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1
Kaya, Safak. "Synthesis And Characterization Of A Polybenzoxazine From A Difunctional Amine And A Trifunctional Phenol." Master's thesis, METU, 2009. http://etd.lib.metu.edu.tr/upload/2/12610497/index.pdf.
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Synthesis of a polymer with benzoxazine units in the main chain backbone by a trifunctional phenol, a difunctional amine, and paraformaldehyde was achieved. Thermal, mechanical and spectroscopic characterization and the viscosity properties of the synthesized polymer were studied. In the first step of this study, a fast and feasible method for the synthesis of the benzoxazine precursors was developed since some methods mentioned in the literature about the synthesis of the benzoxazine derivatives last long time. The second step was to polymerize the benzoxazine precursors thermally. The curing of benzoxazine precursors was done via ring opening polymerization at 150 oC and a final polymerization was observed at about 250 oC.
1H NMR, 13C NMR and FT-IR spectroscopies revealed the characteristic peaks for the formation of benzoxazine ring. Among them, 13C NMR gave important clue on the formation of the benzoxazine.
The thermal characterization of the benzoxazine precursors and the polymers indicated that the ring opening polymerization of these precursors started at around 110 oC and a final polymerization was about at 230 oC. Differential Scanning Calorimetry thermograms of the polybenzoxazine indicated a secondary transition at around 270 oC. An onset decomposition of the benzoxazine oligomers started around 100 oC in Thermal Gravimetric Analysis thermograms performed under N2 atmosphere and two major maximum weight losses were observed at 273 oC and 439 oC. However, polybenzoxazine showed a starting degradation at about 260 oC and the maximum weight loss temperatures were seen at 296 oC and 465 oC.
Viscosity variation of the reaction mixture was studied by Ubbelohde Viscometer at 30 oC. Viscosity results indicated that the increase in the intrinsic viscosity of the reaction mixture till 50th minute and followed by a decrease due to possible branching and the intra-crosslinking of the benzoxazine oligomers. Mechanical properties of the polymer films, prepared by compression molding at 180 0C, were investigated. Test results showed that low tensile strength whereas comparatively high elongation.
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Morrow, Benjamin Joseph. "The synthesis of novel nitroxides and their application as small-molecule antioxidants and profluorescent probes for oxidative stress." Thesis, Queensland University of Technology, 2010. https://eprints.qut.edu.au/39445/1/Benjamin_Morrow_Thesis.pdf.
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The detection and potential treatment of oxidative stress in biological systems has been explored using isoindoline-based nitroxide radicals. A novel tetraethyl-fluorescein nitroxide was synthesised for its use as a profluorescent probe for redox processes in biological systems. This tetraethyl system, as well as a tetramethyl-fluorescein nitroxide, were shown to be sensitive and selective probes for superoxide in vitro. The redox environment of cellular systems was also explored using the tetramethylfluorescein species based on its reduction to the hydroxylamine. Flow cytometry was employed to assess the extent of nitroxide reduction, reflecting the overall cellular redox environment. Treatment of normal fibroblasts with rotenone and 2-deoxyglucose resulted in an oxidising cellular environment as shown by the lack of reduction of the fluorescein-nitroxide system. Assessment of the tetraethyl-fluorescein nitroxide system in the same way demonstrated its enhanced resistance to reduction and offers the potential to detect and image biologically relevant reactive oxygen species directly. Importantly, these profluorescent nitroxide compounds were shown to be more effective than the more widely used and commercially available probes for reactive oxygen species such as 2’,7’-dichlorodihydrofluorescein diacetate. Fluorescence imaging of the tetramethyl-fluorescein nitroxide and a number of other rhodamine-nitroxide derivatives was undertaken, revealing the differential cellular localisation of these systems and thus their potential for the detection of redox changes in specific cellular compartments. As well as developing novel methods for the detection of oxidative stress, a number of novel isoindoline nitroxides were synthesised for their potential application as small-molecule antioxidants. These compounds incorporated known pharmacophores into the isoindoline-nitroxide structure in an attempt to increase their efficacy in biological systems. A primary and a secondary amine nitroxide were synthesised which incorporated the phenethylamine backbone of the sympathomimetic amine class of drugs. Initial assessment of the novel primary amine derivative indicated a protective effect comparable to that of 5-carboxy-1,1,3,3- tetramethylisoindolin-2-yloxyl. Methoxy-substituted nitroxides were also synthesised as potential antioxidants for their structural similarity to some amphetamine type stimulants. A copper-catalysed methodology provided access to both the mono- and di-substituted methoxy-nitroxides. Deprotection of the ethers in these compounds using boron tribromide successfully produced a phenolnitroxide, however the catechol moiety in the disubstituted derivative appeared to undergo reaction with the nitroxide to produce quinone-like degradation products. A novel fluoran-nitroxide was also synthesised from the methoxy-substituted nitroxide, providing a pH-sensitive spin probe. An amino-acid precursor containing a nitroxide moiety was also synthesised for its application as a dual-action antioxidant. N-Acetyl protection of the nitroxide radical was necessary prior to the Erlenmeyer reaction with N-acetyl glycine. Hydrolysis and reduction of the azlactone intermediate produced a novel amino acid precursor with significant potential as an effective antioxidant.
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Richard-Rousseau, Claire. "Inhibition de l'oxydation induite du linolénate de méthyle par des dérivés phénoliques ou par les vitamines E ou C : Effets de synergie de la vitamine C ou de composés aminés sur les propriétés inhibitrices de la vitamine E." Nancy 1, 1986. http://www.theses.fr/1986NAN10017.
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Afin de comprendre le mécanisme d'action des inhibiteurs d'oxydation radicalaire, on a entrepris une étude cinétique détaillée de l'oxydation induite, vers 80**(O)C, en phase liquide, du linolénate de méthyle et de son inhibition par des dérivés phénoliques ou par des molécules d'intérêt biologique comme la vitamine E (alpha-tocophérol) ou la vitamine C (acide ascorbique). On montre que deux types de substances : la vitamine C, d'une part, et des molécules aminées comme le glutathion, d'autre part, exercent un effet de synergie sur les propriétés inhibitrices de la vitamine E lors de l'oxydation induite du linolénate de méthyle. L'interprétation de ces phénomènes de synergie a été rendue possible grâce à une étude cinétique de l'oxydation induite des vitamines E et C seules ou en mélange, à une étude cinétique de l'oxydation induite du mélange vitamine E-glutathion et enfin grâce à une étude par RPE et par spectrophotométrie à écoulement bloqué des radicaux libres alpha -tocophéroxyl et ascorbyl. Enfin, on montre que les deux modes de synergie observés se conjuguent pour conduire à une inhibition extrêmement importante de la consommation d'oxygène. Ce résultat est d'un grand intérêt puisqu'il montre que l'on peut presque à volonté protéger de l'oxydation le linolénate de méthyle ou tout autre substrat polyinsaturé
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Cheng, Ka-wing. "Preventive potential and mechanism of dietary phenolics on the formation of mutagenic heterocyclic amines." Click to view the E-thesis via HKUTO, 2009. http://sunzi.lib.hku.hk/hkuto/record/B4284177X.
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Zhang, Weihe. "Design and Synthesis of Potential Anticancer Agents." Ohio University / OhioLINK, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1288896777.
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Walowski, Christopher. "Using phenyl amide triserine lactone receptors in anion recognition studies." Thesis, California State University, Long Beach, 2014. http://pqdtopen.proquest.com/#viewpdf?dispub=1528066.
