CO_2-甲醇和CO_2-乙醇体系的界面性质

在交叉缔合的均相状态方程的基础上,结合密度梯度理论(density gradient theory,DGT),建立了适用于CO2-甲醇和CO2-乙醇二元体系界面性质研究的状态方程,对CO2-乙醇体系表面张力的关联结果与实验值吻合良好.阐明了CO2分子与甲醇分子和乙醇分子之间的交叉缔合作用对二元体系表面张力计算结果的影响,以及界面相中CO2与醇羟基之间的交叉缔合与温度和压力之间的关系.     

Acoustic absorption and dynamic compressibility studies of dilute and concentrated solutions of polystyrene in toluene and cyclohexane

Acoustic absorption and adiabatic compressibility measurements are reported on solutions of polystyrene (M_n = 89,000) in toluene and cyclohexane. The data in toluene cover a temperature range from 293 to 343°K and a concentration range of 10–400 Kg m^?3 (1–40 wt%). The dependence of acoustic absorption on concentration was found to be linear up to 100 kg m^?3, which corresponds to the concentration at which polymer–polymer interactions cause significant changes in the specific viscosity-concentration relationship. Up to 200 kg m^?3 the data could be fitted to computations based on an artificial separation of the dispersion into contributions from viscoelastic and segmental processes, using parameters obtained from a study of narrow molecular weight distribution samples at 25 kg m^?3. However, neither approach was capable of describing dispersions in the 300, 400 kg m^?3 solutions. The modification of the relaxation spectrum observed at the highest concentrations is ascribed to volume and entropy changes associated with alterations of the local environment around a segment of the polymer chain. These changes have their origin in interchain penetration and polymer–polymer contacts, and indicate that ‘entanglement’ is primarily entropic in effect. The adiabatic compressibility exhibited similar deviations from a simple concentration dependence, and allowed estimation of an incompressible volume increment associated with polymer–polymer interactions in the high-concentration entangled matrix. However, the adiabatic compressibilities of solutions of polystyrene, 10–15 kg m^?3, in cyclohexane showed no deviations from simple behavior in the region of the theta temperature. Measurements of the adiabatic compressibility of polystyrene in mixtures of cyclohexane-toluene have been used to obtain the relative magnitude of solvent and polymer contributions to the excess compressibility.     

Cumulant functions in optical coherence theory

Cumulant functions are introduced to describe the statistical state of a radiation field. These functions are simply related to the optical coherence functions but have some interesting features. It is shown that if the cumulant functions of all orders greater than some numberN ₀ vanish then they also vanish for all orders greater than 2. Thermal field is the only field having this property. This property holds whether the field is described by a classical stochastic process or by a quantum density operator. Further the particular operator ordering used in defining these cumulant functions for the quantized field affects only the second order cumulant function. To describe the statistical state of a vector field such as partially polarized or unpolarized radiation, one would need to introduce cumulant tensors.     

Diffractography vs. holography—A stress analyst's comparison

Holographic interferometry provides an elegant and very sensitive displacement measurement means for the experimental stress analyst. Recently however, a related optical techniques, “diffractography”, has been developed which offers an alternative to holography in many cases, particularly in those experiments where information along one or more discrete lines is sufficient. This paper compares both approaches and presents new experimental data on deflections of a cantilever steel plate obtained using both techniques.     

A diffraction transducer for vibration analysis

The recently described ditfractographic technique¹, utilizing the diffraction of light passing through an aperture formed by two edges, one fixed as a reference, is used to determine small vibratory displacements. The transducer has little or no inertia, is noncontacting, and has high sensitivity and accuracy. A “time averaged” method is presented whereby peak amplitudes can be obtained with no readout instrumentation and no upper-frequency limit. Alternatively, a photodetector can be used to determine vibration amplitudes with frequency response limited only by the detector circuit.     

Rapid isoelectric trapping in a micropreparative-scale multicompartment electrolyzer

A multicompartmental electrolyzer called membrane-separated wells for isoelectric focusing and trapping (MSWIFT) has been developed and tested for micropreparative-scale isoelectric trapping separations. In the MSWIFT, the length of the heat conduction path from the center of the compartments to the wall is less than 1 mm. The compartments are made from 99.8% nonporous alumina that has a high heat conductivity and a high specific heat capacity, leading to adequate Joule heat dissipation even at power loads as high as 5 W. The length of any compartment parallel to the electric field (the intermembrane distance) can be selected to be multiples of 1.5 mm, leading to compartment volumes that are multiples of about 60 muL. A maximum of 20 (1.5 mm long) separation compartments can be readily assembled in the current version of MSWIFT. The MSWIFT has been used to desalt samples, isolate small ampholytic components (amino acids, peptides, and dyes), prefractionate complex protein mixtures and enrich minor components; these separations were achieved in 20-60 min.     

