The effect of olefinic terminal chains on the mesomorphic properties of 4,4'-disubstituted diphenyldiacetylenes

New diphenyldiacetylenes of the type with A, B = H and/or F; m = 0, 1; n = 1-4; and X = C n H 2n + 1 , F, CF 3 or CN were synthesized and their mesomorphic properties determined by hot stage polarizing microscopy and DSC. When m = 0, all of these compounds showed only a nematic phase except when X = CF 3 when both nematic and smectic A phases were seen. Both clearing and melting temperatures were higher than those reported for substitution with the corresponding alkyl chains but the much larger increase in clearing temperatures produced considerably wider nematic phases. Eutectic mixtures of a few of these olefins yielded nematic materials also having much wider temperature ranges and higher clearing temperatures than the eutectic mixtures of the alkyl compounds, while retaining their high birefringence and low viscosities. Such materials are of interest for beam-steering devices.

Four of the diacetylenes with m = 1 ( A, B = H) were also prepared ( X = C 6 H 13 , F, n = 2, 3). When X was C 6 H 13 ( n = 2), the nematic range was smaller in the 2- than in the 1-olefin but wider than in the alkyl series. When X = F, either no nematic phase or a monotropic one was observed, whereas the 1-olefins gave a much wider nematic phase. Both transition temperatures were lower than those for the corresponding 1-olefin and alkyl analogues. The compound with X = C 6 H 13 and n = 2 had a melting temperature below room temperature.     

Inertia-preserving secant updates

Corrections to the last two equations of Ref. 1 are given.     

An ab initio molecular orbital study of Li2O2 and LiO2H

An ab initio molecular orbital study, using a Gaussian basis set, of the geometries of Li₂O₂ and LiO₂H is presented. Consistent with the experimental data available, Li₂O₂ is found to have a rhombic structure; the O-Li-O configuration in LiO₂H is found to form an acute triangle. The bonding in these species is discussed to terms of Mulliken population analyses.     

Thermal studies on trans-dichlorotetramminecobalt(III) complexes

Thermal studies have been carried out on trans-[Co(NH₃)₄Cl₂]X · YH₂O complexes (whereX=IO₃, BrO₃, NO₃, or NO₂ andY=0, 1, or 2) in an effort to find cases of trans to cis isomerization as occurs for the iodate. No evidence of isomerization was found for any of the other compounds. The complexes decompose in a series of steps and these reactions have been identified and kinetic parameters determined.     

The role of kinetic energy in chemical binding

The wavefunctions and various partitions of the energy are examined for a variety of small molecules (H₂, H₃, H₄, HeH, HeH₂, He₂, LiH, and BH) in order to isolate the factors crucial for bond formation. We find that a natural partition of the energy leads to the conclusion that the crucial factor is the exchange, or nonclassical, part of the kinetic energy, T ^x. The change in T ^xupon pushing the atoms towards one another is the dominant term in the binding energy; it is negative when the resulting molecule is stable and positive when it is unstable. We show that T ^x is related to the interference kinetic energy considered by Ruedenberg.

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Zusammenfassung Die Wellenfunktionen und verschiedene Zerlegungen der Energie werden für eine Reihe kleiner Moleküle untersucht (H₂, H₃, H₄, HeH, HeH₂, He₂, LiH und BH), um die Faktoren zu finden, die für die Bindungsbildung ausschlaggebend sind. Die natürliche Zerlegung der Energie läßt die Folgerung zu, daß der bestimmende Faktor der Austauschanteil T ^x(oder nichtklassische Anteil) der kinetischen Energie ist. Die Änderung von T ^xbeim Zusammenführen der Atome ist der dominierende Term für die Bindungsenergie; er ist negativ, wenn das resultierende Molekül stabil ist, und positiv, falls es instabil ist. Es wird gezeigt, daß T ^x im Zusammenhang zum Wechselwirkungsanteil der kinetischen Energie nach Ruedenberg steht.

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Partially supported by a grant (GP-15423) from the National Science Foundation. This paper is based on a portion of the PhD thesis (California Institute of Technology, 1970) by CWW.

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National Science Foundation Predoctoral Trainee.

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Alfred P. Sloan Foundation Research Fellow.

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Contribution No. 3917.     

Characterization of a β-glucanase produced by Rhizopus microsporus var. microsporus, and its potential for application in the brewing industry

Background  

In the barley malting process, partial hydrolysis of β-glucans begins with seed germination. However, the endogenous 1,3-1,4-β-glucanases are heat inactivated, and the remaining high molecular weight β-glucans may cause severe problems such as increased brewer mash viscosity and turbidity. Increased viscosity impairs pumping and filtration, resulting in lower efficiency, reduced yields of extracts, and lower filtration rates, as well as the appearance of gelatinous precipitates in the finished beer. Therefore, the use of exogenous β-glucanases to reduce the β-glucans already present in the malt barley is highly desirable.     

Mass spectrometric study of MgO clusters produced by the gas aggregation technique

Gas phase (MgO) _n ⁺ and (MgO) _n Mg⁺ clusters were produced in a gas aggregation source and studied by using laser-ionization time-of-flight mass spectrometry. A MgO molecule apparently serves as the nucleus for cluster growth, to which Mg and O atoms add. The heat generated by the formation of metal-oxygen bonds, and that added to the cluster by ionization leads to the production of clusters with the stoichiometry of the stable high-temperature oxide. The abundance maxima observed in the mass spectra indicate that the clusters form compact cubic structures similar to pieces of the MgO crystal lattice. The primary fragmentation channel responsible for the observed patterns is probably the loss of MgO monomers.     

Photochemical degradation of hyaluronic acid by singlet oxygen

Changes of the rheological properties of hyaluronic acid (sodium-magnesium salt) solutions after exposure to UV radiation indicate a vigorous decrease in their viscosity, but its still strong shear rate dependence. Whereas the presence of the singlet oxygen sensitizer (anthracene-1-sulphonic acid) brings about a loss of shear dependence; the studied solutions show newtonian behavior.     

Energy and mass-number dependence of the dissociation temperature in hydrodynamical models

Transverse-momentum distributions of andK have been analyzed within a framework of the hydrodynamical model to obtain the dependence of the collective transverse flow and the dissociation temperatureT _d inpp- and -induced multiparticle production reactions. The main outcomes are the steadily increasing transverse flow and a slowly decreasingT _d as the incident energy increases. This behavior is in excellent agreement with early Landau's estimate. An extension of this to nucleus-nucleus collisions correctly gives account of the very soft component which has been observed in heavyion experiments.     

Electroproduction of strangeness

Formalism for the electroproduction of strange particles based on the one photon exchange approximation and the Feynman diagrams representation of hadron current is reviewed. Different photoproduction models are compared with available photo and electroproduction data. New experiments are proposed that may resolve existing uncertainties and inconsistencies. The formation of hypernuclei via kaon electroproduction is investigated theoretically and compared with other reactions involving purely hadronic processes.