几种血卟啉3,8—烷氧（硫）基衍生物产生单重态氧能力的研究

在“血卟啉衍生物”(HPD)肿瘤光动力疗法取得令人瞩目成就的同时,化学家们证明了临床使用的HPD制剂并非原意义上的血卟啉衍生物,而是一种复杂的卟啉混合物,其中血卟啉(HP),羟乙基-乙烯基-次卟啉(HVD),原卟啉(PP)约占总量的80％,Dougherty等分离得到其余20％未知结构羧基卟啉,认为此为HPD的有效成分,经进一步分析测定其主要成分是二血卟啉醚(DHE)。但最近的工作又表明,全合成得到的DHE与HPD有效成分的化学组成及生物活性亦不相同。显然这类药物组分复杂、结构的不确定限制了肿瘤光动力疗法的进一步发展。近年来,人们正试图从已知结构的化合物中探索新的光敏药物,作者在合成出一系列结构确定的单一组分血卟啉     

Synthesis,characterization, and thermal properties of phosphorus‐containing,wholly aromatic thermotropic copolyesters

A series of phosphorus‐containing, wholly aromatic thermotropic copolyesters from acetylated 2‐(6‐oxide‐6H‐dibenz〈c,e〉〈1,2〉oxa phosphorin‐6‐yl)‐1,4‐dihydroxy phenylene, p‐acetoxybenzoic acid, terephthalic acid, and isophthalic acid were prepared by melting polycondensation. The structure and basic properties of the polymers, such as the glass‐transition temperature (T_g), melting temperature (T_m), thermal stability, crystallinity, and liquid crystallinity, were investigated with Fourier transform infrared, elemental analysis, differential scanning calorimetry (DSC), thermogravimetric analysis, wide‐angle X‐ray diffraction, and hot‐stage polarizing optical microscopy. The copolyesters had relatively high T_g values ranging from 183 to 192°C. The T_m values obtained from DSC curves for samples P‐20 and P‐25 were 290 and 287°C, respectively (where the number in the sample name indicates the molar fraction of the phosphorus‐containing monomer in the reactants). The initial flow temperatures of other samples observed with hot‐stage polarizing microscopy were 271–290°C. The 5% degradation temperatures in nitrogen ranged from 431 to 462°C, and the char yields at 640°C were 41–52%. All the copolyesters, except P‐40, were thermotropic and nematic. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1278–1284, 2002     

Flakes of natural carbyne in a diamond mine

Flakes of natural carbyne were found in Liao-Ning diamond mine, China, and examined by HRTEM, XRD and EDX. Lattice fringes and clear SAD patterns were obtained. The interlayer spacings obtained with SAD were in good agreement with those determined on the powders found in Ries crater meteorite by X-ray diffraction. However, they are different in color and shape, the one found in China being black and flaky, but the one in Ries crater meteorite being silver-white and particulate. It was assumed that carbyne might be stabilized by the intercalation of either Si or Fe in nature.     

Electron beam irradiation of ethylene‐propylene terpolymer: Evaluation of trimethylol propane trimethacrylate as a crosslink promoter

The effect of electron beam irradiation on ethylene‐propylene terpolymer (EPDM) was investigated. A 50‐part oil‐extended EPDM with high termonomer (ENB) content (iodine number of base polymer) 19, was selected for this study. An increase in irradiation dose from 0 to 200 kGy resulted in increased crosslinking, measured by an increase in gel contents and better swelling resistance. The effect of the multifunctional monomer trimethylol propane trimethacrylate (TMPTMA) as a crosslink promoter was studied using IR spectroscopy. The IR studies revealed enhanced peak absorbances at 1725, 1257, and 1023 cm^?1 as a result of the increased concentration of C = O and C‐O‐C groups and reduced absorbance at 1630 cm^?1 due decreased concentration of C = C groups with TMPTMA level in the irradiated samples. The presence of TMPTMA increased the level of crosslinking at a given irradiation dose, which was manifested by improvement in tensile properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 968–975, 2005     

分子内敏化鎓盐的合成及光敏性研究

二芳基碘鎓盐和三芳基硫鎓盐是阳离子聚合的光引发剂和光敏产酸物,但他们在300nm以上的光吸收很低,限制了对紫外光的利用效率。为解决此问题,本文合成了一些新的碘鎓盐和硫鎓盐,并用凝胶时间方法考察了它们的光引发效率。实验结果表明,2-苯硫基甲基,2′,4′-二甲基二苯碘鎓盐和9-蒽丙基,二苯基硫鎓盐具有特别高的光引发效率,这归之于光照时这些鎓盐发生了分子内电荷转移反应,即发生了分子内敏化。9-蒽丙基二苯硫鎓盐分子中的蒽基(An)是电子给体也是敏化基团,光照时可发生如下反应:     

Experimental research and prediction of the effect of chemical and biogenic sulfuric acid on different types of commercially produced concrete sewer pipes

New equipment and procedures for chemical and microbiological tests, simulating biogenic sulfuric acid corrosion in sewerage systems, are presented. Subsequent steps of immersion and drying, combined with mechanical abrasion, were applied to simulate events occurring in sewer systems. Both chemical and microbiological tests showed that the aggregate type had the largest effect on degradation. Concrete with limestone aggregates showed a smaller degradation depth than did the concrete with inert aggregates. The limestone aggregates locally created a buffering environment, protecting the cement paste. This was confirmed by microscopic analysis of the eroded surfaces. The production method of concrete pipes influenced durability through its effect on W/C ratio and water absorption values. In the microbiological tests, HSR Portland cement concrete performed slightly better than did the slag cement concrete. A possible explanation can be a more rapid colonisation by microorganisms of the surface of slag cement samples. A new method for degradation prediction was suggested based on the parameters alkalinity and water absorption (as a measure for concrete porosity).     

Internal deterioration of concrete by the oxidation of pyrrhotitic aggregates

This paper presents research results on the causes of a severe concrete deterioration, which occurred in many building foundations approximately 2 years after construction. Concrete samples were investigated with X-ray diffraction (XRD) analysis, a scanning electron microscope (SEM) and a petrographic examination performed with a stereomicroscope. It was found that the early cracking of concrete stemmed from the oxidation of the pyrrhotite found in the anorthosite aggregates used to produce the concrete. The oxidation process led to the precipitation of iron hydroxides having a higher volume than the original pyrrhotite does. The presence of micas (biotite) close to the pyrrhotite seemed to promote and accelerate the oxidation process.     

Morphologies and microstructures of tree-like carbon produced at different reaction conditions in a CVD process

Centimeter-size multi-branched tree-like carbon structures have been generated by the catalytic chemical vapor deposition of toluene using ferrocene as the catalyst precursor and investigated by means of SEM, TEM, and EDX. It is found that a temperature of 1000-1200 °C and a carrier gas flow rate of 1000-2500 ml/min are necessary for the generation of the carbon trees. Their morphologies and microstructures change greatly with the changing reaction conditions. The fractal dimensions of the trees are calculated to quantitatively investigate the influence of different reaction temperatures on the morphologies.