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<p> Since, the bio-availability of iron is low in nature, many enteric bacteria use the siderphore enterobactin to sequester ferric iron. Enterobactin is the strongest known binder of ferric iron with a binding constant of K<sub> a</sub>=10<sub>49</sub>. The triserine lactone backbone of enterobactin has been credited with being an important factor in the high binding constant. The backbone has been previously used in anion binding studies and as an continuation of that work, phenyl amide enterobactin analogs have been synthesized, characterized and used in <sup>1</sup>H NMR titration studies with various halides to determine their binding constants. The phenyl amide enterobactin analogs were found to have binding constants that ranged from approximately 150-7000 L mol<sup>-1</sup>. The binding constant depended on the analog and halide used. The general trend of Cl<sup>-</sup> > Br<sup>-</sup> > I<sup> -</sup> was seen with all receptors.</p>
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Robotham, Ian A. "Mechanistic studies of aromatic substitutions with aniline and phenoxide nucleophiles." Thesis, Durham University, 1997. http://etheses.dur.ac.uk/5063/.
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Kinetic studies are reported of the reactions of 1,3,5-trinitrobenzene with aniline in dimethyl sulfoxide (DMSO). In the presence of buffers containing 1,4- diazabicyclo(2.2.2)octane, (Dabco), and its acid salt, DabcoH(^+), the anilide σ-adduct is formed. The reaction of ethyl 2,4,6-trinitrophenyI ether with aniline in DMSO containing Dabco occurs in two stages. The first gives σ-adduct intermediate on the substitution pathway, which has been identified spectroscopically. The second yields 2,4,6-trinitrodiphenyIamine, the substitution product. Kinetic studies show that proton transfer is rate-limiting both in the formation of the intermediate and in its subsequent acid-catalysed decomposition. Phenoxide is a considerably better leaving group than ethoxide and the substitution reactions of phenyl 2,4,6- trinitrophenyl ethers and phenyl 2,4-dinitronaphthyI ether with aniline in DMSO occur without the accumulation of intermediates. The kinetics indicate both uncatalysed and base catalysed pathways. Values have been determined for the pK(_a) in DMSO of several ammonium ions derived from amines which have previously been widely used as nucleophiles in nucleophilic aromatic substitution reactions; values are also given for four polynitrodiphenylamines used as indicators. Second order rate constants (K(_s)) are presented for the reaction of substituted phenyl 2,4,6-trinitrophenyl ethers with a series of phenolate ions having pK(_a) values both higher and lower than that of the respective leaving groups in aqueous solution. The rate constants for the reverse reaction (k(_-s)) have also been measured. The Brømsted diagram formed when plotting log k(_s) versus pK(_a) shows a change in slope when ΔpK(_a) = 0 (ΔpK(_a) being the difference in pK(_a) values of the leaving group and nucleophile). This is consistent with a two step process involving a discrete σ-adduct intermediate. From the measured β values effective charges have been determined and the overall effective charge map constructed. Kinetic studies have been made for the reactions of substituted phenyl 2,4,6- trinitrophenyl ethers with substituted phenolate ions in 74% DMSO-water (v/v). Two reactions are observed. The evidence suggests that the more rapid involves formation of a 1,1 σ-adduct between the substrate and the phenolate ions. The slower reaction is attributed to hydroxide attack at the 3-position of the substrate.
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Horn, Gabriele [Verfasser], and Franz [Akademischer Betreuer] Worek. "Über neuartige, 4-Amino-2-((diethylamino)methyl)phenol-basierte Reaktivatoren Organophosphat-gehemmter Acetylcholinesterase / Gabriele Horn ; Betreuer: Franz Worek." München : Universitätsbibliothek der Ludwig-Maximilians-Universität, 2021. http://d-nb.info/1240145381/34.
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Cheng, Ka-wing, and 鄭家榮. "Preventive potential and mechanism of dietary phenolics on the formation of mutagenic heterocyclic amines." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2009. http://hub.hku.hk/bib/B4284177X.
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The Best PhD Thesis in the Faculties of Dentistry, Engineering, Medicine and Science (University of Hong Kong), Li Ka Shing Prize,2008-2009<br>published_or_final_version<br>Biological Sciences<br>Doctoral<br>Doctor of Philosophy
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Foley, Mark Kneale. "Characterisation of the interactions between amino acid derivatives and phenolic compounds." Thesis, Bangor University, 2007. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.443633.
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Nguyen, Thi D. T. "Antilarval substituted phenols, distribution of tricyclic pyrones in mice, and synthesis of unnatural amino acids." Diss., Kansas State University, 2014. http://hdl.handle.net/2097/18199.
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Doctor of Philosophy<br>Department of Chemistry<br>Duy H. Hua<br>Three research projects were carried out and they are described below.
The synthesis of substituted phenolic compounds including halogenated di- and trihydroxybenzenes, aminophenols, and substituted di-tert-butylphenols are described. Redox potentials of the synthesized molecules along with various known laccase substrates were measured, and an inverse relationship between the oxidation potential and the efficiency of oxidation by laccase of halogenated hydroxybenzenes and aminophenols is demonstrated. The synthesized substituted phenols were found to be substrates but not inhibitors of laccase. We discovered a new class of di-tert-butylphenols compounds that inhibits the growth of mosquito larvae at low concentrations. Compound 17, 2,4-di-tert-butyl-6-(3-methyl-2-butenyl) phenol caused greater than 98% mortality of third-instar larvae of Anopheles gambiae in the concentration of 0.18 µM. These compounds do not inhibit laccases. It appears that they affect a new target of the mosquito that is different from those of currently existing pesticides.
Two anti-Alzheimer molecules, CP2 and TP70, discovered in our laboratory were studied for their pharmacokinetics and distribution. The distribution of CP2 and TP70 in mouse brain region and various tissues of mice were examined. HPLC analysis revealed that CP2 treatment in primary neurons accumulates in mitochondria fraction. Similarly, the amount of CP2 in the brain tissue from wild type and APP/PS1 mice treated with 25 mg/kg/daily for 2 months also have the highest concentration in the mitochondria fractions in the hippocampus. The results show that CP2 and TP70 can penetrate the blood brain barrier and accumulate in the tissue in significant amounts. Pharmacokinetics and bioavailability of compound TP70 were determined. Area under the curve and bioavailability value F were calculated, and data show that TP70 has a good PK profile and bioavailability.
For the preparation of a novel tripeptidyl norovirus 3C-like protease (3CL[superscript]pro) inhibitor, the P3 unnatural amino acid, (S)-3-hydroxyphenylalanine was synthesized. The P3 is designed to increase the polarity with the addition of the alcohol group. After combining the P3 unnatural amino acid with the P1 and P2 to form the novel tripeptidyl compound, a study comparing the relations between the structure and its activity (SAR) will confirm whether prediction is correct in our pursuit for an antiviral therapeutic drug in the form of a protease inhibitor.
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Smit, Theodoor Martin. "Heteroatom substituted bis(imino)pyridine and bis(phenoxy-amine) transition metal complexes for olefin polymerisation." Thesis, Imperial College London, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.420626.
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Kigabo, Faustin. "Synthese de composes aromatiques par piegeage d'ions carbonium en milieu acide ou superacide." Poitiers, 1987. http://www.theses.fr/1987POIT2261.
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Al-Zubail, Saleh Abdullah. "An evaluation of efficiency of phenylenediamines as corrosion inhibitors for ASTM-A-179 steel in 1.0 N hydrochloric acid at room temperature." Ohio : Ohio University, 1986. http://www.ohiolink.edu/etd/view.cgi?ohiou1183039807.
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Cagatay, Onur. "Rubber Toughening Of Phenolic Resin By Using Nitrile Rubber And Amino Silane." Master's thesis, METU, 2005. http://etd.lib.metu.edu.tr/upload/12606281/index.pdf.
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The aim of this study was to investigate rubber toughening of resol type phenol-formaldehyde resin. For this purpose, phenolic resin was first modified by only acrylonitrile butadiene rubber, and then by using nitrile rubber together with 3-aminopropyltriethoxysilane.
Test specimens were prepared by mixing and casting of liquid phenolic resin in three groups. In the first one, neat phenolic resin specimens were produced. In the second group, phenolic resin was modified with 0.5, 1, 2, and 3 wt.% nitrile rubber, while in the last group modification was carried out by using 0.5 wt.% nitrile rubber together with 1, 2, and 4wt.% amino silane (with respect to nitrile rubber). All specimens were heat cured in the oven.
