丙烯聚合反应过程优化控制系统

介绍丙烯聚合反应过程优化控制系统的总体结构。

烯酮光化二聚反应中非绝热跃迁的经典轨迹方法研究

用经典轨迹方法，在π－ＣＩ势能面水平上计算了烯酮光化二聚的Ｈｕｃｋｅｌ途径和Ｍｏｂｉｕｓ途径的非绝热耦合项．根据非绝热跃迁几率的Ｌａｎｄａｕ－Ｚｅｎｅｒ公式，定义η＝ｌｎＰ（Ｈ）／ｌｎＰ（Ｍ）并用以讨论光化学反应的立体选择性．计算结果表明，光化学反应受两态Ｓ＿１和Ｓ＿０接近交叉处的能量间隙ΔＥ＿ｃ的控制，ΔＥ＿ｃ越小非绝热跃迁几率越大．

小型化PCR仪温度单元优化与实现

高精度、低成本的小型化聚合酶链式反应(PCR)仪的研发对病毒现场快速检测具有重要意义。PCR仪温度单元的快速性、准确性和均一性对样品DNA的扩增效率起决定性作用。针对小型化PCR仪温度单元设计,提出有限元结合遗传算法对基座热包覆结构进行优化。采用基于H桥驱动器的分段比例积分微分(PID)控制方案,实现小型化PCR温度循环控制。搭建了一台16孔PCR仪样机,并对相关指标进行测试与验证。该样机成本仅为600元,可外接24 V电源进行工作,在50μL反应体系中可将稳态误差保持在±0.2℃,升降温速率分别可达到2.7℃/s和2.2℃/s,温度单元表面均一性<0.1℃。通过对15样本的小鼠基因组鉴定,验证了仪器的性能表征。验证结果表明,所提出的优化方案成本低且能大幅提升小型化PCR仪温度单元性能,缩短完成反应所需时间,为病毒现场应急检测设备的研发提供重要技术支撑。

聚氧乙烯菜籽油的研究

本文就聚氧乙烯菜籽油这一新型表面活性剂的合成工艺、反应机理、产物性能等作了概要地论述。

Syntheses and catalytic performances of three coordination polymers with tetracarboxylate ligands

Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed hydrothermally using H4adip(H4adip=5,5′-azanediyldiisophthalic acid),phen(phen=1,10-phenanthroline),bipy(bipy=2,2′-bipyridine),bpa(bpa=bis(4-pyridyl)amine),and zinc and cobalt chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffrac-tion analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhom-bic system Pnna(1 and 2)or P21212(3)space groups.All compounds exhibit 3D frameworks.The catalytic perfor-mances in the Henry reaction of these compounds were investigated.Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70℃.CCDC:2339391,1;2339392,2;2339393,3.

Optimization of reaction for synthesis of polyisobutylene amine between amination agent and epoxy polyisobutylene

An optimization study on the amination reaction of epoxy polyisobutylene for synthesis of polyisobutylene amine is presented. The experimental results indicate that n-butanol and ethylenediamine are the suitable solvent and amination agents for the reaction, respectively. The reaction yield of the amination reaction is notably increased with the enhanced molar ratio of either n-butanol against epoxy polyisobutylene or ethylenediamine against epoxy polyisobutylene. Also, the yield is enhanced with increasing temperature and time during the experimental range. Strikingly, the yield reaches as high as 91. 30% under optimal conditions; with the molar ratio of ethylenediamine, n-butanol and PIBO of 10∶ 6∶ 1, the reaction temperature of 150 ℃ and the reaction time of 6 h. In addition, the yield of the reaction is slightly decreased with the enhanced water content of the system. Accordingly, the mass concentration of water should be controlled within 1. 7% during the reaction.

Thermal nitridation of triazine motifs to heptazine-based carbon nitride frameworks for use in visible light photocatalysis

A thermal nitridation route for the assembly and polymerization of molecular triazine units to heptazine-based covalent frameworks has been successfully established. The obtained conjugated carbon nitride polymers feature nanostructures that show enhanced photocatalytic reactivity for hydrogen production under visible light irradiation.

