改进的Herriott型光学长程池

用凹面反射镜和平面反射镜组成结构简单、光路易调的光多次反射装置,计算了这种光学系统的稳定性条件。考虑实际入射光束的直径和发散角,给出了最大反射次数的求法。制成适用于钛宝石激光光声光谱仪的光56次通过的长程池。理论计算的反射光斑分布与实验观测一致。这个技术有利于提高光声光谱和吸收光谱的探测灵敏度。     

Multi-Physics Modeling of Solid Oxide Fuel Cell Fueled by Methane and Analysis of Carbon Deposition

Internal reformation of low steam methane fuel is important for the high e ciency and low cost operation of solid oxide fuel cell. Understanding and overcoming carbon deposition is crucial for the technology development. Here a multi-physics model is established for the relevant experimental cells. Balance of electrochemical potentials for the electrochemical reactions, generic rate expression for the methane steam reforming, dusty gas model in a form of Fick's model for anode gas transport are used in the model. Excellent agreement between the theoretical and experimental current-voltage relations is obtained, demonstrating the validity of the proposed theoretical model. The steam reaction order in low steam methane reforming reaction is found to be 1. Detailed information about the distributions of physical quantities is obtained by the numerical simulation. Carbon deposition is analyzed in detail and the mechanism for the coking inhibition by operating current is illustrated clearly. Two expressions of carbon activity are analyzed and found to be correct qualitatively, but not quantitatively. The role of anode diffusion layer on reducing the current threshold for carbon removal is also explained. It is noted that the current threshold reduction may be explained quantitatively with the carbon activity models that are only qualitatively correct.     

Shortcut method for evaluation and design of a hybrid process for enantioseparations

Hybrid processes for enantioseparations have a considerable potential for reducing investment and operational costs. An example is the combination of simulated moving bed (SMB) chromatography and selective crystallisation. However, the design of integrated processes is a difficult task. A shortcut method is presented that can serve as a tool for design and estimation of the potential of such processes. The approach requires only limited experimental data and thus allows for systematic parameter studies. The method is based on the determination of the purity-performance characteristic of the SMB process and rigorous application of mass balances. The use of relative mass fluxes allows derivation of simple algebraic expressions for essential process parameters. The significant potential of combining SMB and crystallisation is demonstrated for the example of the separation of mandelic acid enantiomers.     

Start‐up of electrophoresis of an arbitrarily oriented dielectric cylinder

An analytical study is presented for the transient electrophoretic response of a circular cylindrical particle to the step application of an electric field. The electric double layer adjacent to the particle surface is thin but finite compared with the radius of the particle. The time‐evolving electroosmotic velocity at the outer boundary of the double layer is utilized as a slip condition so that the transient momentum conservation equation for the bulk fluid flow is solved. Explicit formulas for the unsteady electrophoretic velocity of the particle are obtained for both axially and transversely applied electric fields, and can be linearly superimposed for an arbitrarily‐oriented applied field. If the cylindrical particle is neutrally buoyant in the suspending fluid, the transient electrophoretic velocity is independent of the orientation of the particle relative to the applied electric field and will be in the direction of the applied field. If the particle is different in density from the fluid, then the direction of electrophoresis will not coincide with that of the applied field until the steady state is attained. The growth of the electrophoretic mobility with the elapsed time for a cylindrical particle is substantially slower than for a spherical particle.     

Treatment of uncorrected measurement bias in uncertainty estimation for chemical measurements

Consistent treatment of measurement bias, including the question of whether or not to correct for bias, is essential for the comparability of measurement results. The case for correcting for bias is discussed, and it is shown that instances in which bias is known or suspected, but in which a specific correction cannot be justified, are comparatively common. The ISO Guide to the Expression of Uncertainty in Measurement does not provide well for this situation. It is concluded that there is a need for guidance on handling cases of uncorrected bias. Several different published approaches to the treatment of uncorrected bias and its uncertainty are critically reviewed with regard to coverage probability and simplicity of execution. On the basis of current studies, and taking into account testing laboratory needs for a simple and consistent approach with a symmetric uncertainty interval, we conclude that for most cases with large degrees of freedom, linear addition of a bias term adjusted for exact coverage ("U(e)") as described by Synek is to be preferred. This approach does, however, become more complex if degrees of freedom are low. For modest bias and low degrees of freedom, summation of bias, bias uncertainty and observed value uncertainty in quadrature ("RSSu") provides a similar interval and is simpler to adapt to reduced degrees of freedom, at the cost of a more restricted range of application if accurate coverage is desired.     