In order to observe behaviors of the specimens, Three-Point Bending, Charpy Impact, Plane-Strain Fracture Toughness, and Dynamic Mechanical Analysis tests were conducted according to the related ISO standards for all specimens groups. Scanning Electron Microscopy was also used for the fractographic analysis of some samples.
It can be concluded that, although there were problems in mixing and casting of liquid resol type phenolic resin, its toughness could be improved by using nitrile rubber and amino silane. Modification by using nitrile rubber and amino silane together was much more effective than by using only nitrile rubber. In this synergistic case for instance, Charpy impact strength and fracture toughness values of the neat phenolic specimens were increased 63% and 50%, respectively. SEM studies indicated that the main rubber toughening mechanism was shear yielding observed as deformation lines especially initiated at the domains of nitrile rubber and amino silane.
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Kitagawa, Kristen. "Studies in the asymmetric reduction of (3s)-3-amino-1-chloro-4-phenyl-2-butanone derivatives." Diss., Georgia Institute of Technology, 2010. http://hdl.handle.net/1853/39464.
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This thesis focuses on the asymmetric reduction of N-protected derivatives of (3S)-3-amino-1-chloro-4-phenyl-2-butanone to their corresponding diastereomeric alcohol products, which are key intermediates in the synthesis of HIV protease inhibitors. Although the stereoselective synthesis of the (S,S) alcohol product is easily achieved, preparing the (R,S) diastereomer is much more challenging. I investigated three diastereoselective reduction processes: 1) Meerwein-Ponndorf-Verley (MPV) reduction, 2) asymmetric transfer hydrogenation, and 3) boron reducing agents. The diastereoselectivity of the MPV reduction still favored the (S,S) product; however, I discovered a significant rate enhancement when the standard catalyst (aluminum isopropoxide) was replaced with aluminum tert-butoxide. Many reaction variables were investigated in the asymmetric transfer hydrogenation reaction and the diastereoselectivity was improved to give a ratio of the desired (R,S) diastereomer to the undesired (S,S) alcohol of 9.5:1. Using chiral oxazaborolidine catalysts, an unprecedented (R,S) to (S,S) ratio of 9.5:1 was achieved. Finally, I investigated the effect of the N-protecting group on the stereoselectivity of the reduction. When the original boc-protecting group was replaced with a phthalimide group, the diastereoselectivity of the MPV reduction was reversed to favor the desired (R,S) product.
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Holubcová, Petra. "Radikálové produkty oxidace vybraných typů fenolů a aminů." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2008. http://www.nusl.cz/ntk/nusl-216416.
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In the framework of diploma thesis, radical products of the oxidation of selected paramethyl phenols and secondary amines were investigated. In the case of para-methyl phenols using EPR spectroscopy the reaction mechanism was proved, where the abstraction of hydrogen from para-methyl group is involved. In this way benzyl radicals are formed, which can be identified by spin-trapping technique using nitroso compounds. The adducts formed undergo the consecutive rearrangement, which leads to the formation of the corresponding nitrones. In addition to phenols, the radical products of the oxidation of some secondary amines using peroxy radicals and peroxy acids were studied. In both cases new types of nitroxyle radicals were generated and the EPR parameters were determined by spectral simulation.
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Lam, Tsang Sing. "Synthesis and characterization of novel polymers : copolymers of Poly(phenyl vinyl sulfoxide) and Poly(amide sulfonamide)s." HKBU Institutional Repository, 1998. http://repository.hkbu.edu.hk/etd_ra/166.
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Maxwell, Michael. "Functionalised poly(organosiloxane)s as supported liquid membranes." Thesis, University of Bath, 1999. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.311252.
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CHAPELANT, LUC. "La robotique de laboratoire : nouveaux modules peri-robotiques. application a la synthese peptidique du 2 - boc amino - n - hydroxy - 3 - phenyl - propionamide." Paris 6, 1997. http://www.theses.fr/1997PA066270.
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L'objet de ce travail est de developper un site robotise versatile de syntheses chimiques en phase liquide destine aux laboratoires de recherche. Ce site doit permettre l'utilisation des connaissances classiques de la chimie organique tout en autorisant un haut niveau de production. Dans un premier temps, nous avons developpe des modules perirobotiques complexes mais robustes afin d'augmenter les potentialites du site en adaptant l'art du chimiste. Nous nous sommes tout d'abord interesses a la distribution de produits sous forme solide en minimisant les connaissances prealables du produit. La purification des solutions en fin de synthese constituant une etape longue et fastidieuse, nous avons automatise cette etape en la scindant en plusieurs taches : filtration, lavage et sechage. Puis, afin d'obtenir nos produits sous une forme seche et stable dans le temps, nous nous sommes preoccupes de l'evaporation du solvant organique. Dans un deuxieme temps, nous avons adapte une synthese peptidique qui permet d'orienter le site vers une nouvelle technique de synthese, la synthese combinatoire. Dans un troisieme temps, afin que notre site ait une fiabilite suffisante, nous avons mis en oeuvre une etude des modes de defaillances pour reduire le nombre d'evenements indesirables provoquant l'echec d'une synthese.
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Beji, Mohamed. "Heterocumulenes alpha -sulfonyles et leurs applications a la synthese de nouvelles structures heterocycliques : alkylation des esters sulfamiques en catalyse par transfert de phase." Paris 7, 1987. http://www.theses.fr/1987PA077183.
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Spáčil, Zdeněk. "Mass Spectrometry of Biologically Active Small Molecules : Focusing on polyphenols, alkaloids and amino acids." Doctoral thesis, Stockholms universitet, Institutionen för analytisk kemi, 2010. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-33233.
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The foci of this dissertation are on advanced liquid chromatography (LC) separation and mass spectrometry (MS) techniques for the analysis of small bioactive molecules. In addition to discussing general aspects of such techniques the results from analyses of polyphenols (PPs), alkaloids and amino acids published in five appended studies are presented and discussed. High efficiency and well understood principles make LC the method of choice for separating analytes in many kinds of scientific investigations. Moreover, when LC is coupled to an MS instrument, analytes are separated in two stages: firstly they are separated and pre-concentrated in narrow bands using LC and then separated according to their mass-to-charge (m/z) ratios in the MS instrument. Some MS instruments can provide highly accurate molecular weight measurements and mass resolution allowing identification of unknown compounds based purely on MS data, thus making prior separation unnecessary. However, prior separation is essential for analyzing substances in most complex matrices – especially useful is the ultra-high performance LC (UHPLC). The advantages of using UHPLC rather than HPLC for the analysis of PPs in tea and wine were evaluated in one of the studies this thesis is based upon. The phenolic composition of red wine was also examined, using a novel LDI technique, following solid phase extraction (SPE). A class of small aromatic molecules (medicinally important alkaloids) also proved to be amenable to straightforward analysis, by thin layer chromatography (TLC) work-up followed by LDI-MS. Finally, a LC-MS method for monitoring neurotoxins (β-N-methyl-amino-L-alanine and 2,3-diaminobutyric acid) in complex biological matrices was developed and applied. Overall, the studies show that careful attention to the physicochemical properties of analytes can provide insights that can greatly facilitate the development of alternative methods to analyze them, e.g. by LDI.<br><p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: In press. Paper 5: Manuscript.</p>
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Kulkarni, Sameer M. "Sol-gel immobilized cyano-polydimethylsiloxane and short chain polyethylene glycol coatings for capillary microextraction coupled to gas chromatography." [Tampa, Fla.] : University of South Florida, 2007. http://purl.fcla.edu/usf/dc/et/SFE0002083.