A two transition state model for radical-molecule reactions: applications to isomeric branching in the OH-isoprene reaction

A two transition state model is applied to the prediction of the isomeric branching in the addition of hydroxyl radical to isoprene. The outer transition state is treated with phase space theory fitted to long-range transition state theory calculations on an electrostatic potential energy surface. High-level quantum chemical estimates are applied to the treatment of the inner transition state. A one-dimensional master equation based on an analytic reduction from two-dimensions for a particular statistical assumption about the rotational part of the energy transfer kernel is employed in the calculation of the pressure dependence of the addition process. We find that an accurate treatment of the two separate transition state regions, at the energy and angular momentum resolved level, is essential to the prediction of the temperature dependence of the addition rate. The transition from a dominant outer transition state to a dominant inner transition state is shown to occur at about 275 K, with significant effects from both transition states over the 30-500 K temperature range. Modest adjustments in the ab initio predicted inner saddle point energies yield predictions that are in quantitative agreement with the available high-pressure limit experimental observations and qualitative agreement with those in the falloff regime. The theoretically predicted capture rate is reproduced to within 10% by the expression [1.71 x 10(-10)(T/298)(-2.58) exp(-608.6/RT) + 5.47 x 10(-11)(T/298)-1.78 exp(-97.3/RT); with R = 1.987 and T in K] cm3 molecule(-1) s(-1) over the 30-500 K range. A 300 K branching ratio of 0.67:0.02:0.02:0.29 was determined for formation of the four possible OH-isoprene adduct isomers 1, 2, 3, and 4, respectively, and was found to be relatively insensitive to temperature. An Arrhenius activation energy of -0.77 kcal/mol was determined for the high-pressure addition rate constants around 300 K.     

Gas phase activation energy for unimolecular dissociation of biomolecular ions determined by focused RAdiation for gaseous multiphoton ENergy transfer (FRAGMENT)

We present a novel approach for the determination of activation energy for the unimolecular dissociation of a large (>50 atoms) ion, based on measurement of the unimolecular dissociation rate constant as a function of continuous-wave CO(2) laser intensity. Following a short ( approximately 1 s) induction period, CO(2) laser irradiation produces an essentially blackbody internal energy distribution, whose 'temperature' varies inversely with laser intensity. The only currently available method for measuring such activation energies is blackbody infrared radiative dissociation (BIRD). Compared with BIRD, FRAGMENT: (a) eliminates the need to heat the surrounding ion trap and vacuum chamber to each of several temperatures (each requiring hours for temperature equilibration); (b) offers a three-fold wider range of effective blackbody temperature; and (c) extends the range of applications to include initially cold ions (e.g., gas-phase H/D exchange). Our FRAGMENT-determined activation energy for dissociation of protonated bradykinin, 1.2 +/- 0.1 eV, agrees within experimental error to the value, 1.3 +/- 0.1 eV, previously reported by Williams et al. from BIRD experiments. Copyright 1999 John Wiley & Sons, Ltd.     

An EPR method for probing surface magnetic fields, dipolar distances, and magnetization fluctuations in single molecule magnets

We outline a spectroscopic method for probing the effective magnetic field B on the surface of crystals of the single molecule magnet (SMM) [(C6H15N3)6Fe8(mu3-O)2(mu2-OH)12]Br7(H2O)Br.H2O, (Fe8Br8). This technique utilizes the line shape changes in the EPR spectra of the organic radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) (g = 2.0036, single peak) adsorbed onto the sample. The temperature dependence of the EPR line shifts scale with the sample's magnetization as measured by a SQUID magnetometer. Analysis of the line shape in terms of dipolar coupling between the DPPH and the SMM molecules on the surface, yields their average dipolar distance. The method's potential for measuring the magnetization fluctuation dynamics is briefly pointed out using the SMM [Mn12O12(CH3COO)16(H2O)4].2CH3COOH.4H2O (Mn12-acetate).     

Chiral salen ligands designed to form polymetallic complexes

Chiral salen ligands capable of forming polymetallic complexes have been designed. The ligands possess substituents in the 4,4′-positions, but have no substituent in the 3,3′-positions to allow a second metal ion access to the salen oxygen atoms. Ligands in which a polyether chain links the 4,4′-positions were prepared and complexed to copper. In addition, acyclic ligands with potential metal coordinating substituents in the 4,4′-positions were prepared and complexed to copper and cobalt. The crystal structure of one of the cobalt complexes shows it to be a trimetallic complex in which a Co(II)(OAc)₂ group coordinates to the salen oxygen atoms of two Co(III)(salen)(OAc) units. In contrast, the crystal structure of a Co(salen) complex with tert-butyl groups attached to the 3,3′-positions is found to be mononuclear. All of the complexes were tested as asymmetric phase transfer catalysts for the asymmetric alkylation of an alanine methyl ester, forming (R)-α-methyl phenylalanine methyl ester with up to 85% ee.