Luminescence spectroscopy as a tool for testing of cure kinetics of epoxy resins

In this paper, steady-state luminescence spectroscopy is used for the analysis of curing of epoxy resin. The advantage of this method is its rapidity, simplicity and sensitivity. Moreover, this method is contactless, and thus non-invasive. The aim is to analyze epoxy resin, mathematically describe its curing kinetics and determine its storage temperature. Using the photoluminescence method, a rapid procedure for obtaining the necessary technological data is achieved. This method is suitable for continuous measurement in production because there is no contact with the material, and the measurement itself can be performed very quickly. The elaborated mathematical model can serve as a basis for creating algorithms for automated data processing in case of fully robotic workplaces.     

An improved SCPF scheme for polarization energy calculations

Convergence of the Self-Consistent Polarization Field (SCPF) method of polarization energy calculations for organic molecular materials is analysed. Use of the Conjugate Gradients method for solving the SCPF equations is proposed. Efficiency of both the original and the newly proposed approach is compared for selected model systems. Brief discussion of the factors influencing the performance of Krylov-space-based methods for polarization energy calculations is presented.     

The evaluation and use of properties of individual ions in slution

A critical examination is given of extra-thermodynamic methods for evaluation of properties of individual ions in solution. The ways in which such data may be applied, or are required in various problems concerning specific properties of electrolyte solutions and in the fields of kinetics, electrochemistry, colloid and interfacial chemistry, are outlined. Special attention is given to the problem of evaluation of individual ionic thermodynamic functions for the hydration of ions but, in some cases, corresponding data for nonaqueous solutions are available for discussion and are of interest in a comparative way. The reliability of the various methods is assessed and estimates of numerical values for various individual ionic functions are tabulated. The question of scales of individual ionic radii, on which some of the derived data depend, is also examined. The dependence of various properties for anions and for cations on ionic radius is discussed and data are plotted comparatively. It is shown that for most, but not all, properties, the values for anions are more sensitive to increasing ionic radius than are the values for cations. This behavior, as well as the exceptions, is of theoretical interest. The significance of ion-specific behavior at interfaces is considered and the importance of interactions between ions of like sign of charge is indicated.Presented at the Symposium on Electrolytes, University of Reading, September 13, 1977.     

Estimation of spinodals from the density profile of the vapor–liquid interface

An extension of a recently proposed method for the calculation of the spinodals in pure fluid systems from the interfacial properties is elaborated, which requires the density profile as only input. The foundation of this approach is the so-called Fuchs-transformation which gives an estimate for the tangential pressure profile from the density profile. Using molecular dynamics simulation data for argon and carbon dioxide as well as lattice Boltzmann simulation data for the argon-like Shan–Chen fluid, the accuracy of the approach is analyzed. The Fuchs-transformation is qualitative, however it is possible to estimate the temperature–density projection of the spinodal. Depending on the underlying correlation function for the interfacial density profile reasonable results are obtained for the liquid and the vapor spinodal. The advantage of this method is that equilibrium data can be used to estimate the spinodal which is experimentally impossible to access because it is a highly non-equilibrium property. In the final consequence of this approach only the coexistence vapor and liquid densities are required to estimate the temperature–density projection of the spinodals.     

Tuning Chemical and Physical Properties of Phosphorus Corroles for Advanced Applications

Although the affinity of metallocorroles to axial ligands is quite low, this is not the case when the chelated element is phosphorus. This work is hence focused on the mechanism of ligand exchange of six-coordinate phosphorus corroles as a tool for affecting their chemical and physical properties. These fundamental investigations allowed for the development of facile methodologies for the synthesis of a large series of complexes and the establishment of several new structure/activity profiles that may be used to understand and predict spectroscopic features and for tailor-made modification of photophysical and electrochemical properties. This is exemplified by the facile access to complexes with terminal groups that are of large potential for practical applications based on click chemistry, optical imaging, and surface science.     

