Formation of particles of metal hydroxides in water solution of polymer

The stages of the formation of metal hydroxide particles in water medium were described. The first stage is the formation of complexes between the stabilizer and metal ion or of metal polyions containing a few metal ions. Dependence between the number of metal ions in polyion and its charge on the pH is described. The second stage is the formation of the metal hydroxide particles by the aggregation of polyions or their adsorption on/in the stabilizer. The distribution of the polyion number in the particles in polyion aggregation is described by the equation p(k) = k(ks-1)(k-1)/ksk and in polyion adsorption on/in the stabilizer particles is more narrow and is described by the equation p(k) = exp(-ks)/ks(-k)/k!, where k and ks are the number and the average number of polyions in the particle.     

尿激酶活性测定方法的比较

根据中国及日本药典,对测定尿激酶活性的两种方法的灵敏度和重复性进行了考察对比,对不同样品测定结果进行了比较。     

Dynamical and statistical effects of the intrinsic curvature of internal space of molecules

The Hamilton dynamics of a molecule in a translationally and/or rotationally symmetric field is kept rigorously constrained in its phase space. The relevant dynamical laws should therefore be extracted from these constrained motions. An internal space that is induced by a projection of such a limited phase space onto configuration space is an intrinsically curved space even for a system of zero total angular momentum. In this paper we discuss the general effects of this curvedness on dynamics and structures of molecules in such a manner that is invariant with respect to the selection of coordinates. It is shown that the regular coordinate originally defined by Riemann is particularly useful to expose the curvature correction to the dynamics and statistical properties of molecules. These effects are significant both qualitatively and quantitatively and are studied in two aspects. One is the direct effect on dynamics: A trajectory receives a Lorentz-like force from the curved space as though it was placed in a magnetic field. The well-known problem of the trapping phenomenon at the transition state is analyzed from this point of view. By showing that the trapping force is explicitly described in terms of the curvature of the internal space, we clarify that the physical origin of the trapped motion is indeed originated from the curvature of the internal space and hence is not dependent of the selection of coordinate system. The other aspect is the effect of phase space volume arising from the curvedness: We formulate a general expression of the curvature correction of the classical density of states and extract its physical significance in the molecular geometry along with reaction rate in terms of the scalar curvature and volume loss (gain) due to the curvature. The transition state theory is reformulated from this point of view and it is applied to the structural transition of linear chain molecules in the so-called dihedral angle model. It is shown that the curvature effect becomes large roughly linearly with the size of molecule.     

Investigation of some modes of flat-bed chromatography

A comparison of different chromatographic methods is presented: column liquid chromatography (CLC), thin layer chromatography (TLC), and continuous-elution flat-bed chromatography (CEFBC), which is in fact a combination of the first two methods. In CEFBC a sample is applied to a sorbent layer in a steady flow of eluent, and the components are detected directly on the layer, or immediately upon leaving it, during the separation process. It is shown that evaluation of the separation processes in CEFBC is best accomplished in terms of the parameters applicable in CLC. The reproducibility of the analytical results obtained by CEFBC is better than in the case of TLC by a factor of 6 to 10, and approaches that known for CLC.     

Crucial importance of translational entropy of water in pressure denaturation of proteins

We present statistical thermodynamics of pressure denaturation of proteins, in which the three-dimensional integral equation theory is employed. It is applied to a simple model system focusing on the translational entropy of the solvent. The partial molar volume governing the pressure dependence of the structural stability of a protein is expressed for each structure in terms of the excluded volume for the solvent molecules, the solvent-accessible surface area (ASA), and a parameter related to the solvent-density profile formed near the protein surface. It is argued that the entropic effect originating from the translational movement of water molecules plays critical roles in the pressure-induced denaturation. We also show that the exceptionally small size of water molecules among dense liquids in nature is crucial for pressure denaturation. An unfolded structure, which is only moderately less compact than the native structure but has much larger ASA, is shown to turn more stable than the native one at an elevated pressure. The water entropy for the native structure is higher than that for the unfolded structure in the low-pressure region, whereas the opposite is true in the high-pressure region. Such a structure is characterized by the cleft and/or swelling and the water penetration into the interior. In another solvent whose molecular size is 1.5 times larger than that of water, however, the inversion of the stability does not occur any longer. The random coil becomes relatively more destabilized with rising pressure, irrespective of the molecular size of the solvent. These theoretical predictions are in qualitatively good agreement with the experimental observations.     

