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Dissertations / Theses on the topic 'Photochemically'

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Published: 5 June 2025
Last updated: 24 June 2025

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1

Erb, Suzanne Dorothe. "Studies of photochemically responsive substrates." Thesis, University of Oxford, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.314847.

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2

Davies, Paul R. "Routes towards photochemically initiated gas release in polymeric systems." Thesis, University of Reading, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.394476.

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3

Nebipasagil, Ali. "Chemically and Photochemically Crosslinked Networks and Acid-Functionalized Mwcnt Composites." Thesis, Virginia Tech, 2011. http://hdl.handle.net/10919/42703.

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PTMO-urethane and urea diacrylates (UtDA, UrDA) were synthesized from a two-step reactions of bis (4-isocyanatocyclohexyl) methane (HMDI) with either α,Ï -hydroxy-terminated poly (tetramethylene oxide) (PTMO Mn 250, 1000, 2000 and 2900 g/mol) or α,Ï -aminopropyl-terminated PTMO and 2-hydroxyethyl acrylate (HEA). PTMO-based ester precursors (EtDA) were also synthesized from α,Ï -hydroxy-terminated PTMO (Mn 1000 and 2000 g/mol). Two bis acetoacetates were synthesized from acetoacetylation of 1,4-butanediol and 250 g/mol hydroxy-terminated PTMO with tert-butyl acetoacetate. 1H NMR spectroscopy confirmed the structure and average molecular weights (Mn)of diacrylates. Mn of these precursors were in the range of 950 to 3670 g/mol by 1H NMR. The rheological properties of diacrylates were studied and activation energies for flow were calculated. Activation energies increased with increasing Mn and hydrogen-bond segment content. Michael carbon addition was employed to covalently crosslink the precursors resulting in networks with gel fractions better than 90%. DSC and DMA experiments revealed that networks had a broad distribution of glass transition temperatures depending on Mn and degree of hydrogen bonding present in the diacrylates. Their Tgâ s varied from -61 ºC to 63 ºC depending on the crosslinking density and hydrogen-bonding segment content. TGA revealed that UtDA and UrDA networks had an improved thermal stability compared to their EtDA counterparts. Tensile properties showed a variation depending on the structure and Mn of diacrylate and BisAcAc precursors. The storage moduli of networks precursor change from 25.3 MPa to 2.0 MPa with increasing Mn of the urethane diacrylate Elongation at break increased from 255% to 755 % for the same networks. The Youngâ s moduli increased from 3.27 MPa for EtDA 2000 to 311.1 MPa for UrDA 2000 which was attributed to increasing degree of hydrogen-bonding. Acid functionalization of C70 P Baytubes multiwalled carbon nanotubes (MWCNT) generated acid-functionalized nanotubes (MWCNT-COOH). Suspension of MWCNT-COOH in organic solvents (chloroform, toluene, THF, DMF and 2-propanol) were prepared. DLS indicated average particle diameters of MWCNT-COOH in DMF and in 2-propanol were 139 nm and 162 nm respectively. FESEM of suspensions revealed aggregate free dispersion of MWCNT-COOH in DMF and 2-propanol. MWCNT-COOH containing composite networks were prepared. FESEM images of fracture surfaces of UtDA showed MWCNT-COOH were well-dispersed in the composites. DMA showed an increase in the rubbery plateau modulus which correlated with the MWCNT-COOH content in the networks. Tensile testing also revealed a relationship between MWCNT-COOH content and youngâ s moduli and strain at break of networks. Storage moduli of networks increased from 25 MPa to 211 MPa with increasing MWCNT-COOH content whereas elongation at break decreased from 255 % to 146 %. UtDAs and pentaerythritol tetraacrylate (PETA) were crosslinked under UV radiation (6 passes, 1.42 ± 0.05 W.cm2 for each pass) in the presence of 2,2-dimethoxy-2-phenylacetophenone (DMPA) (1 wt. % of the mixture) UV initiator. DMA demonstrated the presence of broad glass transition regions with a range of Tgâ s which varied from -60 °C to -30°C. Tensile testing also revealed the relationship between Youngâ s moduli, strain at break and the molecular weight of the diacrylates. The increasing molecular weight of urethane diacrylate precursors caused a drop in the storage moduli of networks from 15.8 MPa to 1.4 MPa and an increase in elongation at break from 76 % to 132 %.<br>Master of Science
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4

Kerrigan, Sarah. "Immunochemical detection of lysergic acid diethylamide using a photochemically linked immunogen." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1997. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp05/nq27177.pdf.

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5

Harikrishna, R. "Synthesis and evaluation of photochemically induced polymerization in novel acrylic monomers." Thesis(Ph.D.), CSIR-National Chemical Laboratory, Pune, 2010. http://dspace.ncl.res.in:8080/xmlui/handle/20.500.12252/3760.

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6

Foley, Loraine Johanna. "Photochemically induced reactions between ozone and halogenated species : a matrix isolation study." Thesis, University College London (University of London), 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.369260.

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7

Sun, Weiquan. "Multi-mode-driven molecular shuttles : photochemically and chemically reactive benzoxazole-containing rotaxanes." Thesis, University of Edinburgh, 2008. http://hdl.handle.net/1842/11437.

