Forecasting the characteristics of the explosives

The key techniques for forecasting of the properties of the explosives were presented. We acquired an array of the properties approximately for 200 explosives on the basis of literature information and own experimental data. Techniques of an evaluation of the main characteristics of the explosive transformation were developed. We forecasted properties of a series of compounds not synthesized earlier by computation methods. The experimental and computed data were combined into vast array of information approximately for 1000 explosives. The systematization of experimental data allows conclusions about the attained levels of efficiency and of safety, and also forecasting the properties of the promising explosives.     

On the adequacy of modeling the concentration dependences of the activity coefficients for the components of solutions

An analysis of the accepted methods for calculating the activity coefficients for the components of binary aqueous solutions was performed. It was demonstrated that the use of the osmotic coefficients in auxiliary calculations decreases the accuracy of estimates of the activity coefficients. The possibility of calculating the activity coefficient of the solute from the concentration dependence of the water activity was examined. It was established that, for weak electrolytes, the interpretation of data on heterogeneous equilibria within the framework of the standard assumption that the dissociation is complete encounters serious difficulties.     

Experiences with the Application of QSAR in the Routine of the Notification Procedure

Abstract

On behalf of the Umweltbundesamt the Fraunhofer Gesellschaft has developed a software system (SAR-system) comprising more than 90 estimation models for endpoints relevant in environmental risk assessment. These estimation models are based on the approach of quantitative structure-activity relationships (QSAR). All models were checked for their validity and application range. In the last months the Umweltbundesamt started to test the applicability of some models concerning the endpoints fish acute toxicity, daphnia acute toxicity and ready (i.e., ultimate) biodegradability in the daily routine of the notification procedure. For testing these models the corresponding confidential data given in the dossiers of substances notified 1993 in Germany, were used. We were able to make calculations for 36% of the notified substances. For the remaining 64% of the chemicals it was impossible to accomplish SAR estimations due to several reasons, e.g., ionic structure of the compounds. Different results for the applicability of the mentioned endpoints are obtained. The predictions of the fish and Daphnia toxicity are in sufficient agreement with the experimental results, in case of the fish toxicity we receive 58% agreement, for the Daphnia toxicity 56% The corresponding values which were obtained in the US EPA/E.C. Joint Project on the evaluation of (quantitative) structure activity relationships were 82.3% and 70.9% About 300 different models were used for the calculations of these endpoints within the framework of the EPA/EC project. The SAR-system presented here contains 8 models for estimating the fish toxicity and 6 models for the Daphnia toxicity. For the prediction of the biodegradability the results obtained with the SAR-system are rather poor and have to be improved. Meanwhile the SAR-system is commercially available and can be ordered at the Fraunhofer Institute for Environmental Chemistry and Ecotoxicology, Schmallenberg (Germany).     

Designing of the jet device as the element of the heat pump

The problems are examined of the effective functioning of the jet device as the main element of the heat pump allowing the recuperation of the low potential thermal energy. Regularities of the ejection, which are the basis for designing of the ejector and ejection apparatus, are described. It is shown that the effective ejection can be reached at developed regime of outflow of the liquid from the nozzle (Re>10⁵). The common expression describing the coefficient of ejection for cases with cylindrical and flat nozzle on jet devices of various scales is presented. It is determined that flat nozzles can develop bigger values of Ke at the other equal conditions. The requirement for designing main elements of the ejector, which have to be followed for achievment of high values of coefficients of ejection, are formulated.     

Polarography,EPR spectra,and the transmission of the influence of the substituents in the anion-radicals of para-nitrodiphenyls

We investigated the polarographic potentials of the single-electron reduction of a series of para-substituted para-nitrodiphenyls to the corresponding anion-radicals as well as the EPR spectra of these radicals. The values obtained for the potentials of the first half-wave and the magnitudes of the splitting in the EPR spectra agree well with Hammett's correlation equation. Quantum mechanical treatment of these anion-radicals gives agreement with the experimental values for the reduction potentials and for the splitting constants in the EPR spectra. It is found that in the diphenyls the inclusion of the second benzene ring weakens the influence of the para-substituents on the electron density distribution by a factor of 2. 5–4. The same magnitudes for the weakening of the influence of substituents on the reactive site were previously found for various chemical reactions.A. M. Golubenkova participated in the work.     

A generalized expression for the ratio of the critical temperature to the critical pressure with the van der Waals surface area

Using an extensive database of experimental critical properties for heavy compounds, which have been compiled mostly from recent literature sources, it is shown that the ratio T_c: P_c (critical temperature over critical pressure) can be expressed in terms of the van der Waals surface area (Q_w), which is readily available for any compound from the group contributions of Bondi (given also in UNIFAC tables). The proposed correlation is based on the hole theory of Kurata and Isida for n-paraffin liquids, which is mathematically equivalent to Flory's theory of polymer solutions. The method is suitable for medium to high molecular weight compounds with unknown critical constants. For example, if only one of the two critical constants is available, then the proposed generalized equation offers a useful rapid procedure for the estimation of the other critical property for use in corresponding states, and other relevant applications where knowledge of the critical properties is required. Furthermore, the T_c: P_c method can be used in many cases for identifying the most suitable among the existing group contribution methods for estimating the critical properties of heavy and complex compounds for which experimental values are, very often, not available.     

