Synthesis and characterization of cobalt(III) complexes with sinambic amplector ligands

The synthesis of the hexadentate ligand 5,6-dimethyl-2,2,9,9-tetra(methyleneamine)-4,7-dithiadecane (1,2-Me(2)EtN(4)S(2)amp) is reported. The diastereiosomers were separated as cobalt(III) complexes using cation exchange chromatography. The rac and mesa isomers were characterized by NMR (C-13, H-1, Co-59), ESI-MS, UV-Vis spectroscopy and cyclic voltammetry. Single crystals of [Co(rac-1,2-Me(2)EtN(4)S(2)amp)] Cl-2(ClO4) (.) 2H(2)O were characterized by X-ray diffraction. The low-temperature (11 K) absorption spectra of the complexes have been measured in Nafion films and from the observed positions of both spin-allowed (1)A(1g) --> T-1(1g) and (1)A(1g) --> T-1(2g) and spin forbidden (1)A(1g) --> T-3(2g) bands, octahedral ligand-field parameters (10Dq, B and C) were determined. These results, in conjunction with the Co-59 NMR data, are used to further explore the relationship between the Co-59 magnetogyric ratio (gamma(Co)) and the product of the nephelauxetic ratio and the wavelength of the (1)A(1g) --> T-1(1g) transition (beta(DeltaE)(-1)) for complexes of mixed donor nitrogen-thioether ligands. (C) 2004 Elsevier Ltd. All rights reserved.

Gold nanoparticles decorated with oligo(ethylene glycol) thiols:kinetics of colloid aggregation driven by depletion forces

We have studied the kinetics of the phase-separation process of mixtures of colloid and protein in solutions by real-time UV-vis spectroscopy. Complementary small-angle X-ray scattering (SAXS) was employed to determine the structures involved. The colloids used are gold nanoparticles functionalized with protein resistant oligo(ethylene glycol) (OEG) thiol, HS(CH(2))(11)(OCH(2)CH(2))(6)OMe (EG6OMe). After mixing with protein solution above a critical concentration, c*, SAXS measurements show that a scattering maximum appears after a short induction time at q = 0.0322 angstrom(-1) stop, which increases its intensity with time but the peak position does not change with time, protein concentration and salt addition. The peak corresponds to the distance of the nearest neighbor in the aggregates. The upturn of scattering intensities in the low q-range developed with time indicating the formation of aggregates. No Bragg peaks corresponding to the formation of colloidal crystallites could be observed before the clusters dropped out from the solution. The growth kinetics of aggregates is followed in detail by real-time UV-vis spectroscopy, using the flocculation parameter defined as the integral of the absorption in the range of 600-800 nm wavelengths. At low salt addition (<0.5 M), a kinetic crossover from reaction-limited cluster aggregation (RLCA) to diffusion-limited cluster aggregation (DLCA) growth model is observed, and interpreted as being due to the effective repulsive interaction barrier between colloids within the depletion potential. Above 0.5 M NaCl, the surface charge of proteins is screened significantly, and the repulsive potential barrier disappeared, thus the growth kinetics can be described by a DLCA model only.

Size-controlled TiO2 nanoparticles on porous hosts for enhanced photocatalytic hydrogen production

Nanocystalline TiO2 particles were successfully synthesized on porous hosts (SBA-15 and ZSM-15) via a sol-gel impregnation method. Resulting nanocomposites were characterized by XRD, TEM, BET surface analysis, Raman and UV-vis diffuse reflectance spectroscopy, and their photocatalytic activity for H2 production evaluated. XRD evidences the formation of anatase nanoparticles over both ZSM-5 and SBA-15 porous supports, with TEM highlighting a strong particle size dependence on titania precursor concentration. Photocatalytic activities of TiO2/ZSM-5 and TiO2/SBA-15 composites were significantly enhanced compared to pure TiO2, owing to the smaller TiO2 particle size and higher surface area of the former. TiO2 loadings over the porous supports and concomitant photocatalytic hydrogen production were optimized with respect to light absorption, available surface reaction sites and particle size. 10%TiO2/ZSM-5 and 20%TiO2/SBA-15 proved the most active photocatalysts, exhibiting extraordinary hydrogen evolution rates of 10,000 and 8800μmolgTiO2 -1 h-1 under full arc, associated with high external quantum efficiencies of 12.6% and 5.4% respectively under 365nm irradiation.