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Qian, Zheng. "Analysis of DNA damage induced by 2-hydroxy amino-1-methyl-6-phenyl-imidazol [4,5-b] pyridine (N-OH-PHIP) in the mutation cluster region of the human APC gene." Available to US Hopkins community, 2002. http://wwwlib.umi.com/dissertations/dlnow/3068198.
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Brodsky, Kathy-Jo. "The synthesis and characterization of bis(4-(3-(4-phenoxy)propionitrile))-N, N-disalicylidene-1,2-phenylenediamino)zirconium(IV), Zr(nitrile)₂ and the attempted synthesis of Zr(amine)₂ and coordination polymers containing Zr(dspOH)₂ /." Online version of thesis, 1994. http://hdl.handle.net/1850/11764.
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Ende, Melita van der [Verfasser], and Michael R. [Akademischer Betreuer] Buchmeiser. "Synthese und Reaktivität von Gruppe IV und Gruppe VI Metallkomplexen mit N-(6-(2-(Diethylboryl)phenyl)pyrid-2-yl)amin- und chelatisierenden N-heterozyklischen Carbenliganden / Melita van der Ende ; Betreuer: Michael R. Buchmeiser." Stuttgart : Universitätsbibliothek der Universität Stuttgart, 2018. http://d-nb.info/1163274909/34.
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Van, der Ende Melita [Verfasser], and Michael R. [Akademischer Betreuer] Buchmeiser. "Synthese und Reaktivität von Gruppe IV und Gruppe VI Metallkomplexen mit N-(6-(2-(Diethylboryl)phenyl)pyrid-2-yl)amin- und chelatisierenden N-heterozyklischen Carbenliganden / Melita van der Ende ; Betreuer: Michael R. Buchmeiser." Stuttgart : Universitätsbibliothek der Universität Stuttgart, 2018. http://d-nb.info/1163274909/34.
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HADDAD-FAHED, OMAIMA. "Catalyse micellaire de reactions de substitution nucleophile aromatique comportant des reactifs electriquement charges." Paris 6, 1987. http://www.theses.fr/1987PA066419.
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Holz, Karsten. "Enol-Konjugate von 1-Phenyl-3-methyl-4-amino-3-pyrazolin-5-on als "minor metabolites" im Stoffwechsel von Metamizo. (Novalgin R) : Untersuchungen zur Analytik, zu Nachweis, Bildung und Verbleib metastabiler Phase-II-Metaboliten bei der Ratte /." [S.l. : s.n.], 1997. http://www.gbv.de/dms/bs/toc/226144828.pdf.
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Picoli, Junior Gilmar José [UNESP]. "Influência do glyphosate no perfil bioquímico e fisiológico de populações de azevém (Lolium multiflorum) suscetíveis e resistentes ao herbicida." Universidade Estadual Paulista (UNESP), 2016. http://hdl.handle.net/11449/135868.
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Previous issue date: 2016-01-25<br>Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)<br>No Brasil, o azevém (Lolium multiflorum) foi identificado como resistente ao glyphosate se tornando um grande problema em determinadas lavouras. Dessa forma, entender o comportamento a nível bioquímico e fisiológico desta planta daninha são ferramentas que auxiliam num manejo eficiente. Com isso, o objetivo deste trabalho foi comparar o perfil bioquímico e fisiológico de populações de azevém suscetíveis e resistentes ao herbicida glyphosate aplicação do mesmo. Foram realizados quatro estudos em casa-de-vegetação com delineamento experimental inteiramente casualizados com quatro repetições sendo semeadas três populações de azevém (Lolium multiflorum) consideradas como suscetível (S), com suspeita de resistência (R1) e resistente (R2) ao herbicida glyphosate. No primeiro estudo foi obtido o controle aos 21 dias após a aplicação (DAA) e quantificada a massa seca aos 28 DAA das três populações. Os tratamentos foram constituídos da aplicação do herbicida glyphosate composto pelas doses: 0, 135, 270, 540, 1080, 2160, 4320, 8640 g e.a. ha-1. O segundo estudo teve como objetivo determinar a atividade da enzima fenilalanina amônia liase (PAL) nas diferentes populações as 12, 24, 48 e 72 horas após a aplicação (HAA). Os tratamentos foram compostos de duas doses (720 g e.a. ha-1 e 1080 g e.a. ha-1) mais uma testemunha sem aplicação. No terceiro estudo foram realizadas avaliações da fotossíntese nas três populações ao 1, 3, 7 e 28 DAA. As variáveis analisadas foram: taxa de assimilação líquida de CO2, condutância estomática, concentração interna de CO2, transpiração, eficiência do uso da água e eficiência instantânea de carboxilação. Os tratamentos foram compostos de duas doses (720 g e.a. ha-1 e 1080 g e.a. ha-1) mais uma testemunha sem aplicação. O quarto estudo teve o objetivo de quantificar compostos alterados da rota do ácido chiquímico. Para isso, foram utilizados os mesmos tratamentos do primeiro estudo e realizadas coletas das folhas aos 5, 11 e 28 DAA. Os compostos analisados foram: glyphosate, AMPA (ácido aminometilfosfônico), ácido chiquímico, ácido quínico, shiquimato-3-fosfato, os aminoácidos aromáticos fenilalanina, tirosina e triptofano, ácido ferúlico, ácido coumárico e ácido cafeico. Na população considerada resistente, a atividade da enzima fenilalanina amônia liase manteve-se alta após a aplicação do glyphosate. Todas as variáveis fisiológicas foram afetadas após a aplicação do glyphosate nas três populações, porém, R2 foi capaz de se recuperar apresentando valores semelhantes à testemunha. Os níveis de ácido chiquímico e quínico apresentaram padrões semelhantes onde houve aumento para as populações suscetíveis com o aumento da dose do herbicida enquanto que para a resistente os valores se mantiveram semelhantes. Ocorreu aumento dos níveis de shiquimato-3-fosfato para a população R2 se mantendo constante para as suscetíveis. Houve redução dos aminoácidos aromáticos com a aplicação do glyphosate para as populações suscetíveis.<br>In Brazil, ryegrass (Lolium multiflorum) was identified as resistant to glyphosate becoming a major problem in certain crops. Thus, understanding the behavior of the biochemical and physiological level of this weed are tools that help in efficient management. Thus, the aim of this study was to compare the biochemical and physiological profile of ryegrass populations susceptible and resistant to glyphosate after spray it. Four studies were carried out in greenhouse with experimental design completely randomized with four replications being seeded three populations of ryegrass (Lolium multiflorum) considered as susceptible (S), suspected of having resistance (R1) and resistant (R2) to the herbicide glyphosate. In the first study was measured the control at 21 days after application (DAA) and at 28 DAA, the dry mass the three populations. The treatments consisted of application of the glyphosate composed of doses: 0, 135, 270, 540, 1080, 2160, 4320, 8640 g a.i. ha-1. The second study aimed to determine the phenylalanine ammonia lyase (PAL) activity in different populations at 12, 24, 48 and 72 hours after application (HAA). The treatments consisted of two doses (720 g a.i. ha-1 and 1080 g a.i. ha-1) plus a control without application. In the third study were carried out photosynthesis assessments at three populations at 1, 3, 7 and 28 DAA. The variables analyzed were: CO2 net assimilation rate, stomatal conductance, CO2 internal concentration, transpiration, water use efficiency and instantaneous carboxylation efficiency. The treatments consisted of two doses (720 g a.i. ha-1 and 1080 g a.i. ha-1) plus a control without application. The fourth study aimed to quantify altered compounds of the shikimic acid pathway. For this, the same treatments of the first experiment were used and made collections of leaves at 5, 11, 28 DAA. The compounds analyzed were: glyphosate, AMPA (aminomethylphosphonic acid), shikimic acid, quinic acid, shikimate 3-phosphate, the aromatic amino acids phenylalanine, tyrosine and tryptophan, ferulic acid, coumaric acid and caffeic acid. The phenylalanine ammonia lyase enzyme was not influenced by glyphosate in resitant population. All physiological variables were affected after the application of glyphosate at the three populations, but R2 was able to recover with values similar to the control. The shikimic and quinic acid levels showed similar patterns where, there was an increase for susceptible populations with increasing doses of the herbicide while in resistant, the values remained similar. There was increase in levels of shikimate-3-phosphate to the R2 population, remaining constant for susceptible. There was a reduction of the aromatic amino acids with the application of glyphosate for the susceptible populations.
