基于分子水平模型生成催化重整Delta-Base数据

采用信息熵最大化理论和重整原料部分物性相结合的方法,研究了在生成Delta-Base数据过程中重整原料分子层面上的变化。模型计算过程中以信息熵最大化为目标,以重整原料的相对分子质量、H/C比、PIONA组成、密度以及芳烃潜含量作为约束条件,并以遗传算法作为优化方法进行模型求解,从分子层面计算两种不同芳烃潜含量重整原料的Delta-Base数据。结果显示,随着原料芳烃潜含量的增加,产品中芳烃含量也增加,可以利用分子水平机理模型生成Delta-Base数据。

原料性质大幅变化情况下催化重整Delta-Base数据的生成方法

针对催化重整原料性质变化幅度较大的情况,提出采用变步长计算结合分子水平机理模型生成装置Delta-Base数据的方法。该方法通过计算原料性质扰动时产品质量分数变化量绝对值随原料性质变化量绝对值的变化率;并将该变化率的值域分成若干等份,根据每次计算得到变化率值域的范围不同,选择下一步计算时的变量扰动步长;继而在计算过程中取每次变量扰动的中点值产品质量分数进行验证,从而在提高计算效率的同时保证了计算结果的准确性。结果表明:利用该方法计算得到的各产品质量分数相对误差较小,基本不超过2.5%;对计算数据拟合可得到不同产品质量分数数据拟合方程,通过拟合方程可生成芳烃潜含量变化三阶段Delta-Base数据;比较原料芳烃潜含量(w)为42%时的产品预测结果,发现Delta-Base数据预测值和拟合方程计算值的平均偏差均为0.16%,说明该方法具有很好的准确性,利用分子水平机理模型生成的Delta-Base数据更能反映真实的分子反应历程。

Characterization of Amino Acid Based Molecular Micelles with Molecular Modeling

The enantiomers of chiral drugs often have different potencies, toxicities, and biochemical properties. Therefore, the FDA and other worldwide regulatory agencies require manufactures to test and prove the enantiomeric purity of chiral drugs. Amino acid based molecular micelles (AABMM) have been used in chiral CE separations since the 1990’s because of their low environmental impact and because their properties can easily be tuned by changing the amino acids in the chiral surfactant head groups. Using molecular dynamics simulations to investigate the structures and properties of AABMM is part of an ongoing study focusing on investigating and elucidating the factors responsible for chiral recognition with AABMM. The results will be useful for the proper design and selection of more efficient chiral selectors. The micelles investigated contained approximately twenty covalently linked surfactant monomers. Each monomer was in turn composed of an undecyl hydrocarbon chain bound to a dipeptide headgroup containing of all combinations of L-Alanine, L-Valine, and L-Leucine. These materials are of interest because they are effective chiral selectors in capillary electrophoresis separations. Molecular dynamics simulation analyses were used to investigate how the sizes and positions of the headgroup amino acid R-groups affected the solvent accessible surface areas of each AABMM chiral center. In addition, headgroup dihedral angle analyses were used to investigate how amino acid R-group size and position affected the overall headgroup conformations. Finally, distance measurements were used to study the structural and conformational flexibilities of each AABMM headgroup. All analyses were performed in the context of a broader study focused on developing structure-based predictive tools to identify the factors responsible for a) self-assembly, b) function, c) higher ordered structure and d) molecular recognition of these amino acid based molecular micelles.

High Lattice Match Growth of InAsSb Based Materials by Molecular Beam Epitaxy

High lattice match growth of InAsSb based materials on GaSb substrates is demonstrated. The present results indicate that a stable substrate temperature and the optimal flux ratios are of critical importance in achieving a homogeneous InAsSb based material composition throughout the growth period. The quality of these epilayers is assessed using a high-resolution x-ray diffraction and atomic force microscope. The mismatch between the GaSb substrate and InAsSb alloy achieves almost zero, and the rms surface roughness of InAsSb alloy achieves around 1.7A over an area of 28μm × 28μm. At the same time, the mismatches between GaSb and InAs/InAs0.73Sb0.27 superlattices （SLs） achieve approximately 100 arcsec （75 periods） and zero （300 periods）, with the surface rms roughnesses of InAs/InAs0.73Sb0.27 SLs around 1.8 A （75 periods） and 2.1A （300 periods） over an area of 20 μm×20 μm, respectively. After fabrication and characterization of the devices, the dynamic resistance of the n-barrier-n InAsSb photodetector near zero bias is of the order of 10^6Ω·cm^2. At 77K, the positive-intrinsic-negative photodetectors are demonstrated in InAsSb and InAs/InAsSb SL （75 periods） materials, exhibiting fifty-percent cutoff wavelengths of 3.8μm and 5.1μm, respectively.

