Analysis on absorption spectra of Nd in poly(methyl methacrylate)

The absorption spectrum of neodymium (III) (Nd³⁺ doped in poly(methyl methacrylate) was measured. The Nephlauxetic effect was found in the spectrum compared to other spectra of Nd³⁺ doped in various matrices. The experimental data used, Slater-Condon parameters (F₂,F₄,F₆) and Lander parameter (ζ_4f) were calculated by the Taylor series expansion based on the assumption that the energy separation between J-levels of the 4fⁿ-configuration is a function of F₂,F₄,F₆ and ζ_4f. The Judd-Ofled intensity parameters (Ω₂,Ω₄,Ω₆) were also calculated. Analysis of the Nephlauxetic effect and the parameters variation on the host matrices was carried out.     

Polarographic Behaviour and Determination of Kinetic Parameters of Lead-Pamoate Complex in Dimethyl Sulfoxide

The polarography of lead ion in dimethyl sulfoxide (DMSO) was investigated in the DMSO concentration range 0–80 vol.%. The complex species identified were Pb₂(DMSO)⁴⁺₃, Pb(DMSO)²⁺₃ and Pb(DMSO)²⁺₆ in [DMSO]<10 vol.%, 10< [DMSO]<43 vol.% and [DMSO]>43 vol.%, respectively. In the presence of pamoic acid, the reduction of lead ion in DMSO was two-electron reversible diffusion-controlled at pH≤6.0, but it became irreversible at pH>6.0. The complex species identified was Pb(D_m)₂(P_m)₃(OH)^6? at pH>6.0. The rate constants of electro-reduction and electro-oxidation, activation energies were determined. The hydrolysis constants of lead ion in dimethyl sulfoxide concentration 40–70 vol.% at pH 4.5–6.0 were found to be of the order of 10^?6. The stability constants of the Pb(DMSO)²⁺₃ and Pb(DMSO)²⁺₀ were also determined to be of the orders of 10¹ and 10⁵, respectively.     

Study of Densities, Viscosities and Ultrasonic Speeds of Binary Mixtures Containing 1,2-Dimethoxyethane and an Alkan-l-ol at 298.15 K

The viscosity deviation (Δη), the excess molar volume (V ^E) and the ultrasonic speed (u) have been investigated from viscosity (η) and density (ρ ) measurements of binary liquid mixtures of 1,2-dimethyoxyethane with methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1-ol, hexan-1-ol or octan-1-ol over the entire range of composition at 298.15 K. The excess volumes are negative over the entire range of composition for all of the mixtures with the exception of hexan-1-ol and octan-1-ol. The excess isentropic compressibilities (K _S ^E) and viscosity deviations are negative for all of the mixtures. The magnitudes of the negative values of V ^E decrease with the number of carbon atoms of the alkan-1-ol. The trend of increasing K _S ^E values with the chain length of the alkanol is similar to that observed in the case of V ^E. Graphs of V ^E, Δ η, K _S ^E, Δ u, L _f ^E and Z ^E against composition are presented as a basis for a qualitative discussion of the results.     

Thermodynamic parameters ΔΔH and ΔΔS as probes for the transition state in the reaction of N-phenyltriazolinedione with alkenes in nucleophilic solvents

The thermodynamic parameters, ΔΔH^# and ΔΔS^#, were determined for the interception of an intermediate, with the structural characteristics of an aziridinium imide, by nucleophilic solvents during the reaction of 2-methyl-2-butene with N-phenyltriazolinedione. The experimentally measured parameters were found to be in favor of an S_N2-‘like’ transition state and showed strong dependence on the bulkiness of the incoming molecule of the nucleophile-solvent.     

Influence of molecular weight on the thermal decomposition of hydroxyl terminated polybutadiene

Thermogravimetric analysis of hydroxyl terminated polybutadiene (HTPB) and its fractions of different molecular weights separated by preparative GPC shows two major stages of weight loss of different nature in a nitrogen atmosphere. The first stage is primarily depolymerisation, cyclisation and crosslinking of molecules and the second stage is mainly the decomposition of the residue from the first stage. The kinetic parameters, viz. activation energy E and pre-exponential factor A using four different non-isothermal integral equations show a systematic increase with increase in molecular weight for the first stage, whereas for the second stage, the effect of molecular weight on E and A values is not prominent. The increase in E and A values for the first stage is attributed to the formation of greater number of cyclised and crosslinked products from molecules of higher dimensions. Quantitative correlations between the kinetic constants and the molecular weight parameters were derived for the first stage as a quadratic curve following the equation: E or ln A = K₁ − K₂/M (where K₁ and K₂ are empirical constants whose values are different for the different molecular weight averages, viz. M_n, M_w and M_z and for the different equations).     

