GAS SORPTION AND TRANSPORT IN POLY (PHENYLENE OXIDE)(PPO)AND ARYL-BROMINATED PPO MEMBRANES

The apparent solubility (S), concentration-average diffusivity (D), and permeability (P), for C0_2, CH_4 and N_2 through PPO and aryl-brominated PPO at 35℃for pressure ranging from 1 to 26 atm are reported. It is found that P, D, and S of the membranes to all the three gases vary with the extent of bromination. S increases with the increase of the percent of bromine in each case, but D to CO_2 increases remarkably only at higher degree of brominafion, and therefore, P to CO_2 is increased by more than 100% over a wide range ofpressure in the case. The solubility data are well described by the dual mode sorption model. It is found that the gas molecules sorbed by the Langmuir mode are relatively more immobilized and the contribution of the nonequilibrinm character of the polymer to gas permeation increases obviously for CO_2 and is hardly changed for CH_4 with increasing bromine content. These observations are interpreted in terms of changes in specific free volume (SFV)and the cohesive energy density (CED) of the polymers.     

A STUDY OF ELECTROCHEMICAL REDUCTION OF SAFRANINE T AND THE ELECTROGENERATED FREE RADICAL TRACING BY ESR

A study of the electrochemical reduction behavior of safranine T by means of electrochemical methods coupled with ESR (electron spin resonance) is presented. Through an "in situ" tracing of the 1-electron reduction intermediate—free radical, the structure of the free radical has been deduced. During the electrochemical reduction the free radical went through a post-electrolysis chemical decay including parallel steps of zero and first order reactions. This fact gives further support and experimental ascertainment of the viewpoint that some electrode processes are clearly related to the enzymatic catalyses~([1]). In accordance with the chemical behavior of safranine T free radicals at various concentrations and at different potentials the authors have advanced a scheme of reaction mechanism and evaluated the kinetic parameters of the reation steps by simulating the experimental curves.     

γ辐照 聚全氟乙丙烯(F46)的电子自旋共振研究 I.真空中俘获自由基的定量研究

A method for determining respectively the concentration of free radicials...CF2-CF2.(RI), ...CF2-CF-CF2...(RII)and...CF2- C(CF3)-CF2...(RIII) trapped in γ-irradiated F46 in vacuum at room temperature by analysing the ESR overlapping spectra is proposed. A quantitative relation between the concentration of free readicals and the total dose of γ-irradiation has been studied. The generating rate o free radicals caused by irradiation, i.e. G-value, has been calculated; it is 2.0 for RIII, 1.2 for RI, and 0.59 for RII. the magnitude of G value of free radicals is in the reverse order of their stability. Hence, we assume that the G value of free radicals in F46 mainly depends on the escaping rate of F2 and other fluorine-containing small molecules from surface of polymer into space. Therefore the looser the molecular chain, the larger becomes the G value of free radical. From that, we consider that both unstable free radicals RIII and RI with larger G-value mainly locate in the amorphous region, and the stable free radical RII with lower G-value is in the crystalline region. Recombinations between free radicals RII and RIII, or between RII and RI are forbidden at the temperature lower than 80C. An explanation for the saturation phenomenon of concentration of free radicals is given.     

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.     

Isomers and [2,3]-Sila-wittig Rearrangement of [（Allyloxy）silyl]lithium Silylenoid in the Gas Phase and THF Solvent

Theoretical calculations of the [2,3]-sila-wittig rearrangement of isomers of [（allyloxy）silyl]lithium （C3H5O）HzSiLi have been performed in the gas phase and THF solvent using the G3MP2B3 method. Seven isomers of silylenoid （C3H5O）H2SiLi, 1-7, are found. The [2,3]-silawittig rearrangement paths are followed using two isomers, 2 and 4, to yield the transition states as well as the products. In the transition state, the silicon center functions as a nucleophile and the aUyl as an electrophile. The interaction between the silicon and allylic sites leads to the formation of SiC（3） bond and the break of O-C（1） bond. Finally, the （allylsilyl）oxylithium （C3H5）H2SiOLi is obtained. The rearrangement paths are confirmed by the intrinsic reaction coordinate （IRC） calculations. The rearrangement mechanisms of reactions of 2 and 4 are similar, and the latter reaction is more favored in the gas phase and THF solvent. Also, the solvent effects are analyzed in this work.     

