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  • 1
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 146-160 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The alkaline hydrolysis of several alkylphosphonates and alkylphosphonyl chlorides has been investigated by molecular mechanics calculations (MM2, 1985 version). The difference of the steric energies (ΔE) between tetracoordinate substrate and pentacoordinate transition state of phosphorus compounds represents the activation energy (ΔE≠) in hydrolysis. The change of ΔE for various alkyl groups relative to methyl group (ΔΔER) is suggested as a measure of the steric effect of substituents. Thus the correlation analysis involving log k and ΔΔER of the branched alkyl group gives good results and it is reasonable to anticipate that analogous treatment using ΔΔER for the straight chain alkyl group is not satisfactory owing to the minor contribution of steric effect of the latter. However, the multiple regression analysis of log k with ΔΔER and Taft's σ* provides very good results. As shown by us, for the hydrolytic reactions studied, the proposed ΔΔER is much better than Taft's Es and Charton's ν, the commonly used well-known steric parameters in the chemistry of carbon compounds.
    Additional Material: 7 Tab.
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 467-478 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The previously developed general method (IDME), which includes calculation of electrostatic and solvation effects on conformational equilibria, has been extended to molecules containing double bonds and conjugated systems. It was applied in connection with MM2 studies to the calculation of the charge distributions and dipole moments, and to the conformational energies of some β-substituted cyclohexenes, exo-methylenecyclohexanes and benzocycloheptenes. Conformational equilibria and dipole moments were well calculated. It was concluded that electrostatic interactions do not play a major role in determining conformational preferences in these compounds. On the other hand, the energies of the preferred conformations of the ten-membered ring in (E)-3β-acetoxy-5,10-seco-1(10)-cholesten-5-one are poorly calculated without the IDME procedure, and fairly well with it.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Alkaline hydrolysis of diethyl alkylphosphonates and alkyl diethylphosphinates was studied in aqueous dimethyl sulphoxide. The behaviour of these acyclic phosphorus esters is very similar to that of some cyclic phosphorus esters. Rate constants were measured at three temperatures over a 30°C range, and the activation functions of the reaction were estimated. The basic hydrolytic process was proved to be a bimolecular AE reaction. Multiple regression analyses involving rate constants and substituent parameters gave, as a rule, poor results using steric constants derived from carbon compounds. However, the substituent steric effect on the rate of hydrolysis of phosphonates and phosphinates studied correlated very well with ΔΔE, representing the difference in steric energy calculated by molecular mechanics. It is attributed to the various degrees of susceptibility of carbon and phosphorus atoms to the steric hindrance of the substituents. Moreover, Newman's rule of six for the hydrolytic reaction of carboxylates was completely eliminated in phosphorus ester hydrolysis.
    Additional Material: 2 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 5 (1992), S. 361-366 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The alkaline hydrolysis reaction of methyl nitrate was simulated by quantum mechanical and molecular mechanical methods. The gas-phase reaction was calculated to proceed with no barrier when ab initio calculations at the STO-3G level were utilized, and with a very small barrier (5.70 kJ mol-1) when the MINDO/3 method was applied. In solution, the solvation energy was estimated to be 70.33 kJ mol-1 by molecular mechanical calculations. Thus the activation energy (76.03 kJ mol-1) of alkaline hydrolysis of methyl nitrate was found to be in good agreement with the available experimental value (82.42 kJ mol-1). The results indicated that the substantial activation barrier in alkaline hydrolysis was essentially solvent-induced.
    Additional Material: 3 Ill.
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  • 5
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Various approaches leading to mono-, di-, and polyfunctionalized phosphonates as well as phosphoryl heterocycles are reported for the systematic study of relationships between chemical structure and biological activity of this most important class of organophosphorus compounds. © 1997 John Wiley & Sons, Inc.
    Additional Material: 30 Ill.
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  • 6
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Examination of several model organophosphorus compounds, bicyclic phosphates (1), p-substituted phenylphosphonates (2), and acidic alkylphosphonates (3) reveals that the polar substituent effect in organophosphorus esters parallels that of carbon compounds. No significant variation in polar effects of different alkyl groups with up to 10 carbon atoms is observed. As demonstrated by us, the commonly used Kabachnik polar constant σΦ for alkyl groups of organophosphorus compounds reflects the steric effect associated with steric hindrance to solvation of acidic anions. Therefore, a set of solvation steric parameters Eps has been calculated from pKa values of organophosphorus acids. This parameter can be applied to describe the structural effect on dissociation of organic acids and, after suitable modification, may reflect the steric effect of alkyl groups in hydrolytic reactions of organophosphorus esters.
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 8 (1987), S. 1051-1056 
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: It has been found that the previous MM2 (or MMP2) description of out-of-plane deformation of aromatic rings sometimes yields distortions which are much too large. As a result, rotational barriers involving distortions of such rings may be calculated to have values which are too low. Examples are collected and discussed. An alternative formulation, which appears to significantly reduce the calculational error, is presented.