Co_3O_4 nanoparticles assembled on polypyrrole/graphene oxide for electrochemical reduction of oxygen in alkaline media

The development of highly efficient catalysts for cathodes remains an important objective of fuel cell research. Here, we report Co3O4 nanoparticles assembled on a polypyrrole/graphene oxide electrocatalyst （Co3O4/Ppy/GO） as an efficient catalyst for the oxygen reduction reaction （ORR） in alkaline media. The catalyst was prepared via the hydrothermal reaction of Co2＋ ions with Ppy-modified GO. The GO, Ppy/GO, and Co3O4/Ppy/GO were characterized using scanning electron microscopy, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The incorporation of Ppy into GO nanosheets resulted in the formation of a nitrogen-modified GO po-rous structure, which acted as an efficient electron-transport network for the ORR. With further anchoring of Co3O4 on Ppy/GO, the as-prepared Co3O4/Ppy/GO exhibited excellent ORR activity and followed a four-electron route mechanism for the ORR in alkaline solution. An onset potential of -0.10 V vs. a saturated calomel electrode and a diffusion limiting current density of 2.30 mA/cm^2 were achieved for the Co3O4/Ppy/GO catalyst heated at 800 ℃; these values are comparable to those for noble-metal-based Pt/C catalysts. Our work demonstrates that Co3O4/Ppy/GO is highly active for the ORR. Notably, the Ppy coupling effects between Co3O4 and GO provide a new route for the preparation of efficient non-precious electrocatalysts with hierarchical porous structures for fuel cell applications.

Effect of TPB on curing reaction of HTPB-TDI

Catalysis effect of triphenyl bismuth （TPB） on kinetics of hydroxyl terminated polybutadiene-toluene diisocyanate （HTPB-TDI） curing reaction was studied by non-isothermal differential scanning calorimetry （DSC）. The characteristic temperature of curing system was measured for calculating kinetic parameters and establishing curing reaction kinetic equations. The results show that activation energy （Ea） of uncatalyzed HTPB-TDI curing system is 51.29 kJmol-1, and TPB decreases Ea to 46.43 kJ＇mol-1. Catalyst lowers reaction temperature and shortens curing time through decreasing ac- tivation energy of curing reaction and accelerating reaction rate. TPB can increase the reaction rate at 27 ℃ to the value of uncatalyzed system at 80 ℃. The catalytic activity reaches the maximum when concentration is 0.5 %.

Palladium nanoparticles in cross-linked polyaniline as highly efficient catalysts for Suzuki-Miyaura reactions

Palladium nanoparticles supported on cross-linked polyaniline with bulky phosphorus ligands were developed.These catalysts showed high efficiency in the Suzuki-Miyaura reaction of aryl chlorides and bromides with phenylboronic acids.Aryl chlorides and bromides with functional groups,such as CN,MeO,CHO,MeCO and NO_2,were converted to the corresponding biphenyls in high yields with catalyst loading.Additionally,the catalysts combined high activity with good reusability;they could be used at least five times for the Suzuki-Miyaura coupling reaction.

Olefin oligomerization via new and efficient Bronsted acidic ionic liquid catalyst systems

Olefin oligomerization reaction catalyzed by new catalyst systems（a Br？nsted‐acidic ionic liquid as the main catalyst and tricaprylylmethylammonium chloride as the co‐catalyst） has been investigat‐ed. The synthesized Br？nsted acidic ionic liquids were characterized by Fourier transform infrared spectroscopy（FT‐IR）, ultraviolet‐visible spectroscopy（UV）, ^1H nuclear magnetic resonance（NMR）, and ^13 C NMR to analyze their structures and acidities. The influence of different ionic liquids, ionic liquid loading, different co‐catalysts, catalyst ratios（mole ratio of ionic liquid to co‐catalyst）, reac‐tion time, pressure, temperature, solvent, source of reactants, and the recycling of catalyst systems was studied. Among the synthesized ionic liquids, 1‐（4‐sulfonic acid）butyl‐3‐hexylimidazolium hydrogen sulfate（[HIMBs]HSO4） exhibited the best catalytic activity under the tested reaction con‐ditions. The conversion of isobutene and selectivity of trimers were 83.21% and 35.80%, respec‐tively, at the optimum reaction conditions. Furthermore, the catalyst system can be easily separated and reused; a feasible reaction mechanism is proposed on the basis of the distribution of experi‐mental products.