Influence of La-doping on phase transformation and photocatalytic properties of ZnTiO3 nanoparticles synthesized via modified sol-gel method

Non-doped and La-doped ZnTiO3 nanoparticles were successfully synthesized via a modified sol–gel method. The synthesized nanoparticles were structurally characterized by PXRD, UV-vis DRS, FT-IR, SEM-EDS, TEM, Raman and photoluminescence spectroscopy. The results show that doping of La into the framework of ZnTiO3 has a strong influence on the physico-chemical properties of the synthesized nanoparticles. XRD results clearly show that the non-doped ZnTiO3 exhibits a hexagonal phase at 800 °C, whereas the La-doped ZnTiO3 exhibits a cubic phase under similar experimental conditions. In spite of the fact that it has a large ionic radius, the La is efficiently involved in the evolution process by blocking the crystal growth and the cubic to hexagonal transformation in ZnTiO3. Interestingly the absorption edge of the La-doped ZnTiO3 nanoparticles shifted from the UV region to the visible region. The photocatalytic activity of the La-doped ZnTiO3 nanoparticles was evaluated for the degradation of Rhodamine B under sunlight irradiation. The optimum photocatalytic activity was obtained for 2 atom% La-doped ZnTiO3, which is much higher than that of the non-doped ZnTiO3 as well as commercial N-TiO2. A possible mechanism for the degradation of Rhodamine B over La-doped ZnTiO3 was also discussed by trapping experiments. More importantly, the reusability of these nanoparticles is high. Hence La-doped ZnTiO3 nanoparticles can be used as efficient photocatalysts for environmental applications.

Utilização de quitosana obtida de resíduos de camarão para avaliar a capacidade de adsorção de íons Fe3+

A quitosana é produzida através de uma desacetilação alcalina da quitina, a qual é encontrada em exoesqueleto de crustáceos, parede celular de fungos e materiais biológicos. Calcula-se que os resíduos de camarão apresentam de 5 a 7% do seu peso total na forma de quitina, sugerindo que estes sejam utilizados para obtenção do biopolímero. Os processos para obtenção destes biopolímeros consiste nas seguintes etapas: desmineralização, desproteinização e desodorização, obtendo-se assim, a quitina úmida. Após seca, passa por uma desacetilação química para a conversão em quitosana úmida, sendo purificada e posteriormente seca. A quitosana, por apresentar grupamentos amino livres em sua estrutura, é uma molécula capaz de formar complexos estáveis com cátions metálicos. O objetivo geral deste trabalho foi obter quitina a partir de resíduos de camarão (Penaeus brasiliensis) com posterior produção de quitosana, e avaliar sua capacidade de complexação com íons Fe3+, em solução. A quitosana produzida foi caracterizada através do grau de desacetiliação e da massa molecular viscosimétrica, Para caracterização estrutural das amostras de quitosana, utilizaram-se espectrometria de infravermelho e espectrofotometria UV-Visível, bem como para o complexo formado de quitosana e ferro. Para analisar a eficiência da remoção deste íon, foram feitas análises em espectrometria de absorção atômica em chama e em espectrofotometria UV-Visível. Uma análise estatística foi realizada para avaliar a percentagem de remoção do íon ferro das soluções, sendo utilizado um planejamento fatorial em dois níveis, tendo como variáveis independentes o pH do meio, a quantidade de quitosana adicionada, a granulometria da mesma e o tempo de reação. A quitosana apresentou grau de desacetilação de 87±2% e massa molecular viscosimétrica de 196±4kDa, sendo esses valores, comparáveis à quitosana disponível comercialmente. Na melhor região de trabalho definida pela análise estatística, obteve-se uma remoção máxima de 85 % do íon ferro das soluções.

Estudo da influência da morfologia de nanopartículas de sílica mesoporosa na liberação do anticancerígeno indol-3-carbinol

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Ceilândia, Programa de Pós-graduação em Ciências e Tecnologias em Saúde, 2015.

