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991.
The surface free energy of a monolithic silica xerogel treated at 1000°C has been measured by inverse gas chromatography in the temperature range 25–150°C using n-alkanes. Values of the dispersive component, S
D, vary from 49.07 mJ·m–2 at 25°C to 17.20 mJ·m–2 at 150°C. The S
D value obtained at 25°C is lower than that found for amorphous and crystalline silicas but higher than that found for glass fibres meaning that the heat treatment at 1000°C changes drastically the structure of the silica xerogel showing a surface similar to a glass. However, the higher value of S
D in comparison to glass fibres can be attributed to the mesoporous structure present in the silica xerogel. In the temperature range of 60–90°C there exists an abrupt change of the S
D values as well as in the dispersive component of the surface enthalpy, h
S
D. Such abrupt change can be attributed to an entropic contribution of the surface free energy. 相似文献
992.
Bruno Ameduri Bernard Boutevin Fouad Malek 《Journal of polymer science. Part A, Polymer chemistry》1994,32(16):3161-3169
The synthesis of maleimides that have pyrazolic or bipyrazolic pendant groups is described. Their homopolymerization and their copolymerization with 2-chloroethyl vinyl ether (CEVE) is reported. The homopolymerizations of such maleimides were performed under various conditions and led to low molecular-weight polymers. However, alternating copolymers were obtained from CEVE as comonomers whatever the monomers feed compositions. A similar behavior was also observed for maleimides that do not exhibit any spacer, whereas for bulky vinyl ethers, random copolymers were produced. A comparison of the thermal behavior between these copolymers (glass transition temperatures, Tg, and decomposition temperatures) and other copolymers having different spacers between the nitrogenated cycles and the chain are related. Thus, an important decrease of Tg, was observed when C3H6CO2CH2 groups were used as the spacer instead of methylene groups. Moreover, the thermal weakness of these copolymers may come from the substituents of the vinyl ether and is discussed. © 1994 John Wiley & Sons, Inc. 相似文献
993.
有机硅化合物是半导体工业中产生硅元件的基本原料和有机合成中的重要试剂,是多年来大家研究较多的分子体系之一.本文报导了用同步辐射加速器产生的真空紫外光,电离St(CH3hCI。分子.在50-120n-m波长范围内,测量了各种离子产物与真空紫外光波长的关系,推算得它的绝热电离电势和离子中几个化学键的键能.1实验装置和方法本工作在国家同步辐射实验室光化学实验站进行.进行分子真空紫外光电离研究的实验系统已在文献山中详细描述.同步辐射加速器产生的真空紫外光波长用Ne气的电离势标定,其误差<士0-Inln.单色仪的分辨率为河凸… 相似文献
994.
Joseph C. P. Koo Janice S. W. Lam Gregory A. Chass Ladislaus L. Torday Andras Varro Julius Gy. Papp 《Journal of Molecular Structure》2003,620(2-3):231-255
The sidechain conformational potential energy hypersurfaces (PEHS) for the γL, βL, αL, and αD backbone conformations of N-acetyl-
-aspartate-N′-methylamide were generated. Of the 81 possible conformers initially expected for the aspartate residue, only seven were found after geometric optimizations at the B3LYP/6-31G(d) level of theory. No stable conformers could be located in the δL, L, γD, δD, and D backbone conformations. The ‘adiabatic’ deprotonation energies for the endo and exo forms of N-acetyl-
-aspartic acid-N′-methylamide were calculated by comparing their optimized relative energies against those found for the seven stable conformers of N-acetyl-
-aspartate-N′-methylamide. Sidechain conformational PEHSs were also generated for the estimation of ‘vertical’ deprotonation energies for both endo and exo forms of N-acetyl-
-aspartic acid-N′-methylamide. All backbone–sidechain (N–H−O–C) and backbone–backbone (N–HO=C) hydrogen bond interactions were analyzed. A total of two backbone–backbone and four backbone–sidechain interactions were found for N-acetyl-
-aspartate-N′-methylamide. The deprotonated sidechain of N-acetyl-
-aspartate-N′-methylamide may allow the aspartyl residue to form strong hydrogen bond interactions (since it is negatively charged) which may be significant in such processes as protein–ligand recognition and ligand binding. As a primary example, the molecular geometry of the aspartyl residue may be important in peptide folding, such as that in the RGD tripeptide. 相似文献
995.
