WATER-BLOWN POLYURETHANE RIGID FOAMS MODIFIED BY CHEMICAL PLASTICATION

1. INTRODUCTIONThese years, HCFC-141b may be the most used blowing agent for its useful properties. But, because of its high global warming effect leading to the destruction of the ozone layer, production of HCFC141b has been forbidden. However, there are…     

Bifurcations and transition states

Bifurcations of reaction channels are related to valley-ridge inflection points and it is examined what happens when these do not coincide with transition states. Under such conditions there result bifurcating regions. There exist a number of different prototypes for such regions which are discussed explicitly on the basis of the pertinent Taylor expansions. When bifurcations occur close enough to transition states then there result bifurcating transition regions. An example for a bifurcating transition region is exhibited which is obtained from a quantum mechanical ab initio calculation for the ring opening of cyclopropylidene to aliene. In general there exist no orthogonal trajectory patterns which could serve as simplified models for channel bifurcations.Operated for the U.S. Department of Energy by Iowa State University under Contract No. W-7405-ENG-82. This work was supported by the Office of Basic Energy Sciences     

Rearrangement during cyclisation of some 3-(2-pyrrolyl) propionic acids and related compounds

Cyclisation of the title compounds leads to mixtures of the expected 4H-cyclopental[b]pyrrol-4-ones (1), the corresponding 6-ones (3) by a single rearrangement, and the cyclopenta[c]pyrrol-4-ones (4) by a double rearrangement, the proportions depending upon the substituents.The ¹H NMR spectra of 2-methyl-4H-cyctopenta[b]thiophen-6-one (3f) shows 6J long range $\text{CH}{}_3\text{CH}{}_2$ coupling, but this is absent in the corresponding pyrroles (3c,d). The ¹³C spectra of 1 and 3 cannot be interpreted on the basis of substituent chemical shifts in pyrroles and thiophens, and are clearly -CH = CH-X (X = NMe, NPh, S) bridged derivatives of cyclopent-2-enone.     

Benzodiazepine analogues. Part 21. 13C NMR analysis of benzoxathiepine derivatives

The influence of substituents and structure on the 13C NMR spectra of four series of benzoxathiepine derivatives has been investigated. Signal assignments in the 13C NMR spectra have been facilitated by the use of several predictive methods, permitting comparison of their relative efficacy.     

Classification of oxide glasses: A polarizability approach

A classification of binary oxide glasses has been proposed taking into account the values obtained on their refractive index-based oxide ion polarizability α_O2−(n₀), optical basicity Λ(n₀), metallization criterion M(n₀), interaction parameter A(n₀), and ion's effective charges as well as O1s and metal binding energies determined by XPS. Four groups of oxide glasses have been established: glasses formed by two glass-forming acidic oxides; glasses formed by glass-forming acidic oxide and modifier's basic oxide; glasses formed by glass-forming acidic and conditional glass-forming basic oxide; glasses formed by two basic oxides. The role of electronic ion polarizability in chemical bonding of oxide glasses has been also estimated. Good agreement has been found with the previous results concerning classification of simple oxides. The results obtained probably provide good basis for prediction of type of bonding in oxide glasses on the basis of refractive index as well as for prediction of new nonlinear optical materials.     

流体熵相关性质的Monte Carlo模拟新方法

提出了用于计算实际体系熵相关性质的Monte Carlo多级取样分子模拟方法. 应用这一方法, 对硬球流体的化学势及Helmholtz自由能进行了估算, 得到了满意的结果. 计算化学势时, 不存在通常试验粒子方法所遇到的高密度问题. 该方法特别适合规律性的系统研究, 较之普通模拟方法要有效得多. 模拟得到的硬球体系无限稀释组份的超额化学势与对比直径的关系, 在相变区域为一条双凹曲线; 无论是在相变区还是在单相区, Carnahan-Starling公式对这一关系的描述均有较大偏差.     