Temperature and pressure effects on zeta potential values of reservoir minerals

An experimental study of the effect of temperature and pressure on zeta potential of typical reservoir minerals, including quartz, kaolinite, and calcite, is presented. Experiments included the design and construction of an electrophoretic cell for zeta potential measurements at variable pressure and temperature. Electrolyte concentration was varied in the range from 0.0001 to 0.1 M in the pH range from 2 to 9. For all the minerals it is found that the zeta potential decreases with temperature at a rate characteristic of each mineral; values are around -2.3 mV/degrees C for quartz, -0.96 mV/degrees C for kaolinite, and -2.1 mV/degrees C for calcite for pressure values less than 45 psi. The effect of pressure is found to depend on the mineral nature and pH of the electrolytic solution. In the case of quartz, a systematic increase in the value of the zeta potential with pressure is observed, whereas a decreasing trend is measured for the kaolinite. In the case of calcite, a decreasing trend is observed for pressures up to 45 psi, whereas the experimental data suggest an increasing trend for higher pressure values.     

A Water-Soluble Polymer-Lumefantrine Conjugate for the Intravenous Treatment of Severe Malaria

Uncomplicated malaria is effectively treated with oral artemisinin-based combination therapy (ACT). Yet, there is an unmet clinical need for the intravenous treatment of the more fatal severe malaria. There is no combination intravenous therapy for uncomplicated due to the nonavailability of a water-soluble partner drug for the artemisinin, artesunate. The currently available treatment is a two-part regimen split into an intravenous artesunate followed by the conventional oral ACT . In a novel application of polymer therapeutics, the aqueous insoluble antimalarial lumefantrine is conjugated to a carrier polymer to create a new water-soluble chemical entity suitable for intravenous administration in a clinically relevant formulation . The conjugate is characterized by spectroscopic and analytical techniques, and the aqueous solubility of lumefantrine is determined to have increased by three orders of magnitude. Pharmacokinetic studies in mice indicate that there is a significant plasma release of lumefantrine and production its metabolite desbutyl-lumefantrine (area under the curve of metabolite is ≈10% that of the parent). In a Plasmodium falciparum malaria mouse model, parasitemia clearance is 50% higher than that of reference unconjugated lumefantrine. The polymer-lumefantrine shows potential for entering the clinic to meet the need for a one-course combination treatment for severe malaria.     

An efficient algorithm for energy gradients and orbital optimization in valence bond theory

An efficient algorithm for energy gradients in valence bond theory with nonorthogonal orbitals is presented. A general Hartree-Fock-like expression for the Hamiltonian matrix element between valence bond (VB) determinants is derived by introducing a transition density matrix. Analytical expressions for the energy gradients with respect to the orbital coefficients are obtained explicitly, whose scaling for computational cost is m(4), where m is the number of basis functions, and is thus approximately the same as in HF method. Compared with other existing approaches, the present algorithm has lower scaling, and thus is much more efficient. Furthermore, the expression for the energy gradient with respect to the nuclear coordinates is also presented, and it provides an effective algorithm for the geometry optimization and the evaluation of various molecular properties in VB theory. Test applications show that our new algorithm runs faster than other methods.     

A general method for coulometric titration of alkylanilines with bromine

A general method is described for the coulometric titration of alkylanilines with anodically generated bromine. The reaction is carried out in water-acetic acid medium and the reactivity is governed by varying the water content and the concentration of bromide ion and by the addition of pyridine. In this way most types of alkylanilines can be titrated quantitatively. Unlike the case for alkylphenols, the bromine consumption is not always higher in the pyridine-containing media than in the pyridine-free. The bromine consumption is also more dependent on the bromide content of the medium than it is for alkylphenols. The mean relative error, for the best medium for each compound, is +/-0.9% for primary alkylanilines, +/-0.9% for secondary and +/-1.2% for tertiary.     

