contained in this thesis are summarised below.
Chapter 1 summarises the available understanding of the basic concepts of photoluminescence and the design strategies to develop solid-state luminescent and AIE (aggregation-induced emission) active materials. This chapter also emphasises in the basic nature of the NPI and BODIPY compounds, their substitution patterns and their inherent characteristics and touches upon the relatively unexplored properties of NPI and BODIPY based materials. The importance and scope of the work reported in the thesis is outlined at the end of the chapter.
Chapter 2 describes a detailed investigation of a series of seven (4-oxoaryl substituted) NPI compounds (1-7) providing an insight into the molecular and cumulative photophysical
behaviour of these compounds. The low ICT characteristics of the NPIs, coupled with the
twisted geometry, facilitated solid-state
luminescence in these materials. The solution and solid-state luminescent properties of these compounds can be directly correlated to their structural rigidity, nature of substituents and solid-state intermolecular interactions (e.g. π-π stacking, C-H•••O interactions etc.). The solid-state crystal structures of the NPI siblings are profoundly affected by the pendant substituents. All of the NPIs (1-7) show antiparallel dimeric π-π stacking interactions in the solid-state which can further extend in parallel, alternate, orthogonal or lateral fashion depending on the steric and electronic nature of the C-4′ substituents. Structural investigations including Hirsfeld surface analysis methods reveal that while strongly interacting systems show weak to moderate emission in their condensed states, weakly interacting systems show strong emission yields under the same conditions. The nature of packing and extended structures also affects the emission colors of the NPIs in the solid-state. DFT computational studies were utilized to understand the molecular and cumulative electronic behavior of the NPIs. Apart from the investigation of solid-state luminescence, other functional potentials of these NPIs were also explored. One of the compounds (i.e. 4) shows chemodosimetric response towards aqueous Hg(II) species with a ‘turn-on’ response. Also, depending on the molecular flexibility of the compounds, promising AIEE (aggregation-induced emission enhancement) features were observed in these NPIs. Later (in Chapter 3), we developed a systematic investigation in a series of purely organic NPIs, restricting various parameters, to attain a thorough understanding of such AIEE properties.
Chapter 3 describes a detailed experimental and computational study in order gain an insight into the AIE (aggregation-induced emission) and AIEE mechanisms in NPI compounds.
Systematic structural perturbation was used to fine tune the luminescence properties of three new 1,8-naphthalimides (8-10) in solution and as aggregates. The NPIs (8-10) show blue emission in solution state and the fluorescence quantum yields depend on their molecular rigidity. In concentrated solutions of the NPIs, intermolecular interactions were found to result in quenching of fluorescence. In contrast, upon aggregation (in THF:H2O mixtures), two of the NPIs show aggregation-induced-emission-enhancement (AIEE). The NPIs also show moderately high solid-state emission quantum yields (~10-12.7 %). The AIEE behaviors of the NPIs depend on their molecular rigidity and nature of intermolecular interactions. The NPIs (8-10) show different extents of intermolecular (π-π and C-H•••O) interactions in their solid-state structures depending on their substituents. Detailed photophysical, computational and structural investigations suggest that only an optimal balance of structural flexibility and intermolecular communication is the effective recipe for achieving AIEE characteristics in these NPIs.
Chapter 4 presents the design, synthesis and detailed investigations and potential applications of a series of NPI-BODIPY dyads (11-13). The NPI and BODIPY moieties in these dyads are electronically separated by oxoaryl bridges and the compounds only differ structurally with respect to methyl substitutions on the BODIPY fluorophore. The NPI and BODIPY moieties retain their optical features in these molecular dyads (11- 13). Dyads 11-13 show dual emission in solution state originating from the two separate fluorescent units. The variations of the dual emission in these compounds are controlled by the structural flexibility of the systems. The
dyads also show significant AIES (Aggregation-Induced-Emission Switching) features upon formation of nano-aggregates in THF-H2O mixtures with visual changes in emission from green to red color. Whereas the flexible and aggregation prone system (i.e. compound 11) shows aggregation-induced enhancement of emission, rigid systems with less favorable intermolecular interactions (i.e. compound 12-13) show aggregation-induced quenching of emission. The emission-intensity vs. the structural-flexibility correlations were found to be reverse in solution and aggregated states. Photophysical and structural investigations suggest that the intermolecular interactions (e.g. π-π stacking etc.) play major role in controlling emission of these compounds in aggregated states. Similar trends were also observed in the solid-state luminescence of these compounds. The applications of the luminescent dyads 11-13 as live-cell imaging dyes was also investigated.
Chapter 5 describes investigations of photophysical properties of a series of six BODIPY dyes (14-19) in which there is a systematic alteration of a common -C6H4Si(CH3)3 substituent. Inrelated constitutional isomers, the systematic increment of steric congestion and lowering of molecular symmetry around the BODIPY core result in a steady increment of
solution and solid- state fluorescence quantum yields. The increasing fluorescence quantum yields (solution, solid state) with increasing steric congestions show that the molecular free rotation and aggregation-induced fluorescence quenching of BODIPYs can be successfully suppressed by lowering the flexibility of the molecules. Photophysical and DFT investigations reveal that the electronic band gap in any set of these constitutional isomers remain almost similar. However, the crystal structures of the compounds reveal that the solid-state colour and quantum yields of the compounds in solid-state are also related to the nature of intermolecular interactions.
Chapter 6 demonstrates the use of DFT computational methods to understand the effect of alkyl groups in governing the basic structural and electronic aspects of BODIPY dyes. As demonstrated in Chapter 4 and Chapter 5, apparently electronically inactive alkyl groups can be of immense importance to control the overall photophysics of BODIPYs. In this context, a systematic strategy su was utilized considering all possible outcomes of constitutionally-isomeric molecules to understand the effects of alkyl groups on the BODIPY molecules. Four different computational methods were employed to ascertain the unanimity of the observed trends associated with the molecular properties. In line with experimental observations, it was found that alkyl substituents in BODIPY dyes situated at 3/5-positions effectively participate in stabilization as well as planarization of such molecules. Screening of all the possible isomeric molecular systems was used to understand the individual properties and overall effects of the typical alkyl substituents in controlling several basic properties of such BODIPY molecules.