Influence of Solid-liquid Interaction and Temperature on the Dynamic Dewetting of a Thin Polymer Film:A Molecular Dynamics Study

Coarse-grained molecular dynamics simulations were carried out to investigate the dewetting behavior of a polymer thin film on partial wetting solid surface at the early stage of the dewetting process. Spontaneous dewetting is initiated by removing a band of strip from both the ends of the liquid polymer film which has achieved equilibrium. The solid-liquid interaction and temperature were varied to show their influence on the dewetting dynamics during dewetting as well as the shape evolution of the liquid ...     

Predicting Rate Constants for Nucleophilic Reactions of Amines with Diarylcarbenium Ions Using an ONIOM Method

The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as different types of atomic radii including UA0, UAKS, UAHF, Bondi, and UFF, and several single-point energy calculation methods (B3LYP, B3P86, B3PW91, BHANDH, PBEPBE, BMK, M06, MP2, and ONIOM method) were exam-ined. By comparing the correlation between experimental rate constants and the calculated values, the ONIOM(CCSD(T)/6-311++G(2df,2p):B3LYP/6-311++G(2df,2p))// B3LYP/6-31G(d)/PCM/UFF) method was found to perform the best. This method was then employed to calculate the rate constants of the reactions between diverse amines and diarylcarbenium ions. The calculated rate constants for 65 reactions of amines with diarylcarbenium ions are in agreement with the experimental values, indicating that it is feasible to predict the rate constant of a reaction between an amine and a diarylcarbenium ion through ab initio calculation.     

NiO/rGO的溶剂热合成以及作为高循环稳定性超级电容器电极材料的性能表征

通过简单的溶剂热法以及其后续热处理过程,制备了NiO纳米花和NiO/还原氧化石墨烯（rGO）复合物。 在NiO/rGO复合物中,rGO作为基底生长NiO,与此同时,NiO则有效的避免了rGO的团聚。 采用热重分析(TG)、场发射扫描电子显微镜(FE-SEM)和X射线衍射对样品的成分、形貌和结构进行了表征。 NiO/rGO复合物（NiO和rGO的质量比为82.7∶17.3）电极呈现优异的电化学性能。 在1 A/g时,初始比电容为514.9 F/g,当材料完全活化后,其比电容高达600 F/g。 同时,在电流密度为10 A/g时,相比于1 A/g时的比电容保持率为83.5%。 此外,该电极材料具有非常优异的循环稳定性,6000次循环后电容衰减率为7.4%。 表明所制备的复合物是一种有应用价值的超级电容器电极材料。     

Determination and Temperature Dependence of Plateau Modulus for Polymerization of Propylene to Isotactic Polypropylene with Ultra-high Molecular Weight under Catalysis of Ziegler-Natta Catalyst

The viscoelastic behavior of isotactic polypropylene with ultra-high molecular weight (UHPPH) and broad molecular weight distribution(MWD), produced in the presence of Ziegler-Natta catalyst, was investigated by means of oscillatory rheometry at 180 and 200 ℃, whose loss modulus(G") plots at 180 and 200 ℃versus the natural logarithm of angular frequency(ω) present a pronounced maximum at 34.35 and 69.21 rad/s, respectively, and do not show a maximum peak at 0. 01-100 rad/s for Ziegler-Natta catalyzing ethylenepropylene random copolymerization (PPR) with a conventional molecular weight and broad MWD. The fact indicates that the high molecular weight is responsible for a maximum peak of G"(ω) vs. lnω curves for UHPPH. This makes it possible to determine the plateau modulus (G0N) of UHPPH from a certain experimental temperature G"(ω) curve directly. For UHPPH, the G0N determined to be 4. 28×105 and 3. 62×105 Pa at 180and 200 ℃, respectively, decreases with the increase of temperature and is independent of the molecular weight, which directly confirms reputation theoretical prediction that the G0N has no relation to the molecular weight.     