Remoción de la hemoglobina por adsorción sobre nanopartículas magnéticas de Fe3O4/TiO2

La remoción de la hemoglobina (Hb) por adsorción de la proteína sobre nanopartículas (Nps) magnéticas de Fe3O4/TiO2 (núcleo/coraza) aplicando un campo magnético externo, fue investigada mediante espectroscopia ultravioleta en el rango del ultravioleta y visible (UV-VIS). Durante la etapa de contacto de las Nps con la Hb se varió la concentración de las Nps y la temperatura, complementariamente durante la etapa de remoción del complejo Fe3O4/TiO2-Hb se varió la intensidad del campo magnético externo. Con una concentración inicial de Nps de 8 mg ml-1, el valor de la absorbancia del sobrenadante disminuye en un 11% con respecto a la solución inicial de Hb (0,8 g l-1) y al aumentar en un 50% la concentración de Nps, el valor disminuye hasta un 17%. Al incrementar la temperatura de 25 a 35ºC disminuye la adsorción de la Hb pero no se observa indicios de desnaturalización de la misma. Durante la etapa de remoción del complejo Fe3O4/TiO2-Hb, al incrementar la fuerza magnética se logra una caída en la intensidad de la absorbancia, casi un 30%. Finalmente, se determinó la demanda bioquímica de oxígeno (DBO5) de la solución inicial de Hb y del sobrenandante, el valor para la solución inicial de Hb fue de 100 mg ml-1 y los resultados obtenidos para todas las soluciones tratadas fueron inferiores (62 mg ml-1) verificando el impacto que tuvo el uso de las Nps magnéticas de Fe3O4/TiO2 en la remoción de la Hb.

Exploring redox-driven self-assembly of mixed metal polyoxometalates

How can we control the experimental conditions towards the isolation of specific structures? Why do particular architectures form? These are some challenging questions that synthetic chemists try to answer, specifically within polyoxometalate (POM) chemistry, where there is still much unknown regarding the synthesis of novel molecular structures in a controlled and predictive manner. This work covers a wide range of POM chemistry, exploring the redox self-assembly of polyoxometalate clusters, using both “one-pot”, flow and hydrothermal conditions. For this purpose, different vanadium, molybdenum and tungsten reagents, heteroatoms, inorganic salts and reducing agents have been used. The template effect of lone-pair containing pyramidal heteroatoms has been investigated. Efforts to synthesize new POM clusters displaying pyramidal heteroanions (XO32-, where X= S, Se, Te, P) are reported. The reaction of molybdenum with vanadium in the presence of XO32- heteroatoms is explored, showing how via the cation and experimental control it is possible to direct the self-assembly process and to isolate isostructural compounds. A series of four isostructural (two new, namely {Mo11V7P} and {Mo11V7Te} and two already known, namely {Mo11V7Se} and {Mo11V7S} disordered egg-shaped Polyoxometalates have been reported. The compounds were characterized by X-ray structural analysis, TGA, UV-Vis, FT-IR, Elemental and Flame Atomic Absorption Spectroscopy (FAAS) analysis and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Cyclic Voltammetry measurements have been carried out in all four compounds showing the effect of the ionic density of the heteroatom on the potential. High-Resolution ESI-MS studies have revealed that the structures retain their integrity in solution. Efforts to synthesize new mixed-metal compounds led to isolation, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate cluster anion, {H2W4V9O33(C6H13NO3)}, by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster. Control experiments (in the absence of the organic compound) have proven that the tripodal ligand plays crucial role on the formation of the isomer. The six vanadium metal centres, which consist the upper part of the cluster, are bonded to the “capping” TEA tripodal ligand. This metal-ligand bonding directs and stabilises the formation of the final product. The δ-Keggin species was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations and changing colour under light. Non-conventional synthetic approaches are also used for the synthesis of the POM clusters comparing the classical “one-pot” reaction conditions and exploring the synthetic parameters of the synthesis of POM compounds. Reactions under hydrothermal and flow conditions, where single crystals that depend on the solubility of the minerals under hot water and high pressure can be synthesized, resulted in the isolation of two isostructural compounds, namely, {Mo12V3Te5}. The compound isolated from a continuous processing method, crystallizes in a hexagonal crystal system, forming a 2D porous plane net, while the compound isolated using hard experimental conditions (high temperature and pressure) crystallizes in monoclinic system, resulting in a different packing configuration. Utilizing these alternative synthetic approaches, the most kinetically and thermodynamically compounds would possibly be isolated. These compounds were characterised by single-crystal X-ray diffraction, FT-IR and UV-vis spectroscopy. Finally, the redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {M18O54(XO4)2} cluster is further investigated using UV-vis spectroscopy as a function of reaction time, showed that more than six complete oscillations interconverting the capsule species present in solution from {P2M18} to {V2M18} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. In an effort to investigate the periodicity of the exchange of the phosphate and vanadate anions, time dependent Uv-vis measurements were performed for a period at a range of 170-550 hours. Different experimental conditions were also applied in order to investigate the role of the reducing agent, as well as the effect of other experimental variables on the oscillatory system.