Comparison of blue–green response between transmission-mode GaAsP-and GaAs-based photocathodes grown by molecular beam epitaxy

In order to develop the photodetector for effective blue-green response, the 18-mm-diameter vacuum image tube combined with the transmission-mode Alo.7Gao.3Aso.9Po.1/GaAso.9Po.1 photocathode grown by molecular beam epitaxy is tentatively fabricated. A comparison of photoelectric property, spectral characteristic and performance parameter be- tween the transmission-mode GaAsP-based and blue-extended GaAs-based photocathodes shows that the GaAsP-based photocathode possesses better absorption and higher quantum efficiency in the blue-green waveband, combined with a larger surface electron escape probability. Especially, the quantum efficiency at 532 nm for the GaAsP-based photocathode achieves as high as 59%, nearly twice that for the blue-extended GaAs-based one, which would be more conducive to the underwater range-gated imaging based on laser illumination. Moreover, the simulation results show that the favorable blue-green response can be achieved by optimizing the emission-layer thickness in a range of 0.4 μm-0.6 μm.

Syntheses of Ferrocenyl Schiff Bases Using Molecular Sieves and AlCl_3 as Catalysts

In order to study the donor ability of ferrocenylimines as directing ortho metalation group（DMG） to lithium alkylide to prepare planar chiral ferrocene, a series of ferrocenyl schiff bases were synthesized by new methods using molecular sieves（0.4nm） and AlCl3 as catalysts. The reaction periods were reduced using these two catalysts in contrast with Al2O3, which was a traditional method used in the literature. In addition, as an important feature of these schiff bases, we found that they were unstable as oils in air or when filtrated through silica gel, but were stable as solids. The structures of the new compounds were confirmed by IR, ^1H NMR and HRMS.

Effect of H impurity on misfit dislocation in Ni-based single-crystal superalloy:molecular dynamic simulations

The effect of H impurity on the misfit dislocation in Ni-based single-crystal superalloy is investigated using the molecular dynamic simulation. It includes the site preferences of H impurity in single crystals Ni and Ni3Al, the interaction between H impurity and the misfit dislocation and the effect of H impurity on the moving misfit dislocation. The calculated energies and simulation results show that the misfit dislocation attracts H impurity which is located at the γ/γ′ interface and Ni3Al and H impurity on the glide plane can obstruct the glide of misfit dislocation, which is beneficial to improving the mechanical properties of Ni based superalloys.

Molecular dynamics study of mosaic structure in the Ni-based single-crystal superalloy

The mosaic structure in a Ni-based single-crystal superalloy is simulated by molecular dynamics using a potential employed in a modified analytic embedded atom method. From the calculated results we find that a closed threedimensional misfit dislocation network, with index of （011）{100} and the side length of the mesh 89.6A, is formed around a cuboidal γ′ precipitate. Comparing the simulation results of the different mosaic models, we find that the side length of the mesh only depends on the lattice parameters of the γ and γ′ phases as well as the γ/γ′ interface direction, but is independent of the size and number of the cuboidal γ′ precipitate. The density of dislocations is inversely proportional to the size of the cuboidal γ′ precipitate, i.e. the amount of the dislocation is proportional to the total area of the γ/γ′ interface, which may be used to explain the relation between the amount of the fine γ′ particles and the creep rupture life of the superalloy. In addition, the closed three-dimensional networks assembled with the misfit dislocations can play a significant role in improving the mechanical properties of superalloys.

Synthesis, Characterizations, Biological, and Molecular Docking Studies of Some Amino Acid Schiff Bases with Their Cobalt(II) Complexes

The synthesis and structural characterization of cobalt(II) complexes of amino acid Schiff bases was prepared from Salicylaldehyde and three amino acid (Valine, Leucine, and Isoleucine)?in basic medium. The metal complexes was synthesized by treating an ethanolic solution of the ligand with appropriate amount of metal salts [1:2] [M:L] ratio. The synthesized Schiff bases and their metal complexes have been investigated on the bases of elemental chemical analysis, FTIR, electronic spectral,?1HNMR,?13CNMR, MS, molar conductance and magnetic susceptibility measurements. The electronic spectra of the metal complexes and their magnetic susceptibility measurements suggest octahedral structures are the probable coordination geometries for the isolated complexes. The Schiff bases and their metal complexes were preliminary scanned against various strains of microbes to study their biological effect.