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Chapter Two describes the use of intercomponent interactions between the benzoxazole-containing motif in the thread and the benzylic amide macrocycle which provides an accessible and efficient method for the synthesis of a model <i>E</i>-[2]rotaxane. Irradiation of this <i>E</i>-isomer produces the corresponding <i>Z</i>-[2]rotaxane, in which the maximum number of intercomponent hydrogen bonds changes from four (<i>E</i>) to two (<i>Z</i>), considerably reducing the binding strength between the thread and the macrocycle. Lying in the macrocycle discrimination between the ‘matched’ (<i>E</i>) and ‘mismatched’ (<i>Z</i>) binding sites, two reversible light-driven molecular shuttles have been generated. Both shuttles exhibit remarkable positional integrity of the macrocycle on the thread before and after the photo stimulus. The synthesis of a hydrogen-bonded benzimidazole-motif-templated [2]rotaxane with excellent yield is reported in Chapter Three. Upon UV irradiation of this <i>E</i>-[2]rotaxane, none of the corresponding <i>Z</i>-isomer is produced and its heavily suppressed photoisomerisation reveals some effects of hydrogen-bonding and/or mechanical interlocking on the benzimidazole-containing binding site. Chapter Four describes how a chemically driven molecular machine has been designed, based on a switchable [2]rotaxane with two different recognition sites. Switching can occur using either the adjustment of pH or addition of zinc ions. This molecular shuttle can switch the macrocycle between two distinct translational forms with high positional integrity and relatively fast dynamics. The study of such a simple process is useful for the future design of molecular devices that mimick the actions of extremely complex bio-motor molecules. Furthermore, the proton- or Zn<sup>2+</sup>-induced large amplitude motion in this bistable molecular shuttle implies that it can act as a potential probe to detect protons or zinc ions. Chapter Five describes the first synthesis and characterisation of a [2]rotaxane containing an octanuclear heterometallic {Cr<sub>7</sub>Ni] wheel. As {Cr<sub>7</sub>Ni} is an antiferromagnetically coupled wheel with a nondiamagnetic ground state (<i>S</i> = ½), this methodology will make it possible to examine such fascinating magnetic properties within interlocked structures for the first time.
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8

Green, Lisa M. "Synthesis and Characterization of Photochemically Tunable Chiral Materials for Optically Addressed Cholesteric Displays." Kent State University / OhioLINK, 2008. http://rave.ohiolink.edu/etdc/view?acc_num=kent1222800499.

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9

Aleotti, Flavia <1993&gt. "Simulation of photoinduced processes in organic chromophores: mapping photochemically relevant states for accurate dynamics." Doctoral thesis, Alma Mater Studiorum - Università di Bologna, 2022. http://amsdottorato.unibo.it/10184/1/PhD-Thesis_AMS_Dottorato.pdf.

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The simulation of ultrafast photoinduced processes is a fundamental step towards the understanding of the underlying molecular mechanism and interpretation/prediction of experimental data. Performing a computer simulation of a complex photoinduced process is only possible introducing some approximations but, in order to obtain reliable results, the need to reduce the complexity must balance with the accuracy of the model, which should include all the relevant degrees of freedom and a quantitatively correct description of the electronic states involved in the process. This work presents new computational protocols and strategies for the parameterisation of accurate models for photochemical/photophysical processes based on state-of-the-art multiconfigurational wavefunction-based methods. The required ingredients for a dynamics simulation include potential energy surfaces (PESs) as well as electronic state couplings, which must be mapped across the wide range of geometries visited during the wavepacket/trajectory propagation. The developed procedures allow to obtain solid and extended databases reducing as much as possible the computational cost, thanks to, e.g., specific tuning of the level of theory for different PES regions and/or direct calculation of only the needed components of vectorial quantities (like gradients or nonadiabatic couplings). The presented approaches were applied to three case studies (azobenzene, pyrene, visual rhodopsin), all requiring an accurate parameterisation but for different reasons. The resulting models and simulations allowed to elucidate the mechanism and time scale of the internal conversion, reproducing or even predicting new transient experiments. The general applicability of the developed protocols to systems with different peculiarities and the possibility to parameterise different types of dynamics on an equal footing (classical vs purely quantum) prove that the developed procedures are flexible enough to be tailored for each specific system, and pave the way for exact quantum dynamics with multiple degrees of freedom.
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10

Gulzar, Naeem [Verfasser], and Martin [Akademischer Betreuer] Klußmann. "C–H Functionalization Via Photochemically Generated Peroxides: Method Development and Mechanistic Studies / Naeem Gulzar. Gutachter: Martin Klußmann." Köln : Universitäts- und Stadtbibliothek Köln, 2014. http://d-nb.info/1064693385/34.

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11

Nelson, Kristin Ann. "Photochemically induced flavor changes in orange juice exposed to light in glass and polyethylene terephthalate at 4°C." [Gainesville, Fla.] : University of Florida, 2005. http://purl.fcla.edu/fcla/etd/UFE0010289.

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12

Blackham, Emma E. "Exploring the reactivity of photochemically generated tricyclic aziridines and their use in the total synthesis of 3-demethoxyerythratidinone." Thesis, University of Bristol, 2016. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.715804.

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13

Kehrlößer, Daniel [Verfasser], and Norbert [Akademischer Betreuer] Hampp. "Photochemistry of Coumarin Functionalized Silica Nanoparticles and Photochemically Induced Drug Delivery Utilizing o-Nitrobenzyl Compounds / Daniel Kehrlößer. Betreuer: Norbert Hampp." Marburg : Philipps-Universität Marburg, 2011. http://d-nb.info/101485170X/34.

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14

Chu, Chu-hui. "Amorphous tungsten oxide and novel molybdenum doped tungsten oxide based sensors made photochemically at room temperature for sub-ppm No[subscript]x detection." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1998. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp02/NQ37691.pdf.

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15

Zhang, Wei. "Development of Photochemically Initiated Direct and Indirect Luminescence Detection Methods for Liquid Chromatography (LC) and Study of Aromatic Sulfonates and Phospholipids Using Reversed Phase Ion-Pair LC-Mass Spectrometry." Miami University / OhioLINK, 2003. http://rave.ohiolink.edu/etdc/view?acc_num=miami1068739487.