A New Formulation of the Lindemann Mechanism of Unimolecular Reactions

A new formulation of the Lindemann mechanism of unimolecular reactions in gaseous phase is presented, without the use of steady state hypothesis. It is hereby shown that the nature of applicability of steady state hypothesis in the regime of high reactant gas pressure is different from that in the regime of low gas pressure. In the former case it is an equilibrium approximation, while in the latter case it is a highly reactive intermediate approximation in no connection with a steady state. Furthermore for the latter case it is shown that in the classical formulation of Lindemann mecbRnism the use of steady state hypothesis is an ad hoc assumption. A highly reactive intermediate in the sense that its concentration is very small during the whole course of reaction is a necessary condition for the applicability of very reactive intermediate approximation. When the two distinctive nature of the applicability of steady state hypothesis is mlxed-up, wrong or useless conclusion may be arrived at. The only possible case of realizing a true steady state in a complex reaction is pointed out.     

Thermodynamic parameters of solvation of nonelectrolytes in aqueous solutions of amides of carboxylic acids

Interaction and reorganization contributions to solvation enthalpies of nonelectrolytes in aqueous solutions of amides of carboxylic acids with different degree of N-substitution and N-methylpyrrolidone are calculated. The data are discussed using structurally thermodynamic characteristics of water-amide systems obtained by us previously. It is found that the type of concentration dependence of the solvation enthalpy of nonelectrolytes in all solutions investigated is determined by the type of reorganization component. It is shown that the highest solvation exothermicity of nonelectrolytes in water is due to the lowest value of the reorganization contribution in spite of that nonelectrolytes interact weaker with water than with non aqueous components.     

Spectrophotometric determination of traces of selenium with diaminobenzidine

Diaminobenzidine is suitable for the spectrophotometric determination of traces of selenium. The reaction is very sensitive, the molecular extinction coefficient being as high as 10,200. The reaction is specific, the most common ions causing no perturbation. The procedure is especially valuable for the determination of traces selenium in tellurium and in sulfur, provided that the latter is present in the sulfate form.     

自由基聚合中平均聚合度的学习

自由基聚合是《高分子化学》课程的重要一章 ,其中 ,平均聚合度是自由基聚合微观动力学的重要研究内容。正确理解其概念 ,掌握各种数学表达式的涵义 ,对高分子化学的学习十分有益 ,本文对不同终止和链转移情况下平均聚合度的表述方法进行了讨论     

Photometric complex-formation titrations of submicromole amounts of metals in the presence of an approximately equivalent amount of indicator

The photometric titration of the metal indicator complex MI with a ligand L is discussed. A tangent procedure is adopted for the determination of the end-point. From this procedure, in combination with an assumed maximum titration error, titration conditions have been derived. A procedure is introduced which, in conjunction with the derived titration conditions, permits the selection of a suitable titration medium by means of a diagram in which log K, log alpha and log chi are plotted vs. pH. The procedure is applied to determination of lead and zinc in the presence of citric acid, the medium used for their paper-electrophoretic separation. The use of citric acid introduces some limitations; it is shown that the method developed is generally applicable.     

A study of the reproducibility of analytical balances

The variation of balance rest point reproducibility over a wide range of sensitivities is surveyed. At low sensitivities, the reproducibility in scale units is a constant. The weighing reproducibility in milligram units in this region is limited by the readability of the scale and may be improved by increasing balance sensitivity or replacing the regular scale with a micro scale and magnifier. As the sensitivity is increased above a certain limit, control of milligram reproducibility passes from scale readability to the mechanical error of the balance. At high sensitivities, reproducibility in milligram units is practically constant and this constant is a criterion of the mechanical character of the balance.     

Physical principles of catalysis of the curing of epoxy polymers in the presence of carbon nanotubes

A structural interpretation of the catalytic action of carbon nanotubes on the curing of epoxy polymers is proposed. It is based on the fractal analysis ideas. It is shown that essentially the only factor determining the kinetics of the curing process is the microgel structure characterized by its fractal dimension. The most important conclusion from the obtained results is the fact that the reaction rate dependences on the structural parameters are described by the same correlation for the epoxy polymer curing reaction both in the presence and absence of carbon nanotubes. This means that the catalytic effect of carbon nanotubes consists in a change in the structure of microgels.     

Enthalpy of swelling of crosslinked copolymers of acrylic acid β-vinyloxyethylamide in water and ethanol

The thermodynamics of swelling of copolymers of acrylic acid β-vinyloxyethylamide with acrylamide and N-vinylpyrrolidone of various compositions in water and ethanol is investigated. It is established that the swelling of the copolymers in water is characterized by high negative enthalpy values and that the swelling in ethanol is an endothermic process. It is found experimentally that the hydrogels obtained experience contraction at elevated temperatures.     