Role of Platinum Deposited on TiO2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions

Titania modified nanoparticles have been prepared by the photodeposition method employing platinum particles on the commercially available titanium dioxide (Hombikat UV 100). The properties of the prepared photocatalysts were investigated by means of the Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), atomic force microscopy (AFM), and UV-visible diffuse spectrophotometry (UV-Vis). XRD was employed to determine the crystallographic phase and particle size of both bare and platinised titanium dioxide. The results indicated that the particle size was decreased with the increasing of platinum loading. AFM analysis showed that one particle consists of about 9 to 11 crystals. UV-vis absorbance analysis showed that the absorption edge shifted to longer wavelength for 0.5% Pt loading compared with bare titanium dioxide. The photocatalytic activity of pure and Pt-loaded TiO2 was investigated employing the photocatalytic oxidation and dehydrogenation of methanol. The results of the photocatalytic activity indicate that the platinized titanium dioxide samples are always more active than the corresponding bare TiO2 for both methanol oxidation and dehydrogenation processes. The loading with various platinum amounts resulted in a significant improvement of the photocatalytic activity of TiO2. This beneficial effect was attributed to an increased separation of the photogenerated electron-hole charge carriers.

Síntese hidrotérmica assistida por micro-ondas de tiO2, e aplicação em nanocompósito

In recent decades have seen a sharp growth in the study area of nanoscience and nanotechnology and is included in this area, the study of nanocomposites with self-cleaning properties. Since titanium dioxide (TiO2) has high photocatalytic activity and also antimicrobial, self-cleaning surfaces in your application has been explored. In this study a comparison was made between two synthesis routes to obtain TiO2 nanoparticles by hydrothermal method assisted by microwave. And after analysis of XRD and SEM was considered the best material for use in nanocomposites. It was deposited nanocomposite film of poly (dimethyl siloxane) (PDMS) with 0.5, 1, 1.5 and 2% by weight of nanoparticles of titanium dioxide (TiO2) by the spraying method. The nanocomposite was diluted with hexane and the suspension was deposited onto glass substrate, followed by curing in an oven with forced air circulation. The photocatalytic activity of the nanocomposite impregnated with methylene blue was evaluated by UV- vis spectroscopy from the intensity variation of absorption main peak at 660nm with time of exposure to the UV chamber. Changes in the contact angle and microhardness were analyzed before and after UV aging test. The effect of ultraviolet radiation on the chemical structure of the PDMS matrix was evaluated by spectrophotometry Fourier transform infrared (FTIR).The results indicated that the addition of TiO2 nanoparticles in the coating PDMS gave high photocatalytic activity in the decomposition of methylene blue, an important characteristic for the development of self-cleaning coatings

Transport in the blood of an anti-tumor water-soluble rutheniun cyclopentadienyl complex: a fluorescence study on albumin binding

Dissertação de mestrado, Qualidade em Análises, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2014

BODIPY-Porphyrazin-Hybride als panchromatische Lichtsammelsysteme für farbstoffsensibilisierte Solarzellen