Numerical Predication of Cracking Reaction of Particle Clusters in Fluid Catalytic Cracking Riser Reactors

Behavior of catalytic cracking reactions of particle cluster in fluid catalytic cracking （FCC） riser reactors was numerically analyzed using a four-lump mathematical model. Effects of the cluster porosity, inlet gas velocity and temperature, and coke deposition on cracking reactions of the cluster were investigated. Distributions of temperature, gases, and gasoline from both catalyst particle cluster and an isolated catalyst particle are presented. The reaction rates from vacuum gas oil （VGO） to gasoline, gas and coke of individual particle in the cluster are higher than those of the isolated particle, but it reverses for the reaction rates from gasoline to gas and coke. Less gasoline is produced by particle clustering. Simulated results show that the produced mass fluxes of gas and gasoline increase with the operating temperature and molar concentration of VGO, and decrease due to the formation of coke.

Oligomerization of 1-Decene: Catalyzation by Immobilized AlCl_3/γ-Al_2O_3 Catalyst in Fixed-bed Reactor

1-Decene was oligomerized over the supported AlCl3/γ-Al2O3 catalyst in a fixed-bed reactor. The effects of temperature and LHSV on oligomerization of 1-decene were investigated and the synthetic PAO was characterized with GC technique. Furthermore, the life of immobilized catalyst was tested and the mechanism of catalyst deactivation was discussed. The results showed that with an increasing temperature, the PAO yield increased and the kinematic viscosity of oil decreased. The GC results indicated that the synthesized PAO was a mixture consisting of dimers, trimers, tetramers and pentamers. The results of chloride content measurements and BET tests showed that catalyst deactivation could be mainly attributed to the loss of active components.

Study on Direct Synthesis of Diphenyl Carbonate with Heterogeneous Catalytic Reaction (VI) Effect of Sn Loading Method and Content on Activity of Sn-Pd Supported Catalyst

The compound metal oxide LaxPbyMnzO used as support was prepared by the sol-gel method, and the catalyst in which Pd was used as active component and Sn as co-active component for direct synthesis of diphenyl carbonate (DPC) with heterogeneous catalytic reaction was obtained by co-calcination and precipitation respectively.The catalyst was characterized by XRD, SEM and TEM respectively. The specific surface area of catalysts was measured by ChemBET3000 instrument, and the activity of the catalysts was tested by the synthesis of DPC in a pressured reactor. The results showed that when the co-active component Sn was added by co-calcination method A, its loading content was equal to 14.43% and active component Pd was loaded by precipitation, the yield and selectivity of DPC could reach 26.78% and 99% respectively.

Hepatitis B virus genotypes in southwest Iran: Molecular, serological and clinical outcomes

AIM: To investigate the associations of hepatitis B virus (HBV) genotype with HBeAg and anti-HBe status, alanine aminotransferase (ALT) levels and HBV-DNA detection in different groups of HBV-infected patients in southwest Iran. METHODS: A total of 89 HBsAg-positive serum samples were collected from the same number of patients. All sera were then investigated to determine HBV DNA and serological markers. For all the polymerase chain reaction (PCR)-positive samples, biochemical, histopathological assays and genotyping were also performed. RESULTS: Genotype D was the only type of HBV foundin different clinical forms of acute and chronic infections. There was a high prevalence of HBeAg-negative HBV- infected patients with chronic hepatitis (52.7%). Out of 55 patients with chronic hepatitis, seven (12.7%) were diagnosed with cirrhosis. A significant association between the presence of anti-HBe antibody and an increase in ALT level, among either HBeAg-negative (P = 0.01) or HBeAg-positive (P = 0.026) patients, was demonstrated. No significant differences were observed between the clinical outcomes of HBeAg-positive and -negative individuals (P = 0.24). CONCLUSION: Genotype D has been recognized as the only type of HBV found in different clinical forms of HBV infections, including cirrhosis, among the residents of southwest Iran. Anti-HBe possibly plays a role in disease progression in some patients with chronic hepatitis, at least for a period of disease.

