针对连续变化法测定络合物稳定常数实验中可能出现的设计缺陷的讨论

连续变化法测定络合物组成和稳定常数是大学化学中的经典学生实验。但针对1：2和1：3的络合反应，实验教科书的设计中可能出现数据点过少也就是溶液配制过少的问题。如果按照要求配制溶液，由于没有完全反应的混合溶液，而其他混合溶液给出的数据又都呈良好的线性，就缺少了用来估算曲线的数据点，结果是，将没有足够的数据对稳定常数进行估算。对这种可能出现的数据点过少的实验设计的原因、结果和解决方法进行了探讨。     

Protein dielectrophoresis: Key dielectric parameters and evolving theory

Globular proteins exhibit dielectrophoresis (DEP) responses in experiments where the applied field gradient factor ∇E² appears far too small, according to standard DEP theory, to overcome dispersive forces associated with the thermal energy kT of disorder. To address this a DEP force equation is proposed that replaces a previous empirical relationship between the macroscopic and microscopic forms of the Clausius–Mossotti factor. This equation relates the DEP response of a protein directly to the dielectric increment δε⁺ and decrement δε⁻ that characterize its β-dispersion at radio frequencies, and also indirectly to its intrinsic dipole moment by way of providing a measure of the protein's effective volume. A parameter Γ_pw, taken as a measure of cross-correlated dipole interactions between the protein and its water molecules of hydration, is included in this equation. For 9 of the 12 proteins, for which an evaluation can presently be made, Γ_pw has a value of ≈4600 ± 120. These conclusions follow an analysis of the failure of macroscopic dielectric mixture (effective medium) theories to predict the dielectric properties of solvated proteins. The implication of a polarizability greatly exceeding the intrinsic value for a protein might reflect the formation of relaxor ferroelectric nanodomains in its hydration shell.     

A pH‐responsive cyclopolymer having phospho‐ and sulfopropyl pendents in the same repeating unit: Synthesis,characterization, and its application as an antiscalant

A new zwitterionic monomer 3‐[diallyl{3‐(diethoxyphosphoryl)propyl}ammonio]propane‐1‐sulfonate has been synthesized and cyclopolymerized to give the corresponding polyzwitterion (±) (PZ) bearing both phosphonate and sulfonate functionalities on each repeating unit. phosphonate ester hydrolysis in PZ gave a pH‐responsive dibasic polyzwitterionic acid (±) (PZA) bearing ? PO₃H₂ units. The PZA under pH‐induced transformation was converted into polyzwitterion/anion (± ?) (PZAN) and polyzwitterion/dianion (± =) (PZDAN) having respective ? PO₃H^? and ? PO₃^2? units. The polymers′ interesting solubility and viscosity behaviors have been investigated in detail. The apparent protonation constants in salt‐free water and 0.1 M NaCl of the ? PO₃^2? in (± =) (PZDAN) and ? PO₃H^– in (± ?) (PZAN) as well as in their corresponding monomeric units have been determined. Evaluation of antiscaling properties of the PZA using supersaturated solution of CaSO₄ revealed ≈100% scale inhibition efficiency at a meager concentration of 20 ppm for a duration of 45 h at 40 °C. The PZA has the potential to be used effectively as an antiscalant in reverse osmosis plant. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5130–5142     

Macrokinetic study on ozone boundary concentration. Effect of temperature

The process of ozone production in pure oxygen using the tubular, high voltage pulse supplied ozonizer was studied. The unusual methodology of conducting kinetics measurements of the ozone synthesis process was presented. It was shown how the process rate changes along the discharge gap. The effect of power density and gas residence time in the discharge gap on the process rate was analysed. The temperature influence on the course of the process, particularly on the ozone boundary concentration and ozone decomposition rate constant, was discussed.     

TSC defect level in silicon produced by irradiation with muons of GeV-energy

Deep level transient spectroscopy has been used to observe the reduced concentrations of vacancy-related defects in γ-irradiated n-type Si containing hydrogen atoms. Data are presented on the efficiency and depth of this damage reduction as a function of the duration and temperature of the exposure to the plasma used to introduce the atomic hydrogen. A 3-hour exposure in an H plasma at 300°C prior to irradiation reduced the concentrations of the O-V, V-V and P-V centres by half or more to a depth of ～20 μm, compared to the control samples.     

Phase transitions and metastable states in TlGaSe2

The results of measurements of the dielectric constant of TlGaSe₂ in temperature range of successive phase transitions are presented. An anomaly in the temperature dependence of the real part of dielectric constant in TlGaSe₂ has been observed at about 242?K in addition to anomalies at 115, 108, and also near 65?K as reported in previous publications. The presence of temperature hysteresis effects in temperature interval between 115 and 242?K allowed making a conclusion about possible existence of an incommensurate phase in the mentioned temperature range. A model of succession of the structural phase transitions in TlGaSe₂ has been suggested.     

Preparation of modified polymer blend and electrical performance

In this study, a modified binary polymer blend made up of polycarbonate and polystyrene blend has been prepared by loading of aluminum oxide (Al₂O₃) as a dopant. The role of alumina with polymer blend system was addressed in view of interfacing criteria. The filler concentration of modified blend was taken as 5, 10, and 15%. The morphological, thermal, and electrical properties were characterized by various techniques. Optical microscopy confirms the homogenous dispersion of Al₂O₃ in blend. The presence of alumina was detected by subatomic level using atomic force microscope (both two and three dimensional approach). The differential scanning calorimetric thermographs demonstrate decreasing softing point as function of alumina loading. The dielectric properties such as dielectric constant, loss, and electrical modulus were studied under DC bias. The effect of DC bias exhibits significant changes at low amount of Al₂O₃. The dielectric polarization supports Maxwell Wagner (MW) theory due to low frequency response. 15% Al₂O₃ gives the highest dielectric constant (ε′) value (3.5?×?10⁵) at 10 Hz. The polymer modified blend with Al₂O₃ may be used as a one of the best dielectric medium.     

On the structure of the microscopic dielectric tensor in incommensurate crystals

A microscopic model for calculating the optical response of incommensurately modulated phases in insulating crystals is presented. The dominant contribution to the dielectric permittivity tensor is shown to originate from the lowest-index reciprocal lattice vectors, thus proving the validity of the mesoscopic approach developed in several earlier studies. The expression for the mesoscopic Fourier component of the dielectric tensor is obtained. These results may be useful in relation to the controversial problem of the optical activity observed in the incommensurate phases of some A₂BX₄ family crystals.     

Chemical Shift and Its Uses as an Electronic Parameter in Structure-Activity Correlations

Apparent correlations are found between the N-H chemical shifts of congeneric series of compounds and the dipole moments of the molecules, such as lactams and thiolactams, cyclic ureas and thioureas. When there is a high degree of correlation, either the N-H chemical shift or the dipole moment of the molecule can be used as an electronic parameter in correlating the biological activity with the chemical structure. In a series of substituted salicylaldehydes the Hammett σ constant gives better correlation with the biological activity than the O-H chemical shift. This is probably due to the anisotropic effect of the substituent besides the electronic effect. Other factors affecting the N-H chemical shift, e.g. intramolecular hydrogen-bonding of nitrosoureas and the deshielding effect of a benzene ring, in o-phenyleneureas are also presented. In spite of the limitations, the chemical shifts of many compounds can be obtained very easily, therefore, their uses in structure-activity correlations deserve further investigation.