Milestones of the development of kinetics of electrode reactions

The birth and the development of the kinetics of electrode processes?Cmostly focusing on the case of the hindered charge transfer step and the early period?Care reviewed. It is shown how this important branch of electrochemistry was established and how and why the ideas of chemical kinetics have been introduced in electrochemistry. The history of electrode kinetics represents a good example for the progress of science in general, since it can be followed how the experimental observations conduce to the development of theory and how the theory influences further research. It is also demonstrated that the acceptance of new ideas is a thorny path. An attempt is made to acknowledge the merit of the scientists whose experimental or theoretical contributions brought paradigmatic changes in the thinking about the nature of electrode processes. In this context, the appropriate naming of equations is also discussed by using the example of the Erdey-Grúz?CVolmer vs. Butler?CVolmer equation. A discussion concerning the present trends is also included, which perhaps may predict the near future. A longer prognosis is avoided since the history of science teaches us that the real breakthroughs could not be predicted.     

掺杂剂对聚乙炔性质影响的理论研究

以多烯烃模拟聚乙炔链,用CNDO/2方法讨论了各种掺杂剂对聚乙炔性质的影响,掺杂剂使孤子宽度收缩变窄,且p型掺杂剂比n型掺杂剂的影响更大,掺杂剂影响聚乙炔链中的电荷密度波,使电荷主要集中分布于掺杂剂附近的碳原子上。掺杂碱金属时,掺杂剂原子的最高占据轨道与聚乙炔中孤子自旋轨道之间的作用由Li到K依次增强,解释了ESR实验结果。     

Study of the influence of concentration on the time for first appearance of crystallization of polyethylene from xylene

An experiment is reported in which a simple laser light-scattering technique is used to measure the time for a critical turbidity to appear during the crystallization of polyethylene in xylene. The effect is examined over the entire range of solution concentration, and it is found that the relation between this concentration and temperature is linear for all solutions, provided that the time for turbidity to develop is arranged to be the same in all cases. In the appendix it is reasoned that similar results could have been obtained if, instead, times had been measured to a given degree of crystallinity rather than of turbidity. Departures from this linearity at low concentrations are taken as indicating multimolecular nucleation for all concentrations greater than about 1%.     

Determination of the concentration dependence of polyelectrolyte diffusion coefficients by application of the Boltzmann gradient method

The concentration dependence of a polyelectrolyte diffusion coefficient in aqueous low salt solution (KCl, 1 mM) is determined from a single dynamic gradient experiment. The Boltzmann method is applied to calculate the diffusion coefficient. A special diffusion cell is constructed that minimizes aberrations in the optical detection of the polyion concentration profile. Bovine serum albumin (BSA) is chosen as a model polyion. To get information about the diffusion process down to very small polyion concentrations, the BSA molecule is fluorescently labeled. The fluorescence intensity is used as a measure of the polyion concentration. The change of the polyion net charge caused by labeling is discussed. The cell is illuminated by an LED, and the fluorescence intensity profile is detected by a CCD camera. Experiments at 5 and 17 degrees C show that the diffusion coefficient of labeled BSA remains constant in the very low polyion concentration range below a threshold of about 1.5 g/l. This is in contradiction to the linear concentration dependence of polyion diffusion coefficients at very low concentrations often postulated in the literature without reference to direct experimental evidence. Our finding is confirmed by dynamic light scattering experiments published recently. An explanation for this behavior based on a modified Donnan osmotic compressibility approach is given.     

Influence of the polarity of the microenvironment of pyrene on the intensity of its solid-phase luminescence

The sorption of pyrene by a filter paper modified with lead acetate is studied by luminescence methods. Based on changes in the vibrational structure of fluorescence spectra of pyrene, it was found that the polarity of the microenvironment of pyrene adsorbed from solutions in ethanol increases with the concentration of acetic or hydrochloric acid in these solutions. It was revealed that, when an acid is added, pyrene fluoresces and phosphoresces more intensely at room temperature. It is shown that this is associated with a more efficient sorption of pyrene by the filter paper from acid solutions in ethanol.     

The evaluation of the possibility of determining the function characterizing the connectedness of pores of various sizes from adsorption measurements

The possibility of determining the function characterizing the connectedness of pores of different types and sizes from the experimental adsorption isotherms is discussed. It is shown that the presence of joints of pores manifests itself by two indications in phase diagrams and adsorption isotherms that contain hysteresis loops. The first indication is related to the appearance of an additional phase transition in the phase diagram and/or a density jump in the isotherm. The second indication is related to different numbers of density jumps in the desorption and adsorption branches of adsorption isotherms. The character of the behavior of the adsorption branch of the isotherm in the case of the presence of regions of joints in a porous system is established.     

Determination of small quantities of xanthate

A new spectrophotometric method for the determination of very small amounts of xanthate in solutions, particularly cyanide solutions from gold-extraction plants, is described. It is based on the formation and extraction of copper(II) xanthate. The coefficient of variation is 1.0% at the 40-ppm level and 3.4% at the 4-ppm level and the lower limit of determination is approximately 0.5 ppm. Copper(II) xanthate normally decomposes into copper(I) xanthate and dixanthogen, but in the proposed method the decomposition is delayed.