THERMODYNAMIC STUDY OF ADSORPTION OF PHENOLIC COMPOUNDS FROM AQUEOUS SOLUTION BY A WATER-COMPATIBLE HYPERCROSSLINKED POLYMERIC ADSORBENT

Equilibrium data for the adsorption of phenolic compounds, i.e., phenol, p-cresol, p-chlorophenol and p-nitrophenol from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent (NJ-8) within temperature range of 283-323 K were obtained and correlated with a Freundlich-type of isotherm equation, so that equilibrium constants KF and n were obtained. The capacities of equilibrium adsorption for all the four phenolic compounds on the NJ-8 from aqueous solutions are around 2 times as high as those of Amberlite XAD-4, which may be attributed to the unusual micropore structure and the partial polarity on the network. The values of the enthalpy (always negative) are indicative of an exothermic process, which manifests the adsorption of all the four phenolic compounds on the two polymeric adsorbents to be a process of physical adsorption. The negative values of free energy change show that the solute is more concentrated on the adsorbent than in the bulk solution. The absolute free energy values of adsorption for NJ-8 are always higher than those for Amberlite XAD-4, which indicates that phenolic compounds are preferentially adsorbed on NJ-8. The negative values of the adsorption entropy are consistent with the restricted mobilities of adsorbed molecules of phenolic compounds as compared with the molecules in solution. The adsorption entropy values of phenolic compounds for NJ-8 are lower than those for Amberlite XAD-4, which means the micropores of NJ-8 require more orderly arranged adsorbate.     

INQUIRY OF PHOTOSENSITIZATION MECHANISM OF YANGZHOU HEMATOPORPHYRIN DERIVATIVE(YHPD)

By the use of the advanced ESR technique and through comparing with BHPD, the characteristic of YHPD photosensitization is discussed in this paper in the respect of the primary process of photosensitization. The experiment results showed: (ⅰ) not only ~1O_2, but also free radicals(O_2· OH and YHPD)can be formed by the aid of YHPD; and (ⅱ) as to the ability of producing ~1O_2, YHPDBHPD. Two points are indicated: first, the photosensitized damage of YHPD is interrelated to not only ~1O_2, but also free radicals (O_2. OH and YHPD); second, although the photosensitized damage of YHPD is stronger than that of BHPD, yet the photosensitized damage is negatively correlated to the yield of ~1O_2 but positively correlated to those of O_2 and OH. Based on these two points, it is suggested that activated oxygen free radicals(O_2 and. OH) instead of ~1O_2 play the main role as instantaneously activated material in the photosensitized damage of YHPD.     

FLASH PHOTOLYSIS STUDY OF INSULIN

The transient absorption spectra of the initial UV-photolysis products of insulin and des-pentapeptide (B26--30)-insulin (DPI) were determined and compared with that of freetyrosine. The far-UV band of the spectra (<300 nm) has not been reported before. Theirmain initial photoproducts are p-alanylphenoxyl radical (λ_(max)=410,390nm) and an uniden-tified radical (λ_(max)=270 nm). The photolysis yields are closely correlative with the disso-ciation rate of hydroxyl group on phenol ring of tyrosine residues, which in turn dependson the exposed degree of these residues. The quantum yields of the phenoxyl radicals form-ed in photolysis of insulin and DPI were determined and compared with that of free tyro-sine. Based on the comparison, the number of light accessible tyrosine residue in insulin andDPI can be calculated, which provides more quantitative information on the exposed degreeof tyrosine residues in these two proteins.     