Molecular modeling study of the effect of base methylation on internal interactions and motions in DNA and implication to B-Z conformation change

Methylation in the bases of DNA is known to induce B-Z conformation change. In this work, molecular mechanics and normal mode analysis are used to probe how certain methylation affects the internal interactions and thermodynamic motions in the DNA double helixes in both B and Z conformations, and its implication to B-Z conformation change. By molecular modeling with Insight II, two cases involving cytosine C5 and guanine C8 methylation on both B and Z-form DNA duplex d(CGCGCG)2 are studied in comparison with the corresponding unmethylated duplexes. The internal interaction energies computed based on a molecular mechanics force field and the entropies due to internal motions computed according to a normal mode analysis are in fare agreement with respective observed thermodynamic quantities. The analysis on the computed individual energy terms suggests that the observed B-Z conformation change induced by methylation is primarily driven by enthalpic factors. A combination of changes in Van der Waals interaction, electrostatic interaction and hydrogen bonding likely contributes to the change of enthalpy that favors Z-conformation in the methylated states.

Chiral Recognition of Dansyl Derivatives with an Amino Acid-Based Molecular Micelle: A Molecular Dynamics Investigation

In this study, the chiral separation mechanisms of Dansyl amino acids, including Dansyl-Leucine (Dans-Leu), Dansyl-Norleucine (Dans-Nor), Dansyl-Tryptophan (Dans-Trp) and Dansyl-Phenylalanine (Dans-Phe) binding to poly-sodium N-undecanoyl-(L)-Leucylvalinate, poly (SULV), were investigated using molecular dynamics simulations. Micellar electrokinetic chromatography (MEKC) has previously shown that when separating the enantiomers of these aforementioned Dansyl amino acids, the L-enantiomers bind stronger to poly (SULV) than the D-enantiomers. This study aims to investigate the molecular interactions that govern chiral recognition in these systems using computational methods. This study reveals that the computationally-calculated binding free energy values for Dansyl enantiomers binding to poly (SULV) are in agreement with the enantiomeric order produced in experimental MEKC studies. The L-enantiomers of Dans-Leu, Dans-Nor, Dans-Trp, and Dans-Phe binding to their preferred binding pockets in poly (SULV) yielded binding free energy values of -21.8938, -22.1763, -21.3329 and -13.3349 kJ·mol-1, respectively. The D-enantiomers of Dans-Leu, Dans-Nor, Dans-Trp, and Dans-Phe binding to their preferred binding pockets in poly (SULV) yielded binding free energy values of -14.5811, -15.9457, -13.6408, and -12.0959 kJ·mol-1, respectively. Furthermore, hydrogen bonding analyses were used to investigate and elucidate the molecular interactions that govern chiral recognition in these molecular systems.

Molecular Simulation of Chain Initiation Mechanism in Oxidation of Lubricant Base Stock

Chain initiation reactions in the oxidation process of lubricant base stock molecules were studied by molecular simulations.Two ways to initiate lubricant oxidation were investigated.They included the dissociation of chemical bonds in base stock molecules and the reaction between base stock molecules and oxygen(O_(2)),respectively.Reaction activation energy of above methods was calculated.The results show that C‒C bonds are more likely to break than C‒H bonds to generate free radicals by the pyrolysis of chemical bonds.The C‒C bonds with tertiary carbon atoms are preferential positions to crack.However,their bond dissociation energy is above 360 kJ/mol,which is difficult to occur under lubricant working conditions.The chain initiation is more likely to occur by the way that O_(2) attacks the two atoms in C‒H bonds at the same time,and is then embedded into the C‒H bond to produce hydrocarbon peroxides.And then,the O‒O bond is cracked to form hydroxyl radicals and alkoxy radicals.The C‒H bonds with tertiary carbon atoms are preferential reaction sites,the reaction activation energy of which is about 190.11 kJ/mol.

平面十二配位MB_(8)C_(4)(M=Ca,Sr,Ba)分子轮团簇的理论研究

基于第一性原理计算,在B3LYP/def2-TZVP水平下对碱土金属(Ca, Sr, Ba)掺杂的硼碳环团簇的稳定性、化学成键及芳香性进行研究.结果表明, MB_(8)C_(4)团簇的全局极小结构是以Ca为中心的完美平面分子轮.对于SrB_(8)C_(4)团簇,十二配位分子轮和拉长状八配位结构能量相近,可能共存于其异构体中.随着掺杂金属原子半径的增加,拉长状八配位结构逐渐趋于稳定,为BaB_(8)C_(4)团簇的基态结构.电荷分析结果表明,轮状结构是一个高电荷转移化合物,可被视为[M]~(2+)[B_(8)C_(4)]~(2-)离子复合物.成键分析揭示分子轮结构具有10σ/8π冲突芳香性,且中心金属与外围硼碳环之间存在微弱的共价作用.磁感应环电流密度分析进一步证实轮状结构的成键特征.该体系可视为双重芳香轮状结构的一个反例.拟合出了体系的红外光谱,并对主要特征峰进行了归属分析.