Naumov P. Jordanovska V. Boyanov B. Jovanovski G. 《Journal of Thermal Analysis and Calorimetry》2001,66(2):469-477
The complexes [M(HIm)4(H2O)2](sac)2 (M=Co, Ni) and [Cd(HIm)2(sac)2]2 with saccharin (sac) and imidazole (HIm) were synthesized and their thermal (TG, DTG and DTA) behaviour in the interval from
room temperature up to 1000°C in a static air atmosphere was investigated. Irrespectively of whether the deprotonated saccharinato
residues are present as ligands or ions or both as ligands and ions, the anhydrous complexes regularly decompose in two stages.
The thermal data of 16 saccharinato complexes (including the title compounds) were correlated with the respective structural
data. The general thermal stability order of the saccharinato complexes can be represented as: Pb(II)<Zn(II)<Co(II)Ni(II)<Cd(II)
(the stability of the Cu saccharinates depends on the particular compound) and is dictated by
several structural factors, e.g. metal ionic radii, participation of the water in the coordination sphere of the metal and
other structural characteristics.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
996.
Nicola Armaroli Gianluca Accorsi JohnN. Clifford Jean‐Franois Eckert Jean‐Franois Nierengarten 《化学:亚洲杂志》2006,1(4):564-574
Oligophenylenevinylene (OPV)‐terminated phenylenevinylene dendrons G1 – G4 with one, two, four, and eight “side‐arms”, respectively, were prepared and attached to C60 by a 1,3‐dipolar cycloaddition of azomethine ylides generated in situ from dendritic aldehydes and N‐methylglycine. The relative electronic absorption of the OPV moiety increases progressively along the fullerodendrimer family C60G1 – C60G4 , reaching a 99:1 ratio for C60G4 (antenna effect). UV/Vis and near‐IR luminescence and transient absorption spectroscopy was used to elucidate photoinduced energy and electron transfer in C60G1 – C60G4 as a function of OPV moiety size and solvent polarity (toluene, dichloromethane, benzonitrile), taking into account the fact that the free‐energy change for electron transfer is the same along the series owing to the invariability of the donor–acceptor couple. Regardless of solvent, all the fullerodendrimers exhibit ultrafast OPV→C60 singlet energy transfer. In CH2Cl2, the OPV→C60 electron transfer from the lowest fullerene singlet level (1C60*) is slightly exergonic (ΔGCS≈0.07 eV), but is observed, to an increasing extent, only in the largest systems C60G2 – C60G4 with lower activation barriers for electron transfer. This effect has been related to a decrease of the reorganization energy upon enlargement of the molecular architecture. Structural factors are also at the origin of an unprecedented OPV→C60 electron transfer observed for C60G3 and C60G4 in apolar toluene, whereas in benzonitrile, electron transfer occurs in all cases. Monitoring of the lowest fullerene triplet state by sensitized singlet oxygen luminescence and transient absorption spectroscopy shows that this level is populated through intersystem crossing and is not involved in photoinduced electron transfer. 相似文献
997.
