Optimized Biocatalytic Synthesis of 2-Selenopyrimidine Nucleosides by Transglycosylation**

Selenium-modified nucleosides are powerful tools to study the structure and function of nucleic acids and their protein interactions. The widespread application of 2-selenopyrimidine nucleosides is currently limited by low yields in established synthetic routes. Herein, we describe the optimization of the synthesis of 2-Se-uridine and 2-Se-thymidine derivatives by thermostable nucleoside phosphorylases in transglycosylation reactions using natural uridine or thymidine as sugar donors. Reactions were performed at 60 or 80 °C and at pH 9 under hypoxic conditions to improve the solubility and stability of the 2-Se-nucleobases in aqueous media. To optimize the conversion, the reaction equilibria in analytical transglycosylation reactions were studied. The equilibrium constants of phosphorolysis of the 2-Se-pyrimidines were between 5 and 10, and therefore differ by an order of magnitude from the equilibrium constants of any other known case. Hence, the thermodynamic properties of the target nucleosides are inherently unfavorable, and this complicates their synthesis significantly. A tenfold excess of sugar donor was needed to achieve 40−48 % conversion to the target nucleoside. Scale-up of the optimized conditions provided four Se-containing nucleosides in 6–40 % isolated yield, which compares favorably to established chemical routes.     

交错巷道巷间围岩承载结构稳定性分析

针对普遍存在的矿井交错巷道围岩体稳定性及支护问题,运用极限平衡分析和弹塑性力学建立交错巷道巷间围岩稳定性分析判别方程,探讨了交错巷道巷间围岩稳定性主要影响因素,并进行了工业性试验。结果表明:交错巷道巷间围岩体受围岩水平应力集中叠加影响,围岩破坏自巷间围岩体上下表面向中部延伸,加之巷间围岩体尺寸有限,一旦破坏贯通将致使巷间围岩承载存在失稳隐患;交错巷道巷间距越小,越近乎平行布置都会加剧巷间围岩破坏且诱发巷间围岩破坏贯通,合理设计断面尺寸及下方巷道合理支护强度可有效控制并维持围岩稳定;现场采用交错巷道联合支护方案后,交错位置上巷道断面完整无较明显变形且下巷道围岩最大变形量小于100 mm,支护效果显著。     

油田含CO2伴生气变压吸附材料实验研究

变压吸附工艺是国内小规模CO_2驱产出气处置的常用手段,而吸附剂是吸附分离的基础。选用6种沸石类吸附剂,测试了CO_2/CH4单组分吸附平衡等温线,分析了温度对吸附量的影响。优选了两种材料进行了CO_2-CH4混合气体竞争吸附实验,重点分析了温度、压力、气体组分、CO_2含量等因素对吸附剂吸附分离效果的影响,评价了油、水含量对吸附剂的损伤。实验结果表明:吸附剂的分离系数与混合气体中CO_2含量无明显相关性,但吸附体系压力的变化对混合气体分离效果影响较大。在初始气体CO_2摩尔分数50%、温度20℃、压力2.5MPa条件下,优选的吸附剂13X对混合气体的分离系数为25。油水的存在会对吸附剂的分离性能产生较大影响,在温度20℃、压力2.5 MPa、13X吸附剂含水摩尔分数10%及含油摩尔分数10%条件下,吸附总量分别下降32%和78%,分离系数分别下降48%和78%。     

悬浮床加氢脱硫尾气水蒸气转化制氢热力学

以悬浮床加氢脱硫尾气为水蒸气转化制氢原料，采用改进的原子序数矩阵法构建了包含6个独立反应的化学反应体系。分别考察各个独立反应在不同反应温度下，标准摩尔反应焓、吉布斯自由能变及平衡常数的变化规律；借助HYSYS流程模拟软件中的GIBBS反应器，研究反应器出口温度、反应压力及水碳物质的量之比对产物平衡组成的影响。热力学研究结果表明：烷烃碳数越高，水蒸气转化反应的平衡常数、吉布斯自由能变和标准摩尔焓对温度的敏感性越高，达到相同转化效果所需的反应温度越低。HYSYS模拟确定该体系下最适宜的反应条件为反应器出口温度700℃、反应压力100kPa、水碳物质的量之比4。     

