硅氮化合物在改进聚硅氧烷热稳定性中的作用

本文研究了聚硅氧烷在硅氮化合物或二苯基二羟基硅烷、水以及它们同时存在下的热稳定性。硅氮化合物能使聚硅氧烷在350℃的热稳定性大大提高;而二苯基二羟基硅烷和水能促进硅氧烷主链的降介,但同时有硅氮化合物存在,这种促进作用将会消失。所以硅氮化合物能阻止由硅羟基和水引起的降介。同时也是获得耐350℃聚硅氧烷的简便方法。     

PHOTOTOXIC EFFECTS OF NATURALLY OCCURRING POLYACETYLENES AND α-TERTHIENYL ON HUMAN ERYTHROCYTES

Hemolysis, K⁺ leakage and acetylcholinesterase (AChE) inhibition in human erythrocytes were observed with certain naturally occurring polyacetylenes and a thiophene derivative, α-terthienyl. K' leakage, subsequent hemolysis and AChE inactivation by phenylheptatriyne (PHT), a phototoxic compound, were considerably enhanced by UV light (312–400 nm). The same was true with α-terthienyl and with certain other polyacetylenes. Oxygen enhanced AChE inactivation and hemolysis with α-terthienyl in light. With PHT, only AChE inhibition was significantly enhanced in oxygen. Falcarindiol, a non-phototoxic polyacetylene, did not inactivate this enzyme but caused hemolysis in the dark. Inhibition of AChE and hemolysis by these compounds appear to be unrelated phenomena. These results indicate that certain polyacetylenes are capable of damaging biological membranes in light, and others in dark.     

STABILIZATION OF SEMIQUINONE INTERMEDIATES IN THE PHOTOREDUCTION OF PHENANTHRENEQUINONE BY COMPLEX FORMATION

Abstract— The yellow color of 9,10-phenanthrenequinone in alcohol solution is bleached under the influence of exciting radiation in a band of wavelengths extending from the ultraviolet to the visible green. The bleaching is due to a photoreduction of the quinone yielding 9,10-dihydroxyphenanthrene. In the presence of certain divalent metal ions, irradiation of the quinoid material results in a blue-green long lived intermediate which may be further photo-reduced to the colorless 9,10-diol. The blue-green photo-intermediate is a cation-semiquinone complex.     

CHARACTERIZATION OF RADIATION CROSSLINKING DENSITY OF F-40

In this paper, radiation-induced crosslinking mechanism and characterization of the crosslinking density of F-40 and F-4 by X-ray photoelectron spectroscopy (XPS) have been studied. The dose of gelation of F-40 obtained from XPS is 4.1×10~4 Gy. It is found that crosslinking density is the largest in the range of certain dose for F-40 and F-4.     

氟塑料-30的辐射交联

F-30—乙烯和三氟氯乙烯的一种交替共聚物,它在一定的条件下容易辐射交联。交联后的F-30其力学性能有显著提高。 关于F-30的分子量测定,还没有报道。我们利用Flory的弹性理论,在熔点以上测定了F-30的应力-应变曲线,计算得交联G值为1.4,根据Charlesby-Pinner关系式我们得到F-30的凝胶化剂量为1.6兆拉特,并由所得数据估算出F-30的重均分子量为2.1×10~5。     

用非线性非平衡热力学讨论动电效应

本文用非线性非平衡热力学讨论了动电效应.首先,解释了实验值与旧理论不符的问题.其次,给出了旧理论处理动电效应的近似条件.最后,提出了一个新看法,在一定条件下,对某种液体和某个膜,当△P、△φ达一定值时,动电效应也可能出现耗散结构.     

NEW METHODS FOR THE PREPARATION OF SULFOXIMINES

Abstract

Three methods that have been developed in our laboratory for the preparation of sulfoximines are described. Two of these involve the efficient, high yield oxidation of certain sulfilimines (iminosulfuranes) with ruthenium tetroxide (catalytic Ru0₂ + sodium periodate or hypochlorite cooxidant) and m-chloroperoxybenzoic acids, respectively, in biphasic systems. The third method is the direct preparation of sulfoximines from DMSO-t-butyl hypochlorite-aromatic amines. The scope and limitations of the procedures will be described.     

