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1.
N. Rajendiran M. Swaminathan 《Journal of photochemistry and photobiology. A, Chemistry》1995,90(2-3):109-116
A comparative study of absorption and fluorescence maxima of 4,4′-diaminodiphenyl sulphone (4DADPS), 3,3′-diaminodiphenyl sulphone (3DADPS) and 2-aminodiphenyl sulphone (2ADPS) in different solvents reveals that (i) solvatochromic shifts are found to be mainly due to interaction of solvents with amino group, (ii) in any one solvent the net solvatochromic shifts of two amino groups are less than that of one amino group, (iii) fluorescence shift from cyclohexane to water is a maximum for 4DADPS and a minimum for 2ADPS and (iv) 4DADPS and 3DADPS possess more twisted intramolecular charge transfer character than 2ADPS. The excited-state acidity constants, determined by fluorimetric titration and Förster cycle methods, have been reported and discussed. 相似文献
2.
Rajendiran TM Kirk ML Setyawati IA Caudle MT Kampf JW Pecoraro VL 《Chemical communications (Cambridge, England)》2003,(7):824-825
Binuclear manganese complexes Mn2(III/IV)(dtsalpn)2DCBI, 1, Mn2(III/III)(dtsalpn)2HDCBI, 2, containing the ligand dicarboxyimidazole (DCBI) have been prepared in order to address the issue of imidazole bridged and ferromagnetically coupled Mn sites in high oxidation states of the OEC in Photosystem II (PS II). Temperature dependent magnetic susceptibility studies of 1 indicates that the interaction between the two Mn(III)/Mn(IV) ions is ferromagnetic (J = +1.4 cm(-1)). Variable temperature EPR spectra of 1 shows that a g = 2 multiline is as an excited state signal corresponding to S = 1/2. 相似文献
3.
A. Anton Smith K. Kannan R. Manavalan N. Rajendiran 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(1-2):161-167
Absorption and fluorescence spectra of bicalutamide (BCA) in different solvents and aqueous β-cyclodextrin (β-CD) solutions
are reported. The solid inclusion complex of BCA with β-CD is prepared and investigated by FT-IR, 1H NMR, differential scanning colorimetry (DSC) and scanning electron microscopy (SEM). The Stokes shift of BCA is correlated
with various solvent polarity scales like E
T(30), BK and f(D,n). β-CD studies show that (i) the absorption and emission maxima of BCA are shifted to red, (ii) the absorbance is slightly
decreased whereas emission intensity is increased largely with an increasing β-CD concentration, (iii) BCA forms 1:1 inclusion
complex with β-CD and (iv) intramolecular charge transfer (ICT) emission is present in the excited state. 相似文献
4.
Spectral characteristics of sudan I (SDI), sudan II (SDII) and mordant violet-5 (MV5) have been studied in various solvents
and β-cyclodextrin (β-CD). The inclusion complex of the above molecules with β-CD was analyzed by UV-visible, fluorometry,
and DFT methods. The solvent study shows that azo-hydrazo tautomer is present in these molecules. The increase in the fluorescence
intensity and a large bathochromic shift in the S1 state indicate these molecules forms 1:1 inclusion complex with β-CD. 相似文献
5.
Rajendiran N Balasubramanian T 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2007,68(3):894-904
The absorption and fluorescence spectra of syringaldazine (SYAZ) has been recorded in solvents of different polarity, pH and beta-cyclodextrin (beta-CD) and compared with syringaldehyde (SYAL). The inclusion complex of SYAZ with beta-CD is investigated by UV-vis, fluorimetry, AM 1, FT-IR, (1)H NMR and scanning electron microscope (SEM). DeltaG value suggests the inclusion process is an exothermic and spontaneous. In all solvents a dual fluorescence is observed for SYAZ, whereas, SYAL shows a dual luminescence only in polar solvents. The excitation spectra for the 410 nm is different from 340 nm indicate two different species present in this molecule. In pH solutions: (i) a large red shifted maxima is observed in the dianion and is due to large interactions between the aromatic ring and (ii) the large blue shift at pH approximately 4.5, is due to dissociation of azine group and formation of aldehyde. beta-CD studies reveal that, SYAZ forms a 1:2 complex from 1:1 complex with beta-CD. 相似文献
6.
Gillon B Mathonière C Ruiz E Alvarez S Cousson A Rajendiran TM Kahn O 《Journal of the American Chemical Society》2002,124(48):14433-14441
The spin population distribution in the ferromagnetically coupled hetero-bimetallic chain compound [MnNi(NO(2))(4)(en)(2)] (en = 1,2-ethanediamine) has been investigated by means of polarized neutron diffraction experiments, and the results compared with those from theoretical estimates obtained via calculations based on density functional theory on dinuclear molecular models of the chain. The spin distributions obtained from experiment and from theory are consistent and reflect a larger spin delocalization from the Ni atom due to the more covalent character of the Ni-N bonds compared to the Mn-O ones. Also a nearly isotropic spin distribution is observed for the more ionic d(5) Mn(2+) ion and a clearly anisotropic distribution for the d(8) Ni(2+) ion. The use of dinuclear molecular models for the calculation of the exchange coupling constant between Ni and Mn provide upper and lower limits (+17.6 and -4.2 cm(-)(1)) for the experimentally determined value (+1.3 cm(-)(1)), depending on how the missing part of the chain is simulated, but yield essentially the same spin distribution. The Mn(II)-Ni(II) weak ferromagnetic coupling in the chain is interpreted in a spin delocalization mechanism as resulting from the weakness of the overlap between the magnetic orbitals centered on nickel and those centered on manganese which are only weakly delocalized on the ligands. 相似文献
7.