Elements of the topology of the region of the existence of the metastable states of a two-component vapor

Entire regions of the metastable states for binary and single-component systems were constructed. It was established that the regions include temperature intervals from absolute zero to critical temperatures, and from vapor—condensate equilibrium to the conditions of spinodal decomposition of supersaturated vapor in the system. Algorithms for determining the regions of metastable states are presented. The data obtained on their basis are noted to coincide qualitatively with known results. Correlations found earlier are employed to calculate the critical pressures and temperatures for the binary systems in the study.     

On the solution of the N-completeness problem

A solution is given for the problem of N-completeness which arises in practical calculations for many electron systems because of the necessity of employing a finite basis set of antisymmetric two-particle functions.     

On the scaling of the interface energy of the liquid clusters in the disordered nanoporous medium

Similarity of the extrusion curves of non-wetting liquid in a nanoporous medium with different initial fill volume fractions is observed experimentally. The similarity can be explained by the scaling of the interface energy and the self-similarity of the infinite percolation cluster of fluid-filled pores. Understanding the physical processes leading to the observed phenomena is a foundation for the development of high-performance devices for damping and energy storage on the basis of such heterogeneous systems.     

Solving the adsorption integral equation with Langmuir-kernel and the influence of temperature on the stability of the solution

Adsorption energy distribution functions can be calculated from measured adsorption isotherms by solving the adsorption integral equation. In this context, it is common practice to use general regularization methods, which are independent of the kernel of the adsorption integral equation, but do not permit error estimation. In order to overcome this disadvantage, we present in this paper a solution theory which is tailor-made for the Langmuir kernel of the adsorption integral equation. The presented theory by means of differentiation and Fourier series is the basis for a regularization method with explicit terms for error amplification. By means of simple and complicated adsorption energy distribution functions we show for ideal gas adsorption isotherms without measurement error that reliable distribution functions can be obtained from the isotherms. Furthermore we show how the stability of the solution depends on temperature.     

Theoretical calculation of the excited states of the KCs molecule including the spin-orbit interaction

For the molecule KCs the potential energy has been calculated for the 72 lowest molecular states Omega. Using an ab initio method the calculation is based on nonempirical pseudopotentials within the range of 5.0a0-34.0a0 of the internuclear distance R. Gaussian basis sets have been used for both atoms and spin-orbit effects have been taken into account through a semiempirical spin-orbit pseudopotential added to the electrostatic Hamiltonian. The spectroscopic constants for 60 states have been calculated by fitting the calculated energy values to a polynomial in terms of the internuclear distance R. The components of the spin-orbit splitting for (1,2,5,6) 3Pi and (1) 3delta have been identified. The comparison of the present results with those available in the literature shows a very good agreement, while the other results, to the best of our knowledge, are given here for the first time.     

On the calculation of the acyclic polynomial

Graphical methods are developed for recursive evaluation of the acyclic polynomial. Analytical formulas of the acyclic polynomials for several specific series of graphs are given. Mathematical properties of the derivatives of the acyclic polynomial are given.     

Relation of the decay of free radicals in irradiated polyethylene to the molecular motion of the polymer and the configurations of the free radicals

Decay reactions of the free radicals produced in irradiated polyethylene (high-density and low-density materials) were examined in connection with the molecular motion of the matrix polymer. Three temperature regions, in which the free radicals decay very rapidly, at around 120, 200, and 250°K, were designated T_A, T_L, and T_B, respectively. The decay of the free radicals at these temperatures had activation energies in high-density polyethylene of 0.4 kcal/mole for T_A, 9.4 kcal/mole for T_L, and 18.4 kcal/mole for T_B. In low-density polyethylene these quantities were 0.7 kcal/mole for T_A, 23.1 kcal/mole for T_L, and 24.8 kcal/mole for T_B. Comparison of time constants for the decay reactions and for molecular motion of the matrix polymer indicate that the decay in T_A and T_B is closely related to molecular motion in the amorphous regions of the polymer. The decay of the free radicals at T_L in high-density polyethylene is due to molecular motion associated with local mode relaxation at lamellar surfaces, while that of low-density polyethylene is due to local mode relaxation in the completely amorphous region. Steric configurations of the free radicals which decay in the respective temperature regions were also investigated.     

Errors in the application of the JWKB method to calculating the survival factor in dissociative electron attachment using the local complex potential

The accuracy of the JWKB method for determining the survival factor defined for dissociative electron attachment (DEA) processes is examined for a range of electronic resonance lifetimes within the local complex potential approximation. The author concludes that the accuracy is inadequate for molecules with properties commonly found for shape resonance induced DEA. More accurate methods using the uniform Airy function approximation give much better results, but the direct numerical integration of Schrodinger's equation appears simpler still.     

