煤吸附水的微观机理

根据煤大分子和表面的结构特点，应用分子热力学和表面物理化学理论分析了煤表面自由能的特征和煤吸附水的微观机理．结果表明，煤对水分子的吸收从微观上看是由于水分子与煤表面相互吸引作用的结果，这些作用力包括分子间力和氢键．煤对水分子的吸附是多层吸附，吸附第一层水主要是由于煤对水分子的氢键作用占主要地位，对其余水分子层的吸附主要是由于分子间力引起的长程力作用的结果．对水分子与煤表面的分子间力进行了估算，结果是分子间力中色散作用力占主要地位．讨论了添加活性剂润湿煤体的作用，认为这是从微观上改变了水分子与煤表面的吸引作用力的结果．研究煤吸附水的微观机理为现场优化提高煤层润湿性措施奠定了理论基础．     

含偶氮基团的弯曲型分子的光谱特性研究

偶氮连接基团(—NN—)有着特殊的热化学和光化学行为,在适当波长光的照射下,能发生可逆的顺反异构反应,从而发生吸收波长的变化。在分子设计、光定位、光致变色和热致变色等方面,偶氮连接基团的非线性光化学性质都有着潜在的应用价值。文章以含有偶氮基作为侧翼的弯曲型分子作为研究对象,比较了弯曲型和直线型分子的吸收光谱;并用计算机模拟计算了弯曲型分子的角度,发现分子弯曲角和紫外可见吸收光谱存在着密切的关系。     

Idiosyncratic Drug-Induced Liver Injury: Mechanistic and Clinical Challenges

Idiosyncratic drug-induced liver injury (IDILI) remains a significant problem for patients and drug development. The idiosyncratic nature of IDILI makes mechanistic studies difficult, and little is known of its pathogenesis for certain. Circumstantial evidence suggests that most, but not all, IDILI is caused by reactive metabolites of drugs that are bioactivated by cytochromes P450 and other enzymes in the liver. Additionally, there is overwhelming evidence that most IDILI is mediated by the adaptive immune system; one example being the association of IDILI caused by specific drugs with specific human leukocyte antigen (HLA) haplotypes, and this may in part explain the idiosyncratic nature of these reactions. The T cell receptor repertoire likely also contributes to the idiosyncratic nature. Although most of the liver injury is likely mediated by the adaptive immune system, specifically cytotoxic CD8+ T cells, adaptive immune activation first requires an innate immune response to activate antigen presenting cells and produce cytokines required for T cell proliferation. This innate response is likely caused by either a reactive metabolite or some form of cell stress that is clinically silent but not idiosyncratic. If this is true it would make it possible to study the early steps in the immune response that in some patients can lead to IDILI. Other hypotheses have been proposed, such as mitochondrial injury, inhibition of the bile salt export pump, unfolded protein response, and oxidative stress although, in most cases, it is likely that they are also involved in the initiation of an immune response rather than representing a completely separate mechanism. Using the clinical manifestations of liver injury from a number of examples of IDILI-associated drugs, this review aims to summarize and illustrate these mechanistic hypotheses.     

Introducing immobilized metal phthalocyanines as spin-injection and detection layers in organic spin-valves: Spin-tunneling and spin-transport regimes

In (organic) spin-valve devices, two ferromagnetic electrodes having different coercive fields are used to achieve an anti-parallel configuration necessary to enforce spin-flip of electrons within the semiconductor spacer layer. Here we report a use of immobilized magnetic organic molecules as spin-injection and spin-detection layers to form pre-fabricated spin-valve devices. While immobilized manganese- and nickel-phthalocyanines were used as spin-injection and spin-detection layers both, copper phthalocyanine acted as the spacer layer in the all-organic spin-valve devices.In the current-voltage characteristics of parallel and anti-parallel configurations, the electrical resistance was always higher for the latter one implying positive magnetoresistance in the material. By lowering thickness of the spacer layer down to a monolayer region, a tunneling regime could be achieved; spin-flip process in organic spin-valves has been found to be facile in the tunneling regime as compared to that during the spin-transport process through a thicker spacer layer.     

Core Cross-Linked Amphiphilic Star-Block Copolymers with (Meth)acrylic Acid Shells Prepared by Atom Transfer Radical Polymerization

Core cross-linked amphiphilic star-block copolymers were prepared by hydrolysis of the outer shell of star-block copolymers prepared using copper mediated atom transfer radical polymerization (ATRP). In an arm-first approach, linear poly(tert-butyl methacrylate) macroinitiators (PtBMA-Cl) were extended with styrene to yield PtBMA-b-PS-Cl and then cross-linked with divinylbenzene (DVB) in order to yield (PtBMA-b-PS)_arms-PDVB_core star-block copolymers. Then, PMAA-b-PS block and (PMAA-PS)_arms-PDVB_core star-block copolymers were obtained by hydrolysis of the PtBMA blocks in both linear and cross-linked copolymers, as confirmed by ¹H NMR analyses. The amphiphilic character of these copolymers was confirmed by solubilisation in water. Several factors affecting the polymer aggregation and solubility such as the length, the composition of the arms and the catalyst used were studied. An acrylate analogue, that is, (PAA-b-PS)_arms-PDVB_core, was also prepared for comparison purposes. Atomic force microscopy (AFM) and differential scanning calorimetry (DSC) were used to elucidate the morphology and the thermal behaviour of the star-block copolymers.     

两亲聚合物对湿法磷酸的助滤性能及机理研究

以实验室自制单体A、丙烯酰胺(AM)、二甲基二烯丙基氯化铵(DMDAAC)为原料,过硫酸盐氧化还原体系为引发剂,采用水溶液共聚法合成一种用于湿法磷酸助滤的两亲聚合物PADA-10。对所得聚合物的助滤性能进行研究,结果表明:磷酸料浆体系中加入PADA-10后,过滤速度提高了约4.3倍,滤饼水分降低了约10.8%。对PADA-10助滤机理的初步探究结果表明:PADA-10能在一定pH值范围内中和磷石膏表面电荷,使磷石膏微晶絮凝成团,添加PADA-10后滤饼的孔隙率增加;同时,PADA-10能增强磷石膏颗粒的疏水性,使磷酸滤液表面张力降低了5.2 mN/m,磷石膏表面接触角增大了3.4°。