Effects of Inorganic Salts on Micellization and Solubilization in an Aqueous Solution of Poly(ethylene oxide)/Poly(propylene oxide)/Poly(ethylene oxide) Triblock Copolymer

The effects of inorganic salts on micellization and solubilization of prednisolone in aqueous solution of poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) triblock copolymer (Pluronic P85) were studied. The effect of inorganic salts on decrease in the cloud point and the critical micelle concentration (cmc) of Pluronic P85 was the order of Na₂HPO₄ > NaH₂PO₄ > NaCl > NaBr. Moreover, it was found that Pluronic P85 forms two kinds of micelles: monomolecular micelles and polymolecular micelles. The polymolecular micelle increased with increasing amount of added inorganic salts. Moreover, solubilization behavior is explained from the standpoint of salting out for prednisolone and association characteristics of Pluronic P85.     

单分子链胶束的胶束化行为与相关新概念的提出

采用水溶液均聚合方法,制备了阳离子型表面活性单体（2-丙烯酰胺基）乙基十四烷基二甲基溴化铵（AMC14AB）的均聚物,使用荧光探针法、表面张力测定及电导测定法,重点考察了均聚物P（AMC14AB）在水溶液中的胶束化行为与表面吸附现象．在水溶液中,均聚物P（AMC14AB）呈现单分子链胶束的聚集形态,具有零临界胶束浓度（CMC=0）,从开始加入P（AMC14AB）起,水溶液中随即产生单分子链胶束,不存在Krafft温度．P（AMC14AB）在溶液表面也发生表面吸附,使水的表面张力下降,即P（AMC14AB）也具有表面活性;随着浓度增大,表面吸附量增大,水的表面张力持续下降;当表面吸附达到饱和时,表面张力一浓度曲线上出现突变点,该点应该定义为饱和的表面吸附浓度（SSAC）,而不应该再称为临界胶束浓度．P（AMC14AB）单分子链胶束溶液对疏水有机物（甲苯）的增溶情况,明显不同于普通小分子表面活性剂十六烷基二甲基溴化铵（CTAB）的多分子胶束溶液,甲苯增溶量-P（AMC14AB）浓度的关系曲线上无突变点,而且对甲苯的增溶能力高于CTAB的多分子胶束溶液．     

Electrical Conductivity in TCNQ Salts of Bis(4-dimethylaminophenylimino) sulfur and its Structural Analogues

Four compounds, N,N,N',N'-tetramethyl-p-phenylene diamine, N,N,N',N'-tetramethyl-benzidine, 4,4'-bis(dimethylamino)azobenzene and bis(4-dimethylaminophenylimino)sulfur (BAPIS) were examined electrochemically and spectroscopically. Each was shown to be a fairly good donor forming in its first oxidation state a radical-cation. The latter two materials surprisingly exhibited only single one-electron oxidations. Conformational flexibility about the -NSN- unit was studied by NMR spectroscopy and ab initio molecular orbital theory. The experimental ΔG* for a cis-trans to trans-cis interconversion in BAPIS was found to be 11.9 kcal/mole.

The four donors all form 1:1 adducts with TCNQ. The compaction resistances of the complexes have been measured as a function of temperature. Of the four, (BAPIS)(TCNQ) appears to be a one-dimensional material. The other three complexes behave as typical mixed stack organic semiconductors.     

新型共价交联纳米胶囊的构筑、调控与功能

利用共价自组装的方法，将刚性组装基元与柔性链在一定条件下进行横向交联，可以方便地制备出单层高分子纳米胶囊.相比于传统的非共价超分子囊泡，这种新型的共价纳米胶囊具有结构稳定、尺度可控且分散性优异等诸多优点.因此，如何利用化学合成的手段来制备新型的纳米胶囊，并进一步实现对其结构调控和性能的探究具有十分重要的意义.针对这些问题，分别发展了功能化的柱[5]芳烃、四苯乙烯、卟啉、三嗪、苯硼酸酐等不同类型构筑基元，并使之与两端具有活性位点的柔性烷基链在适当的溶剂中进行聚合反应，最终获得了一系列的共价纳米胶囊.通过对其结构的修饰和调控，发现这些功能化的高分子纳米胶囊在光捕获、人工酶、抗菌材料以及药物载体等领域具有诸多潜在应用价值.未来，新型共价高分子纳米胶囊的开发、功能化以及应用有望得到进一步的拓展.     