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16

Bobbitt, Kevin L. (Kevin Lee). "Photochemical Silene Syntheses." Thesis, North Texas State University, 1987. https://digital.library.unt.edu/ark:/67531/metadc501274/.

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We report the attempted syntheses of two photochemical dimethylsilene precursors, both of which are derived from polyphenyl silanorbornadiene skeletons. Possible synthetic schemes and our results are reported herein. Photolysis of 1,2-divinyl-1,1,2,2-tetramethyl-1,2-disilane at room temperature in a cyclohexane solution of 1,3-butadiene produces 1,1-dimethyl-2-(vinyldimethylsilylmethyl) silene which is trapped in high yields to afford the E- and Z-1,1-dimethyl-2-(vinyldimethylsilylmethyl)-3-vinyl-1-silacyclobutanes in 42 and 29% yields, respectively, along with minor amounts of 1,1-dimethyl-2-(vinyldimethylsilylmethyl)-1-silacyclohex-3-ene, 9%. Low Pressure Flow Pyrolysis at 450º C of either the E- or Z-isomer provides a relatively mild thermal source of the silene in the gas phase. Two products, 1,1,3,3-tetramethyldisilacyclohex-3-ene and 2,2,5,5-tetramethyl-2,5-disilabicyclo[2.2.1]hexane, are formed from an intramolecular rearrangement of the silene. Other reactions of the 3-vinylsilacyclobutanes include geometric isomerization, ring expansion to the silacyclohex-3-ene, and a homodienyl-1,5-hydrogen shift to 3,3,6,6-tetramethyl-3,6-disiladeca-1,4,8-triene. Synthetic schemes, successful and unsuccessful, for hydrido silene, acylpolysilene, and fluorine substituted silene precursors are discussed in the final chapter.
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17

Plummer, David A. "On-line chemistry in a mesoscale model assessment of the Toronto emission inventory and lake-breeze effects on air quality /." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape9/PQDD_0028/NQ39304.pdf.

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18

Baker, James R. "Photochemical studies towards stemoamide." Thesis, University of Bristol, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.414177.

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19

Tan, Changqing. "Photochemical Silaylide, Silylene and Silene Syntheses." Thesis, University of North Texas, 1990. https://digital.library.unt.edu/ark:/67531/metadc501256/.

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The synthesis of o-(N,N-dimethylamino)methylphenyl tris (trimethylsilyl) silane (II), a photochemical precursor of o- (N,N-dimethylamino) methylphenyl (trimethylsilyl) sila ammonium ylide (intramolecular silylene complex) and otolyl(trimethylsilyl)silylene is reported. Photolysis of II at room temperature in a cyclohexane solution of triethyl silane produced the silylene ylide and the presumably uncomplexed isomer, a silylene, which is trapped to afford the 2-(o-(N,N-dimethylamino)methylphenyl) -1,1,1-triethyl 3,3,3-trimethyltrisilane, 33% yield. A second decomposition pathway, a photodeamination, produced o-tris(trimethyl silyl) silyltoluene. UV spectra of the silaammonium ylide formed in the photochemical reaction of II was observed at 77k in hard or soft matrices.
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20

Grosser, E. "Photochemical oxidant air pollution : peroxyacetyl nitrate (PAN) as an indicator of photochemical activity." Master's thesis, University of Cape Town, 1990. http://hdl.handle.net/11427/8282.

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Bibliography: leaves 75-84.<br>Photochemical smog is formed by the interaction of sunlight with nitrogen oxides and hydrocarbons. These precursors are principally emitted by anthropogenic sources. As the major component of the photochemical oxidants is ozone, it is used as the indicator of photochemical smog and air quality standards today are therefore based on ozone. Another important photochemical oxidant is peroxyacetyl nitrate (PAN). Many authors believe that PAN is a better indicator of photochemical activity than ozone, because PAN has, unlike ozone, no large natural sources. Thus, the occurrence of high PAN concentrations is unequivocally related to anthropogenic pollution. The objectives of this work are to summarise the current research on the formation of photochemical smog with emphasis on PAN and to investigate the photochemical smog situation in South Africa using PAN as an indicator.
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21

Nappi, Manuel. "Novel aminocatalytic and photochemical reactions." Doctoral thesis, Universitat Rovira i Virgili, 2014. http://hdl.handle.net/10803/403371.

