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41.
In this paper we present a series of work covering a range of aspects relating molecular simulation to experiment. The importance
of surface mediation type effects to the adsorption of simple and complex gases is demonstrated. Coupled with the adsorption
of simple gases is their projection area when used for surface area determination. The pressure dependence of a projection
area is demonstrated for argon at 77 and 87.3 K. A simple model is used to account for the degree of graphitisation of a surface
is demonstrated and used to account for the isosteric heat behaviour of non-graphitised carbon blacks. Turning from surfaces
to porous solids, an alternative treatment of experiment data (either sub or super critical) is presented that avoids the
ambiguity of excess amounts adsorbed. Using this method one is able to obtain pore size distributions and amounts adsorbed
without relying on such things as helium expansion volumes. Since this type of method is usually applied to composite solids
we also demonstrate the correct method for calculating the heat of adsorption using independent sets of simulations. The final
topic covered in this paper is an example of the information that can be gained from the heat capacity of an adsorbed phase. 相似文献
42.
Xilin Ren Chingkuang Tu Deepa Bhatt J. Jefferson P. Perry John A. Tainer Diane E. Cabelli David N. Silverman 《Journal of Molecular Structure》2006,790(1-3):168-173
Incorporation of 3-fluorotyrosine and site-specific mutagenesis have been used with stopped-flow spectrophotometry and pulse radiolysis to investigate the catalytic properties of human manganese superoxide dismutase (MnSOD). All of the nine tyrosine residues in each of the four subunits of the homotetramer of human MnSOD were replaced with 3-fluorotyrosine. Previous studies showed that the crystal structures of the unfluorinated and fluorinated human MnSOD are nearly superimposable with the root-mean-square deviation for 198 -carbon atoms at 0.3 Å. However, the catalytic activity kcat/Km of the fluorinated MnSOD at 30 μM−1 s−1 was less than unfluorinated wild type at 800 μM−1 s−1. Comparison of the values of kcat/Km for fluorinated and unfluorinated wild-type andY34F MnSOD showed that this decrease for the fluorinated enzyme was in significant part due to 3-fluorotyrosine residues distant (>7 Å) from the active-site metal, not to 3-fluorotyrosine at position 34 close (5 Å) to the metal. Although many rate constants for the catalysis are decreased by this fluorination, the rate of dissociation of the product-inhibited complex appears unchanged by the presence of fluorinated tyrosines. These results suggest that Tyr34 is not a proton donor in the release of the product-inhibited complex, which involves protonation of a peroxo complex of the metal with release of hydrogen peroxide. 相似文献
43.
Trace analysis of rapamycin in human blood by micellar electrokinetic chromatography 总被引:1,自引:0,他引:1
A capillary electrophoretic method with UV detection at 278 nm has been developed for analysis of the immunosuppressant rapamycin (sirolimus) in human blood at low microgram per liter levels. Separation has been achieved in an acidic carrier electrolyte containing sodium dodecylsulfate and 30% (v/v) acetonitrile. For sample clean-up and preconcentration, an off-line solid-phase extraction step using a silica-based reversed-phase material and an on-capillary focussing technique were employed. The latter allows the injection of increased sample volumes without excessive band broadening. Although this new method is less sensitive than existing liquid chromatographic procedures combined with mass spectrometry, it is fully suited to routine analysis of rapamycin in blood from patients treated with this drug. Last but not least the low costs make it an attractive alternative to established methods. 相似文献
44.
三效催化剂作用下的NO+CO催化反应机理 总被引:1,自引:0,他引:1
NO与CO在Pt/Rh/Pd及载体组成的三效催化剂上的氧化还原应用是控制汽车尾气对空气污染的一个关键反应,这一反应随着近年来对环境保护的日益重视而成为国内外研究的热点,本文主要综述了NO及CO在Pt,Rh,Pd上的吸附及反应机理的实验及理论研究现状,总结得出:在三效催化剂对NO CO的催化反应中,Pt,Pd对CO的催化氧化起主要作用,而Rh对NO的解离有很好的活化作用。 相似文献
45.
46.