精确计算化学键解离能的ONIOM-G3B3方法及其在抗氧化剂研究中的应用

通过对179个有机化合物C—H, N—H, O—H键离解能的理论计算, 系统评估了高精度组合从头算方法(ONIOM-G3B3)和密度泛函理论方法(B3LYP)在预测键离解能上的可靠性. 研究发现ONIOM-G3B3方法可以准确预测各类有机化合物的键解离能, 精度达到5.9 kJ/mol. 运用ONIOM-G3B3方法成功预测了两类重要的天然抗氧化剂维生素E族和茶多酚族的键解离能, 并进一步讨论了抗氧化活性、自由基清除机理及其构效关系.     

A New Approach to Inducing Silicon Tethered Ring-closing Metathesis Reactions

IntroductionGrubbs catalyst bis(tricyclohexylphosphine)benzylidene ruthenium( ) dichloride1 can be usedin a variety of ring- closing metathesis (RCM )reactions,cross metathesis(CM) reactions andring- opening metathesis polymerization(ROMP) [1— 4 ] .It remains metathetically active inthe presence of a variety of functional groups,suchas carbonyls,alcohols,and amides[1] .The use ofcatalyst1 in the synthesis has drawn more andmore attention[5— 13] . However,this catalyst is veryexpensive,an…     

Purification of Single-walled Carbon Nanotubes Grown by a Chemical Vapour Deposition (CVD) Method

ＩｎｔｒｏｄｕｃｔｉｏｎＳｉｎｇｌｅ ｗａｌｌｅｄｃａｒｂｏｎｎａｎｏｔｕｂｅｓ(ＳＷＮＴｓ)ｈａｖｅｂｅｅｎｓｙｎｔｈｅｓｉｓｅｄｂｙｕｓｉｎｇｖａｒｉｏｕｓｍｅｔｈｏｄｓ[1— 3] ａｎｄｔｈｅｃｈｅｍｉｃａｌｖａｐｏｕｒｄｅｐｏｓｉｔｉｏｎ (ＣＶＤ )ｍｅｔｈｏｄｈａｓｂｅｅｎｃｏｎｓｉｄｅｒｅｄａｓａ ｐｒｏｍｉｓｉｎｇｍｅｔｈｏｄｔｏ ｐｒｏｄｕｃｅＳＷＮＴｓｏｎａｎｉｎｄｕｓｔｒｉａｌｓｃａｌｅ[3— 5] .Ｈｏｗｅｖｅｒ ,ａｌｌｔｈｅＳＷＮＴ ｐｒｏｄｕｃｔｓｓｙｎｔｈｅｓｉｓｅｄｔｏｄａｔｅｃｏ…     

Cosolvent Effect on the Tautomerism of Ethyl Acetoacetate in Supercritical CO_2

There are some unique advantages for chemical reactions in SCFs. For example, reaction rates, yields, and selectivity can be tuned by pressure or small amount of cosolvent. SCFs can be used to replace environmentally undesirable solvents. It is not surprised that in recent years the use of SCFs as solvents for chemical reaction media has received much attention. However, mechanism for the effect of pressure and cosolvents on chemical reactions is not very clear. Tautomeric reactions are id…     

Synthesis and Structure of E-2-(2,4,6-tri tert butylphenylphosphinyl)-2-〔N-(tert-butyldimethylsilyl)-N-(p-chrolophenyl)〕amino-1-(2,4,6-tri tert-butyl-phenyl)phosphacthylene

1　INTRODUCTIONItwaswellknown thatelementsofthesecondary and higherrow are in generaldifficulty to form multiplebondsin which apπ hybridized stateisinvolved〔1〕.Thus,simple compounds containing multiple phosphorus carbon bonds,such as methyl dynephosphine( HC≡P) 〔2 - 3〕 and methylenephosphine( H2 C=PH〔4〕,are notstableat room temperature.Three methods to stabilize compounds containing double ormultiple bond involving phosphorusatom in the pπ hybridized state are often used.The f…     

Mono-Allylation of Gem-Diacetates with Allylsamarium Bromide

Our group have explored the reaction of allylsamarium bromide with a variety of substrates, such as N-(2-aminoalkyl)benzotriazoles1, imines2, nitriles3, diorgano diselenides4, disulfides5, isocyanates6 and nitroalkenes7. Here we wish to report the monoallylation of gem-diacetates with allylsamarium bromide. Gem-diacetates are stable in neutral and basic media, thus they are frequently used to protect aldehydes8. However, the presence of two leaving groups at the same carbon may make carbon …