Solvent effects on spectrophotometric titrations and vibrational spectroscopy of 5,10,15-triphenyl-20-(4-hydroxyphenyl)porphyrin in aqueoius DMF

The spectrophotometric titration by sodium hydroxide of 5,10,15-triphenyl-20-(4-hydroxyphenyl)porphyrin ((OH)(1)PH2) is studied as a function of solvent composition of DMF-H2O binary solvent mixture ([OH-] = 0.04 M). Combining the structure changes of the porphyrin and the "four orbital" model of Gouterman, many features of the optical spectra of this deprotonated para-hydroxy-substituted tetraphenylporphyrin in different composition of binary solvent mixtures can be rationalized. In highly aqueous solvents, the changes of the titration curves are shown to be mainly due to hydrogen-bonding of the oxygen of the phenoxide anion group by the hydroxylic solvent, Which decreases the energy of the phenoxide anion pi orbital. Thus the phenoxide anion pi orbital cannot cross over the porphyrin Tr orbital being a different HOMO. However, its energy is close to that of the porphyrin pi orbitals. As a result, in the visible region, no charge-transfer band is observed, while in the visible-near region, the Soret peak split into two components. In nonaqueous solvents, the changes are mainly attributed to further deprotonation of pyrrolic-Hs of (OH) 1PH2 by NaOH and coordination with two sodium ions to form the sodium complex of (OH) 1PH2, which turns hyperporphyrin spectra of deprotonated of phenolic-H of (OH)(1)PH2 into three-banded spectra of regular metalloporphyrin.

Synthesis and characterization of hyperbranched poly(ester-amide)s based on gallic acid and DL-2-aminobutyric acid

A novel AB(3)-type monomer was prepared from gallic acid and DL-2-aminobutyric acid, and used for the synthesis of the biocompatible hyperbranched poly(ester-amide)s by self-polycondensation. The polymers were characterized via FTIR and NMR spectroscopy and thermal analysis, and the average degree of branching of the polymers was estimated to be 0.75. The polymers with abundant acetyl end groups were found to be amorphous with lower intrinsic viscosity, better thermal stability and excellent solubility.

Synthesis of the complex fluoride LiBaF3 and optical spectroscopy properties of LiBaF3 : M(M = Eu,Ce) through a solvothermal process

The complex fluoride LiBaF3 and LiBaF3:M(M = Eu, Ce) is solvothermally synthesized at 180 degreesC and characterized by means of X-ray powder diffraction, scanning electron microscopy, thermogravimetric analysis and infrared spectroscopy. In the solvothermal process, the solvents, molar ratios of initial mixtures and reaction temperature play important roles in the formation of products. The excitation and emission spectra of the LiBaF3:M(M= Eu,Ce) have been measured by fluorescence spectrophotometer. In the LiBaF3: Eu emission spectra, there is one sharp line emission located at 360 nm arising from f --> f transition of Eu2+ in the host lattice, and typical doublet 5d-4f emission of Ce3+ in LiBaF3 powder is shown.

Chemical bond properties and Mossbauer spectroscopy in (La1-xMx)(2)CuO4(M=Ba, Sr)

By using the average band-gap model, the chemical bond properties of (La1-x, M-x)(2)CuO4(M=Ba, Sr) were calculated. The calculated covalencies for Cu-O and La-O bond in the compounds are 0.3 and 0.03 respectively. Mossbauer isomer shifts of Fe-57 doped in La2CuO4 and Sn-119 doped in La2CuO4 were calculated by using the chemical surrounding factor defined by covalency and electronic polarizability. Four valence state tin and three valence iron sites were identified in Fe-57 and Sn-119 doped La2CuO4.

Chemical bond properties and Mossbauer spectroscopy in REBa2Cu3O7 (RE = Eu, Y)

By using the chemical bond theory of complex crystals, the chemical bond properties of REBa2Cu3O7 (RE = Eu, Y) were calculated. The calculated covalencies for Cu(1)-O and Cu(2)-O bond in REBa2Cu3O7 compounds are 0.41 and 0.28 respectively. Mossbauer isomer shifts of Fe-57 doped, and Sn-119 doped in REBa2Cu3O7-x were calculated by using the chemical environmental factor, h(e), defined by covalency and electronic polarizability. Four valence state tin ion and iron ion sites were identified in Fe-57 and Sn-119 doped REBa2Cu3O7-x superconductors.