HBsAg抑制聚乙二醇化α干扰素治疗敏感性的初步分子机制

目的:对HBsAg引起干扰素治疗无效的机制进行初步探讨,为乙肝患者的治疗提供新思路。方法:分别以HBIG和RNAi技术调节HepG2.2.155细胞内HBsAg含量,再用Western blot、qRT-PCR和ELISA等方法检测PP2Ac、PRMT1蛋白及mRNA水平;分析干扰素对HBsAg诱导的PP2Ac表达有无影响。结果:用HBIG可以增加细胞内HBsAg含量,当HBsAg增加时PP2Ac的水平也会提高;当存在干扰素时,并不会影响HBsAg对PP2Ac的作用,而且PP2Ac的下游蛋白PRMT1表达会降低;用RNAi技术下调HBsAg的表达时,PP2Ac的蛋白和mRNA的水平也会下降。结论:HBsAg可以上调PP2Ac的表达,从而抑制了PRMT1的活性,影响干扰素治疗的敏感性。HBsAg可以影响Peg-IFNα的敏感性,可能是提高慢性乙型肝炎患者疗效的一个潜在靶标。

Multivariate Statistical Process Monitoring of an Industrial Polypropylene Catalyzer Reactor with Component Analysis and Kernel Density Estimation

Abstract Data-driven tools, such as principal component analysis （PCA） and independent component analysis （ICA） have been applied to different benchmarks as process monitoring methods. The difference between the two methods is that the components of PCA are still dependent while ICA has no orthogonality constraint and its latentvariables are independent. Process monitoring with PCA often supposes that process data or principal components is Gaussian distribution. However, this kind of constraint cannot be satisfied by several practical processes. To ex-tend the use of PCA, a nonparametric method is added to PCA to overcome the difficulty, and kernel density estimation （KDE） is rather a good choice. Though ICA is based on non-Gaussian distribution intormation, .KDE can help in the close monitoring of the data. Methods, such as PCA, ICA, PCA.with .KDE（KPCA）, and ICA with KDE,（KICA）, are demonstrated and. compared by applying them to a practical industnal Spheripol craft polypropylene catalyzer reactor instead of a laboratory emulator.

Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform

Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform under irradiation with light were studied. The reactions were separately carried out under air, oxygen, and nitrogen. The obtained results showed that this reaction belongs to the pseudo-first-order reaction with a rate constant kobs of 1.4×10?5 s?1 at room temperature. The presence or absence of air, oxygen, and nitrogen did not have obvious effects on the reaction rate under irradiation with light.

Preparation of high viscosity average molecular mass poly-L-lactide

Poly-L-lactide（PLLA） was synthesized by ring-opening polymerization fi＇om high purity L-lactide with tin octoate as initiator, and characterized by means of infi＇ared, and ^1H-nuclear magnetic resonance. The influences of initiator concentration, polymerization temperature and polymerization time on the viscosity average molecular mass of PLLA were investigated. The effects of different purification methods on the concentration of initiator and viscosity average molecular mass were also studied. PLLA with a viscosity average molecular mass of about 50.5×1^04 was obtained when polymerization was conducted for 24 h at 140℃ with the molar ratio of monomer to purification initator being 12 000. After purification, the concentration of tin octoate decreases; however, the effect of different purification methods on the viscosity average molecular mass of PLLA is different, and the obtained PLLA is a typical amorphous polymeric material. The crystallinity of PLLA decreases with the increase of viscosity average molecular mass.

Mitotic phosphorylation of PRC1 at Thr470 is required for PRC1 oligomerization and proper central spindle organization

During cell division, chromosome segregation is orchestrated by the interaction of spindle microtubules with the centromere. A dramatic remodeling of interpolar microtubules into an organized central spindle between the separating chromatids is required for the initiation and execution ofcytokinesis. Central spindle organization requires mitotic kinesins, the chromosomal passenger protein complex, and microtubule bundling protein PRC 1. PRC 1 is phosphorylated by Cdc2 at Thr470 and Thr481 during mitosis. However, the functional relevance of PRC 1 phosphorylation at Thr470 has remained elusive. Here we show that expression of the non-phosphorylatable mutant PRC 1T470A but not the phospho-mimicking mutant PRC 1^T470E causes aberrant organization of the central spindle. Immunoprecipitation experiment indicates that both PRC 1^T470A and PRC 1^T470E mutant proteins associate with wild-type PRC 1, suggesting that phosphorylation of Thr470 does not alter PRC 1 self-association. In addition, in vitro co-sedimentation experiment showed that PRC 1 binds to microtubule independent of the phosphorylation state of Thr470. Gel-filtration experiment suggested that phosphorylation of Thr470 promotes oligomerization of PRC 1. Given the fact that prevention of the Thr470 phosphorylation inhibits PRC 1 oligomerization in vitro and causes an aberrant organization of central spindle in vivo, we propose that this phosphorylation-dependent PRC 1 oligomerization ensures that central spindle assembly occurs at the appropriate time in the cell cycle.