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L’aminocatàlisi asimètrica ha permès desenvolupar la reacció de Diels-Alder de manera catalítica i asimètrica, mitjançant la generació in situ d’intermedis orto-quinodimetà. La ruta del indol-2,3-quinodimetà pot realitzar-se ara catalíticament utilitzant una amina secundària quiral. Així, aquesta estratègia pot ser utilitzada per a la síntesi d’una gran varietat de compostos nitrogenats i derivats de tetrahidrocarbazols que contenen espirooxindols amb rendiments elevats i excel•lents estereoselectivitats. El potencial d’aquesta ruta aminocatalítica permet la seva aplicació en una amplia varietat de dienòfils. La implementació d’una seqüència multicatalítica de la reacció Diels-Alder/benzoí “one-pot”, basada en la combinació, sense precedents, de trienamina i catàlisi de carbens ha permès la preparació de derivats de tetrahidrocarbazols complexes amb una elevada estereoselectivitat. La reacció aza-Michael organocatalítica asimètrica mitjançant l’activació del nitrogen nucleòfil de dienamines també ha estat estudiada. Organocatalitzadors “self-assembly” com la combinació de (R)-àcid 2-indolincarboxílic i 9-epi-quinina derivada de la esquaramida han estat reconeguts com el millor sistema catalític per a aquesta desafiant adició. El indazol ha estat escollit per la seva habilitat per la formació d'una dienamina centrada en l'àtom de nitrogen. La reacció β-aldòlica directa entre cetones cícliques y cetones aromàtiques s’ha aconseguit a través de la combinació sinèrgica de la catàlisi fotoreductora i l’organocatàlisi. Radicals diaril oximetil o alquil-aril oximetil, transitòriament generats a través de la reducció d’un sol electró de precursors cetònics, es combinen fàcilment amb espècies radicalàries β-enaminil-5πe, generades mitjançant l’oxidació fotoinduïda de enamines, per a produir adductes de γ-hidroxicetona. Finalment, s’ha desenvolupat un protocol per a la perfluoroalquilació aromàtica directa i la trifluorometilació de α-ciano arilacetats. Aquesta estratègia en absència de metall, que es produeix a temperatura ambient i sota irradiació de llum visible, és impulsada per l’activitat fotoquímica de complexos electrònics dador-acceptor (EDA) formats in situ per la interacció de enolats generats transitòriament i iodurs de perfluoroalquil.<br>La aminocatálisis asimétrica ha permitido desarrollar la reacción de Diels-Alder de manera catalítica y asimétrica, a través de la generación in situ de intermedios orto-quinodimetano. La ruta del indol-2,3-quinodimetano, puede realizarse ahora catalíticamente utilizando una amina secundaria quiral. Así, esta estrategia puede ser utilizada para la síntesis de una gran variedad de compuestos nitrogenados y derivados de tetrahidrocarbazoles con rendimientos elevados y excelentes estereoselectividades. El potencial de esta ruta aminocatalítica permite su aplicación en una amplia variedad de dienófilos. La implementación de una secuencia multicatalítica de la reacción Diels-Alder/benzoino “one-pot”, basada en la combinación, sin precedentes, de trienamina y catálisis de carbenos ha permitido la preparación de derivados de tetrahidrocarbazoles complejos con una elevada estereoselectividad. La reacción aza-Michael organocatalítica asimétrica mediante activación del nitrógeno nucleófilo de dienaminas ha sido estudiada. Organocatalizadores “self-assembly” como la combinación de (R)-ácido-2-indolincarboxílico y 9-epi-quinina derivada de la escuaramida han sido reconocidos como el mejor sistema catalítico para esta desafiante adición. El indazol fue elegido por su habilidad por la formación de una dienamina centrada en el átomo de nitrógeno. La reacción β-aldólica directa entre cetonas cíclicas y cetonas aromáticas se ha logrado a través de la combinación sinérgica de la catálisis fotoreductora y la organocatálisis. Radicales diaril oximetil o alquilo-arilo oximetil, transitoriamente generados a través de la reducción de un solo electrón de precursores cetónicos, se combinan fácilmente con especies radicalarias β-enaminil-5πe, generadas por la oxidación fotoinducida de enaminas, para producir aductos de γ-hidroxicetona. Finalmente, se ha desarrollado un protocolo simple para la perfluoroalquilación aromática directa y la trifluorometilación de α-ciano arilacetatos. Esta estrategia en ausencia de metal, que se produce a temperatura ambiente y bajo irradiación de luz visible, es impulsada por la actividad fotoquímica de complejos electrónicos dador-aceptor (EDA) formados in situ por la interacción de enolatos generados transitoriamente y yoduros de perfluoroalquilo.<br>Asymmetric aminocatalysis has allowed to develop the hitherto elusive catalytic asymmetric Diels-Alder reaction of in situ generated ortho-quinodimethane intermediates. The indole-2,3-quinodimethane strategy, originally conceived for the straightforward synthesis of indole alkaloids more than 30 years ago, can now be made catalytic with a chiral secondary amine. This strategy can then be used to synthesize a structurally diverse range of complex nitrogen-contain compounds and spirooxindole-containing tetrahydrocarbazoles with high chemical yields and excellent stereoselectivities. The potential of aminocatalytic indole-2,3-quinodimethane strategy can be expanded to include a variety of different dienophiles. The implementation of a multicatalytic, one-pot Diels-Alder/benzoin reaction sequence, based upon the unprecedented combination of trienamine and carbene catalysis, led to the highly stereoselective preparation of complex tetrahydrocarbazole derivatives. The asymmetric organocatalytic aza-Michael reaction via dienamine activation of the nucleophilic nitrogen has been studied. Self-assembly organocatalysts, such as the combination of (R) 2-indoline carboxylic acid and 9-epi-quinine squaramide derivative, was recognized as the best catalytic system for this challenging addition. Indazole was chosen as model nucleophilic partner due to its acidity and ability to form the N-centered dienamine. The direct β-aldol reaction between cyclic ketones with aryl ketones has been achieved via the synergistic combination of photoredox catalysis and organocatalysis. Diaryl oxymethyl or aryl−alkyl oxymethyl radicals, transiently generated via single-electron reduction of ketone precursors, readily combine with β-enaminyl 5πe– radical key species, generated by photon-induced enamine oxidation, to produce γ-hydroxyketone adducts. Finally, an operationally simple protocol for the direct aromatic perfluoroalkylation and trifluoromethylation of α-cyano arylacetates has been reported. This metal-free approach, which occurs at ambient temperature and under visible-light irradiation, is driven by the photochemical activity of electron donor–acceptor (EDA) complexes, formed in situ by the interaction of transiently generated enolates and perfluoroalkyl iodides.
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22

Cuadros, Huertas Sara. "Exploiting Organocatalysis in Photochemical Processes." Doctoral thesis, Universitat Rovira i Virgili, 2019. http://hdl.handle.net/10803/668446.

