Search results for " Spectroscopy"
showing 10 items of 6851 documents
Influence of synthesis conditions on the performance of chitosan–Heteropolyacid complexes as membranes for low temperature H2–O2 fuel cell
2015
Flat, free-standing chitosan/phosphotungstic acid (PTA) polyelectrolyte membranes were prepared by in-situ ionotropic gelation process at room temperature on porous alumina support firstly impregnated by H3PW12O40. Scanning electron microscopy revealed the formation of compact and homogeneous membranes, whose thickness resulted to be dependent on chitosan concentration and reticulation time. X-ray diffraction and Fourier transform infrared spectroscopy (FTIR) evidenced the formation of almost amorphous membrane without appreciable concentration of not protonated NH2 groups and PTA3- ions with preserved Keggin structure. Membranes were tested as proton conductor in low temperature H2-O2 fuel…
Ab initio calculations and vibrational spectroscopy on the phenylenediamine isomers
1998
Molecular orbital calculations at HF and MP2 levels have been performed using the 6-3IG** basis set for full geometry optimization of the phenylenediamine isomers. Our results show that only a transoid conformer is found for o-phenylenediamine, whereas cis and trans conformers exist for m- and p-phenylenediamine. Vibrational normal modes have been also analyzed for the gas phase and in chloroform solution, and compared with experimental data we have obtained using FTIR spectroscopy. © 1998 Elsevier Science B.V.
Synthesis and spectroscopic investigations (IR, NMR and Mössbauer) of tin(IV) and organotin(IV) derivatives of bis(pyrazol-1-yl) alkanes: X-ray cryst…
1995
A series of 1:1 adducts of the type [(L)R(n)SnX(4-n)] . zH(2)O (L = bis(4-methylpyrazol-1-yl)methane (L(4)), bis(3,4,5-trimethylpyrazol-1-yl)methane (L(T)), 1,2-bis(pyrazol-1-yl)ethane (L(A)) or 1,2-bis(3,5-dimethylpyrazol-1-yl)ethane (L(B)); R = Me, Et, Bu or Ph; X = I, Br or Cl; n = 0, 1 or 2; z = 1, 1.5 or 2), and the likely polynuclear [(L(A))(5)(SnCl4)(4)] . (H2O)(5) and [(L(B))(2)(SnCl4)(3)] . 1/2[Et(2)O] have been characterized in the solid state and in solution by analyses, spectral (IR, Mossbauer, and H-1, C-13 and Sn-119 NMR) data and conductivity measurements. When L(T) reacts with SnCl4, cleavage of a carbon (sp(3))-nitrogen bond was observed and the adduct [(3,4,5-trimethylpyra…
Synthesis and electrochemical study of a new doubly-metallated compound with the ferrocene-labelled phosphine PPh2(C5H4)Fe(C5H5)
1993
Abstract Direct reaction of the metalled compound Rh 2 (μ 2 -O 2 CCH 3 ) 3 [μ 2 -(C 6 H 4 ) PPh 2 ]·(H 2 O) 2 with PPh 2 Fc [Fc = (C 5 H 4 )Fe(C 5 H 5 )] in chloroform solution yields the corresponding mono-adduct Rh 2 (O 2 CCH 3 ) 3 [(C 6 H 4 )PPh 2 ]·(PPh 2 Fc) ( 1 ), which has been characterized by 31 P NMR spectroscopy. Photochemical irradiation of 1 in chloroform gives the compound Rh 2 (μ-O 2 CCH 3 ) 2 (η 2 -O 2 CCH 3 )[μ 2 -(C 6 H 4 )PPh 2 ][PPh 2 Fc]·(H 2 O) ( 2 ) in practically quantitative yield. Compound 2 , by thermal treatment in chloroform solution, yields cleanly the doubly-metallated compound Rh 2 (μ 2 -O 2 CCH 3 ) 2 [μ 2 -(C 6 H 4 )PPhFc][μ 2 -(C 6 H 4 )PPh 2 ]·(H 2 O) 2 ( …
Supramolecular PEG-co-oligo(p-benzamide)s prepared on a peptide synthesizer.
