Asymmetric synthesis of alpha-amino acids by the strecker synthesis.
Asymmetric synthesis of alpha-amino acids by strecker synthesis, including production of optically active l-analine
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Asymmetric synthesis of alpha-amino acids by strecker synthesis, including production of optically active l-analine
Asymmetric synthesis of alanine by hydrogenolytic asymmetric transamination, noting temperature effect
Asymmetric synthesis of alpha-amino acids by strecker synthesis, including production of optically active l-aniline
This invention relates to processes for preparing asymmetrical biphenyl tetracarboxylic acids and the corresponding asymmetrical dianhydrides, namely 2,3,3',4'-biphenyl dianhydride (a-BPDA), 2,3,3',4'-benzophenone dianhydride (a-BTDA) and 3,4'-methylenediphthalic anhydride (-MDPA). By cross-coupling reactions of reactive metal substituted o-xylenes or by cross-coupling o-xylene derivatives in the presence of catalysts, this invention specifically produces asymmetrical biphenyl intermediates that are subsequently oxidized or hydrolyzed and oxidized to provide asymmetric biphenyl tetracarboxylic acids in comparatively high yields. These asymmetrical biphenyl tetracarboxylic acids are subsequently converted to the corresponding asymmetrical dianhydrides without contamination by symmetrical biphenyl dianhydrides.
It is shown that the explanation of terrestrial contamination of the Murchison meteorite is consistent with the analysis of extracts from the meteorite reported by Engel and Nagy (EN) (1982) and is much more probable than their suggestion that the excess of L-enantiomers for several protein amino acids is due to asymmetric synthesis or decomposition. The low abundance of serine and threonine reported by EN may be due to their decomposition during the derivatization procedure, and the absence of methionine, tyrosine, and phenylalanine can be attributed to various causes. The amount of contamination in EN's extracts are estimated from a mass balance of the amino acid enantiomers, and it is found that the amino acids in the HCl could be due entirely to contamination while in the water extract the amount of contamination ranges from about 40 to 97 percent, depending on the amino acid. The argument that contaminants were preferentially extracted by EN's procedure cannot account for the failure to detect methionine, tyrosine, and phenylalanine.
We have previously observed the magnetite plaquettes in carbonaceous chondrites using scanning electron microscope (SEM) imaging, examined the crystal orientation of the polished surfaces of magnetite plaquettes in CI Orgueil using electron backscattered diffraction (EBSD) analysis, and concluded that these magnetite plaquettes are likely naturally asymmetric materials. In this study, we expanded our EBSD observation to other magnetite plaquettes in Orgueil, and further examined the internal structure of these remarkable crystals with the use of X-ray computed microtomography.
Optically active alanine synthesis from oxaloaceti acid by hydrogenolytic asymmetric transamination, noting role of decarboxylation
The study is concerned with the polymerization of diamines 2a-d with readily available dianhydrides, i.e., 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and pyromellitic dianhydride (PMDA). The synthesis and polymerization of asymmetric diamines containing substituted alkylene ether linkages are also investigated. It is assumed that the flexibility introduced into the polymer chain through the use of such diamines would result in moderate glass transition temperatures that would allow the systems to be melt processed. Mixtures of diamines are also copolymerized so as to further disrupt the polymer's symmetry and recurrence regularity. The properties of the resulting polymers are briefly discussed.
Optically active alpha-amino acids synthesis from esters of alpha-keto acids by hydrogenolytic asymmetric transamination
Solvent effect in catalytic hydrogenation reaction of Schiff bases of alpha-keto acids with optically active alpha-alkylbenzylamine
The graviresponse of the leaf-sheath pulvinus of oat (Avena sativa) involves an asymmetric growth response and asymmetric processes involving degradation of starch and cell wall synthesis. Cellular and biochemical events were studied by investigation of the activities of related enzymes and changes in cell walls and their constituents. It is suggested that an osmotic potential gradient acts as the driving factor for growth, while wall extensibility is a limiting factor in pulvinus growth.
2-Phenyl-isoindole was investigated as the rigid core unit in a series of asymmetric mesogenic molecules. When the 2-phenyl-isoindole core was terminated with a hexyl tail, no mesophase formation could be observed. When 4-n-(tridecafluorohexyl) was used, however, we observed both monotropic and enantiotropic phase behavior. We found that most functionalities at the anhydride 5-position results in the formation of smectic A (SmA) phases in the temperature range of 70-180 C. Functionalities at the anhydride 4-position suppress mesophase formation. Large substituents (-Br, -NO2) and symmetric substitution patterns (5,6-dichloro, 4,7-dichloro and 4,5,6,7-tetrachloro) on the anhydride moiety increase the melting point and destabilize the mesophase. Temperature dependent X-ray diffraction experiments suggest an interdigitated SmA packing for this family of compounds.
Recent interest in oblique-wing aircraft has focused on the potential aerodynamic performance advantage of a variable-skew oblique wing over a conventional or symmetric sweep wing. Unfortunately, the resulting asymmetric configuration has significant aerodynamic and inertial cross-coupling between the aircraft longitudinal and lateral-directional axes. Presented here is a decoupling control law synthesis technique that integrates stability augmentation, decoupling, and the direct incorporation of desired handling qualities into an output feedback controller. The proposed design technique uses linear quadratic regulator concepts in the framework of explicit model following. The output feedback strategy used is a suboptimal projection from the state space to the output space. Dynamics are then introduced into the controller to improve steady-state performance and increase system robustness. Closed-loop performance is shown by application of the control laws to the linearized equations of motion and nonlinear simulation of an oblique-wing aircraft.
