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131.
Rabindra N. Roy James J. Gibbons Guilio LaCross Jr. Charles W. Krueger 《Journal of solution chemistry》1976,5(5):333-343
The two thermodynamic dissociation constants of glycine at 11 temperatures from 5 to 55°C in 50 mass % methanol-water mixed solvent have been determined from precise emf measurements with hydrogen-silver bromide electrodes in cells without liquid junction. The first acidic dissociation constant (K
1)for the process HG+H++G± is expressed as a function ofT(oK) by the equation pK
1 = 2043.5/T – 9.6504 + 0.019308T. At 25°C, pK
1is 2.961 in the mixed solvent, as compared with 2.350 in water, with H°=1497 cal-mole–1, G°=4038 cal-mole–1, S°=–8.52 cal-°K–1-mole–1, and C
p
o
=–53 cal-°K–1-mole–1. The second acidic dissociation constant (K
2)for the process G±H++G– over the temperature range studied is given by the equation pK
2 = 3627.1/T – 7.2371 + 0.015587T. At 25°C, pK
2is 9.578 in MeOH–H2O as compared with 9.780 in water, whereas H° is 10,257 cal-mole–1, G° is 13,063 cal-mole–1, S° is –9.41 cal-°K–1-mole–1, and C
p
o
is –43 cal-°K–1-mole–1. The protonated glycine becomes weaker in 50 mass % methanol-water, whereas the second dissociation process becomes stronger despite the lower dielectric constant of the mixed solvent (=56.3 at 25°C). 相似文献
132.
ShuXiaCAO JianChenZHANG MingYuNIU KuiLU XinChengLIAO YuFenZHAO 《中国化学快报》2004,15(6):652-654
N-Phosphoryl peptide libraries were constructed by transformation from homo-oligopeptide libraries, which was synthesized by self-assembly of amino acids with the assistance of phosphorus oxychloride. Electrospray ionization mass spectrometry (ESI-MS) was used to monitor the reaction. 相似文献
133.
The computational results for curcumin at the B3LYP/6-31G(d,p) level show that the enol form of curcumin is more stable than the diketo form because of an intramolecular hydrogen bond, which extends the conjugation effect in the enol chain, formed in the enol structure. Cis-diketone form can not be obtained, presumably due to the strong repulsion between the carbonyl dipoles aligned in parallel. According to the phenolic O-H bond dissociation enthalpy, curcumin in its most stable form can be suggested to be a relatively good antioxidant. In order to avoid overcoming H-bond interaction and to improve the antioxidant activity of curcumin, a catechol moiety was incorporated into curcumin for designing a novel antioxidant. It is found that the designed molecule is much more efficient to scavenge radical than curcumin, comparable to vitamin E. Moreover, the ionization potential of the designed molecule is similar to that of curcumin, indicating that the designed molecule can not display the prooxidant effect. 相似文献
134.
利用时间分辨激光光解技术研究了季铵盐型离子液体[Me3NC2H4OH]Zn2Cl5(简写R-Zn2Cl5)的光解行为, 研究发现离子液体能被266 nm激光单光子电离, 生成阳离子自由基、[Zn2Cl5]•中性自由基和水合电子, 观察到胆碱激发三线态的存在, 并测定了离子液体光电离的量子产额为0.04. 利用266 nm激光对离子液体、胆碱、氯化锌、氯化钠的光解行为比较, 发现胆碱阳离子的贡献很小, [Zn2Cl5]-阴离子起主要作用. 采用氧化性自由基SO4•-引发离子自由基, 揭示其光电离机理, 测定离子液体的动力学反应速率常数, SO4•- 460 nm的衰减速率常数为1.3×109 L•mol-1•s-1, 320 nm离子自由基瞬态产物的生成速率常数为1.5×109 L•mol-1•s-1, 两者很接近, 说明SO4•-自由基的衰减与瞬态自由基的生成是同步的. 相似文献
135.
136.
Shi-Xing Liu Ya-Qiu Lang Xue-Shen Liu Pei-Zhu Ding Yue-Ying Qi 《Journal of mathematical chemistry》2007,41(2):113-122
The classical dynamics of 1D H2+ in an intense field are discussed. The initial conditions are chosen at random in the field-free case, and then the Hamiltonian
canonical equations of H2+ system in the intense laser field are solved numerically by mean of the symplectic method under these initial conditions.