gem-Difluorinative 1,2-azide migration of vinyl azides enables an expedient synthesis of β-difluoroalkyl azides

正Organic azides have shown versatile reactivity to induce various organic transformations for the synthesis of nitrogencontaining organic molecules such as 1,3-dipolar cycloadditions with unsaturated bonds, the Curtius rearrangement,and formation of nitrogen-centered radicals, most of which are driven by the entropic loss of molecular dinitrogen [1].Among organic azides, vinyl azides have shown unique re-     

COULOMETRIC TITRATION OF MYLIS

A method for the determination of Mylis by coulometrictitration was developed.The titration was carried out in a mixture of1 mol/L KBr-2 mol/L HCl(1:1)and bromine was generated at the anode,Mylis reacted with one mole of bromine with a n value of 2.The advantages of this method are simple and rapid,it can be used toanalyze small amount of sample.     

CHEMISTRY OF THE PERFLUORO AND POLYFLUORO ORGANIC COMPOUNDS——THE RELATIVE EASE OF FORMATION OF TWO PERFLUOROALKYL R ADICALS

The relative rates of formation of perfluoro iso-propyl radicals (i—C_3F_7,5(i)) and perfluoro n-propyl radicals (n—G_3F_7, 5(n)) are reported. The relative rate constants of β-scission and of bromine abstraction by perfluoro-(α-alkoxyethyl)radicals(RFOCFCF_3:R_F=i—C_3F_7, 3(i); R_F=C_3F_, 3(n)), designated as kr(i) and k,(n), were measured at 7 temperatures in the range of 50—80℃, thence the ratio of the relative rate constants of formation of perfluoro iso-propyl radicals (5(i) and perfluoro n-propyl radicals (5(n)), K_β(i):K_β(n), were obtained. These ratios range from 540—680 at 50℃ to 400—590 at 80℃, much larger than those of the corresponding hydrocarbon radicals. Finally, the differences of activation-free-energy differences between 3(i) and 3 (n), △G~≠(i—n), together with the corresponding enthalpy and entropy terms, △H~≠(i—n), △S~≠(i- n), were calculated. These kinetic parameters indicate that the much higher rate of formation of the perfluoro iso-propyl radicals is caused     

THE STUDY OF PHYCOBILIPROTEINS IN Porphyra yezoensis——THE PHYSICAL AND IMMUNO-CHEMICAL PROPERTIES OF R-PHYCOERYTHRIN~*

There are two kinds of phycoerythrin of different physical properties in Porphyra yezoensis. Their molecular weights are different. They are both composed of a-subunit and β-subunit. Their polymeric forms are (αβ)n. The absorption bands and fluorescence emission bands of the smaller molecules show hypsochromic shifts of several rims relative to that of the polymeric molecules. The isoelectric point of the former is lower than that of the latter. It is worthy of note that the smaller molecules display binding activities with guinea pig antisera. Through using radioimmunoassay, when the depression of the biuding activity of ~(125)I-insulin reaches 50%, the required quantity of the smaller molecules of R-phycoerythrin would be ca. 0.1mg, corresponding to ca. 8μ units of insulin used in a parallel experiment (26 units corresponding to 1 mg of insulin).     

TPE based aggregation induced emission fluorescent sensors for viscosity of liquid and mechanical properties of hydrogel

Two amphiphilic TPE E/Z isomers with aggregation induced emission(AIE) property have been synthesized and characterized. The logarithmic fluorescent intensity of the two molecules was in positive relationship with logarithmic viscosity of liquid. To note, the Z-TPE isomer exhibited more sensitivity in the viscosity of liquid sensing in comparison with the corresponding E-TPE counterpart(around 1.80 folds).Furthermore, two molecules could be used as fluorescent sensors for mechanical properties(v...     