Comparative Molecular Mechanics and Quantum Mechanics Study of Monohydration of Nucleic Acid Bases

DNA is the most important biological molecule and its hydration contributes essentially to the structure and functions of the double helix. We analyze the monohydration of the individual bases of nucleic acids and their methyl derivatives using methods of Molecular Mechanics (MM) with the Poltev-Malenkov (PM), AMBER and OPLS force fields, as well as ab initio Quantum Mechanics (QM) calculations at MP2/6-31G(d,p) level of theory. A comparison is made between the calculated interaction energies and the experimental enthalpies of microhydration of bases, obtained from mass spectrometry at low temperatures. Each local water-base interaction energy minimum obtained with MM corresponds to the minimum obtained with QM. General qualitative agreement was observed in the geometrical characteristics of the local minima obtained via the two groups of methods. MM minima correspond to slightly more coplanar structures than those obtained via QM methods, and the absolute MM energy values overestimate corresponding values obtained with QM. For Adenine and Thymine the QM local minima energy values are closer to those obtained by the PM potential (average of 0.72 kcal/mol) than by the AMBER force field (1.86 kcal/mol). The differences in energy between MM and QM results are more pronounced for Guanine and Cytosine, especially for minima with the water molecule forming H-bonds with two proton-acceptor centers of the base. Such minima are the deepest ones obtained via MM methods while QM calculations result in the global minima corresponding to water molecule H-bonded to one acceptor and one donor site of the base. Calculations for trimethylated bases with a water molecule corroborate the MM results. The energy profiles were obtained with some degrees of freedom of the water molecule being frozen. This data will contribute to the improvement of the molecular mechanics force fields.

Binding of Quinoline-Based Inhibitors to <i>Plasmodium falciparum</i>Lactate Dehydrogenase: A Molecular Docking Study

Development of new antimalarial drugs continues to be of great importance due to the resistance of the malaria parasite to currently used drugs. Glycolytic enzymes have emerged as potential targets for the development of new drugs due to the reliance of the parasite on glycolysis for energy. In this study, molecular docking was used to study the binding of some quinoline-based drugs to the glycolytic enzyme lactate dehydrogenase. The docking studies identified two potential binding sites for each ligand, one of them being the cofactor-binding site. For all ligands studied, there was the comparable binding to the cofactor-binding site as well as the secondary binding site when the cofactor was absent. All ligands showed significantly lower binding affinity than NADH for the cofactor binding site. The alternative site was the site of preference when docking was done in the presence of the cofactor. While binding to the cofactor site may support other studies suggesting potential for competitive inhibition, the fact that the binding affinities of all the ligands are significantly lower than that for NADH in this site suggests that these ligands will be ineffective competitive inhibitors. The identification of an alternative binding site with comparable affinity that is not affected by the presence of the cofactor may suggest the possibility of non-competitive inhibition that requires further exploration.

原油直接催化裂解UPC工艺过程模拟与反应参数多目标优化

原油直接催化裂解技术可以实现从原油到三烯(乙烯、丙烯、丁烯)、三苯(苯、甲苯、二甲苯)的一步跨越,对我国炼化行业的转型升级具有重要意义。以全馏分石蜡基中原原油(159~780℃)为原料,采用混合馏分结构与分子组成集总建模策略,对原油直接催化裂解制烯烃(UPC)反应过程进行建模与工艺参数校准,并基于工业试验数据验证了其准确性。以多产烯烃、控制焦炭生成为目的,利用NSGA-Ⅲ多目标优化算法对模型进行了优化,得到优化后的操作参数。采用优化后的操作参数,即在第一段预热闪蒸温度为194.32℃、第二段预热闪蒸温度为228.16℃、第一段提升管反应器出口温度为615.73℃、第二段提升管反应器出口温度为622.59℃的条件下,UPC工艺得到的乙烯和丙烯收率之和为53.367%,焦炭收率为8.311%。此外,由于现行税费体系燃料型工艺路线税收贡献明显高于化工型工艺路线,UPC工艺参数优化后,烯烃收率大幅度提升,燃料油收率大幅度下降,原油生产总值降低44.30元t。