Potential energy surfaces for rotations around two central CN bonds in N-(deoxyguanosin-8-yl)-2-acetylaminofluorene (AAF–dG) and its deacetylated derivative (AF–dG) were studied using Amber 95 molecular mechanics. Both of these adducts are known to be strong mutagens and carcinogens. New Amber 95 force field parameters were derived for the linkage connecting guanine and fluorene moieties in AAF–dG and AF–dG. For this purpose, we determined ab initio MP2/cc-pVDZ//B3-LYP/6-31G* and polarized continuum model Hartree–Fock/6-31G* potential energy surfaces of smaller model systems that included the N-methylimidazole–acetylaniline and N-methylimidazole–aniline adducts. The molecular mechanics parameters were adjusted to minimize differences between the gas-phase ab initio and molecular mechanics surfaces of these model systems. The resulting parameters were transferred to AF–dG and AAF–dG. The barrier for the rotation of the fluorene residue in AF–dG was found to be less than 2 kcal/mol. Such a small barrier renders the fluorene moiety freely rotatable at room temperature. In contrast, the fluorene rotation in AAF–dG is hindered by a significantly larger barrier of 10 kcal/mol. This barrier corresponds to conformations in which the fluorene and acetyl groups lie in the same plane, and is largely due to steric repulsion. Similarly, the coplanar arrangement of guanine and the bridging amino or acetyl groups is disfavored by 5–10 kcal/mol, with AAF–dG again being the more rigid of the two molecules. Energy minima for a rotation around a bond between guanine and the bridging nitrogen are found at ±80° in AAF–dG, and at 120° and –90° for AF–dG. Overall, the fluorene–dG linkages in AF–dG and AAF–dG adducts have significantly different equilibrium structures and torsional flexibilities. These differences may be contributing factors for the observed disparity in mutagenic effects of these adducts.Electronic Supplementary Material: Supplementary material is available in the online version of this article at Acknowledgements. This work was supported by the NSF REU grant no. CHE-0243825 to Loyola University Chicago. We thank to Tom Ellenberger and Shuchismita Dutta for providing us with their results prior to publication. 相似文献
998.
E. T. Denisov 《Russian Chemical Bulletin》2005,54(4):914-923
Interatomic distances in the reaction centers of the addition reactions of (i) H· to the C=C, C=O, N≡C, and C≡C bonds, (ii) ·CH3 radical to the C=C, C=O, and C≡C bonds, and (iii) alkyl, aminyl, and alkoxyl radicals to olefin C=C bonds were determined
using a new semiempirical method for calculating transition-state geometries of radical reactions. For all reactions of the
type X· + Y=Z → X— Y—Z· the r
#
X...Y distance in the transition state is a linear function of the enthalpy of reaction. Parameters of this dependence were determined
for seventeen classes of radical addition reactions. The bond elongation, Δr
#
X...Y, in the transition state decreases as the triplet repulsion, electronegativity difference between the atoms X and Y in the
reaction center, and the force constant of the attacked multiple bond increase.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 894–902, April, 2005. 相似文献
999.
Z. H. Zhang Z. J. Ku H. R. Li Y. Liu S. S. Qu 《Journal of Thermal Analysis and Calorimetry》2005,79(1):169-173
The solid-state ternary complex of terbium chloride with L-tyrosine and glycine, [Tb(Tyr)(Gly)3Cl3·3H2O], was synthesized and characterized. Using a solution-reaction isoperibol calorimeter, the enthalpy of reaction for the following reaction, TbCl3·6H2O(s)+Tyr(s)+3Gly(s)=Tb(Tyr)(Gly)3Cl3·3H2O(s)+3H2O(l), was determined to be (5.1±0.6) kJ mol-1. The standard enthalpy of formation of Tb(Tyr)(Gly)3Cl3-3H2O at T=298.15 K has been derived as -(4267.3±2.3) kJ mol-1. The thermal decomposition kinetics of the complex was studied by non-isothermal thermogravimetry in the temperature range of 325-675 K. Two main mass loss stages existed in the process of the decomposition of the complex, the kinetic parameters for the second stage were analyzed by means of differential and integral methods, respectively. Comparing the results of differential and integral methods, mechanism functions of the thermal decomposition reaction for its second stage were proposed. The kinetic equation can be expressed as: d/dt=Aexp(-E/RT)(1-)2. The average values of the apparent activation energy E and pre-exponential factor A were 213.18 kJ mol-1 and 2.51·1020 s-1, respectively. 相似文献
1000.