水合物形成促进剂研究进展

添加促进剂是高效制备水合物的研究热点，促进剂及其添加量对水合物生成效果至关重要。本文主要从热力学促进剂和动力学促进剂两大类型进行分析：总结了可溶水相热力学促进剂和不可溶水相热力学促进剂的浓度对水合物形成相平衡的影响；从表面活性剂、纳米粒子和相变材料等添加剂，阐述了动力学促进剂添加量对水合物生成诱导时间、储气量和生成速率等方面的影响。促进剂都存在最佳浓度的添加量，并且不同类型促进剂复配更有利于水合物生成。目前添加促进剂后水合物形成机理的研究大多从宏观现象推测，部分学者通过拉曼光谱、X射线衍射和显微观察探索分析促进剂对水合物形成的微观影响，这方面研究有待于进一步开展。添加量作为水合物形成促进剂的重要指标，研究者应得到水合物形成促进剂的最佳浓度与所研究对象的关联性。     

负径向电场对带电粒子俘获率影响的数值模拟

本文采用数值方法求解Grad-Shafranov方程反演EAST典型长脉冲放电实验(炮号33068)的平衡位形和磁场分布，进而结合粒子在托卡马克电磁场中的运动方程，模拟氘离子在负径向电场存在时的运动轨迹，并统计不同负径向电场下的氘离子俘获率。结果表明：随负径向电场的增大，氘离子轨迹由扩张通行轨迹向外翻香蕉轨迹再向内翻香蕉轨迹，最后向压缩通行轨迹演变；氘离子俘获率随负径向电场的增大而减小，氘离子初始速度越小，其变化越大。     

不锈钢酸洗污泥对烧结黏结相与平衡相的影响

 不锈钢酸洗污泥安全填埋占用土地且难以消除对环境的危害，将酸洗污泥作为烧结配料使用有望回收其中铁、铬、镍等金属，并充分利用其中的熔剂组分，实现酸洗污泥在冶金企业的闭路资源化利用。铁矿粉配加酸洗污泥烧结黏结相强度试验表明，随着酸洗污泥配加比例的增加，黏结相强度先增加后减小，且随着碱度的增加整体减小，当酸洗污泥配加比例为10%时，试样中赤铁矿、磁铁矿质量分数最大，枪晶石质量分数较小，在碱度为1.5时于1 280 ℃焙烧4 min，试样的黏结相强度最大可达15.12 kN。平衡相烧结试验表明，配加酸洗污泥能改善烧结矿质量，铁矿粉配加10%的酸洗污泥，碱度为1.5，1 300 ℃烧结240 min后，烧结矿的矿相组成和微观结构最好，综合性能最佳。     

Relationships of tensile strength with crosslink density for the high-carbon black-filled EPDM compounds with various softeners

Equilibrium swelling and rheological tests were adopted to systematically investigate the effects of softener type and dosage on the crosslink densities. The results turned out that the chemical crosslink density could be distinguished from the physical crosslink density by comparing the results of equilibrium swelling and rheological tests. The liquid butadiene (LB) as a softener leads to the greatest reduction in crosslink density, followed by polyethylene wax (PW) and paraffinic oil (PO). The tensile strength decreases with increasing PO content while shows peak values with increase of LB and PW contents. The dependencies of chemical crosslink density on the aging time under 150°C are quite different for the three softeners, which can be expected from the double crosslinking networks consisting of small softener and large main crosslinking networks. Further investigation has been performed to correlate the tensile strength with chemical crosslink density of ethylene propylene diene monomer elastomer vulcanizates. Three different linear relationships can be obtained for the softeners independent of the aging time. It can now be expected from this study that the role of some new softeners in rubber compounds is not only confined to plasticization but also forms crosslinking networks in the peroxide-cured rubbers.