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El treball descrit en aquesta dissertació es centra en la implementació d’estratègies organocatalítiques per superar les limitacions de processos fotoquímics establerts. Específicament, dues transformacions impulsades per la llum han estat estudiades: (i) la fotoenolizació de 2-alquilbenzofenones per accedir a intermedis enòlics transitoris (fotoenols), i (ii) la ruptura homolítica fotoinduïda de derivats ditiocarbonílics per produir radicals. Per un costat, el procés de fotoenolizació acoblat amb la reactivitat de tipus Diels-Alder (seqüència fotoenolizació/ Diels-Alder) és una reacció fotoquímica històrica amb aplicacions conegudes en síntesi total. Malgrat això, una variant asimètrica d’aquest procés no ha estat encara reportada. Els Capítols II i III demostren com l’organocatàlisi asimètrica proporciona eines simples i efectives per fer participar a les espècies fotoenòliques en processos de tipus Diels-Alder i aldòlics altament estereoselectius. Per un altre costat, la ruptura fotolítica de espècies ditiocarboníliques capaces d’absorbir la llum visible, és un mètode conegut per la generació de radicals sota condicions suaus de reacció. Aquesta tecnologia fa ús de quantitats estequiomètriques de compostos ditiocarbonílics fàcilment accessibles. Encara que aquesta estratègia ha millorat considerablement les condicions per accedir a la reactivitat de tipus radicalària, aquesta requereix la síntesi prèvia de compostos que continguin la funcionalitat ditiocarbonílica. El Capítol IV detalla com aquest mètode de generació de radicals pot ser realitzat catalíticament, mitjançant el disseny d’un catalitzador<br>El trabajo descrito en esta disertación se centra en la implementación de estrategias organocatalíticas para superar las limitaciones de procesos fotoquímicos establecidos. Específicamente, dos transformaciones promovidas por la luz han sido estudiadas: (i) la fotoenolización de 2-alquilbenzofenonas para acceder intermedios enólicos transitorios (fotoenoles), y (ii) la ruptura homolítica fotoinducida de derivados ditiocarbonílicos para producir radicales. Por un lado, el proceso de fotoenolización acoplado con la reactividad de tipo Diels-Alder (secuencia fotoenolización/ Diels-Alder) es una histórica reacción fotoquímica con aplicaciones conocidas en síntesis total. Sin embargo, una variante asimétrica de este proceso no ha sido reportada. Los Capítulos II y III demuestran cómo la organocatálisis asimétrica proporciona herramientas simples y efectivas para hacer participar a las especies fotoenólicas en procesos de tipo Diels-Alder y aldólicos altamente esteroselectivos. Por otro lado, la ruptura fotolítica de especies ditiocarbonílicas capaces de absorber luz visible, es un conocido método para la generación de radicales bajo condiciones suaves de reacción. Esta tecnología hace uso de cantidades estequiométricas de compuestos ditiocarbonílicos fácilmente accesibles. Aunque esta estrategia ha mejorado considerablemente las condiciones para acceder a la reactividad de tipo radicalaria, ésta requiere la síntesis previa de compuestos que contentan la funcionalidad ditiocarbonílica.<br>The work described in this dissertation focuses on the implementation of organocatalytic strategies to overcome limitations of established photochemical processes. Specifically, two known light-driven transformations have been studied: (i) the photoenolization of 2-alkyl-benzophenones to access transient enol-intermediates (photoenols), and (ii) the photoinduced homolytic cleavage of stoichiometric dithiocarbonyl derivatives to produce radicals. On the one hand, the photoenolization process coupled with classical Diels-Alder chemistry (photoenolization/Diels- Alder sequence) is an historical photochemical reaction with known applications in total synthesis. However, an asymmetric catalytic variant of this light-driven transformation has remained elusive over the years. Chapter II and Chapter III demonstrate how asymmetric organocatalysis provides simple but effective catalytic tools to engage photoenols in highly stereoselective Diels-Alder and Aldol-type processes, respectively. On the other hand, the photolytic cleavage of visible-light-absorbing dithiocarbonyl-based compounds is a known effective method for the mild generation of radicals. This technology uses stoichiometric amounts of easy-to make dithiocarbonyl-based substrates, capable of triggering the formation of open-shell intermediates upon direct light-excitation. Although this strategy has greatly enhanced the conditions to access radical-type reactivity, it still relies on purposely designed stoichiometric reagents.
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Konstantinov, Alexandre D. "Photochemical reactions of chloroaromatic compounds." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape7/PQDD_0002/NQ40377.pdf.

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Brookman, Jennifer. "Photochemical studies on selected biomolecules." Thesis, University of the West of Scotland, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.398322.

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Buckland, S. J. "Photochemical studies in organophosphorus chemistry." Thesis, City University London, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.482525.

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26

Malyshev, Dimitriy. "Photochemical Synthesis of Niobium Nanoparticles." Thèse, Université d'Ottawa / University of Ottawa, 2014. http://hdl.handle.net/10393/30999.