NEUROTOXICITY OF TETRAPHENYLPORPHINESULFONATE TPPS4 and ITS RELATION TO PHOTODYNAMIC THERAPY*

Abstract Tetraphenylporphinesulfonate (TPPS₄) is a synthetic porphyrin that localizes in certain tumors to a higher absolute concentration and with more favorable tumor to other tissue ratios than any other porphyrin yet studied. Its utilization for photodynamic therapy and other applications has been inhibited by reported neurotoxicity. We injected TPPS₄ over a broad dose range of 5-150 mg kg^?1 and observed the effects on peripheral nerve in groups of animals sacrificed 35, 70 and 140 days later. No immediate deaths or phototoxic manifestations were seen. Light and electron microscopy, however, revealed cytoskeletal abnormalities and nerve fiber degeneration affecting both myelinated and unmyelinated fibers in all the time and dose groups. These findings have similarities to those of other experimental toxic neuropathies, and may also be related to the preponderance of autonomic manifestations in patients with porphyric neuropathy. The morphological changes consisted of tangles of fibrillar material in the myelinated fibers and loss of neurotubules in the unmyelinated fibers. Our studies indicate a direct interaction of TPPS₄ with tubulin. This biological mechanism may be involved in the selective distribution of certain parenterally administered porphyrins.     

新型铈组稀土显色剂对乙酰基偶氮胂两类显色反应的研究

本文探讨了两类显色反应的特点和转化关系,并测定了两种络合物的组成。     

THE INFLUENCE OF THE FILM CONTACT ANGLE OF EMULSION DROPLETS ON THE DISPERSIBILITY OF THEIR SEDIMENTS.

In certain W/0 emulsions, the films between the flocculated water droplets and the adjoining menisci show a very large contact angle θ. Because this phenomenon indicates a strong interaction of the droplets, we investigated its influence on the redispersion of sediments formed in such emulsions.

Two models describing the yield stress of such sediments were developed using calculations that relate the yield stress of a string of emulsion droplets to the value of θ. The first model estimates the maximum yield stress that can be accounted for by capillary forces. The second model considers the yield stress of sediments consisting of droplet aggregates joined by single chains of droplets.

These theories were found to describe satisfactorily cone penetration and redispersion experiments performed on two series of W/O emulsions that exhibited a wide range of values of Θ.     

STUDIES ON THE ADSORPTION OF ANTIBIOTICS OF THE TETRACYCLINE GROUP ONTO SULFOCATIONITES

The adsorption processes of antibiotics of the tetracyline group (ATG) by several home-made sulfocationites are studied in this paper.The results show that the adsorption may be of nonequivalent normality under certain pH condition.The adsorption mechanism is discussed with infrared spectrometry.It can be concluded that ATG can interact with sulfocationites by ion exchange mechanism or ion-transfer mechanism or both of them.     

糠酸阳离子交换树脂的半导体性能研究

本文根据糠酸阳离子交换树脂的红外吸收光谱和ESR,讨论了它的化学结构。认为在特定的反应条件下,糠酸呋喃环经过开环,失羧和交联反应,生成了共轭的不饱和C=C键。由ESR发现这种树脂有未成对电子,其g因子为2.0088,树脂中未成对电子是高度共轭的非定域化的,从而确定了它具有半导体性。由树脂的电阻率与温度的关系,发现这种树脂是一种本征半导体;它在不同的外加电压下,可见光和紫外光辐照时,有明显的光电效应。     

REPAIR OF 313-NM INDUCED LESIONS AND PHOTOPROTECTION IN YEAST CANDIDA GUILLIERMONDII

Abstract. The present communication is concerned with the effects of near-UV radiation (300–380 nm) on yeast Candida guilliermondii. It was found that certain doses of 313 nm irradiation caused inactivation of the yeast which was exhibited in a way different from the lethal action of far-UV radiation. It was also found that the cells inactivated by 313 nm are capable of recovering vitality, if incubated for some time in a non-nutrient medium. The yeast inactivated by far-UV radiation also proved to be capable of recovering, though to a lesser degree. Both 334 nm radiation and non-lethal doses at 313 nm induced the photoprotective effect against far-UV damage. The effect was exhibited if there was a certain time interval (2–4 h) between the exposures to photoprotective light and subsequent far-UV radiation. Within this time interval the extent of photoprotection was dependent on temperature.     

