PHOTOPHYSICS STUDIES OF ORGANIC COMPOUNDS——NANOSECOND LASER PHOTOLYSIS AND TRANSIENT ABSORPTION SPECTRA STUDIES OF PYRENE-AROMATIC AMINES

Nanosecond time-resolved transient absorption spectra of pyrene-triphenylamine, pyrenediphenylamine, pyrene-N, N-dibenzylaniline systems in various solvents have been investigated. In nonpolar solvent, pyrene-triphenylamine exciplex and pyrene-N, N-dibenzylaniline exciplex were observed directly. In acetonitrile, the pyrene anion radical, triphenylamine and diphenylamine cation radicals were detected. On the basis of the present experimental facts, the mechanism of fluorescence quenching processes of pyrene in polar and nonpolar solvents has been established.     

Novel Transient Species of DNA Bases From Laser Photolysis

The laser photochemistry and photosensitization of DNA bases were carried out by using a nanosecond kinetic spectroscopy. A novel triplet state of thymine and its OH adduct were observed in N_2 and N_2O saturated aqueous solution respectively. The transient absorption spectra of triplet cytosine, cytidine and deoxycytidine monophosphoric acid were observed for the first time. Triplet guanosine was confirmed and its pK, value, 8.7, was obtained. Kinetic studies of the growth-decay of the above transient species were performed and their reaction mechanisms were elucidated in detail.     

Combined Transient Spectra and Semiempirical Calculation of [60]Fullerenes Attached with Piperidinodithiocarboxylate and 7-Chloro-phenazine

[60]Fullerenes attached with piperidinodithiocarboxylate dyad （1） and 7-chloro-1,2,3,4-tetrahydrophenazine （2） were efficiently synthesized through Diels-Atder cycloaddition with dienes. The physical properties of the triplet states of these compounds, in which strong electron acceptor moieties were covalently attached to C60 cores, were investigated by nanosecond laser flash photolysis. The excited triplet states in benzonitrite have been evaluated by observing the transient absorption bands in the near-IR region. The HOMO and LUMO were calculated by semiempirical methods AM1, which could predict the intramolecular photoinduced electron transfer in 1 and 2, and the nanosecond transient absorption spectra observed experimentally in solution were in excellent agreement with the calculated ones.     

Interaction between hypocrellin and aliphatic amines

The interaction of hypocrellin, including hypocrellin A (HA) and hypocrellin B (HB), with aliphatic amines in deaerated solutions has been studied by ESR and nanosecond transient absorption spectra. In polar solvents, the acid-base interaction between hypocrellin and amines was observed without irradiation. The signals of semiquinone radical anions of hypocrellm and the spin-trapping adduct of α-phenyl-N-tertbutyl-ratrone (PNB) with the aminoalkyl radicals have been detected in photoinduced ESR studies. The transient absorption of excited triplet state of HA and semiquinone radical anion of HA have been observed in laser flash photolysis studies.     

STUDY ON POLYSULFONE-POLYESTER BLOCK COPOLYMERS

Synthesis and characterization of a series of Polysulfone (PSF)-Polyester (PEs) block copolymers were studied.The degree of randomness (B) of these block eopolymers was calculated from the intensities of their proton signals in ~1H NMR spectra and lies in the region of 0相似文献   

EFFECT OF SOLVENT ON THE COPOLYMERIZATION OF 2,2,6,6-TETRAMETHYL 4-PIPERIDINYL METHACRYLATE WITH STYRENE

The radical copolymerizations of 2,2,6, 6-tetramethyl 4-piperidinyl methacrylate (TMPM) with styrene in various solvents have been studied. The monomer reactivity ratios r_1 and r_2 were determined. It is observed that in all of these reaction systems, there are appreciable solvent effects on both r_1 and r_2, which can be correlated to the difference in chemical shifts of olefinic protons of TMPM. And the variance of the copolymer microstructure in various media was discussed.     

Characterization of transient species in laser photolysis of aromatic amino acids using acetone as photosensitizer

The photochemical processes of aromatic amino acids were investigated in aqueous solution using acetone as photosensitizer by KrF (248 nm) laser flash photolysis. Laser-induced transient species were characterized according to kinetic analysis and quenching experiments. The intermediates recorded were assigned to the excited triplet state of tryptophan, the radicals of tryptophan and tyrosine. The excited triplet state of tryptophan produced via a triplet-triplet excitation transfer and the radicals arising from electron transfer reaction has been identified. Neither electron transfer nor energy transfer between triplet acetone and phenylalanine can occur in photolysis of phenylalanine aqueous solution which contains acetone. Furthermore, triplet acetone-induced radical transformation: Trp/N-Tyr→Trp-Tyr/O was observed directly in photolysis of dipeptide (Trp-Tyr) aqueous solution containing acetone, and the transformation resulting from intramolecular electron transfer was suggested.     

