碳热还原SO2反应选择性的热力学分析及实验探究

针对燃煤烟气SO_2脱除技术面临的可持续发展困境,以固体碳材料为还原剂的碳热SO_2还原制硫磺技术具有重要发展前景,其中抑制非目标副产物的伴生是实现SO_2定向还原的关键。基于吉布斯自由能最小原理对碳热还原SO_2反应进行平衡产物量的计算,并通过固定床-FTIR实验分析反应的气相产物,探究了硫产率、副产物CO、COS和CS_2的生成规律。基于温度对反应热力学平衡的影响,结合副反应,来推断出合理的反应机理。在摩尔比n(C)∶n(SO_2)≤1.0时体系中主要发生反应C+SO_2→S+CO_2,副产物CS_2生成量级仅为10~(-4),理论硫产率可维持在0.9以上。过量的碳会促进COS由主反应物一步生成,高温、碳过量会促进COS向CS_2的转化反应。相关研究结果对实际应用时最佳工况的选取以及单质硫选择性的提高具有重要指导意义。     

Developing an Updated Strategy for Estimating the Free-Energy Parameters in RNA Duplexes

For the last 20 years, it has been common lore that the free energy of RNA duplexes formed from canonical Watson–Crick base pairs (bps) can be largely approximated with dinucleotide bp parameters and a few simple corrective constants that are duplex independent. Additionally, the standard benchmark set of duplexes used to generate the parameters were GC-rich in the shorter duplexes and AU-rich in the longer duplexes, and the length of the majority of the duplexes ranged between 6 and 8 bps. We were curious if other models would generate similar results and whether adding longer duplexes of 17 bps would affect the conclusions. We developed a gradient-descent fitting program for obtaining free-energy parameters—the changes in Gibbs free energy (ΔG), enthalpy (ΔH), and entropy (ΔS), and the melting temperature (Tm)—directly from the experimental melting curves. Using gradient descent and a genetic algorithm, the duplex melting results were combined with the standard benchmark data to obtain bp parameters. Both the standard (Turner) model and a new model that includes length-dependent terms were tested. Both models could fit the standard benchmark data; however, the new model could handle longer sequences better. We developed an updated strategy for fitting the duplex melting data.     

Al-Cu-Fe系初生准晶相凝固过程的热力学分析

采用XRD,SEM和TEM等方法,研究了铸态 Al58.8Cu36.6Fe3.5Si1.1合金(973K保温2.5h后水淬)的显微组织及相组成.观察到铸态样品中存在4种不同的相,即初生准晶I相、Φ相、θ-Al2Cu相和η-AlCu相.对准晶I相及其晶体近似相R相,提出相应的自由能计算模型及算法,从理论上说明准晶(Al61.89Cu25.61Fe11.10)I相是高温稳定相,当温度低于938K时,将形成其晶体近似相R相.     

Brick by brick computation of the gibbs free energy of reaction in solution using quantum chemistry and COSMO‐RS

The computational modeling of reactions is simple in theory but can be quite tricky in practice. This article aims at the purpose of providing an assistance to a proper way of describing reactions theoretically and provides rough guidelines to the computational methods involved. Reactions in liquid phase chemical equilibrium can be described theoretically in terms of the Gibbs free energy of reaction. This property can be divided into a sum of three disjunct terms, namely the gas phase reaction energy, the finite temperature contribution to the Gibbs free energy, and the Gibbs free energy of solvation. The three contributions to the Gibbs free energy of reaction can be computed separately, using different theoretico‐chemical calculation methods. While some of these terms can be obtained reliably by computationally cheap methods, for others a high level of theory is required to obtain predictions of quantitative quality. To propose workflows which can strike the balance between accuracy and computational cost, a number of benchmarks assessing the precision of different levels of theory is given. As an illustrative example, the low‐temperature hydrogenation reaction of acetaldehyde to ethanol in solvent toluene is shown. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3944–3954, 2017     

Development of free-energy-based models for chaperonin containing TCP-1 mediated folding of actin