Study of geometrical parameters in N-H...N type of hydrogen bonds

Geometrical parameters associated with N-H ... N types of hydrogen bonds have been analysed using crystal structure data on nucleic acids, amino acids and related compounds. Histograms depicting the frequency distribution of N-H ... N length (l) and H-N ... N angle (θ) have been drawn and conclusions on the favoured geometry of such bonds have been arrived at. The distribution ofl shows a pronounced maximum in the range between 2.9? and 3.0? with an overall average of 2.98 ?. The θ distribution shows a pronounced maximum for the hydrogen bond angle in the range 0°-10°, with a rapid fall-off in frequency for nonlinear hydrogen bonds. The frequency shows a cos⁶θ dependence as compared to cos²θ dependence term used earlier to predict the angular dependence of hydrogen bond potential energy in proteins and polypeptides.     

聚丙烯酰胺与混合表面活性剂的相互作用

通过粘度和紫外吸收光谱的测定，研究了ＰＡＭ与Ｒ１２ＳＯ３Ｎａ－Ｒ１１ＣＯＯＮａ混合表面活性剂之间的相互作用，结果表明，ＰＡＭ可与混合表面活性剂形成复合物，从而使体系表现出典型聚电解质的粘度行为。可能的机理是，以疏水力形成的Ｒ１２ＳＯ３＾－—Ｒ１１ＣＯＯＨ（Ｎａ）预胶束或二聚体通过ＰＡＭ－Ｒ１１ＣＯＯＨ间的氢键力相结合。进而使大分子链上带有大量负电荷，静电斥力引起大分子链伸展，因而产生电粘效应。     

Equations describing lamellar structure parameters and melting points of polyethylene-<Emphasis Type="Italic">co</Emphasis>-(butene/octene)s

Time- and temperature-dependent SAXS-experiments were used to determine the effect of octene and butene co-units on the lamellar structure and the melting properties of polyethylene. As expected, melting points decrease with increasing co-unit content, but crystal thicknesses are not affected and depend on the crystallization temperature only. Results can be cast into some simple equations which describe the dependence:

用~(13)C NMR弛豫研究星形聚苯乙烯在溶液中的分子运动(Ⅱ)

对不同支化度和不同支链链长的20％(W/V)星形聚苯乙烯溶液测定了~(13)C NMR弛豫参数,用1g-x~2分布、Cole-Cole分布和构象跳跃模型对主链的分子运动进行了分析讨论,并对芳环侧基的内旋转运动也进行了分析,求出了活化能和跳跃速率。结果表明,轻度化学交联对相关时间分布有一定影响,对链段运动的势垒没有明显影响。支链链长对~(13)C NMR弛豫的影响和对线形聚合物的影响是类似的。     

Enantioseparation of chiral N-imidazole derivatives by electrokinetic chromatography using highly sulfated cyclodextrins: mechanism of enantioselective recognition

Baseline separation of ten new substituted [1-(imidazo-1-yl)-1-phenylmethyl)] benzothiazolinone and benzoxazolinone derivatives, with one chiral center, was achieved by CD-EKC using highly sulfated CDs (alpha, beta, gamma highly S-CDs) as chiral selectors. The influence of the type and concentration of the chiral selectors on the enantioseparations was investigated. The highly S-CDs exhibit a very high enantioselectivity power since they allow excellent enantiomeric resolutions compared to those obtained with the neutral CDs. The enantiomers were resolved with analysis times inferior to 2.5 min and resolution factors R(s) of 3.73, 3.90, 1.40, and 4.35 for compounds 1, 2, 3, and 5, respectively, using 25 mM phosphate buffer at pH 2.5 containing either highly S-alpha-CD, highly S-beta-CD, and highly S-gamma-CD (3 or 4% w/v) at 298 K, with an applied field of 0.30 kV/cm. The determination of the enantiomer migration order for the various analytes and the study of the analyte structure-enantioseparation relationships display the high contribution of the interactions between the analytes phenyl ring and the CDs to the enantiorecognition process. The thermodynamic study of the analyte-CD affinities permits us to improve our knowledge about the enantioseparation mechanism.