STUDIES ON CRITICAL CONCENTRATION OF LIQUID CRYSTALLINE ETHYLCELLULOSE

Critical concentrations of lyotropic liquid crystalline ethylcellulose in more than tensolvents were determined using both Abbe refractometer and polarized microscopy. Criti-cal concentration C_(crit) of forming liquid crystal phase decreased with increasing solubilityparameter δ of solvent until approaching the δ of polymer. Although the alcohols usedas solvents had the same variation rule, the critical concentration values of their solutionswere much higher, due to their excessive large hydrogen bond component of δ. The experi-ments of using mixed solvents which showed good linear relation between C_(crit) and δ alsoproved this rule. A technique of Transmission Optical Analysis was first used to estimatethe concentration dependence of critical phase transition temperature T_(crit) of EC, and aT-C phase diagram could be drawn.     

NMR STUDIES ON POLYETHER-POLYURETHANE ZWITTERIONOMERS——CHAIN STRUCTURE AND PHASE SEPARATION

The ~1H and ~(13)C NMR spectra of polyether-polyurethancs (A) based on 4, 4'-diphenylmethanediisocyanate (MDI), N-methyl diethanolamine (MDEA), and polytetramethyleneoxide (PTMO)and the zwitterionomers derived from A with various degree of ionization was assigned by comparingwith model compounds. Phase separation of the samples was visualized through pulsed NMR investigations. The FIDsignals of these multiphase elastomers were recorded and decomposed by non-linear least squaresregression into fast Gaussian and slow exponential components assodated with the hard, the soft andthe interface respectively. Thus pulsed NMR gives both qualitative and quantitative informationabout the existence of multiphases and the relative amounts of materials in each phase.     

STUDIES ON ORGANOPHOSPHORUS COMPOUNDS XXXV——SUBSTITUENT EFFECT OF ORGANOPHOSPHORUS COMPOUNDS ON ~(31)P NMR SPECTROSCOPY

The linear relationship between the chemical shift of the resenant nucleus and the localvan der Waals steric energy calculated by molecular mechanics with MM2 force field wasextended to various organophosphorus compounds including alkyl-phosphates, -phosphonates,-phosphinates as well as -phosphine oxides. The conformational equilibria of a series of alkylO,O-1,3--propylene-and O, O-1,4-butylenephosphonates were studied by the molecular mechanicscalculations and the dynamic ~(31)P NMR spectroscopic method. As shown by these experimentaldata, the former existed in a chair form, and the latter in a twist boat form with an equatorialalkyl group in both configurations, either in gaseous state or in non-polar solvent.     

STUDIES ON THE POLYSILANE CONSISTING CYCLODISILAZANE UNITS IN THE MAIN CHAIN

Since the reactivity of Me_2SiCl_2(Ⅰ) and ■(Ⅱ) are very different. it is difficult to cocondensate the above two monomers with sodium in general Wurtz reaction. We have proposed a modified method to prepare copolymer containing permethylpolysilane segments and cyclodisilazane units by reaction of (Ⅱ)with Na at first, then adding (Ⅰ) into the mixture to proceed with further reaction.The obtained copolysilanes are pale yellow elastic substance and soluble in common solvents. The amounts of N in the copolymers are influenced by the operating conditions of the synthetic method. The resultant products were characterized by IR, UV, NMR, and elementary analysis. The highest molecular weight determined by gel permeation chromatography is 60000.     

MICROPOROUS PVDF-HFP-BASED POLYMER MEMBRANES FORMED FROM SUPERCRITICAL CO2 INDUCED PHASE SEPARATION

Microporous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membranes following supercritical CO_2 induced phase separation process were prepared using four solvents.The solid electrolytes of PVDF-HFP were formed by microporous PVDF-HFP membranes filled and swollen by a liquid electrolyte.The effect of the solvents on the morphology and structure,electrolyte absorptions and lithium ionic conductivity of the activated membranes were investigated.It was approved that all the membrane had the simi...     

Laser photolysis of interaction of poly-guanylic acid (5'''') with anthraquinone-2-sulfonate

The electron transfer reaction between triplet anthraquinone-2-sulfonate and poly-guanylic acid (5') in CH3CN-H2O (97 : 3) has been investigated by 248 nm (KrF) laser flash photolysis. The transient absorption spectra and kinetics obtained from the interaction of triplet anthraquinone-2-sulfonate and poly[G] demonstrate that the primary ionic radical pair, radical cation of poly[G] and radical anion of anthraquinone-2-sulfonate have been detected simultaneously. The free energy changes in the process of the electron transfer were also calculated.     

Electronic spectroscopy and photochromic mechanism of bis-Schiff bases, N, N''''-bis(2-hydroxy-1-naphthylidene)-1,4-phenyldiamine

The steady state and transient state absorption spectra and fluorescence spectra of N,N'-bis(2-hy-droxy-1-napbthylidcne)-1,4-phenyldiamme ( BNP ) in cyclohexane and acetonitrile were determined.The pho-tochromic mechanism was discussed In nonpolar solvents,BNP exists mainly in the enol form and has the absorption maximum in the UV region In polar solvents,however,both the enol and proton transfer tautomer are formed,but the farmer is the main one Fluorescence emissions result from the excited state of proton transfer product.     