基于分子动力学模拟的矿物基础油泡沫破裂性能研究

润滑油中的泡沫会增加设备间的磨损,减少油品中的泡沫可以有效降低能源消耗。选用四种矿物型基础油的代表性烃类组分构建了泡沫液膜的分子模拟体系,通过分子动力学模拟分析了液膜破裂过程的微观机理,并计算了单组分及混合组分液膜的破裂时间作为液膜稳定性的评价指标。在此基础上,研究了基础油结构与添加剂、抗泡剂的加入对油基泡沫液膜破裂时间的影响。结果显示,在液膜破裂的过程中,初始孔洞的出现,会显著加快液膜破裂进程,在各基础油体系中加入添加剂、抗泡剂后,液膜破裂时间变化与扩散系数的变化一致,符合泡沫破裂的排液机理。提出的研究方法可从分子层面深入分析油基泡沫的稳定性及破裂机理,探索减少润滑油品泡沫的方法。

有机硅烷对介孔Y型分子筛理化特性及费托性能影响研究

为了合成对汽油段、柴油段产物有高选择性的催化剂载体,以多种有机硅烷为模板剂原位合成了高结晶度介孔Y型分子筛,考察了硅烷剂浓度以及有机硅烷剂中的取代基对Y型分子筛性能的影响,并以合成的介孔分子筛为载体通过浸渍法负载钴制备了催化剂,考察了催化剂的费托反应性能;采用X射线衍射、比表面积测试、扫描电子显微镜等测试手段分析了介孔分子筛及催化剂的物性特征,分别使用气相色谱质谱联用仪、气相色谱对反应产物进行了定性和定量分析。结果表明:有机硅烷剂中的硅与硅凝胶中的硅摩尔比为1∶30时达到饱和,继续提高硅烷剂浓度将导致分子筛结晶度下降,且大量的微孔损失,粒径明显减小。通过改变有机硅烷剂的取代基链长,分子筛的平均介孔尺寸可在4.9~9.0 nm进行调控。极性有机硅烷剂更有利于合成高结晶度与大比表面积的介孔分子筛,其中最大比表面积达到683.7 m^(2)/g,且相较于相同链长的非极性有机硅烷剂合成的分子筛其微孔孔容增加了约30%,而介孔孔容几乎相同。在以合成气为原料气的费托合成实验中,极性有机硅烷剂合成的分子筛催化剂对柴油段C_(10-20)产物具有较高选择性,最高达31.1%;非极性有机硅烷剂合成的分子筛催化剂对汽油段C_(5-12)产物具有较高选择性,最高达39.7%。

炼化生产计划优化中的分子建模方法

为了实现生产方案优化,提高石油炼化加工效益,应用模型开展生产计划优化测算是国内外石化企业的普遍做法。当前国内一些企业采用的传统炼化生产计划优化模型比较宏观,无法精确反映原料组分变化对产品收率和性质的影响,因此有必要在优化模型中引入分子管理理念,实现装置的分子水平建模。文章提出一种在全厂炼化计划优化模型中开展分子建模的方法:首先将二次反应装置构建为多个逻辑装置,其次采用多Delta-base结构描述反应后分子产物随原料组分变化的关系,最后采用分方案物性传递技术将分子组分合成为实际产物以实现产品组分的动态计算。该方法在自主研发的国产炼化计划优化软件平台RIPO上实现。采用某企业数据,建立了包括常减压蒸馏、连续重整和芳烃联合装置分子模型的全厂生产计划优化模型。结果表明,该方法可以实现精细化的分子水平建模和优化,优化结果反映了原料组分及加工方案对目标产品收率和性质的影响,为提高炼化经济效益提供了支持。

非预灌式低分子量肝素腹壁皮下注射操作的循证实践

目的:实施非预灌式低分子量肝素腹壁皮下注射操作的循证实践,降低病人瘀斑发生率,提高护理质量。方法:应用循证护理的方法获取最佳证据,并以基于证据的持续质量改进模式为理论框架,选取2022年11月1日—2023年8月31日在福建医科大学附属第一医院行非预灌式低分子量肝素腹壁皮下注射的病人为研究对象,比较证据应用前后非预灌式低分子量肝素腹壁皮下注射的病人瘀斑发生率及知识知晓率,护士对非预灌式低分子量肝素腹壁皮下注射规范护理的掌握率。结果:经过11条最佳证据的循证实践后,非预灌式低分子量肝素腹壁皮下注射的病人瘀斑发生率明显下降,差异有统计学意义(P<0.001),病人知晓率提高,护士掌握率高于证据应用前。结论:循证护理规范了非预灌式低分子量肝素腹壁皮下注射的操作,可改善护理质量,保证药物疗效,促进医疗安全。