Spectrometric investigation on the thermooxidative degradation of ethylene oxide and tetra-hydrofuran co-polyether

The thermooxidative degradtion of ethylene oxide and tetra-hydrofuran (EO-THF) co-polyether has been studied by electron spin resonance (ESR), Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy. The initial degradation site was found to be at the a-carbon of the ether bond. Two free radicals which derived from dehydrogenation and oxygen addition were successfully detected by spin-trapping technique which used alpha -phenyl-N-tert-butyl nitrone(PBN) as spin trap. Both FT-IR and NMR have been used to follow structural changes of the copolyether during degradation. Nearly 20 product fragments including formate, carbonate, methyl, alcohol, methylene-dioxy, hydroperoxide and semiformal have been characterized by D-1 and D-2 NMR. The thermooxidtion of co-polyether preferred to occur on the THF units especially at the alternating linkage of EO and THF. Antioxidant (BHT) not only retarded the thermooxidation but also modified the degradation products with less ester and methylene-dioxy groups hut more hydroxyl and methyl groups.

NMR and UV-Vis study on phenyl-capped oligoaniline salts

Phenyl-capped oligoanilines in the oxidized state and their salts (by camphor sulfonic acid, CSA) were comparatively studied by UV-Vis and NMR spectroscopy. The UV-Vis spectra revealed a similar electron transfer behaviour and similar structure in the tetraaniline to those in polyaniline. Upon formation of the salt, H-1 NMR CH peaks of the oligomers showed large shifts to lower fields. The longer the molecule of a oligomer is, the more the shift, indicating that the charge brought into the N atoms by the proton was redistributed over the whole molecule. The CH and quaternary carbon peak-shifts support the electron cloud motion route H -->C -->C -->N -->H. This is in agreement with the four ring BQ derivatives model.

Effect of lanthanum ions on tRNA(Phe) structure: Imino proton NMR spectroscopy

The effect of lanthanum ions on the structural and conformational change of yeast tRNA(Phe) was studied by H-1 NMR. The results suggest that the tertiary base pair (G-15)(C-48), which was located in the terminal in the augmented dihydrouridine helix (D-helix), was markedly affected by adding La3+ and shifted 0.33 downfield. Based pair (U-8)(A-14), which is associated with a tertiary interaction, links the base of the acceptor stem to the D-stem and anchors the elbow of the L structure, shifted 0.20 upfield. Another imino proton that may be affected by La3+ in tRNA(Phe) is the tertiary base pair (G-19)(C-56). The assignment of this resonance is tentative since it is located in the region of highly overlapping resonances between 12.6 and 12.2. This base pair helps to anchor the D-loop to the T psi C loop.

SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF THE DAWSON-TYPE TUNGSTOPHOSPHATE HETEROPOLY COMPLEXES SUBSTITUTED BY NIOBIUM

Eight new complexes alpha(2)-M(7-m)H(m)[P2W17NbO62]. H2O and alpha-1, 2, 3-M(g-m)H(m) [P2W15Nb3O62]. XH(2)O(M=K, TMA, TEA, TBA) were synthesized and characterized by IR and UV spectroscopy, polarography, XPS and XRD methods. P-31 and W-183 NMR studies show that the niobium atoms in the anions are on the polar sites. The crystal of alpha-1, 2, 3-K7H2 [P2W15Nb3O62]. 30H(2)O is hexagonal, its cell parameters: a=1.9836(4), b=1.9836(9), c=1.5498(6)nm, alpha=beta=90 degrees, gamma=120 degrees.

SYNTHESIS AND CHARACTERIZATION OF ALPHA,BETA-TRIINDIUM SUBSTITUTED HETEROPOLYTUNGSTATES

The complexes of alpha,beta-K(a)H(b)XW(9)O(37)(InH2O)(3) . xH(2)O (X = Si, Ge; a+b = 7) were synthesized from their lacunary precursors alpha,beta-XW(9)O(34)(10-) (X = Si, Ge) and characterized by elemental analysis, W-183 NMR, IR and UV spectroscopy and polarography. W-183 NMR spectra of the title complexes consist of two lines with intensity ratio 2:1, as expected for the C-3 nu structure of trisubstituted A alpha- and A beta-Keggin anions.