In farbstoffsensibilisierten Solarzellen (DSSC) spielen Chromophore, die als Lichtsammel- und Energie-/Elektronentransfersysteme fungieren, eine zentrale Rolle. Phthalocyanine mit ihren intensiven Absorptionsbanden um 400 nm und 700 nm besitzen großes Potential für die effektive Sensibilisierung von Solarzellen. Trotz ihrer vielversprechenden physikochemischen Eigenschaften und intensiver Bemühungen erreichen Phthalocyanin-sensibilisierte Solarzellen nicht die Effizienzen, die bisher mit anderen Chromophorklassen erzielt werden konnten. In der vorliegenden Dissertation wurde die Entwicklung effizienter Lichtsammelsysteme für DSSC auf der Basis von Aza-substituierten Phthalocyaninen, sogenannten Pyrazinoporphyrazinen, verfolgt. Ein besonderer Fokus lag dabei auf einer Verbesserung der Absorptionseigenschaften der Chromophore im Bereich ihrer intrinsischen Absorptionslücke zwischen den Maxima um 400 nm und 700 nm. Um diese optische Lücke zu schließen wurden komplementär absorbierende BODIPY-Farbstoffe kovalent an synthetisch maßgeschneiderte Porphyrazine gebunden. Insgesamt wurden sechs neue Porphyrazin-Sensibilisatoren synthetisiert und photophysikalisch sowie elektrochemisch charakterisiert. Alle in dieser Arbeit untersuchten Porphyrazine tragen sterisch anspruchsvolle Tri(p-tolyl)propinyl-Gruppen um Agglomerationen zu vermeiden. Darüber hinaus wurden die Porphyrazine peripher entweder mit Hydroxy- oder Carboxygruppen als Bindungsstellen für oxidische Materialien ausgestattet sowie mit sechs BODIPY-Auxiliarfarbstoffen funktionalisiert, deren Substitutionsmuster variiert wurden. Zur Darstellung der komplexen Porphyrazine wurde eine Syntheseroute erarbeitet, die statistische Cyclisierungen unterschiedlicher Dinitril-Vorstufen beinhaltete und es ermöglichte, funktionelle Gruppen erst am vorgeformten Makrocyclus einzuführen. Die photophysikalische Untersuchung der hochfunktionalisierten Farbstoffe erfolgte über UV/Vis- und Fluoreszenzspektroskopie. Im Fall der BODIPY-Porphyrazin-Hybride schließt die zusätzliche Absorptionsbande der peripheren BODIPY-Einheiten die intrinsische Absorptionslücke der Porphyrazine. Die Hybride zeigen somit eine breite Absorption über den gesamten sichtbaren Spektralbereich mit hohen Extinktionskoeffizienten von ca. 4·10^5 M^−1cm^−1. Mittels Fluoreszenz- und Anregungsspektren wurde ein photoinduzierter Energie-transfer von den BODIPY-Einheiten auf den Porphyrazinkern nachgewiesen. Das elektrochemische Verhalten der BODIPY- und Porphyrazin-Verbindungen wurde mittels Cyclo- und Square-Wave-Voltammetrie untersucht. Die Effizienzen der Lichtenergieumwandlung wurden mit Hilfe von selbst-hergestellten und standardisierten farbstoffsensibilisierten Solarzellen bewertet. Alle Solarzellen zeigten eine messbare Photoaktivität unter Bestrahlung. Die Wirkungsgrade der Zellen lagen jedoch alle unter 1 %. Generell führten die Carboxyl-funktionalisierten Porphyrazine zu besseren Wirkungsgraden als die analogen, mit der tripodalen Ankergruppe ausgestatteten Derivate. Die mit Hilfe von Adsorptionsisothermen ermittelten Bindungskonstanten der Adsorption der Farbstoffe auf der TiO2-Oberfläche zeigten, dass beide Hafteinheiten eine feste Verankerung der Chromophore auf den TiO2-Elektroden ermöglichten. Insgesamt wirkte sich die Präsenz der peripheren BODIPY-Farbstoffe positiv auf die Wirkungsgrade der Solarzellen aus, jedoch nur in geringem Maß. Dieses Ergebnis wurde hauptsächlich auf die geringe Energiedifferenz zwischen der Leitungsbandkante des TiO2 und den LUMO-Energieniveaus der Chromophore zurückgeführt. Zusätzlich scheinen konkurrierende Prozesse wie die direkte Photoelektroneninjektion von den BODIPY-Einheiten in das TiO2 eine wichtige Rolle zu spielen. Neben der Anwendung in DSSC wurde die Wechselwirkung der Porphyrazine mit Graphen untersucht. Hierzu wurden A3B-Porphyrazine mit Pyrenyl-Seitenketten ausgestattet, die eine nicht-kovalente Verankerung des Chromophors auf Graphen ermöglichen. UV/Vis- und Fluoreszenzmessungen gaben u.a. erste Hinweise auf eine elektronische Kommunikation zwischen den beiden Hybridpartnern.