STUDIES ON THE SEQUENCE STRUCTURE OF TPA/EG/PHB LIQUID CRYSTALLINE COPOLYESTERS

In this paper, the sequence structure of TPA/EG/PHB liquid crystalline copolyesters made from different synthetic methods has been studied by ~1H-NMR with the help of computer program of processing peaks. The results showed that the ether bonds were not observed in TPA./EG/PHB copolyesters and the synthetic process had a great effect on their sequence structure. Under certain conditions, the high,random TPA/EG/PHB copolyesters which were considered to have higher performances than PET/xPHB could be obtained.     

Organic solvent enhanced α-helical formation of a nonadecapeptide derived from Trichosanthin (TCS 182-200)

A model peptide,TDK,was studied by circular dichroism to elucidate the effect of organic solvent on α-helical formation.The α-helicities enhanced by various alcohol solvents,especially fluorine-substituted alcohols were systematically compared.The relations between α-helical formation of a peptide and external environment were also discussed in detail.These environmental elements mainly include hydrophobicity dielectric constant and acidity of the solvents.     

Enhancement of intramolecular excimer formation and photodimerization of anthrylmethyl α,ω-alkanedioates via hydrophobic interactions

The fluorescence spectra and photodimerization of anthrylmethyl a,w-alkanedioates (A-Mn-A) both in organic and in aqueous organic mixed solvents have been studied.In aqueous organic mixed solvents strong intramolecular excimer emission is detected and the quantum yield for the intramolecular photodimerization is significantly greater than those in organic solvents.These observations suggest that hydrophobic interactions force A-Mn-A molecule to self-coil.The ratio of the head-to-head to head-to-tail products in the intramolecular photodimers of A-Mn-A depends on the length of the linking chain.This work presents a successful example of application of hydrophobic interactions to enhancement of large-ring formation.     

STUDIES ON THE ESR CHARACTERISTICS OF FOUR PIPERIDINE NITROXYL RADICALS——CHARACTERISTICS IN THE SOLID STATE,CONCENTRATION EFFECTS AND SOLVENT EFFECTS IN SOLUTIONS

The ESR characteristics are studied for four piperidine nitroxyl radicals in the solidstate and in solutions. They all exhibited singlet ESR spectra in the solid state, but tripletspectra in solutions at a concentration lower than 1×10~(-2)M. The effects of the free radi-eal coneentration and the polarity trod the viscosity of solvents were observed and comparedon five ESR spectral parameters. Linear correlations could be found between the hyperfinesplitting constant A_N and the solvent polarity parameter, namely, Kosower Z value, Ex-perimental data showed also linear relations of the rotational correlation time τ of free rad-icals with the solvent viscosity, η. We have further found that the relative height of thehigh-field peak varied inversely with η. These ESR characteristics of nitroxyl radicals arediscussed.     

STRUCTURAL STUDIES ON CRYSTALLINE 3,4—POLYISOPRENE

In the paper,the structures of the crystalline 3,4-polyisoprene(3,4-PI)which was first synthesized in our institute,were investigated by using Wide AngleX-ray Diffraction(WAXD);Small Angle X-ray Scattering(SAXS)and Laue photography invarious polymerization conditions and elongate ratios.It was found that reducingreaction velocity was favourable for crystalline capacity.The polymeric structures weredependent mainly on nitrogen electron donor.The degree of crystallinity and long periodwere increased with elongate ratio,but crystalline size was decreased.The polymersused in the work belong to inhomogeneous particulate system.The particulate radii werebetween 35-164A.     

STUDIES ON GRAFT COPOLYMERIZATION OF DL—LACTIDE ON CORN STARCH AND BIODEGRADABILITY OF THE COPOLYMERS

The starch/D,L-lactide graft copolymers were synthesized by reacting D,L-lactide with corn starch in N,N-dimethylacetamide(DMAM)in the presence of triethylamine(NEt3)and anhydrous lithium chloride.The effect of reaction time and the molar ratio of D,L-lactide to glucose structural unit of starch on monomer conversion(C%),graft(G%)and graft efficiency(GE%)were studied,The C%,G%and GE% could approach 37.3% 179.7%and 68.0%,respectively when the molar ratio of D,L-lactide to glucose structuralunit of starch is 10:1 and the graft copolymerization was carried out at 80-85℃ for 4hr under nitrogen atmosphere.The Fourier transforms infra-red (FTIR) spectroscopy.differential scanning calorimetry(DSC)and X_ray diffraction (XRD) spectroscopy were used in order to characterize the graft copolymers.FTIR spectra show that absorption band at 1740cm^-1 confirmed the formation of ester bond,indicating the starch /D,L-lactide graft copolymers were produced,the DSC characteristic results show the melting temperature of the graft copolymer were elevated slightly as the molar ratio of D,L-lactide to glucose structural units of starch increased and the X-ray diffraction spectra show the synthesized graft copolymers were amorphous.The degradability of graft copolymer was tested with the aid of acid,alkali and microbe such as bacillus subtilis and staphylococcus aureus.The results of water rsistance show the graft copolymer produced can be used as a component of impermeable coating for cardboard.