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This thesis focuses on the development of method to the photochemical synthesis of niobium nanoparticles (NbNP) using Irgacure 907 (I-907) photoinitiator. This investigation is composed of two parts; whereas the mechanistic study of formation of particles was investigated first, and then followed by particles property characterization. By studying the mechanism of formation we were able to obtain knowledge on how to control the size of NbNP. This knowledge provided us with ability to generate a library of nanoparticles with the varying sizes. Furthermore, the study of I-907 photoproducts has given insight for an alternative method for the synthesis of NbNP using a milder reducing agent, 4-(methylthio)benzaldehyde (MSBA). Exposure of NbNP to air causes their oxidation leading to the formation of niobium oxide nanoparticles (NbONP). The oxidation of NbONP was characterized with variety of techniques (XPS, EDS and HRTEM) that demonstrated the core-shell structure of the nanoparticles. These methods indicated that the core is metallic Nb0 and the shell is the niobium oxide, Nb2O5. Since Nb2O5 is known be a strong Brønsted acid, we tested the Brønsted activity of NbONP with pH sensitive dye coumarin-6 (C6) (monitored using fluorescence and UV-vis). The results of these spectroscopic experiments indicated that NbONP can protonate C6, thus serving as confirmation for the acidity of NbONP. Furthermore, particles with varying sizes were tested with C6 to check if the difference in size affects the acidity. It was observed that the particles with the larger sizes have the strongest acidity and the particles of smaller sizes are less acidic.
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Spokes, Lucinda Jane. "Photochemical redox reactions in seawater." Thesis, University of East Anglia, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.294086.

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28

Ji, Xiaoyue. "Photochemical transformations of lignin models." Thesis, Queen's University Belfast, 2015. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.679240.

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The main aim of this project was to investigate the photochemical degradation pathways of lignin models using singlet oxygen and other photo-induced reactive species, in order to understand the photochemical transformations of the lignin polymer and other lignin-like polymers. The sensitized photolytic oxidation of lignin models containing the 13-0-4' lignin substructures using visible light, Rose Bengal and oxygen was studied in an attempt to understand and develop photocatalytic oxidation as a method for the conversion of lignin into added-value chemicals, Initial studies using a simple model dimer and attempting to replicate a published method[1] resulted in significant differences in the products when compared with the previous literature studies. A time study was carried out and a possible mechanism of a photo catalysed dimerization has been proposed. The observed radical coupling reaction has been shown to precede the eventual cleavage of a key benzylic ether bond in the tetramer and the formation of a quinone product and guaiacol by-product. Similar radical couplings were also observed for 13-5' dimer and trimer lignin models, Identification of the coupling products was obtained by spectroscopic characterization and corroborated by independent synthesis. Batch and flow reactors were tested and compared for the photolysis reactions. The flow reactor was proved to be more efficient than the batch reactor in terms of time-space conversion and yield. It was also shown that the flow reaction is a good method for the study of mechanism and optimization of the conditions required for the process, The dimerization process was then used for the preparation of three novel unsymmetrical coupling products. Successful cross-coupling of lignin models in this way provides a flexible new synthetic strategy for the preparation of more complex lignin models which is competitive with previous synthetic routes.
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Cosgrove, Sebastian Cronin. "Direct photochemical amination of aromatics." Thesis, University of Leeds, 2017. http://etheses.whiterose.ac.uk/17796/.

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The formation of aromatic carbon to nitrogen bonds is one of the most important processes used in the chemical industry. It is prevalent in many biologically-relevant molecules such as pharmaceuticals and agrochemicals. A modified Hofmann-Löffler-Freytag reaction, which allowed the direct functionalisation of aromatic C-H bonds using N-haloamines under UV-irradiation in highly acidic media, was first reported by Bock et al. in 1965.1 The reported conditions used concentrated sulfuric acid as solvent and demonstrated a minimal substrate scope. Here, it has been shown that UV-irradiation of N-chloroamines with 10 equivalents of methanesulfonic acid in DCM allows for the intramolecular amination of unfunctionalised aryl C-H bonds to form tetrahydroquinolines. These novel conditions have been extended to 30 examples including in a concise synthesis of the alkaloid natural product angustureine. Furthermore, studies have helped elucidate a potential mechanism of the reaction and led to the discovery of a 1,2-alkyl migration reaction. The reaction has also been shown to work in a continuous photochemical reactor. This was extended to work in a two-stage reactor where amines were chlorinated and reacted in situ to form tetrahydroquinolines directly. Some of the substrates produced with the photochemical methodology have been tested in enzymatic deracemizations using genetically modified monoamine oxidase enzymes. Whilst modest activity was observed for a series of N-substituted tetrahydroquinolines, a group of natural products containing N-unsubstituted tetrahydroquinoline cores were successfully deracemized, with ee’s as high as 90% obtained.
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Kral, Andrew. "Photochemical transformations of dichloroacetamide safeners." Thesis, University of Iowa, 2018. https://ir.uiowa.edu/etd/6164.

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Safeners are widely used ingredients in commercial herbicide formulations, but their environmental fate has garnered relatively little scrutiny because of their classification as “inert” by the US EPA. Here, we investigated the photolysis of one popular class of safeners, dichloroacetamides, to better understand their persistence and formation potential for bioactive transformation products in surface waters. Of four commonly used dichloracetamide safeners only benoxacor underwent direct photolysis. Benoxacor had a half-life of 7.7 min when irradiated at pH 7, thus photolysis will likely be an important fate pathway in surface waters. Other dichloroacetamide safeners AD-67, dichlormid, and furilazole, while resistant to direct photolysis, were slowly degraded by indirect photolysis pathways in the presence of common photosensitizers including nitrate, nitrite, and humic acids. Half-lives of these compounds were greater than 8 hours. Reactive entities involved in these reactions are likely •OH and 1O2 as verified by selective quenchers, such as isopropanol (•OH) and sodium bromate (1O2). Where possible, we identified photoproducts using NMR and high-resolution mass spectrometry. Only benoxacor photolysis yielded detectable and identifiable transformation products. These products were generally more polar, and were entirely dechlorinated through photolysis, suggesting they are likely to have limited bioactivity relative to benoxacor.
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Sutton, Paul David. "Studies in infrared multiple photon excitations." Thesis, University of Oxford, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.291598.