    Additional Material: 2 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 17 (1996), S. 1013-1024 
    ISSN: 0192-8651
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Although no crystal structures of mixed-chain phosphatidylcholines with unsaturated sn-2 acyl chains exist, the force field method in conjunction with the experimentally determined structure of saturated identical-chain phosphatidylcholine can be applied to simulate molecular structure for mixed-chain phosphatidylcholines. In this study, the packing models of mixed-chain 1-palmitoyl-2-linoleoyl-phosphatidylcholines in bilayers at temperatures below the gel-liquid crystalline phase transition temperature or T 〈 Tm are simulated by using Allinger's MM3(92) force field. Our results indicate that the unsaturated sn-2 acyl chains of the mixed-chain lipid can fold into two energy-minimized topologies: the crankshaftlike and the U-shaped motifs. The folded region in the crankshiftlike sn-2 acyl chain is characterized by a sequence s- Δs+s+Δs-, and the U-shaped chain arises from the characteristic sequence s-Δs+s-Δs+, where s± denotes the ± skew conformation and Δ the cis carbon-carbon double bond. These modeled structures of 1-palmitoyl-2-linoleoyl-phosphatidylcholines in the bilayer at T 〈 Tm should not be regarded as highly rigid structures, since torsion angles of carbon-carbon bonds associated with sequences s Δs+s+Δs and s Δs+s-Δ s+ can fluctuate somewhat without appreciably affecting the steric energy of the corresponding lipid bilayer. © 1996 by John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
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  • 9
    Publication Date: 2018-08-30
    Description: Remote Sensing, Vol. 10, Pages 1370: Using SAR-Derived Vegetation Descriptors in a Water Cloud Model to Improve Soil Moisture Retrieval Remote Sensing doi: 10.3390/rs10091370 Authors: Junhua Li Shusen Wang The water cloud model (WCM) is a widely used radar backscatter model applied to SAR images to retrieve soil moisture over vegetated areas. The WCM needs vegetation descriptors to account for the impact of vegetation on SAR backscatter. The commonly used vegetation descriptors in WCM, such as Leaf Area Index (LAI) and Normalized Difference Vegetation Index (NDVI), are sometimes difficult to obtain due to the constraints in data availability in in-situ measurements or weather dependency in optical remote sensing. To improve soil moisture retrieval, this study investigates the feasibility of using all-weather SAR derived vegetation descriptors in WCM. The in-situ data observed at an agricultural crop region south of Winnipeg in Canada, RapidEye optical images and dual-polarized Radarsat-2 SAR images acquired in growing season were used for WCM model calibration and test. Vegetation descriptors studied include HV polarization backscattering coefficient ( σ H V ° ) and Radar Vegetation Index (RVI) derived from SAR imagery, and NDVI derived from optical imagery. The results show that σ H V ° achieved similar results as NDVI but slightly better than RVI, with a root mean square error of 0.069 m3/m3 and a correlation coefficient of 0.59 between the retrieved and observed soil moisture. The use of σ H V ° can overcome the constraints of the commonly used vegetation descriptors and reduce additional data requirements (e.g., NDVI from optical sensors) in WCM, thus improving soil moisture retrieval and making WCM feasible for operational use.
    Electronic ISSN: 2072-4292
    Topics: Architecture, Civil Engineering, Surveying , Geography
    Published by MDPI Publishing
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  • 10
    Publication Date: 2017-08-22
    Description: Materials, Vol. 10, Pages 974: Preparation and Characterization of Cyclotrimethylenetrinitramine (RDX) with Reduced Sensitivity Materials doi: 10.3390/ma10080974 Authors: Yuqiao Wang Xin Li Shusen Chen Xiao Ma Ziyang Yu Shaohua Jin Lijie Li Yu Chen The internal defects and shape of cyclotrimethylenetrinitramine (RDX) crystal are critical parameters for the preparation of reduced sensitivity RDX (RS-RDX). In the current study, RDX was re-crystallized and spheroidized to form the high-quality RDX that was further characterized by purity, apparent density, size distribution, specific surface area, impact sensitivity, and shock sensitivity. The effects of re-crystallization solvent on the growth morphology of RDX crystal were investigated by both theoretical simulation and experiment test, and consistent results were obtained. The high-quality RDX exhibited a high purity (≥99.90%), high apparent density (≥1.811 g/cm3), spherical shape, and relatively low impact sensitivity (6%). Its specific surface area was reduced more than 30%. Compared with conventional RDXs, the high-quality RDX reduced the shock sensitivities of PBXN-109 and PBXW-115 by more than 30%, indicating that it was a RS-RDX. The reduced sensitivity and good processability of the high-quality RDX would be significant in improving the performances of RDX-based PBXs.
    Electronic ISSN: 1996-1944
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Published by MDPI Publishing
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