Retrieval of atmospheric trace gases from DOAS/MAX-DOAS ground-based spectra

The study of the atmospheric chemical composition is crucial to understand the climate changes that we are experiencing in the last decades and to monitor the air quality over industrialized areas. The Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) ground-based instruments are particularly suitable to derive the concentration of some trace gases that absorb the Visible (VIS) and Ultra-Violet (UV) solar radiation. The zenith-sky spectra acquired by the Gas Analyzer Spectrometer Correlating Optical Differences / New Generation 4 (GASCOD/NG4) instrument are exploited to retrieve the NO2 and O3 total Vertical Column Densities (VCDs) over Lecce. The results show that the NO2 total VCDs are significantly affected by the tropospheric content, consequence of the anthropogenic activity. Indeed, they present systematically lower values during Sunday, when less traffic is generally present around the measurement site, and during windy days, especially when the wind direction measured at 2 m height is not from the city of Lecce. Another MAX-DOAS instrument (SkySpec-2D) is exploited to create the first Italian MAX-DOAS site compliant to the Fiducial Reference Measurements for DOAS (FRM4DOAS) standards, in San Pietro Capofiume (SPC), located in the middle of the Po Valley. After the assessment of the SkySpec-2D’s performances through two measurement campaigns taken place in Bologna and in Rome, SkySpec-2D is installed in SPC on the 1st October 2021. Its MAX-DOAS spectra are used to retrieve the NO2 and O3 total VCDs, and aerosol extinction and NO2 tropospheric vertical profiles over the Po Valley exploiting the Bremen Optimal estimation REtrieval for Aerosol and trace gaseS (BOREAS) algorithm. Promising results are found, with high correlations against both in-situ and satellite data. In the future, these data will play an important role for air quality studies over the Po Valley and for satellite validation purposes.

Lawsonia Inermis-mediated Synthesis Of Silver Nanoparticles: Activity Against Human Pathogenic Fungi And Bacteria With Special Reference To Formulation Of An Antimicrobial Nanogel.

Lawsonia inermis mediated synthesis of silver nanoparticles (Ag-NPs) and its efficacy against Candida albicans, Microsporum canis, Propioniabacterium acne and Trichophyton mentagrophytes is reported. A two-step mechanism has been proposed for bioreduction and formation of an intermediate complex leading to the synthesis of capped nanoparticles was developed. In addition, antimicrobial gel for M. canis and T. mentagrophytes was also formulated. Ag-NPs were synthesized by challenging the leaft extract of L. inermis with 1 mM AgNO₃. The Ag-NPs were characterized by Ultraviolet-Visible (UV-Vis) spectrophotometer and Fourier transform infrared spectroscopy (FTIR). Transmission electron microscopy (TEM), nanoparticle tracking and analysis sytem (NTA) and zeta potential was measured to detect the size of Ag-NPs. The antimicrobial activity of Ag-NPs was evaluated by disc diffusion method against the test organisms. Thus these Ag-NPs may prove as a better candidate drug due to their biogenic nature. Moreover, Ag-NPs may be an answer to the drug-resistant microorganisms.

Esi(+)-ms And Gc-ms Study Of The Hydrolysis Of N-azobenzyl Derivatives Of Chitosan.

New N-p-chloro-, N-p-bromo-, and N-p-nitrophenylazobenzylchitosan derivatives, as well as the corresponding azophenyl and azophenyl-p-sulfonic acids, were synthesized by coupling N-benzylvchitosan with aryl diazonium salts. The synthesized molecules were analyzed by UV-Vis, FT-IR, 1H-NMR and 15N-NMR spectroscopy. The capacity of copper chelation by these materials was studied by AAS. Chitosan and the derivatives were subjected to hydrolysis and the products were analyzed by ESI(+)-MS and GC-MS, confirming the formation of N-benzyl chitosan. Furthermore, the MS results indicate that a nucleophilic aromatic substitution (SnAr) reaction occurs under hydrolysis conditions, yielding chloroaniline from N-p-bromo-, and N-p-nitrophenylazo-benzylchitosan as well as bromoaniline from N-p-chloro-, and N-p-nitrophenylazobenzyl-chitosan.