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Carniato, Denis. "Nouveaux inhibiteurs de l'alanine racemase : les acides α-aminophosphoniques β-fonctionnalisés". Paris 6, 1986. http://www.theses.fr/1986PA066029.
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L'objectif de ce travail a été de concevoir, de synthétiser et d'évaluer les molécules polyfonctionnelles susceptibles d'inhiber spécifiquement deux enzymes de la biosynthèse du peptidoglycane, constituant essentiel de la paroi bactérienne: l'alanine racemase et la d-alanimne: d-alanine ligase. Leur inhibition devrait conduire à la formation d'une paroi altérée, ce qui doit rendre le microorganisme non viable. Les molécules synthétisées, basées sur le concept d'inhibiteurs irréversibles de type "substrats suicides", sont des acides α-aminophosphoniques et phosphiniques β-fonctionnalisés. Ils se sont avérés être de bons inhibiteurs compétitifs des enzymes de Pseudomonas aeruginosa (Gram-) et de streptococcus faecalis (Gram+), mais aucune irréversibilité n'a pu être observée. Cette étude a mis en évidence des incertitudes quant au mécanisme d'inhibition de l'alanine racemase par les acides α-aminophosphoniques.
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Haelters, Jean-Pierre. "Synthèse de dérivés phosphono-indoliques-benzofuranniques et -pyrroliques à partir d'hydrazones phosphonates." Brest, 1987. http://www.theses.fr/1987BRES2002.
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Des derives phosphonoindoliques sont prepares par cyclisation d'arylhydrazones d'oxoalkylphosphonates selon fisher et par cyclodeshydratation d'arylamino-1 et arylamino-3 oxo-2 propylphosphonates selon bischler. Des indolyl-2 et indolyl-3 phosphonates, des indolylmethyl-2 et des indolylmethyl-3 phosphonates diversement substitues et leurs acides phosphoniques correspondants sont decrits. Toutes structures sont analysees par rmn **(1)h, **(31)p et 1**(3)c. L'analogue phosphore de l'intermediaire a aussi ete prepare. L'extention de la reaction de bischler aux aryloxycetones permet d'atteindre des benzofuryl-2 phosphonate et de benzofurylmethyl-3 phosphonates. Deux nouveaux reactifs sont utilises pour acceder aux arylaminocetones et aux aryloxycetones : les chloro-1 et chloro-3 methoxycarbonylhydrazono-2 propyl-phosphonates de diethyle, composes qui, traites en milieu basique, donnent des azoenes qui additionnent les anilines et les phenols. Ces azoenes additionnent aussi les carbanions, notamment les carbanions derives de cetones pour conduire, apres hydrolyse soit a des derives du pyrrole, soit a des dioxy-2, -5-alkylphosphonates precurseurs de cyclopentenones selon wittig-horner
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Renaud, Jean-Paul. "Oxydations d'alcanes et d'alcènes par des systèmes métalloporphyriniques modelés du cytochrome P-450." Paris 6, 1986. http://www.theses.fr/1986PA066139.
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La synthèse d'une pophyrine de fer à "anses de panier" chirale comportant des aminoacidés de configuration déterminée est décrite. On a étudié sa pureté optique et sa conformation en solution. Dans une deuxième partie on décrit un nouveau système oxydant catalytique utilisant l'eau oxygénée en présence d'une porphyrine de manganèse et d'imidazole permettant la conversion quantitative d'alcènes en époxydes et d'alcanes en alcools et cétones.
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Reinaud, Olivia. "Nouvelles methodes d'alkylation regioselective d'orthoquinones originales : synthese de differentes classes de produits naturels quinoniques." Paris 6, 1987. http://www.theses.fr/1987PA066200.
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Lange, Catherine. "Chimie des insectes : synthèse, par réaction entre dienamines et aldéhydes insaturés, de molécules potentiellement toxiques. Analyse d'un écosystème termite-fourmi." Paris 6, 1986. http://www.theses.fr/1986PA066234.
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Synthèse de dérivés dihydroaryles ortho-substitués en particulier par un groupe aldéhyde. Obtention par l'addition de diels-alder entre dienamines acycliques conjuguées et aldéhydes insaturés. Elle s'effectue avec de très bonnes régiosélectivité et stéréospécificité. L’inhibition des acétylcholinestérases par ces dihydrobiaryles se situe au niveau du carbofurane et de la néostigmine. Étude d'un écosystème termite-fourmi. Les relations entre termites de différents genres et entre termites et fourmis font intervenir les composes présents dans la cuticule. La spectrométrie de masse a été l'outil utilisé avec la mise au point d'un nouveau gaz d'ionisation chimique: l'oxyde d'éthylène.
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Safsaf, Abdelaziz. "Etude structurale par diffraction des rayons x d'un phosphonate et de quelques hydroxydiphosphonates." Paris 13, 1989. http://www.theses.fr/1989PA132001.
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Pour les acides phosphoniques, diphosphoniques et diphosphonates organiques acides, la corrélation entre la longueur p-oh et la distance oh. . . O est linéaire. Les molécules d'éthanédiphosphonate-1,1 (hydroxy-1 "0,0,0',o'"-tetramethyl) et les molécules dérivées, possedent une relative flexibilité (corrélation linéaire entre l'angle p-c-p et le décalage des deux groupes acides phosphoniques)
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Liang, Shing Cheng, and 梁心丞. "The study of chemical and biological characteristics of complexes Ga-67 labeling with pyridyl amine phenol and imine phenol derivatives." Thesis, 1996. http://ndltd.ncl.edu.tw/handle/91868606540808914279.
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Wong, Ernest Shing Yan. "Coordination chemistry of Group 13, Technetium and Rhenium metal complexes with Hexadentate Amine Phenol Ligands." Thesis, 1996. http://hdl.handle.net/2429/6222.
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A series of neutral and monocationic group 13 metal complexes with hexadentate
tripodal, linear and pyridine amine phenolates were prepared and characterized by elemental analyses and various spectroscopic techniques (IR, UV, LSIMS, NMR). X-ray crystallographic structural analyses of selected Al³⁺, Ga³⁺ and In³⁺ complexes were also performed. It was
observed that the coordination behavior of the amine phenolates and the stability of the resulting metal complexes were closely related to the flexibility of the ligand, the type and spatial organization of the donor atoms, as well as to the electronic and steric demands of the coordinated metal ion.
Coordination of tripodal N₃O₃ tris(aminomethyl)ethane based amine phenolates
(XTAM³⁻) to Al³⁺, Ga³⁺ and In³⁺ resulted in neutral mono-ligand metal complexes. The N₃O₃
donor set was suitable for coordination to all three group 13 metal ions. As the size of the metal ion increased from Al³⁺ to In³⁺, XTAM³⁻ adjusted to the steric demands of the coordinated metal in a subtle fashion, such that no significant identifiable bond angle change was observed.
This flexibility allowed it to coordinate to various metals of differing sizes. Paramagnetic Tc(III), Tc(IV) and Re(IV) complexes with XTAM³⁻ were prepared via the substitution and reduction/complexation methods. The coordination of XTAM³⁻ to Tc and Re demonstrated the potential use of the hexadentate amine phenolates as ligands for coordination to Tc and Re in intermediate oxidation states.