A persistent, mesoscale region of intense eyewall convection contained within Hurricane Bonnie on 23 August 1998 is examined from multiple observations synthesized from the NASA ER-2 and DC-8 aircraft. The intense convection occurred late in the day as Bonnie was attaining its minimum central pressure and during a stage when the inner core featured a markedly asymmetric structure. The main purpose of this paper is to describe the internal structure of a convective burst and its relationship to the warm core using a synthesis of high-resolution satellite, aircraft radar, and in situ data. An exceptionally vigorous eyewall tower penetrating to nearly 18 km is described. A second intense eyewall tower, adjacent to the eye, is shown to be associated with a mesoscale subsiding current of air that extends horizontally nearly 20 km into the eye interior. The subsidence occupies a substantial depth within the eye and appears to be a much larger scale feature than the convectively-induced, symmetric overturning which commonly occurs on the upper-level flanks of convective towers in other tropical environments.
The main goal of the Japanese Aerospace Ex-ploration Agency (JAXA) Hayabusa-2 mission is to visit and return to Earth samples of a C-type asteroid (162173) 1999 JU3 in order to understand the origin and nature of organic materials in the Solar System. Life on Earth shows preference towards the set of organics with particular spatial arrangements, this 'selectivity' is a crucial criterion for life. With only rare exceptions, life 'determines' to use the left- (L-) form over the right- (D-) form of amino acids, resulting in a L-enantiomeric excess (ee). Recent studies have shown that L-ee is found within the alpha-methyl amino acids in meteorites [1, 2], which are amino acids with rare terrestrial occurrence, and thus point towards a plausible abiotic origin for ee. One of the proposed origins of chiral asymmetry of amino acids in meteorites is their formation with the presence of asymmetric catalysts [3]. The catalytic mineral grains acted as a surface at which nebular gases (CO, H2 and NH3) were allowed to condense and react through Fisher Tropsch type (FTT) syntheses to form the organics observed in meteorites [4]. Magnetite is shown to be an effective catalyst of the synthesis of amino acids that are commonly found in meteorites [5]. It has also taken the form as spiral magnetites (a.k.a. 'plaquettes'), which were found in various carbonaceous chondrites (CCs), including C2s Tagish Lake and Esseibi, CI Orgueil, and CR chondrites [e.g., 6, 7, 8]. In addition, L-ee for amino acids are common in the aqueously altered CCs, as opposed to the unaltered CCs [1]. It seems possible that the synthesis of amino acids with chiral preferences is correlated to the alteration process experienced by the asteroid parent body, and related to the configuration of spiral magnetite catalysts. Since C-type asteroids are considered to be enriched in organic matter, and the spectral data of 1999 JU3 indicates a certain de-gree of aqueous alteration [9], the Hayabusa-2 mission serves as a perfect chance to attest this argument. In order to understand the distribution of spiral magnetites among different meteorite classes, as well as to investigate their spiral configurations and correlation to molecular asymmetry, we observed polished thin sections of CCs using scanning electron microscope (SEM) imaging. Individual magnetite grains were picked, embedded in epoxy, thin-sectioned using an ultra-microtome, and studied with electron backscatter diffraction (EBSD) in order to reconstruct the crystal orientation along the stack of magnetite disks.
Cellulose synthesis inhibitors 2,6-dichlorobenzonitrile and coumarin inhibit the normal gravitropic response of the leaf-sheath pulvini in several grasses. These inhibitors induce thickenings that are mostly distributed in the radial walls. Their distribution patterns follow a previously published equation that describes the geometry of asymmetric growth in the leaf-sheath pulvinus. It is proposed that radial transport of growth promotors may account for the observed asymmetric growth rather than the classical concept of lateral downward transport in an horizontally placed shoot. Electron microscopic observation of an interaction between the tonoplast membrane and statoliths suggests that such an interaction might be a basis for gravity perception in grass leaf-sheath pulvini.
Copernicus and IUE measurements of neutral hydrogen column densities have been taken for about 140 stars distributed between 10 and 3000 pc from the sun and plotted in several maps to directly yield estimates of contours of neutral hydrogen column density in the 5-500 x 10 to the 17th/sq cm range. These maps show that low column density neutral hydrogen is asymmetrically distributed around the sun with a 'hole' in the neutral hydrogen located in the third quadrant. This distribution mirrors that of nearby B stars associated with the Gould belt. The maps clearly show the directions in which observations at wavelengths less than 912 A will be most successful.
A reliability-based structural synthesis procedure was developed to tailor laminates to meet reliability-based (ply) strength requirements and achieve desirable laminate responses. The main thrust is to demonstrate how to integrate the optimization technique in the composite laminate tailoring process to meet reliability design requirements. The question of reliability arises in fiber composite analysis and design because of the inherent scatter that is observed in the constituent (fiber and matrix) material properties during experimentation. Symmetric and asymmetric composite laminates subject to mechanical loadings are considered as application examples. These application examples illustrate the effectiveness and ease with which reliability considerations can be integrated in the design optimization model for composite laminate tailoring.