The effect of the order of the autocatalysis on the transverse stability of reaction fronts

A linear stability analysis of planar reaction fronts to transverse perturbations is considered for a system based on an autocatalytic reaction of general order p. Dispersion curves, plots of the growth rate sigma against a transverse wavenumber k, are obtained for a range of values of p and D, where D is the ratio of the diffusion coefficients of autocatalyst and substrate. A value D(0) of D, dependent on p, is found at which sigma(max), the maximum value of sigma in the unstable regime, is largest, with D(0) increasing as p is increased. An asymptotic analysis for small wavenumbers is derived, which enables the region in the (p, D) parameter space for instability to be determined. An analysis for D small is undertaken, which leads to upper bounds on the wavenumber for a possible instability.     

Correlation between Lipophilicity of the Ligands and the Hepatobiliary Properties of the Radiopharmaceuticals: Approach to the Development of New IDA Derivatives

The partition coefficient (log P) for n-octanol/water system was calculated applying PACO program for various theoretically possible mono and dihalogenated IDA derivatives. Some of the synthesized ligands (SOLCOIODIDA, IODIDA and DIIODIDA) were labeled with the technetium-99m. The biodistribution and influence of bilirubin on their biokinetics were investigated in rats. The correlation between partition coefficients of ligands increase (log P) and better hepatobiliary properties of ^99mTc-IDA derivatives was determined. The values of log P increase from 1.16 for SOLCOIODIDA, 3.11 for IODIDA to 3.47 for DIIODIDA. In correlation with these results, biliary excretion decreased for 59% for ^99mTc-SOLCOIODIDA and 11% for ^99mTc-IODIDA and ^99mTc-DIIODIDA under hyperbilirubinemia (3.5 min after injection) and 45%, 11% and 0.38% respectively (15 min after injection). The highest biliary excretion had ^99mTc-DIIODIDA (55.4% for 3.5 min). Considering the correlation between hepatobiliary properties and log P, the evaluation of biological properties for various trifluoromethyl mono and dihalogenated IDA derivatives was performed on the basis of the calculated log P in order to synthetize a new radiopharmaceutical for hepatobiliary scintigraphy.     

HEPT类化合物的QSAR研究

为定量结构／活性相关性研究提取了量子化学参数,拓扑指数Am,分子连接性指数^mxt及疏水性常数,同时应用正交变换和最佳变量子集算法（Leaps-and-Bonds)进行了变量压缩和选择,进而实施了多元回归分析,并由此结果进行了HEPT类化合物（1－[(2-hydroxyethoxy)methyl]-6-(phenylthio)-thymine derivatives)的结构／活性关系的理论解释,进行了人工神经网络法对于该类化合物的活性预测,其结构明显好于多元回归法。     

Diagrammatic expansion of the long-range intermolecular potential and the total contribution of the first hyperpolarizability

The potential for pure dispersion forces can be defined in terms of a simple classical cluster expansion. The diagrams for the first hyperpolarizability contribution are summed for a one frequency model.     

Molecular electron affinities and the calculation of the temperature dependence of the electron-capture detector response

The use of the electron-capture detector (ECD) to measure molecular electron affinities and kinetic parameters for reactions of thermal electrons is reviewed. The advances of the past decade are emphasized and include the multistate electron-capture detector model and the use of semi-empirical self-consistent field quantum mechanical calculations and half wave reduction potential values to support gas phase experimental results. A procedure for the evaluation of the adiabatic electron affinities of the main group elements and the homonuclear diatomic molecules is presented. Potential excited states are identified for the magnetron (MGN) values for quinones, thermal charge transfer (TCT) values for CS2, C6F6, SF6 and photoelectron spectroscopy (PES) values for O2, NO, nitromethane, and the nucleic acids. Literature electron affinities are then evaluated. The temperature dependence of the electron-capture detector can be calculated using values for kinetic rate constants and electron affinities to optimize response and temperature sensitivity in analytical procedures. The temperature dependence for adenine, guanine, thymine and cytosine are predicted for reactions with thermal electrons. Using the recent advances, the new adiabatic electron affinities are: all in electron volts (eV), 4-F-benzaldehyde (0.57 +/- 0.05) and acetophenones (APs) 4-F-AP (0.52 +/- 0.05); 2-CF3-AP (0.79 +/- 0.05); 3-CF3-AP (0.79 +/- 0.05); 4-CF3-AP (0.89 +/- 0.05); 3-CI-AP (0.67 +/- 0.05); and 4-Cl-AP (0.64 +/- 0.05). The adiabatic electron affinities of chloro and fluorobenzenes range from 0.17 to 1.15 eV and 0.13 to 0.86 eV.