Monocationic Ga³⁺ and In³⁺ complexes with linear amine phenolates (Xbad²⁻ and
Xbadd²⁻) based on triethylenetetraamine and N,N’-(³⁻aminopropyl)ethylenediamine were
prepared; no analytically pure, Al³⁺ complex could be isolated. The N₄O₂ donor set of the linear amine phenolates was softer than the N₃O₃ set of XTAM³⁻ and hence was less suitable for coordination to the harder Al³⁺ ion. Structural analyses of [Ga(Brbad)]ClO₄ and
[Ga(Brbadd)] ClO₄, and NMR spectral data revealed the mode of coordination of the Xbad²⁻ ligand to be different from that of the longer backbone Xbadd²⁻. Increasing the length of the amine phenolate altered the mode of coordination.
The introduction of pyridine nitrogen atoms into the amine phenol framework reduced
the overall hardness of the donor atom set. Monocationic Ga and In complexes with N₂N₂O₂
pyridine amine phenolates (Xbbpen²⁻) were prepared with ease, while no Al complex could be isolated. Only minor differences between the structures of the Ga and In complexes were observed, suggesting that the cavity of Xbbpen²⁻ was large enough to accommodate ions as large as In³⁺ without causing significant steric strain to be imposed onto its framework. Stability constant study of Ga and In complexes with sulfonated linear amine phenolates
(Sbad⁴⁻ and Sbadd⁴⁻) showed the Ga complexes to be ~3 orders of magnitude more stable
than the corresponding In complexes. The selectivity of the linear amine phenolates for Ga³⁺ over In³⁺ was consistent with the fact that, while the affinity of amine for Ga³⁺ and In³⁺ was similar, 2-oxybenzyl groups definitely has an affinity for Ga³⁺ over In³⁺. In contrast, the stability constants of Ga and In complexes with sulfonated pyridine amine phenolate (Sbbpen⁴⁻
) were very similar to each other. The introduction of the pyridine nitrogen atoms into the amine phenolate donor set muted the selectivity of the amine phenol for Ga³⁺ over In³⁺. The stability constants of the Ga and In complexes with Sbbpen⁴⁻ were 7-10 orders of magnitude higher than those of the linear amine phenolate complexes. This was due to the donor atoms in Xbbpen²⁻ being more pre-arranged for coordination than those of linear amine phenolates.
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林俊男. "Synthesis and Characterization of NewOrganosoluble Poly(ether-imide)s with Benzo-thiazole Pendent Groups derived from 2,2-Bis[4-(4-amino-2-(2-benzothiazole)phenoxy)phenyl]propane,and 2,2-Bis[4-(4-amino-2- (2-benzo- thiazole)phenoxy)phenyl]hexafluoropropan." Thesis, 2002. http://ndltd.ncl.edu.tw/handle/11092789139763556118.
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碩士<br>國立臺灣科技大學<br>化學工程系<br>90<br>Abstract
A series of polyimides containing benzothiazole pendent groups were synthesized from two new diamines. The diamines(3a and 3b) were derived by a nuclephilic substitution of the bisphenols (4,4´-isopropylidendiphenol and 4,4´-(hexafluoroisopropylidene)di- phenol) with 3-(2-benzothiazole)-4-chloronitrobenzene in the presence of K2CO3 and then were reduced. A series of poly(ether imide)s bearing benzothiazole pendent groups were prepared from the diamines 3 with various aromatic dianhydride via the one-step method that included ring-opening polyaddition to form the poly(amic acid)s followed by chemical imidization to the polyimides(5 and 6). The polyimides with inherent viscosities ranging from 0.31 to 0.71 dl/g showed good solubilities in common solvents such as 1-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide(DMAc), chloroform, and tetrahydro- furan. The polyimide derived from pyromellitic dianhydride(PMDA) was even soluble in NMP and DMAc. Tough, transparent films of the soluble polyimides were cast from solution. These films have tensile strengths of 64-120 Mpa, and elongations to break of 3-8 ﹪. Glass transition temperatures ranged from 264 to 318°C and above with the polymers showing little or no weight loss by TGA up to 400°C in both air and nitrogen. The glass transition temperatures of the polyimides increased 16 to 53°C (compared to the polyimide analogs without benzothiazole pendent groups).
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Wu, Jun-Yi, and 吳俊毅. "Ultrafast Photoionization Induced Proton Transfer Dynamic in Phenol-Amide Cation Complex." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/yq3yud.
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碩士<br>國立清華大學<br>化學系<br>105<br>We report studies of ultrafast proton transfer (PT) reaction of phenol-N-methylformamide(PhOH-NMF) and phenol-N,N-dimethylformamide (PhOH-DMF) cation complexes by using femtosecond pump-probe photoionization-photofragmentation spectroscopy (fs-PIPF). Neutral PhOH-NMF and PhOH-DMF complexes prepared in a free jet are photoionized by femtosecond [1+1] resonance-enhanced multiphoton ionization via S1 state, and the subsequent dynamics occurring in the cations is probed by delayed pulses that result in ion fragmentation. The observed probe-wavelength dependence of the transients are consistent with a spectral evolution from the initial non-PT to final PT states. The combination of experimental results and DFT calculations suggest that a low barrier is present along [PhOH-NMF]+ cation proton transfer reaction coordinate. There are three distinct time scales in [PhOH-NMF]+ experiments : τ_1≈0.23 ps is assigned to an initial wave-packet motion, τ_2=3 ps~18 ps is assigned to the proton transfer, and τ_3=40ps~81 ps is attributed to to complex isomerization. The experiments revealed that PT in [PhOH-DMF]+ cation also proceeds in three distinct steps: τ_1≈0.3 ps an initial wave-packet motion, followed by a slower relaxation τ_2≈2 ps and a final step τ_3=15ps~17 ps of complex isomerization.
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Chiang, Chang-Han, and 江昌翰. "Synthesis of Naturally Occurring Phenolic Amide of." Thesis, 2001. http://ndltd.ncl.edu.tw/handle/40172302602691115019.
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碩士<br>中國文化大學<br>應用化學研究所<br>89<br>Magnolamide, a novel phenolic amide, was isolated and characterized from the leaves of Magnolia coco. The stems and leaves of Magnolia coco (Lour.) DC. (Magnoliaceae) are used as a Chinese herbal medicine against liver disease. As we know hydroxycinnamic acid conjugated with aliphatic amine such as tyramine, putrescine, speridine, spermine, and serotonin was found from various plants. A number of amides are known to have biological activities. Magnolamide was the first naturally occuring amide which has a (2-formyl-5-hydroxymethyl)-pyrrolybutylamine moiety as an amine unit. In order to confirm the structure and further study the biological activities, we were prompted to investigate the synthesis and antioxidative activity of magnolamide. Here, a facile preparation of magnolamide from pyrrole-2,5-dicarboxaldehyde was established in six steps, the structure of which was determined by spectroscopic analysis and by comparison with published data of the natural product.
In preliminary test, cch11 and magnolamide exhibited stronger LDL-oxidation inhibitory activities than resveratrol.
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Hudgens, Debjani Patangia. "Di- and mono- phenyl amine based sodium channel blocker for the treatment of pain." 2007. http://wwwlib.umi.com/dissertations/fullcit/3305891.
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Lin, Hsiao-Ching, and 林小菁. "Studies on the antioxidant effect of (polyhydroxy-benzylidene)-(hydroxy-phenyl)amines." Thesis, 2005. http://ndltd.ncl.edu.tw/handle/57097823436056331855.
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碩士<br>嘉南藥理科技大學<br>化妝品科技研究所<br>93<br>Abstract
In this study we aim to originally systhesize a series of highly productive (polyhydroxy-benzylidene)-(hydroxyl-phenyl)amines and observe their antioxidant capacity estimated in four different systems. 1. The effect on DPPH radical savenging 2. The effect on trolox equivalent antioxidant capacity 3. The effect on scavenge nitric oxide. 4. The effect on liposome assay.