Selective Electrochemical Epinephrine Sensor Using Self‐Assembled Monomolecular Film of 1,8,15,22‐Tetraaminophthalocyanatonickel(II) on Gold Electrode

This article describes the highly sensitive and selective determination of epinephrine (EP) using self‐assembled monomolecular film (SAMF) of 1,8,15,22‐tetraamino‐phthalocyanatonickel(II) (4α‐Ni^IITAPc) on Au electrode. The 4α‐Ni^IITAPc SAMF modified electrode was prepared by spontaneous adsorption of 4α‐Ni^IITAPc from dimethylformamide solution. The modified electrode oxidizes EP at less over potential with enhanced current response in contrast to the bare Au electrode. The standard heterogeneous rate constant (k°) for the oxidation of EP at 4α‐Ni^IITAPc SAMF modified electrode was found to be 1.94×10^?2 cm s^?1 which was much higher than that at the bare Au electrode. Further, it was found that 4α‐Ni^IITAPc SAMF modified electrode separates the voltammetric signals of ascorbic acid (AA) and EP with a peak separation of 250 mV. Using amperometric method the lowest detection limit of 50 nM of EP was achieved at SAMF modified electrode. Simultaneous amperometric determination of AA and EP was also achieved at the SAMF modified electrode. Common physiological interferents such as uric acid, glucose, urea and NaCl do not interfere within the potential window of EP oxidation. The present 4α‐Ni^IITAPc SAMF modified electrode was also successfully applied to determine the concentration of EP in commercially available injection.     

Retardation of monomolecular reactions in the solid phase

The rate constants of initial monomolecular stages of thermal decomposition in the solid phase were measured for 22 organic compounds. The ratio of rate constants of decomposition in the melt and solid state, characterizing the reaction retardation in the crystal lattice, was determined. The retardation effect was compared to the physical properties of the crystal. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1261–1264, July, 1999.     

Multiphoton dissociation of C3F6O

Major characteristics of multiphoton absorption and multiphoton dissociation of hexafluoropropene oxide (HFPO) were studied. Spectral relationships of the average number of IR photons absorbed per molecule and the yield of multiphoton dissociation were determined in the range of 1040-985 cm^–1 at different laser fluences. At the laser line 1025.3 cm^–1, the effect of collisions with buffer gases on the HFPO multiphoton absorption and multiphoton dissociation was studied and theq-factor was determined (q = O.6 at= 0.55J cm^–2). Characteristic features of HFPO decomposition under collisional conditions (p _HFPO> 0.1 Torr) were discussed. An anomalous difference in the values for quantum efficiency of multiphoton dissociation for long-wave and short-wave wings of HFPO absorption band was revealed. A procedure for correlating the experimental and theoretical data on the yield of multiphoton dissociation (when theq-factor is unknown) was suggested, and corresponding calculations were performed for the frequency 989.6 cm^–1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1927–1932, November, 1994.     

A STRUCTURALLY BASED ANALYTIC MODEL OF GROWTH AND BIOMASS DYNAMICS IN SINGLE SPECIES STANDS OF CONIFERS

A theoretically based analytic model of plant growth in single species conifer communities based on the species fully occupying a site and fully using the site resources is introduced. Model derivations result in a single equation simultaneously describes changes over both, different site conditions (or resources available), and over time for each variable for each species. Leaf area or biomass, or a related plant community measurement, such as site class, can be used as an indicator of available site resources. Relationships over time (years) are determined by the interaction between a stable foliage biomass in balance with site resources, and by the increase in the total heterotrophic biomass of the stand with increasing tree size. This structurally based, analytic model describes the relationships between plant growth and each species’ functional depth for foliage, its mature crown size, and stand dynamics, including the self‐thinning. Stand table data for seven conifer species are used for verification of the model. Results closely duplicate those data for each variable and species. Assumptions used provide a basis for interpreting variations within and between the species. Better understanding of the relationships between the MacArthur consumer resource model, the Chapman–Richards growth functions, the metabolic theory of ecology, and stand development resulted.     

Cd‐Doping Effects on The Properties of Polycrystalline α‐In2Se3 Thin Films

The X‐ray diffraction has revealed that the polycrystalline hexagonal structured α‐In₂Se₃ thin films grown at substrate temperature of 200 °C with the unit cell parameters a = 4.03 Å and c = 19.23 Å becomes polycrystalline hexagonal structured InSe with a unit cell parameters of a = 4.00 Å and c = 16.63 Å by Cd‐doping. The analysis of the conductivity temperature dependence in the range 300‐40 K revealed that the thermionic emission of charged carriers and the variable range hopping are the predominant conduction mechanism above and below 100 K, respectively. Hall measurements revealed that the mobility is limited by the scattering of charged carriers through the grain boundaries above 200 K and 120 K for the undoped and Cd‐doped samples, respectively. The photocurrent (I_ph) increases with increasing illumination intensity (F) and decreasing temperature up to a maximum temperature of ∼100 K, below which I_ph is temperature invariant. It is found to have the monomolecular and bimolecular recombination characters at low and high illumination intensities, respectively. The Cd‐doping increases the density of trapping states that changes the position of the dark Fermi level leading to the deviation from linearity in the dependence of I_ph on F at low illumination intensities.     

Influence of the Structure of a Macromolecular System on the Processes of Association of Molecules of Rhodamine 6G in Aqueous‐Polyelectrolytic Solutions

The processes of association of rhodamine6G molecules in aqueous solutions of polyacrylic acid are studied by spectroscopic methods. The efficiency of formation of the dimers of rhodamine 6G as a function of the concentration of the polyelectrolyte and its chain length is established. The angles between monomer molecules in the dimers of rhodamine 6G are determined for different concentrations of the polyacrylic acid and lengths of the polyion chain.