The probabilities of survival, dissociation, ionization, and Coulomb explosion of H2+ system in the intense laser field are obtained for different laser intensity based on the classical theory. 相似文献
137.
Abohachem Laguecir Serge Ulrich Jérôme Labille Nicolas Fatin-Rouge Serge Stoll Jacques Buffle 《European Polymer Journal》2006,42(5):1135-1144
Monte Carlo simulations, experimental titrations and fluorescence correlation spectroscopy experiments were used to investigate the conformational and electrical properties of polyacrylic acids (PAA). On the one hand, titration curves were calculated to get an insight into the role of pH on the degree of ionization and conformation of PAA chains. On the other hand, experimental potentiometric titrations of PAA were also achieved for different PAA molecular weights and compared to the calculated titration curves obtained by Monte Carlo coarse grained simulations. It was found that for a large range at intermediate PAA ionizations, a good correlation is obtained between experimental and simulations data thanks to the prominence of electrostatic interactions in this domain. The effect of ionic concentration and PAA molecular weight on the titration curves was also investigated. In order to get a better understanding of PAA conformational behavior, we also investigated PAA diffusion properties in aqueous solutions as a function of pH and ionic strength by fluorescence correlation spectroscopy (FCS), thanks to its high sensitivity to measure diffusion coefficients of tracer solutes. Good qualitative agreements were observed between experimental diffusivities and polymer properties calculated from MC simulations. It was shown that the high molecular weight PAA chains display more significant changes in diffusivity in agreement with the ionization degrees and conformational changes observed in the simulations. 相似文献
138.
Contributions to the Chemistry of Halosilane Adducts. XXII. Hydrogen Bonding and Ionization of Pentacoordinated Si-Compounds. Preparation, Properties, Crystal and Molecular Structure of 2,2-Dimethyl-2,3-dihydro-1H-[1,4,2]diazasilolo[4,5-α]pyridinium-chloride-Chloroform(1/1), The title compound ( 1 ) is obtained by the reaction of 2-trimethylsilylaminopyridine and Me2CH2ClSiCl in CHCl3. The SiCl bond is ionic (X-ray structure determination). 1 crystallizes monoclinic space group P21/c (Z = 8). The asymmetric unit contains two symmetrically nonequivalent molecular cations of 1 , two Cl anions and two CHCl3. Silicon is tetracoordinate with Si? N-bond distances of 1.766 Å and 1.777 Å. The shortest SiCl distances (3.908 and 4.110 Å) correspond to ionic interactions. Both Cl anions are hydrogen bonded to CHC13. Additionally one C1? is hydrogen bonded to the NH groups of two neighbouring cations. Structural comparison with related compounds suggests these interactions to be responsible for the transition from pentacoordination to tetracoordination at Si (ionization of the Sic1 bond). 1H- and 29Si-NMR investigations of 1 show this transition to be dependent on the combined effect of NH…?C1? and C13CH…?C1? interactions. 1 is completely ionized in CDCl3 in the temperature range ?80° to +80°C while in the weaker acceptor solvent benzonitrile a temperature dependent shift from the ionic tetracoordinate to the pentacoordinate structure is observed with increasing pentacoordination with increase of temperature. 相似文献
139.
Egorochkin A. N. Voronkov M. G. Skobeleva S. E. Zderenova O. V. 《Russian Chemical Bulletin》2001,50(1):35-42
The first vertical ionization potentials (I) of phosphorus compounds P(Xi)3, OP(Xi)3, SP(Xi)3, (4-XC6H4)3P, and PCX are related to the inductive, resonance, and polarizability parameters of inorganic, organic, and organometallic substituents X by dependences of the type I = I
H + aI + bR
+ + c, where I
H is the I value for X = H. The I values are also affected by hyperconjugation. The ratio of the contributions of the resonance (bR
+) and polarizability (c) effects to the I value is determined by the degree of delocalization of the unpaired electron and the positive charge in the radical cations formed upon ionization of neutral molecules. The R
+ resonance parameters of organosilicon, organogermanium, and organotin substituents bound to the P
·+ radical cation center were calculated for the first time. 相似文献
140.