A free-energy-based approach is used to describe the mechanism through which chaperonin-containing TCP-1 (CCT) folds the filament-forming cytoskeletal protein actin, which is one of its primary substrates. The experimental observations on the actin folding and unfolding pathways are collated and then re-examined from this perspective, allowing us to determine the position of the CCT intervention on the actin free-energy folding landscape. The essential role for CCT in actin folding is to provide a free-energy contribution from its ATP cycle, which drives actin to fold from a stable, trapped intermediate I₃, to a less stable but now productive folding intermediate I₂. We develop two hypothetical mechanisms for actin folding founded upon concepts established for the bacterial type I chaperonin GroEL and extend them to the much more complex CCT system of eukaryotes. A new model is presented in which CCT facilitates free-energy transfer through direct coupling of the nucleotide hydrolysis cycle to the phases of actin substrate maturation.     

直接碳化原位合成WC-Co复合粉的反应过程

以偏钨酸铵(AMT)、可溶性钴盐、有机碳源为原材料,采用喷雾转化、直接碳化原位合成法,成功制备出WC-Co复合粉末。利用XRD、SEM等分析方法对粉末样品物相组成、微观形貌、粒度分布进行了研究。研究表明,由于Co对W碳化的促进作用,在900℃时,W就被完全碳化为WC,远低于W正常被碳化完全的温度;W的碳化过程主要依靠钨粉颗粒表面与含碳气氛热解后沉积在钨颗粒表面上的碳元素的反应以及碳向钨粉颗粒内部的扩散来实现,属固-固反应;由于生成W2C的自由能比WC的更低,W很快先被碳化为W2C,然后再进一步碳化为WC;W/Co/C碳化反应体系沿WCo3,Co6W6C,W2C-Co,WC-Co步骤进行反应;随着温度的升高,反应体系可不经过前两步,而直接生成W2C-Co,再进一步碳化为WC-Co复合粉。     

催泪弹药剂焚烧销毁参数的确定

为了能安全有效地销毁废旧催泪弹,确定最佳的焚烧销毁参数,根据最小自由能法计算了催泪弹药剂在不同温度,空气过量系数分别为1.2、1.4、1.6、1.8、2.0下发生燃烧反应的平衡产物,验证了焚烧炉焚烧法销毁废旧催泪弹的可行性。并对烟气中相关生成物的浓度变化规律进行了研究和讨论,分析确定了催泪弹药剂安全焚烧销毁所需的最佳焚烧温度为1473 K及空气过量系数为1.6。     

Analysis and Interpretation of the Impact of Missense Variants in Cancer

Large scale genome sequencing allowed the identification of a massive number of genetic variations, whose impact on human health is still unknown. In this review we analyze, by an in silico-based strategy, the impact of missense variants on cancer-related genes, whose effect on protein stability and function was experimentally determined. We collected a set of 164 variants from 11 proteins to analyze the impact of missense mutations at structural and functional levels, and to assess the performance of state-of-the-art methods (FoldX and Meta-SNP) for predicting protein stability change and pathogenicity. The result of our analysis shows that a combination of experimental data on protein stability and in silico pathogenicity predictions allowed the identification of a subset of variants with a high probability of having a deleterious phenotypic effect, as confirmed by the significant enrichment of the subset in variants annotated in the COSMIC database as putative cancer-driving variants. Our analysis suggests that the integration of experimental and computational approaches may contribute to evaluate the risk for complex disorders and develop more effective treatment strategies.     

基于受限波兹曼机的推荐算法研究

本文针对推荐系统中传统推荐算法在处理较稀疏数据效果表现不佳的问题,将一种最新的机器学习方法带入到推荐算法中,利用多层波兹曼机组成的深度结构模型与传统最近邻推荐方法相结合,形成一种新的推荐模型算法。本文还利用有限步吉布斯采样的最小化散度差（Constrastive Divergence）方法解决了该模型的无监督训练问题,并且通过预训练和反馈微调使得模型的训练得以实现;最后利用深度结构抽取的抽象特征结合最近邻方法进行预测推荐。另外,本文利用传统基于相似度最近邻方法,矩阵分解方法和新模型算法在相关数据集上进行多组实验,实验结果表明该算法不仅在稀疏的数据上也表现出更好的效果,并且拥有着更快的收敛速度。