Conformation and internal mobility of 5H-dibenzo[a,d]cycloheptene derivatives in solution. Conformational analysis of highly flexible structures,part II

Summary The conformational possibilities of 5-(3-N,N-dimethylaminopropyl)-5H-dibenzo[a,d]cycloheptene (1), 5-(3-N,N-dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (2), and 5-(3-N,N-dimethylaminopropyl)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (3) are analysed using empirical force field methods. Minimum energy conformations, interconversion pathways, interconversion graphs and interconversion energies are examined in view of the analysis of conformer equilibria of1,2, or3 in solution. In addition, some basic requirements of the analysis of fast interconverting conformers using the lanthanide induced shift method are discussed.

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Konformation und interne Beweglichkeit von 5H-Dibenzo[a,d]cyclohepten Derivaten in Lösung. Konformationsanalyse hochflexibler Strukturen, Teil 2

Zusammenfassung Die konformativen Möglichkeiten von 5-(3-N,N-dimethylaminopropyl)-5H-dibenzo[a,d]cyclohepten (1), 5-(3-N,N-dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten (2) und 5-(3-N,N-dimethylaminopropyl)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten (3) wurden mit Hilfe empirischer Kraftfeldmethoden analysiert. Jene Konformationen, die einem energetischen Minimum entsprechen, sowie Interkonversionswege, Interkonversionsgraphen und Interkonversionsenergien wurden in Hinblick auf die Analyse der Konformerengleichgewichte von1,2 oder3 in Lösung untersucht. Weiters werden noch einige grundlegende Voraussetzungen für die Analyse von sich schnell ineinander umwandelnden Konformeren mittels der Lanthaniden-induzierten Verschiebungsmethode besprochen.

     

Synthesis of new colloidal formations during the strengthening of different activated hydrated metallurgical slags

This paper reports on a comparison of experimental researches on the hydration hardening of different types of dumped ferrous slag (DFS) (blast furnace, open hearth, electric steel and converter), non-activated and activated with small (2%) additions of Portland cement or lime. Activation was found to accelerate the strengthening processes in the early stages of hydration resulting from the growth of colloidal sol–gel new formations in a more alkaline environment. Over time, these formations became denser and transformed into stone-like amorphous materials with a uniaxial strength of up to 47.6 MPa at 1 year of age. All these types of slag can, therefore, be used in different applications, for example, like traditional binders, such as Portland cement, to different ceramic goods, new construction materials, etc. But till now the results of this research were used only for the preparing of binder materials for natural soils strengthening as road bases in Russia. Highways whose roadbeds were built with these DFS as binder materials have shown excellent performance indices in different parts of Russia, including Siberia and northern regions.     

Fermentation characteristics and the dynamic trend of chemical components during fermentation of Massa Medicata Fermentata

As a representative of traditionally fermented Chinese medicine, Massa Medicata Fermentata (MMF) shows the functions of invigorating the spleen and stomach and promoting digestion, which plays an important role in the treatment of gastrointestinal diseases. The fermentation mechanism and the key factors that affect the quality of MMF have not been revealed yet, which has become an urgent issue that limits its clinical application. This article aims to systematically and comprehensively reveal the transformation of physical properties and the dynamic trend of chemical components including substrate components, volatile components, and lactic acid as anaerobic fermentation product during MMF fermentation. Along with obvious hyphae growth observed for MMF, the weight of MMF decreased, and the moisture and temperature increased. Through the quantified 14 components from substrate, ferulic acid increased from 45.53 ± 6.94 to 141.89 ± 78.40 μg/g, while glycosides and phenolic acids declined except caffeic acid. Also, within the 66 volatile components analyzed, alcohols and acids increased, while aldehydes and ketones decreased. Lactic acid was not detected in the fermentation substrate, but an apparent increase in lactic acid content was observed along with the increased fermentation days, resulting in 2.54 ± 0.15 mg/g on day 8. Based on the tested components, the fermentation process of MMF was discriminated into three distinct stages by principal component analysis, and an optimal fermentation time of four days was proposed. The results of this study will be of great significance to clarify the characteristics of fermentation and conduce to improving quality standards of MMF.     

Copper Promoted Au/ZnO-CuO Catalysts for Low Temperature Water-gas Shift Reaction

IntroductionThe water-gas shift(WGS)reaction is an impor-tant step in many important chemical processes[1].Re-cently,the renewed interest in the removal of CO bythe WGS reaction has grown significantly because of theincreasing attention to pure hydrogen p…