Xin-hua Wan Hui-lin Tu Ying-feng Tu Dong Zhang Ling Sun Qi-feng Zhou Yu-ping Dong Mao Tang Department of Polymer Science & Engineering College of Chemistry Peking University Beijing China Department of Materials & Chemical Engineering Beijing Institute of Technology Beijing China 《高分子科学》1999,(2):189-192
The first TEMPO-mediated "living" free radical polymerization of liquid crystallinemonomer, 2, 5-bis[(4-methoxyphenyl)oxycarbonyl]styrene(MPCS), was carried out at 130℃ withBPO as an initiator. The molecular weight of the polymer can be varied from rather low values to highvalues while maintaining narrow polydispersity. It was observed that the polymerization of MPCSproceeded much faster than that of styrene. A tentative explanation for this fast polymerization wassuggested. 相似文献
47.
N-type semiconducting polymers are attractive for organic electronics, but desirable electron-deficient units for synthesizing such polymers are still lacking. As a cousin of rylene diimides such as naphthalene diimide (NDI) and perylene diimide (PDI), anthracene diimide (ADI) is a promising candidate; its polymers, however, have not been achieved yet because of synthetic challenges for its polymerizable monomers. Herein, we present ingenious synthesis of two dibromide ADI monomers with dibromination at differently symmetrical positions of the ADI core, which are further employed to construct ADI polymers. More interestingly, the two obtained ADI polymers possess the same main-chain and alkyl-chain structures but different backbone conformations owing to varied linking positions between repeating units. This feature enables their different optoelectronic properties and film-state packing behavior. The ADI polymers offer first examples of conjugated polymer conformational isomers and are highly promising as a new class of n-type semiconductors for various organic electronics applications.Two anthracene diimide (ADI) polymers with the backbone conformational isomerism, new members of aromatic diimide polymers family, have been synthesized as a class of highly promising n-type semiconductors for organic electronics. 相似文献
48.
相转移催化合成对甲氧基肉桂酸-2-乙基己酯的研究 总被引:5,自引:1,他引:5
对甲氧基肉桂酸 2 乙基己酯是一种有效的UVB防晒剂[1 ,2 ] ,一般采用Claisen Schmidt缩合反应制得[3] ,但由于催化剂KOH处于水相 ,对反应物不能充分起到催化作用导致产率较低[4] 。我们利用乙二醇 (PEG)为相转移催化剂合成立体专一的反式对甲氧基肉桂酸 2 乙基己酯 ,产率提高到 72 .5 %。合成路线如下 :1 实验部分1 .1 仪器与试剂BIO RAPFT45 0红外光谱仪 ,用液膜法测试 ;Brurer AM 30 0超导核磁共振仪 (溶剂DC Cl3) ;MAT/44S ,GC MS型色质联用谱仪 ;试剂均为分析纯 ,上海化学试剂… 相似文献
49.
Tomislav Došlić 《Journal of mathematical chemistry》2007,41(3):217-229
A global forcing set in a simple connected graph G with a perfect matching is any subset S of E(G) such that the restriction of the characteristic function of perfect matchings of G on S is an injection. The number of edges in a global forcing set of the smallest cardinality is called the global forcing number
of G. In this paper we prove several results concerning global forcing sets and numbers of benzenoid graphs. In particular, we
prove that all catacondensed benzenoids and catafused coronoids with n hexagons have the global forcing number equal to n, and that for pericondensed benzenoids the global forcing number is always strictly smaller than the number of hexagons. 相似文献
50.
N. N. Kolos V. D. Orlov E. K. Slobodina E. Yu. Yur'eva S. P. Korshunov Zyong van Tué 《Chemistry of Heterocyclic Compounds》1992,28(2):222-227
1,2,4-Triazolo[3,4-b]-1,3,4-thiadiazines, hydrazones, and -thio adducts were obtained by reactions of 4-amino-3-mercapto-1,2,4-triazole with -bromoacetophenones, aldehydes, and ,-unsaturated ketones. Conditions that promote the cyclocondensation of the -thio adducts to the previously undescribed 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazepines were found. The chemical and spectral properties of the compounds obtained are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 267–272, February, 1992. 相似文献