ESR STUDIES OF SPIN-TRAPPED RADICALS IN GAMMA-IRRADIATED POLYCRYSTALLINE PYRIMIDINE NUCLEOSIDES——THYMIDINE AND DEOXYCYTIDINE HYDROCHLORIDE

Room-temperature free radicals produced in gamma-irradiated polyerystalline thymidine and deoxy-cytidine hydrochloride were studied by spin-trapping and ESR methods with NtB (nitroso-t-butane) serv-ing as the spin trap. Three types and two types of base radicals were identified for them respectively,which was completely consistent with the results in single-crystal ESR studies, and thereby standard ESRspectra of their R·spin adducts were obtained. In addition, ribose radicals HOC(5')HC(4')H 相似文献   

ESR STUDY OF PLASMA-TREATED POLYTETRAFLUOROETHYLENE FILMS

The plasma treatment of polytetrafluoroethylene (PTFE) films was carried out in a capacitively coupled reactor with external electrodes. The free radicals generated in the process of treatment were detected by ESR techniques. The ESR spectra tended to indicate that the free radicals of the pLasma-treated PTFE film sample were turned into peroxy radicals on exposure to air. The extrema separation (W) of the ESR spectrum of the peroxy radical increased with the lowering temperature and underwent a sudden change within the temperature range of 170 to 190K. The ESR spectrum observed at 77K was quite different from that observed at room temperature. Finally, the effects of treatment time, input power and system pressure on radical concentration of the treated samples were studied. The attenuation of the peroxy radical at room temperature was also investigated.     

Synthesis, Crystal Structure and Magnetic Properties of Cobalt(II) Complex Involving Imino Nitroxide Radicals

1 INTRODUCTION The synthesis and study of transition metal com-plexes incorporating organic free radicals have arou-sed great interest in the field of molecular magne-tism[1]. Nitronyl nitroxide radicals (NITR), stable or-ganic radicals, have been widely used as molecularunits in the design and construction of magnetic ma-terials[2～5]. These radicals are especially attractivedue to that their donor atoms can assemble an exten-ded coordination geometry with changing magneticcoupling. A…     

Synthesis and Crystal Structure of an Azide Bridged Binuclear Zinc(II) Complex Including the Reduced Derivative of Nitronyl Nitroxide,[Zn(Him2Py)(N3)2]2

1 INTRODUCTION The design and synthesis of transition metal complexes with organic free radicals is one of the major challenges in the field of molecular magnetic materials[1,2]. Nitronyl nitroxide radicals are normal- ly used as spin carriers due to th…     

INDUCTION—POLYMERIZATION OF PREPARING POLYMERS OF REGULAR STRUCTURE

Induction-Polymerization is a novel method for preparing polymers of regular structure. In the presence of a special macromolecular compound, monomer molecules are aggregeted regularly around one or more growth points and polymerized to polymer of regular structure. Regularity of structure of the polyacrylamide prepared by this means has been verified with electron diffractograms, DSC curve and IR spectrum of the polymer.     

ESR STUDIES OF SPIN-TRAPPED RADICALS IN GAMMA-IRRADIATED POLYCRYSTALLINE PYRIMIDINE NUCLEOSIDES——CYTIDINE, DEOXYCYTIDINE, URIDINE AND DEOXYURIDINE

Room-temperature free radicals produced in four gamma-irradiated polycrystalline pyrimidine nucleosides (cytidine, deoxycytidine, uridine and deoxyuridine) were studied by an improved spin trapping and ESR methods with NtB (nitroso-t-butane) serving as the spin trap. The presence of three types of radicals was ascertained in all samples, i.e. —C(5)H—C(6) H_2—and —C(5)H_2—C(6)H— base radicals, and —C(5')H_2— ribose radical evolving from HOC(5')H—C(4')H<. In addition, radicals in which the unpaired electron was located on ribose C(1') and C(4') sites were tentatively distinguished. Stress was laid on the discussion of the mechanism of formation of ribose radicals.