2007
An automated synthesis protocol has been developed for the preparation of oligo(p-benzamide)s on solid support using a commercial peptide synthesizer employing a variation of standard Fmoc chemistry. Bis(trichloromethyl carbonate) in NMP was used to activate the aromatic carboxylic acids for acylation of secondary aromatic amines on solid support. N-Protected hepta(p-benzamide) was automatically prepared on solid support and manually converted to a solid supported block co-oligomer by attaching a poly(ethylene glycol) chain. Cleavage from the support could be achieved with minimal loss of the p-methoxybenzyl N-protective group. While the N-protected block co-oligomer was molecularly dissolv…
Tautomeric preferences of phthalones and related compounds
2007
Abstract Multinuclear magnetic resonance and IR spectra prove that although 2-(diacylmethyl)pyridines and 2-(diacylmethyl)quinolines are β-diketones, their proton transfer product present in chloroform solution is not ketoenol but enaminone (earlier opinions were contradictory). Quinoline derivatives are less zwitterionic by character than the respective pyridyl congeners. The β-diketone form itself may also be rarely present in the solution. X-ray data show that 2-(2(1H)-pyridinylidene)-1H-indene-1,3(2H)-dione, i.e., enaminone tautomer of 2-(pyridin-2-yl)-2H-indene-1,3-dione, is also the only form present in crystal. Ab initio calculations show that the enaminone is usually more stable tha…
CHLOROPHYLL a AGGREGATES IN HYDROCARBON SOLUTION, A PICOSECOND SPECTROSCOPY AND MOLECULAR MODELING STUDY
1993
Chlorophyll a aggregates in 3-methylpentane solution have been studied by using picosecond absorption and fluorescence spectroscopy and molecular modeling. Chlorophyll a aggregates give rise to reversible temperature changes in the absorption and fluorescence spectra. Time-dependent anisotropies were used to estimate rotational correlation times of the aggregates. These were indicative of the sizes of the aggregates. The rotational diffusion of the monomer and the two identified aggregates was hydrodynamic over the viscosity range studied (0.29–1.8 cP). Molecular mechanics calculations were used to predict the minimum energy structures of several chlorophyll a dimers suggested earlier in th…
Molecular structures of chlorophyll a aggregates: spectroscopic and molecular modeling study
1993
Molecular structures of chlorophyll a aggregates have been studied. Spectroscopic properties of these aggregates have been studied by absorption and fluorescence spectroscopy in hydrocarbon solution at various temperatures. Observed spectroscopic shifts were interpreted in terms of simple exciton theory. Exciton splittings were estimated from computer optimized models of previously suggested Chl a aggregate structures.
Synthesis and Functional Reconstitution of Light-Harvesting Complex II into Polymeric Membrane Architectures.
2015
One of most important processes in nature is the harvesting and dissipation of solar energy with the help of light-harvesting complex II (LHCII). This protein, along with its associated pigments, is the main solar-energy collector in higher plants. We aimed to generate stable, highly controllable, and sustainable polymer-based membrane systems containing LHCII-pigment complexes ready for light harvesting. LHCII was produced by cell-free protein synthesis based on wheat-germ extract, and the successful integration of LHCII and its pigments into different membrane architectures was monitored. The unidirectionality of LHCII insertion was investigated by protease digestion assays. Fluorescence …
Refinement of a structural model of a pigment-protein complex by accurate optical line shape theory and experiments.
2007
Time-local and time-nonlocal theories are used in combination with optical spectroscopy to characterize the water-soluble chlorophyll binding protein complex (WSCP) from cauliflower. The recombinant cauliflower WSCP complexes reconstituted with either chlorophyll b (Chl b) or Chl a/Chl b mixtures are characterized by absorption spectroscopy at 77 and 298 K and circular dichroism at 298 K. On the basis of the analysis of these spectra and spectra reported for recombinant WSCP reconstituted with Chl a only (Hughes, J. L.; Razeghifard, R.; Logue, M.; Oakley, A.; Wydrzynski, T.; Krausz, E. J. Am. Chem. Soc. U.S.A. 2006, 128, 3649), the "open-sandwich" model proposed for the structure of the pig…