强电解质混合溶剂体系的电导法分析

在生产和科研中经常需要同时测定强电解质浓度和混合溶剂的比例。本文在研究强电解质+水+醇三元溶液电导特性的基础上,建立了两参数经验性电导工作方程,将溶液电导率的测量与电导滴定相结合,可以方便准确地定出此类三元溶液的组成。     

多组份含金属盐透明树脂的合成

本文将双烯聚醚砜大分子单体(BPS-MA)引入含金属(Pb、Ba等)盐单体的苯乙烯体系中进行聚合,发现单体配比与树脂透明性密切相关。对于Pb(MA)_2/St/MA/BPS-MA四元体系,欲获得透明树脂,BPS-MA用量大于20％时,摩尔比MA/[Pb(MA)_2]可由原来的5.5降至2.2左右,并且可获得n_D>1.60的透明材料。光学性能测试结果表明,Pb(MA)_2、BPS-MA量增加,n_D增大,阿贝数v_D略降低;MA量增加,n_D下降v_D略增加。适当的配比可望制备出性能优异的多组份含金属盐透明聚合物材料。     

ON THE ACCURACY OF DIFFERENTIAL MEASUREMENTS OF THE MINIMAL ERYTHEMA DOSE: INFLUENCE OF THE DISCRETENESS OF THE SCALE

The minimal erythema dose (MED) is often used as a quantity by which the influence of certain treatments of the skin can be measured. Differential measurements are performed by assessing the difference of the MED on the skin treated in some way and the untreated skin.
As the MED-measuring scale is discrete, the question is sometimes raised whether it is possible to measure differences smaller than one scale unit. In the present paper it is shown that this is indeed possible; in principle the discreteness of the scale does not impose any restriction on the smallest value of the difference that can be measured. The discreteness of the scale introduces an extra random variation into the measurement. This variation is estimated theoretically. It is automatically included in the usual error analysis.
The discreteness variance is small when compared to other variance components, which are computed from an analysis of variance of actual experiments. Reducing the discreteness variance, by reducing the dose decrement of the MED-measuring scale, therefore, does not enhance the overall accuracy considerably. Finally, it is found that the assessments of the MED by the various observers do not differ significantly from each other, and that multiple assessments do increase the accuracy, especially for small effects.     

THEORETICAL CALCULATIONS OF THE TRANSITIONS OF PHOTOCOLORED FORMS OF CHROMENES

Abstract— –Theoretical prediction (MO-SCF-CI) of numbers, energies and intensities of transitions are compared with experimental data for the photocolored products of three types of chromenes. Generally good results are obtained. Several conclusions resulted from variation of parameters: (1) When all carbon-carbon bonds are considered equal in length, there is good agreement between experiment and theory regarding band locations and intensities, however, very poor correlation exists between theory and experiment when calculations are done on a model where the carbon-carbon bonds are alternately single and double, (2) theoretical calculations employing the Mataga approximation for the two-center repulsion integrals gives superior correlation with the experimental spectra in comparison with the Pariser-Parr approximation, and (3) variation of certain parameters (as I.P., E.A., β) did produce changes in the results, especially in the oscillator strengths, but there was no clear best choice, and therefore, conventional parameters were used.     

十二醇聚乙二醇醚分子量分布与其溶液界面性能的关系

利用高纯单一十二醇聚乙二醇醚C₁₂E_n摸似配制Gauss分布型混合物,测定其水溶液的表面张力、增溶量及去污率。实验结果表明,聚乙二醇链长不同分布的醇醚混合物属于理想混合。混合溶液的Γ_∞、Πcmc 随分布宽度增加而增大。形成表面吸附膜及胶束时,短 EO 链分子占先。胶束溶液对乙苯的增溶量随分子中EO数增多而增大。宽分布C₁₂E_n的去污率优于窄分布,但在一定分布范围内,其影响不显著。     

电化学合成聚苯胺粉末电极的电化学行为研究

我们曾用慢速动电位扫描法研究化学合成聚苯胺粉末的电化学行为.本文对恒电位电解合成聚苯胺粉末进行了研究.用这种方法制备的粉末由于合成溶液中不含氧化剂因而纯度高.本文还报导了这种聚苯胺粉末电极的交流阻抗测量结果.交流阻抗法曾用于聚苯胺膜的电导和化学合成聚吡咯的电阻测定. 所用盐酸、氟硼酸、硅氟酸、苯胺均为分析纯;苯胺经常压蒸馏提纯;硫酸为超纯;磷酸为分析纯;高氯酸为优级纯.溶液皆用两次蒸馏水配制.     

STERIC EFFECTS IN REACTIONS OF METAL COMPLEXES. THE LIGAND SUBSTITUTION PROCESSES

Abstract

A model for the calculation of the activation energy for the ligand substitution processes in the metal complexes, occuring in the polar solvents, is suggested. The model takes into account sharp repulsion between the ligands at small distances. The structure of the transition state is analysed depending on the sharp repulsion distance between the ligands, symmetry factor α, and position of the incoming group with respect to the outgoing group (cis or trans). It is shown that for certain values of the parameters cis-substitution may be preferable than trans-substitution.