STUDY ON RARE EARTH-HEDTA-SERINE TERNARY SYSTEM BY POTENTIOMETRY AND FLUORESCENCE SPECTROSCOPY

In this pare earth-HEDTA-serine (Ser) ternary system has been studied by potentiometric titration at 25 degrees C with an ionic strength of 0.15 mol.L-1 (NaCl). The excitation and fluorescence spectra of TbCl3, Tb-Ser, Tb-HEDTA and Tb-HEDTA-Ser have hem determined at room temperature. The stability constants of these ternary complexes have been obtained, It lieu been found that Tb-HEDTA-Ser ternary system exhibit characteriatic fluorescence spectrum of Tb3+ sensitized by two ligands,The results mean that the chemical hood between the control ion and the ligand in this ternary system is predominantly ionic in character,and the energy transfer from ligand to Tb8+ is performed by a kind of abort-range electron exchange action.

Crystallographic and NMR studies on sterols from green alga Chaetomorpha basiretorsa Setchell

Chemical investigation of the ethanol extract of the marine green alga Chaetomorpha basiretorsa Setchell led to the isolation of a new sterol stigmast-4,28-dien-3 alpha 6 beta-diol 1 in addition to the five known sterols of beta-lawsaritol 2, saringosterol 3, 24-hydroperoxy-24-vinyl - cholesterol 4, beta-stigmasterol 5, 29-hydroxystigmasta-5, 24(28) -dien-3 beta-ol 6. Compounds were isolated by normal phase silica gel and Sephadex LH - 20 gel colum chromatography, reverse phase HPLC and recrystalization. Their structures were elucidated by spectroscopic methods including MS, IR 1D/2D NMR and X-ray analysis. Cytotoxicity of compounds was screened by using the standard WIT method. All these compounds were isolated from the green alga Chaetomorpha basiretorsa Setchell for the first time and they were inactive (50% inhibitory concentration was greater than 10 mu g /cm(3)) against KB, Bel -7402, PC - 3M, Ketr 3 and MCF - 7 cell lines.

Crystallization and Si incorporation mechanisms of SAPO-34

In this study of the synthesis of SAPO-34 molecular sieves, XRD, SEM, XRF, IR and NMR techniques were applied to monitor the crystalloid, structure and composition changes of the samples in the whole crystallization process in order to get evidence for the crystallization as well as Si incorporation mechanism of SATO-34. XRD results revealed that the crystallization contained two stages. In the first 2.5 h (the earlier stage), high up to similar to80% of relative crystallinity could be achieved and the crystal size of SAPO-34 was almost the same as that of any longer time, indicating a fast crystallization feature of the synthesis. In this stage, IR revealed that the formation of SAPO-34 framework structure was accompanied by the diminution of hydroxyls, suggesting that crystal nuclei of SAPO-34 may arise from the structure rearrangement of the initial gel and the condensation of the hydroxyls. NMR results reveal that the template and the ageing period are crucial for the later crystallization of SAPO-34. Preliminary structure units similar to the framework of SAPO-34 have already formed before the crystallization began (0 h and low temperature). Evidence from IR, NMR, and XRF shows that the formation of the SAPO-34 may be a type of gel conversion mechanism, the solution support and the appropriate solution circumstance are two important parameters of the crystallization of SAPO-34. Meanwhile, NMR measurements demonstrated that about 80% of total Si atoms directly take part in the formation of the crystal nuclei as well as in the growth of the crystal grains in the earlier stage (<2.5 h). Evidence tends to support that Si incorporation is by direct participation mechanism rather than by the Si substitution mechanism for P in this stage (<2.5 h). In the later stage (>2.5 h), the relative content of Si increased slightly with a little decrease of Al and P. The increase of Si(4Al) and the appearance of the Si(3Al), Si(2Al), Si(1Al) and Si(OAl) in this stage suggest that substitution of the Si atoms for the phosphorus and for the phosphorus and aluminum pair takes place in the crystallization. The relationship among structure, acidity and crystallization process is established, which suggests a possibility to improve the acidity and catalytic properties by choosing a optimum crystallization time, thus controlling the number and distribution of Si in the framework of SAPO-34. (C) 2002 Elsevier Science Inc. All rights reserved.