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Yearwood, Graham de Lisle. "Ruthenium (II) polyaza-cavity complexes as structural and photochemical probes of electron transfer reactivity." Thesis, City University London, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.280661.

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33

Estapa, Margaret L. "Photochemical Reactions of Particulate Organic Matter." Fogler Library, University of Maine, 2011. http://www.library.umaine.edu/theses/pdf/EstapaM2011.pdf.

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34

Liu, Zhen. "Characterizing the photochemical environment over China." Diss., Georgia Institute of Technology, 2012. http://hdl.handle.net/1853/43668.

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The rapid rising anthropogenic emissions driven by economic growth over China documented by satellite observations and bottom-up inventories have led to severely degraded air quality, and also have been suggested to be linked to the recent upward trends of tropospheric O₃ over the regions downwind of China. Multi-scale modeling analyses facilitated by ground-level, aircraft and satellite observations have been conducted to understand the atmospheric chemistry over China. Analyses using a 1-D photochemical model constrained by measurements at Beijing in August of 2007 suggest that reactive aromatic VOCs are the major source (~75%) of peroxy acetyl nitrate (PAN). Detailed radical budget analyses reveal the very fast ROₓ (OH + HO₂ + RO₂) production, recycling and destruction driven by VOC oxidation and heterogeneous processes. Photoenhanced aerosol surface uptake of NO₂ is found to be the predominant source of nitrous acid (HONO) during daytime (~70%). 3-D regional modeling analyses of tropospheric vertical column densities of glyoxal (CHOCHO) from SCIAMACHY show that anthropogenic emissions of aromatic VOCs are substantially underestimated (by a factor of 5 - 6, regionally varied) over China. Such an underestimation is the main cause of a large missing source of CHOCHO over the region in current global models, and could also partly explain the underestimation of organic aerosols in previous modeling studies.
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Ziolkowski, Lori. "Marine photochemical production of carbon monoxide." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2000. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape2/PQDD_0015/MQ57228.pdf.

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36

Hott, John Lester. "Photochemical alterations of ocular lens proteins." Diss., Georgia Institute of Technology, 1991. http://hdl.handle.net/1853/30087.

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37

Marsh, R. R. "Studies of some photochemical pericyclic reactions." Thesis, University of Oxford, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.375284.

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38

Carton, Fernando Lorenzo. "Photochemical investigation of antibacterial fluoroquinolone drugs." Thesis, Manchester Metropolitan University, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.499357.

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The primary photophysical properties of several antibiotic drugs of the fluoroquinolone class have been studied in order to understand better and rationalize the mechanisms leading to phototoxicity due to these drugs. The light absorption and emission properties of various fluoroquinolones have been characterized and, in most cases, they were found to be dependant on medium conditions such as pH and buffer content. Fluoroquinolones have been found capable of binding to DNA, affecting their emission from the excited state. Light-induced production of excited species by FQs and their subsequent reactivity are thus influenced by the characteristics of the medium. Finally, an unprecedented behaviour has been found for the triplet state of fluoroquinolones ciprofloxacin, sarafloxacin, enoxacin norfloxacin when it is formed in the presence of certain inorganic salts commonly used as buffers. The triplet state formed at the end of the excitation pulse reacts with anions such as phosphate and bicarbonate to form another triplet state of lower energy. This previously unreported effect has implications in the photo toxic potential of fluoroquinolones in cellular environments.
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Migani, Annapaola. "A theoretical study of photochemical stability." Thesis, King's College London (University of London), 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.271408.

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40

Cantrell, Ann. "Photochemical studies of organic UVA sunscreens." Thesis, Keele University, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.323702.

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41

Noble, Lynda. "Photochemical rearrangement and dehalogenation of polyhalogenodiazines." Thesis, University of Sunderland, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.329818.

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42

Jobling, Maragaret. "Organometallic photochemical reactions in supercritical fluids." Thesis, University of Nottingham, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.334514.

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43

Gulácsy, Christina Elizabeth. "Photochemical and spectroscopic studies of ketoaziridines." Thesis, University of Bath, 2016. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.698993.

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While alcohols have successfully undergone kinetic resolutions, amines pose a challenge due to their nucleophilic nature. Aziridines were identified as potential substrates as a result of their synthetic utility and reduced nucleophilicity. Using a helical aminopyridine catalyst, the kinetic resolutions of ketoaziridines were explored. Initial attempts revealed anomalous kinetic behaviour [slow conversion and non-first order]. Non-buffered noncatalytic control reactions demonstrated unexpected reaction dynamics, as gauged by HPLC and 1H NMR. Stopped-flow spectroscopy revealed photochemical sensitivity of the aziridine. As a result of this new information, the project evolved into a study of the photochemical behaviour of ketoaziridines and their spectroscopic properties. UV-vis absorbance and fluorescence spectroscopy were used to probe the photochemical reactivity of ketoaziridines. These studies suggested a two-step mechanism where an azomethine ylide formed a reactive intermediate, ultimately to form 2,5-diphenyloxazole. Kinetic analysis revealed the mechanism was autocatalytic with respect to oxazole formation. TD-DFT calculations suggested the mechanism proceeded via a diradical species upon irradiation. This mechanistic route was studied by investigating the presence of a magnetic field effect on the kinetics of absorption and emission changes, in collaboration with the Manchester Institute of Biotechnology. Further studies demonstrated a radical species, derived from the irradiation of aziridine, may be used as a photoinitiator in the polymerization of methyl methacrylate. This work also involved development of a synthetic platform to diphenyloxazoles, where functionality may be installed in the initial steps. Use of this strategy allowed for the synthesis of a natural product, texaline.
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Loewenheim, L. "Photochemical smog in greater Cape Town." Master's thesis, University of Cape Town, 1988. http://hdl.handle.net/11427/15446.