高锰酸钾-甲醛化学发光体系测定甲氧氯普胺

基于在甲醛的作用下,高锰酸钾对甲氧氯普胺的氧化作用而产生化学发光的现象,建立了一种新的用流动注射-化学发光法测定甲氧氯普胺含量的方法.该方法测定甲氧氯普胺的线性范围为0.2~100 mg/L,检出限为0.1 mg/L.对于8 mg/L的甲氧氯普胺标准溶液连续11次测定的相对偏差为1.2%.该方法可用于对制药废水、片剂和针剂中甲氧氯普胺含量的测定.     

A light-through-side cell and co-used furnace designed for micro-Raman spectra study on volatile melts

A new type of sample cell specially designed for micro-Raman spectra study on volatile melts is described.The cell is made of quartz.The lower section of the cell is circular ring-shaped and the one-end-closed hole in the cell is used for locating the heating body.The tube attached to the cell lid for placing the thermal couple is inserted into the sample,which ensures that the temperature measurement accuracy is good.The cell can be sealed for reducing the effect of the composition change caused by the inhomogeneous volatilization.During the Raman spectra scanning,the laser beam is transmitted into the cell through the side but not the top.Meanwhile,a furnace has been designed to match the cell.The heating body is closely coupled with the sample cell, and there is a hole on the side wall of the furnace for the entrance of the microlens.The assembly has performed well in the tested Raman spectrum measurement of molten NaNO₃ at 602℃.     

Modeling of Mechanical Properties of Polymeric Systems with Branching/Crosslinking,Particularly Their Mechanical Resistence and Stability

A theoretical method for the estimation of mechanical characteristics of polymeric structures is proposed. This method uses the statistical polymer method for modeling branched/crosslinked structures. The proposed method is utilized for the estimation of mechanical resistance and stability of microporous polymeric materials. An engineering method for the evaluation of mechanical stability and resistance of polymeric materials is derived.     

Anhydrous Sol-Gel Synthesis of Titania-Doped Siloxane Polymer for Integrated Optics

Sol-gel synthesis of organic-inorganic hybrid materials for planar waveguides and devices has received growing interest due to its low-cost processing and good suitability for doping. Titania is an important optical dopant, but homogeneous incorporation of titania in silica is difficult to be achieved by the conventional sol-gel process (aqueous system) because of the significant difference between the hydrolysis rates of the precursors. In this paper, we report an anhydrous sol-gel process for synthesising titania-doped siloxane polymers. The process consists of a hydrolysis of 3-methacryloxypropyltrimethoxysilane (MPS) with boric acid under anhydrous conditions, and a condensation with dimethyldimethoxysilane (DMDMS), diphenyldimethoxysilane (DPhDMS) and titanium ethoxide (TET). Optical characterisations for the produced titania-doped polymer were performed, and results showed that TET doping is useful for reducing the OH concentration of the synthesised polymer and is also effective for improving the optical quality of spin coatings. DMDMS and DPhDMS are favourable in reducing the birefringence and in increasing the thermostability of the material, and the methacryl groups of MPS are UV-polymerizable, which is useful for low cost fabrication of waveguides by photolithographic process. The results of ellipsometry scanning measurements show that titania is homogeneously incorporated in the hybrid matrix, suggesting that the anhydrous sol-gel process is useful for preparation of UV-sensitive titania-doped siloxane polymers for optical applications.     

Polarizability and Kerr constant of proteins by boundary element methods

A precise implementation of the boundary element method has been applied to the computation of the polarizability and the Kerr constant of eight soluble proteins. The method is demonstrated to be accurate and precise by comparison with analytical values for spheroids. Two different integral equations have been solved: (1) an exact equation with explicit dielectric constant dependence, and (2) an exact equation for a metallic body. The dielectric dependence for the metallic body case is built in with a generalization of the ellipsoid formula. Both methods agree quantitatively with each other for low relative dielectric constants. A full tensor expression for the Kerr constant yields perfect agreement with experiment for some proteins and badly under reports for the rest. The protein structure is obtained from a crystallographic database and is assumed rigid throughout the TEB measurement. Electrolyte effects are neglected. The Kerr constant is dominated by the protein dipole moment and is quite sensitive to the orientation of the dipole moment relative to the principal axes of the polarizability tensor. Several possible reasons for the large discrepancy between some computed and measured values are discussed.