Excimer emission of caffeine with α-CD and β-CD were studied by UV-visible, fluorescence, time-resolved fluorescence, FTIR, 1H NMR and molecular modelling techniques. Changes in the absorbance and fluorescence and lifetime of the caffeine with cyclodextrin (CD) solutions indicate (i) caffeine shows dual emission in the CD solutions, (ii) normal emission originates from a monomer and the longer wavelength emission is due to excimer and (iii) in both CDs caffeine forms 1:2 inclusion complex. Carbonyl stretching frequency moved to higher wave numbers and broadening of the N–H stretching band indicated the formation of inclusion complex. The resonance of the methyl protons of caffeine show remarkable upfield or downfield shift in the 1H NMR, which indicates imidazole ring of the caffeine entrapped in the CD cavities. Investigations of energetic, thermodynamic and electronic properties of PM3 computational calculations confirmed the stability of the inclusion complex. 相似文献
8.
Jayapalan Kasthuri Jayadevan Santhanalakshmi Nagappan Rajendiran 《Transition Metal Chemistry》2008,33(7):899-905
The oxidative coupling of phenols with 4-aminoantipyrine (AmNH2) has been studied by UV–visible spectroscopy using platinum nanoparticles as catalyst. The rate of antipyrilquinoneimine
dye formation depends on the nature of substrates, temperature, pH, and the use of microheterogeneous media such as sodium
dodecylsulphate (SDS), cetyl trimethylammonium bromide (CTAB) and Triton X-100 (TX-100). The reactivity trend observed for
differently substituted phenols follows the order: 3,5-dimethylphenol > phenol > o-chlorophenol > o-nitrophenol. The rate of dye formation is greater at acid pH than at basic pH and the optimum pH is 5.4. A reaction pathway
is proposed, involving the activation of o-chlorophenol with AmNH2 by metal nanoparticles and concomitant reactions of free radicals. Transmission electron microscopy results show that the
particle size is 20 nm for the platinum nanoparticles involved in catalysis.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
9.
A. Antony Muthu Prabhu G. Venkatesh N. Rajendiran 《Journal of solution chemistry》2010,39(7):1061-1086
The absorption and fluorescence spectra of sulfamethoxazole (SMO), sulfisoxazole (SFO), sulfathiazole (STO) and sulfanilamide
(SAM) in different solvents, pH and β-cyclodextrin (β-CD) have been analyzed. The inclusion complexes of the above sulfa drugs with β-CD were investigated by UV-visible spectroscopy, fluorometry, DFT, SEM, FT-IR and 1H NMR. The solvent study indicates that the position of the substituent (oxazole or thiazole group) in the SAM molecule (R–SO2–NH-group) is not the key factor to change the absorption and emission behavior of these sulpha drug molecules. In aqueous
solution, a single fluorescence band (340 nm) was observed whereas in solutions of β-CD dual emission (430 nm) was noticed in sulpha drug compounds. Formation of the inclusion complex in SMO, SFO and STO should
result dual emission which is due to a Twisted Intramolecular Charge Transfer band (TICT). The β-CD study indicates that (i) sulpha drugs form 1:1 inclusion complexes with β-CD and (ii) the red shift and the presence of TICT in the β-CD medium confirms heterocyclic ring encapsulated in the β-CD cavity with the aniline ring present on the out side of the β-CD cavity. 相似文献
10.
J. Premakumari G. Allan Gnana Roy A. Antony Muthu Prabhu G. Venkatesh V. K. Subramanian N. Rajendiran 《Journal of solution chemistry》2011,40(2):327-347
The spectral characteristics of 2,4-dihydroxyazobenzene (DHAB, sudan orange G) and 4-hydroxyazobenzene (HAB) have been studied
in various solvents, different hydrogen ion and β-cyclodextrin (β-CD) concentrations, and are compared with azobenzene (AB). The inclusion complexes of the above molecules with β-CD were analyzed by UV-vis spectrometry, flourometry, FT-IR, 1H NMR, SEM and DFT methods. The solvent study shows that only the azo form is present in DHAB and HAB molecules. The unusually
large red shift observed in acidic solutions indicates both molecules exhibit azo-hydrazo tautomerization. In the β-CD solutions, the increase in fluorescence intensity and large bathochromic shift in the S1 state indicates that DHAB and HAB form 2:2 inclusion complexes, whereas AB forms a 1:1 inclusion complex. 相似文献