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Bibliography: leaves 124-131.<br>Photochemical smog is the name given to a complex sequence of chemical reactions that occurs in the presence of sunlight. These reactions comprise a mix of organic and inorganic compounds, including a number of toxic secondary pollutants such as ozone (O3) and peroxyacetyl nitrate. These substances are commonly referred to as oxidants and are the result of numerous reactions of primary pollutants or precursors (including nitrogen oxides (NOx) and non- methane hydrocarbons (NHHC)) emitted from vehicle exhausts and to some extent industry, O3 is the major constituent of the photochemical oxidants, and its concentration is often used to determine the severity of photochemical smog. Limited research on photochemical smog in Cape Town has been undertaken, and this study has concentrated on providing a more detailed understanding of photochemical precursor and oxidant levels in the urban atmosphere of Greater Cape Town. This was approached by the investigation and assessment of the spatial and temporal behaviour of photochemical pollutants, making use of automatic monitor data collected from 1984 to 1986, and supplemented by data collected during a spatial survey in April and Hay of 1987. Precursor levels were found to be strongly influenced by the seasonal cycle of the weather and were highest in winter when stable atmospheric conditions prevailed, particularly during morning rush hours, O3 behaviour was complex and lacked any definite relationship to season or to selected meteorological variables, although the limited data indicated high levels during the early spring months. Peak levels were generally experienced on fair weather days during the early afternoon hours at the time of maximum ultraviolet radiation, O3 levels did not exceed the USEPA 1-hour standard of 0.12ppm during 1985 and 1986. The spatial distribution of precursor and oxidant concentrations showed the NOx levels to be spatially dependent, following the major arterial roads. NHHC levels were spatially less well defined than NOx, and O3 levels were spatially relatively uniform, exhibiting depletion due to scavenging by nitric oxide (NO) in areas close to main traffic routes. High NOx levels were experienced predominantly in the city centre, while the suburbs tended to experience the higher O3 levels. Cape Town was not considered to have a photochemical smog problem of the same magnitude as Los Angeles or Sydney, ( due to a number of factors which contributed to the complex situation (such as high NO levels, relatively low NMHC levels and strong winds in summer). However in the Northern Suburbs, the absence of high NO levels together with additional NMHC emissions from nearby industry led to the recognition of this area as one of potential photochemical smog formation.
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45

Islangulov, Radiy Rashitovich. "Low Power Photoluminescence and Photochemical Upconversion." Bowling Green State University / OhioLINK, 2006. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1162244082.

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Vaidyalingam, Anand S. "Photochemical studies of zeolite-based systems /." The Ohio State University, 2001. http://rave.ohiolink.edu/etdc/view?acc_num=osu1486401895208909.

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Georgopoulos, Panagiotis Gerasimou Seinfeld John H. Seinfeld John H. "Mathematical studies of photochemical air pollution /." Diss., Pasadena, Calif. : California Institute of Technology, 1986. http://resolver.caltech.edu/CaltechETD:etd-02012007-092322.

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48

Zhu, Zhengmao. "Photochemical modification of polyethylene terephthalate surface." W&M ScholarWorks, 2005. https://scholarworks.wm.edu/etd/1539623471.

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The prospect of obtaining desired surface-mediated characteristics while retaining bulk-mediated physical properties and avoiding potential environmental issues with wet chemical technology lends considerable appeal to photochemical approaches to surface modification.;We undertook a combined experimental and computational approach to investigate the effect of deep UV irradiation on the polyethylene terephthalate (PET) surface. its response to 172 nm UV from a xenon examiner lamp in the absence of oxygen was characterized with X-ray Photoelectron Spectroscopy (XPS), Time of Flight/Secondary Ion Mass Spectrometry (ToF/SIMS), transmission infrared spectroscopy (IR), and Atomic Force Microscopy (AFM). The surface chemistry details suggested that the primary photochemical reactions involved a Norrish type I based decarbonylation and a Norrish type II process yielding terminal carboxylic acid groups, consistent with the possible photochemistry from n-pi* type lowest singlet excited states of PET according to the computational modeling results. By directly populating n-pi* type excited states, 172 nm UV promoted effective surface photochemistry of PET with further helps from the high UV absorptivity and the high surface mobility of the molecules.;Utilizing this active surface radical chemistry, a new grafting strategy was developed to impart desirable functional properties to the surface. A broad range of grafting chemicals can be employed in their vapor forms, demonstrated with an alkene or an alkane. Surface analysis with XPS, ToF/SIMS, AFM, and water contact angle measurements confirmed the effectiveness of the approach, supporting the notion of the surface radical initiated processes.;A potentially useful anti-stain/soil coating was developed by grafting with a fluorocarbon species. Surface analysis suggested that the grafted fluorocarbon formed a nano-scale self-assembled monolayer. The coating had a similar water contact angle as that of a pure fluoropolymer but a better oil repellency due to the special molecular orientation in the graft layer.;A potential antimicrobial application was demonstrated with amine chemicals. Structure characterization and computational modeling results suggested that the photochemistry of the UV active grafting chemicals also played an important role in the grafting process. A double bond structure in the amine species protected the amine functional groups and the resulting coating demonstrated antimicrobial activity against E. coli.
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Kumar, M. U. "Photochemical transformations of some organic molecules." Thesis(Ph.D.), CSIR-National Chemical Laboratory, Pune, 1986. http://dspace.ncl.res.in:8080/xmlui/handle/20.500.12252/3242.

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50

Gladstone, Robert Vernon. "Methods for the monitoring of peroxy radicals and measurement of NO←2 photolysis in the atmosphere." Thesis, University of York, 1995. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.261101.

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