The results of the study shows : the estimations of both the capture of DPPH and TEAC assay are similar, as the indicator in the two systems are the reduction of free radicals. The results show that A ring has obvious influence on the type, number and position of substituent. However, B ring is decisive only in the positions of substituents and have little to do with the types and existence of substituent. As a whole, A ring has greater effect than B ring, and substituents at the ortho and para position are best effective on antioxidant: DPPH assay IC 50 (2.90~3.40ppm) is 2.5 times better than trolox(7.5~8ppm), TEAC assay IC 50 (0.91~1.02ppm) is about 5-6 times better than trolox(5.56ppm).
In liposome and NO assay systems, they are found that in low density of A ring monohydroxyl substituent at A ring are better than dihydroxy or trihydroxy substituents. But, in higher density the suppressive effect in these three composites are about the same. However, the more hydroxy groups of benzylidene phenyl amines are methylated to be methoxy groups at A ring, while the less effect on the antioxidant capacity. But, the methoxy group or not substituent at B ring are not poor effects than hydroxy groups at B ring.
This results indicate that the type, number and positions of subtituents, in benzylidene-phenyl amines to play a critical role in exerting the antioxidant
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Lin, Shiau Feng, and 林曉峰. "The Properties of Mannich Bases Derived from Poly(oxyalkylene)amines and Phenols." Thesis, 2000. http://ndltd.ncl.edu.tw/handle/43791605205824932529.
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碩士<br>國立中興大學<br>化學工程學系<br>88<br>The Mannich reaction of poly(oxyalkylene)amine, alkyl-phenol, and formaldehyde gives a series of mixing products, namely Mannich Bases. The structures of these adducts were constituted of the poly(oxyalkylene) segments, phenols, and amines which identified by GPC, H1-NMR, amine titration etc. These products were divided into two classes according to the nature of products: one is lipophilic Mannich Bases; the other is hydrophilic Mannich Bases. The lipophilic Mannich Bases are water-insoluble. And, the hydrophilic Mannich Bases consist of poly(oxyethylene)-segments which could associate with water. This renders the Mannich Bases hydrophilic water-soluble, and surface-active.
In part one, the lipophilic Mannich Bases were applied on epoxy curing system. The reaction profiles of amine adducts with epoxides were observed in DSC. The results showed that these adducts could lower the reaction temperatures and activation energies. Besides, the cured polymers also had higher Tg, better thermal stability and improved mechanical strength.
In part two, the fundamental surfactancy of hydrophilic Mannich Bases is discussed. These novel surfactants lowered the surface tension of water and interfacial tension of water/toluene (or water/n-hexane) to 31 ~ 33 dyne/cm and 5 dyne/cm, respectively. Some adducts of this series also had cloud points as same as the nonionic surfactants. But the cloud point disappeared in acidic environment due to the increased solubility by the formation of quaternary salt. The aggregating behaviors of these surfactant molecules were also observed by light scattering technique (hydrodynamic diameter) and H1-NMR in different solvents.
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Pan, Chih Ming, and 潘志明. "Study on the treatment of phenol and amino acid in aqueous solution via TiO2/Apatite photocatalyst." Thesis, 2007. http://ndltd.ncl.edu.tw/handle/05272431769482210630.
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碩士<br>嘉南藥理科技大學<br>環境工程與科學系暨研究所<br>95<br>This study aimed at removing organics in aqueous solution via photo catalysis. A more efficient photo catalyst, i.e. TiO2/Apatite, was synthesized by the sol-gel method. The improved efficacy of TiO2/Apatite may be attributed to the combination of photo catalytic capability of TiO2 and absorption capability of Apatite. The organics tested were phenol and glycine (an amino acid) and their removing efficiency were based to screen for the optimal catalyst loading and composition of TiO2/Apatite.
The results show that Apatite has the most BET surface area as it was prepared at Apatite/P.P. = 1：1. Moreover, for removing phenol, the optimal ratio of TiO2/Apatite is 5：1 while it is 9：1 for the removal of glycine. The most efficient catalyst loading is 0.75 g/L for both organics tested.
Under the above mentioned optimal reaction conditions, the following efficiency was obtained. For 100ppm phenol, 45 ％ phenol conversion and 24 ％ COD removal was achieved after 6 hrs reaction；for 50 ppm, 55 ％ phenol conversion and 35 ％ COD removal was achieved after 4 hrs reaction；for 100 ppm glycine, 50 ％ COD removal was achieved after 4 hrs reaction.
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Ngue, Chin-May, and 魏清梅. "Redox-Active Coordination Polymers Constructed By Tris(4-(1H-1,2,4-triazol-1-yl)phenyl)amine Ligand." Thesis, 2018. http://ndltd.ncl.edu.tw/handle/8w7t88.
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博士<br>國立臺灣大學<br>化學研究所<br>107<br>It is possible to alter the properties of redox-active materials by altering their redox state. The incorporation of a redox-active ligand in the construction of multifunctional materials has received limited attention despite the potentially high versatility. The tris(1,2,4-triazolphenyl)amine (TTPA) ligand with its triarylamine as a core is well-known for its redox and spectral properties. The TTPA ligand has significant potential for the development of coordination polymers where interplay exists between redox, optical, and host–guest properties. This thesis investigates the synthesis, design and physical properties of coordination polymers with TTPA incorporated within them.
Two dimensional coordination polymers can be achieved by merely incorporated the TTPA ligand with Cu2+ and Mn2+ metal ions to afford [MnTTPACl2·DMF]n (1) and {[CuTTPACl2]·2DMF}n (2). The redox-active behaviour of 1 and 2 was interrogated using chemical oxidants, solid state cyclic voltammetry and in situ solid state spectroelectrochemical techniques. Frameworks with higher dimensionality 3–6 can be obtained when the TTPA ligand is inserted with carboxylates as a co-ligand. Besides remained an electroactive framework, additional physical properties were observed and characterised. The robust and permanent porosity of {[Zn3(TTPA)2(DHTP)3]·2DMF}n (3), (DHTP = dihydroxyl terepthalic acid) is confirmed by gas adsorption measurements. Compound 3 has a Brunauer-Emmett-Teller (BET) surface area of 715.76 m2/g. 3 shows favorable interaction with carbon dioxide. One highlight of 3 is its photoluminescence intensity could be tuned “on” and “off”. {[Co2(µ-OH2)(TTPA)(DTDN)2·DMF]·H2O}n (4), (DTDN = dithiodinicotinic acid) constructed using Co2+ as the metal precursor, the binuclear centre of the framework allows for magnetic measurement. Magnetic studies indicated that 4 exhibits antiferromagnetic interactions and undergoes a field-induced spin-flop transition. {[Co(TTPA)(TDC)(H2O)]·2DMF}n (5), (TDC = thiophene dicarboxylate) and {[Cd(TTPA)(TDC)]·2H2O}n (6) were synthesised under same reaction conditions except for the use of different metal ions. The degree of interpenetration could be controlled by the metal ions as the sole reaction variable, and it subsequently influenced the coordination behaviour of TDC2– (thiophene dicarboxylate) ligand. Therefore 5 is 2-fold interpenetrated, and 6 is 4-fold interpenetrated. Spectral, fluorescence and host-guest properties of the frameworks were able to tune as a function of the redox state. In situ UV/Vis/NIR, fluorescence spectroelectrochemical techniques in both the solution and solid-states formed an integral part of the characterization of these compounds.
The thesis describes a systematic approach towards the study of the fundamental and applied aspects of redox activity as a platform for multifunctional systems. The functionalities can be controlled and fine-tuned.
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顧得祥. "Studies of The Methods For Synthesis of alpha-Amino Acids― Preparation And Application of (R)-6-(4-Methoxy-phenoxy- methyl)-3,6-dimethyl-5-phenyl-3,6-dihydro-[1,4]oxazin-2-one." Thesis, 2003. http://ndltd.ncl.edu.tw/handle/65997809469815054987.
Full textAbstract:
碩士<br>國立中興大學<br>化學系<br>91<br>This thesis describes our studies on the asymmetric synthesis of alpha-amino acids utilizing monocyclic iminolactones as chiral templates. Chiral auxiliaries 17 and 35 were prepare in three and five steps with the overall yield of 60 % and 53 % respectively. The stereocenter was established by employing Sharpless asymmetric dihydroxylation to furnish compounds 16 and 32 with 94 % and 96 % entiantiomeric excess (e.e.) respectively. No recemization of compounds 17, 35 during the transformations was observed.
When alkylation of chiral template 20 was carried out using LDA as the base, deprotonation at C-6 occurred leading to the formation of unwanted product 27. Consequently, the structure of 27 was confirmed by single X-ray crystal analysis. Use of chiral template, 37 having methyl group in place of C-6 hydrogen, has been prepared. Benzylation or allylation with benzyl or allyl bromide using different bases, such as LDA or potassium carbonate and a phase-transfer catalyst (PTC), resulted in the formation of the alkylated product 38 with 68-75% yield and >98% diastereoselectivity.
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Shahinas, Dea. "Structural and Functional Insights on Regulation by Phenolic Compounds." Thesis, 2008. http://hdl.handle.net/1807/17222.
Full textAbstract:
The shikimate pathway is a primary metabolic pathway involved in the synthesis
of aromatic compounds in plants, fungi, apicomplexan parasites and microbes.
The absence of this pathway in animals makes it ideal for the synthesis of
antimicrobial compounds and herbicides. Additionally, its branching into indole
hormone synthesis and phenylpropanoid secondary metabolism makes this
pathway attractive for metabolic engineering. Here, the focus is on the first step
of the shikimate pathway catalyzed by DAHP synthase. This step consists of the
condensation of phosphoenol pyruvate and erythrose-4-phosphate to make
DAHP, which undergoes another six catalytic steps to synthesize chorismate, the
precursor of the aromatic amino acids. Arabidopsis thaliana contains three DAHP
synthase isozymes, which are known to indirectly regulate downstream pathways
in response to wounding and pathogen stress. The model presented here
proposes that DAHP synthase isozymes are regulated by the end products
tyrosine, tryptophan and phenylalanine.
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Yao, Hsueh-Hua, and 姚學華. "X-ray Crystal Structures, Radiochemical Properties, and Animal Biodistribution of Cu(II) Complexes with Tetradentate Imine and Amine Phenols." Thesis, 1997. http://ndltd.ncl.edu.tw/handle/21788131128423824126.
Full textAbstract:
博士<br>國立清華大學<br>原子科學系<br>85<br>Tetradentate imine and amine phenols with an N2O2 donor set can
chelate Cu(II) atom to form the Cu(II) complexes with neutral-
lipophilicity and low molecular weight, being premised to
develop as a cerebral blood flow agent. The main purpose of
this study is to identify the crystal structures, chemical, and
biological characteristics of the Cu(II) imine and amine
phenols. The potential of these Cu(II)-62 complexes has been
evaluated as a clinical tracer for Positron Emission Tomography
(PET). Preliminary characteristics of the Cu(II) complexes with
a series of tetradentate N2O2 ligands, including imine phenols,
have been reported lately. Here we have then focused on crystal
structures of a series of Cu(II) imine phenols. In addition,
because the short half-life of Cu-62 is undesirable for
laboratory research, we have employed longer lived Cu-64 readily
available from the Tsing Hua open pool reactor (THOR), as the
radiocopper in this study. Thirteen Cu(II) imine phenols and
methoxyl-substituted imine phenols with varying lengths of the
alkylenediamine backbone have been prepared and their structures
determined by X-ray diffraction. Most of the Cu(II) imine
phenols studied show four-coordinate, mononuclear, and neutral
complexes with low molecular weights. Elongation of the
alkylenediamine backbone results in the degree of distortion
from square plane, the enlargement of dihedral and N-Cu-N
angles, and the tendency to adopt a mononuclear structure. The
tendency to form H-bonding between the solvent molecule and the
phenol O or the water molecule attached to Cu(II) ion limits the
diffusibility of the Cu(II) imine phenols to cross the cell
membrane. Cu(II) amine phenols are readily formed and are also
neutral-lipophilic. These complexes are less lipophilic than
those with the corresponding Cu(II) imine phenols.
Lipophilicity of the Cu(II) amine phenols is enhanced either by
the addition of methyl groups to the alkylenediamine backbone or
by the alkyl substitution in the bridging carbon atoms. An
alkaline condition to prevent protonation of the amine N atoms
and to facilitate deprotonation of the phenol groups is required
for the coordination of amine phenol ligands to Cu(II) ion. In
solid state, the free ligand exhibits a stretched out, planar
conformation which is significantly distinct from the folded,
dinuclear, square-planar based pyramidal one upon Cu(II)
coordination. In rat biodistribution studies the Cu(II)-64
amine phenols are cleared from the blood rather rapidly and
excreted mainly via hepatobiliary way and partially via urinary
system. Judging from their very low uptake in any particular
organ, none of the Cu(II) complexes studied appears to be
suitable for PET imaging. The very low uptake of Cu(II)-64
amine phenols in the brain cells may be attributed to the H-
bonding formation of phenol O, amine N atoms, and the solvent
molecule attached to Cu(II) ion, as well as the large molecular
weight due to the dinuclear association between Cu(II) and
phenol O atoms.
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Wang, Kai-Min, and 王凱民. "Chemistry of Metal Complexes ContainingN-phenyl-N′-cyano-formamidine,2-Aminothiazole or 2-Amino-2 thiazoline." Thesis, 2007. http://ndltd.ncl.edu.tw/handle/10049039733699265406.
Full textAbstract:
碩士<br>中原大學<br>化學研究所<br>95<br>This thesis includes two parts discussing the synthesis, structure andintermolecular interactions of metal complexes containing polydentate ligands.
Part I.
The reactions of the unsymmetrical N-Phenyl-N′-cyano-formamidine (HPhCNF) ligand with Cd(NO3)2 · 4H2O and Co(NO3)2 · 6H2O affordedtwo complexes of the type M(HPhCNF)2(NO3)2(THF), (M = Cd, 1 ; M =Co), 2 which were characterized by single-crystal X-ray diffraction method and elemental analyses.Both the metal center of complexes 1 and 2 adopt pentagonal bipyramidal geometry. The metal atoms were bonded to two nitrogen atoms
of cyano group, four chealting nitrate oxygen atoms, and one oxygen atom of THF solvent group. In these two complexes, C-H---O and N-H---O
hydrogen bonds were found to link the molecules.
Part II.
The reactions of 2-aminotkiazole (2-AT) with AgClO4, AgNO3,Ag2SO4, and Zn(OAc)2 · 2H2O afforded four new complexes of the types of
[Ag(2AT)2ClO4], 3 [Ag(2AT)2NO3], 4 [Ag2(2AT)2(SO4)][Ag2(2AT)2](SO4)] · 2(CH3OH), 5 and Zn(OAc)2(2AT)2, 6. Their crystal structures were
characterized by single-crystal X-ray diffraction method and elementalanalyses. In complexes 3 and 4, the silver metal centers adopt linear geometry that were bonded to two nitrogen atoms of 2-AT. The molecules
adopting linear geometry were interlinked through N-H---O hydrogen bonds.
Molecules in complexes 5 were linked through extensive Ag---S, Ag---O, Ag---Ag, S---S, S---O, O---O, hydrogen bondings, and π – π staking
interactions. In complex 6, the zinc metal centers were bonded to two nitrogen atoms of two different 2-AT groups, one monodentate acetate and one chealting acetate anion, to form a distorted square pyramidal geometry.
The molecules were linked through N-H---O hydrogen bonds and S---S interaction.
In compounds 7 and 8, the protonated 2-Amino-2-thiazoline cations, [H(2A2T)]+ were interacted with nitrate and perchlorate anions through
hydrogen bonds, forming 1-D hydrogen-bonded tapes.
The eight complexes were characterized by single-crystal X-ray diffraction method and elemental analyses.