General strategy for a short and efficient synthesis of 3-hydroxy-4-methylprolines (HMP)

The non-proteinogenic amino acid 3-hydroxy-4-methylproline (HMP) is an active constituent of some potent antimicrobials including echinocandins, nostopeptins, pneumocandins, sporiofungin and mulundocandins. A synthesis has been achieved in 10 steps with 29% overall yield; the Evans’ aldol reaction using Crimmins’ modified method was pivotal to the success of the strategy.     

Effects of diamines and their fluorinated groups on the color lightness and preparation of organosoluble aromatic polyimides from 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]‐hexafluoropropane

To investigate the position and amount of the CF₃ group affecting the coloration of polyimides (PIs), we prepared 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]hexafluoropropane ( 2 ) with four CF₃ groups with 2‐chloro‐5‐nitrobenzotrifluoride and 2,2‐bis(4‐hydroxyphenol)hexafluoropropane. A series of soluble and light‐colored fluorinated PIs ( 5 ) were synthesized from 2 and various aromatic dianhydrides ( 3a – 3f ). 5a – 5f had inherent viscosities ranging from 0.80 to 1.19 dL/g and were soluble in amide polar solvents and even in less polar solvents. The glass‐transition temperatures of 5 were 221–265 °C, and the 10% weight‐loss temperatures were above 493 °C. Their films had cutoff wavelengths between 343 and 390 nm, b* values (a yellowness index) ranging from 5 to 41, dielectric constants of 2.68–3.01 (1 MHz), and moisture absorptions of 0.03–0.29 wt %. In a comparison of the PI series 6 – 8 based on 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane, 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]propane, and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane, we found that the CF₃ group close to the imide group was more effective in lowering the color; this means that CF₃ of 5 , 7 , and 8f was more effective than that of 6c . The color intensity of the four PI series was lowered in the following order: 5 > 7 > 6 > 8 . The PI 5f , synthesized from diamine 2 and 4,4′‐hexafluoroisopropylidenediphthalic anhydride, had six CF₃ groups in a repeated segment, so it exhibited the lightest color among the four series. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 922–938, 2003     

Kinetic Parameters of Ion-Exchange Membrane in Amino Acid Solutions

Kinetic parameters of amino acid cations in an MK-40 ion-exchange membrane are calculated from the conductivity data. A theoretical quantum-chemical analysis of experimental activation energies for conduction suggests a mechanism of elementary act of transport of amino acid cations in the membrane.     

On the Essential Self-Adjointness of Wick Powers of Relativistic Fields and of Fields Unitary Equivalent to Random Fields

The essential self-adjointness on a natural domain of the sharp-time Wick powers of the relativistic free field in two space-time dimension is proven. Other results on Wick powers are reviewed and discussed.     

Non-protein amino acids in peptide design

An overview of the use of non-protein amino acids in the design of conformationally well-defined peptides, based on work from the author’s laboratory, is discussed. The crystal structures of several designed oligopeptides illustrate the useα-aminoisobutyric acid (Aib) in the construction of helices, D-amino acids in the design of helix termination segments and^DPro-Xxx segments for nucleating ofβ-hairpin structures.β- andγ-amino acid residues have been used to expand the range of designed polypeptide structures. Dedicated to Professor C N R Rao on his 70th birthday     

新疆野生黑加仑与马林果实的营养成分分析

通过对新疆野生黑加仑和野生马林的脂肪油，8种微量元素，17种氨基酸以及维生素C的含量进行测定得出：黑加仑脂肪油含量为17．9％，马林的脂肪油含量为22．3％，其中，黑加仑脂肪油中，r－亚麻酸的含量为19．02％，而马林中，其含量为9．40％，黑加仑中K，Na,Ca,Cu,Zn,Fe的含量比马林中的含量高，而Mn,Mg元素的含量却比马林含量低；马林的维生素C含量为16．22mg/g，黑加仑的含量为108mg/g，黑加仑的氨基酸的总量为1．63％，马林为1．14％。     

Corn stover fractions and bioenergy

Information is presented on structure, composition, and response to enzymes of corn stover related to barriers for bioconversion to ethanol. Aromatic compounds occurred in most tissue cell walls. Ferulic acid esterase treatment before cellulase treatment significantly improved dry weight loss and release of phenolic acids and sugars in most fractions over cellulase alone. Leaf fractions were considerably higher in dry weight loss and released sugars with esterase treatment, but stem pith cells gave up the most phenolic acids. Results help identify plant fractions more appropriate for coproducts and bioconversion and those more suitable as residues for soil erosion control.     

Reintroduced solids increase inhibitor levels in a pretreated corn stover hydrolysate

Following detoxification of the liquid hydrolysate produced in a corn stover pretreatment process, inhibitor levels are seen to increase with the re-addition of solids for the ensuing hydrolysis and fermentation processes. The solids that were separated from the slurry before detoxification of the liquor contain approx 60% (w/w) moisture, and contamination occurs owing to the diffusion of inhibitors from the moisture entrained in the porous structure of the corn stover solids into the bulk fluid. This evidence suggests the need for additional separation and detoxification steps to purge residual inhibitors entrained in the moisture in the solids. An overliming process to remove furans from the hydrolysate failed to reduce total organic acids concentration, so acids were removed by treatment with an activated carbon powder. Smaller carbon doses proved more efficient in removing organic acids in terms of grams of acid removed per gram of carbon powder. Sugar adsorption by the activated carbon powder was minimal.     

Essential domains and two conjectures in dimension theory

This note investigates two long-standing conjectures on the Krull dimension of integer-valued polynomial rings and of polynomial rings in the context of (locally) essential domains.

     

Organic synthesis based on cathodic deprotonation of acids

The results of studies on electrosynthesis involving carb- and heteroanions generated by cathodic deprotonation of acids (CDA), carried out in the laboratory headed by the author, are surveyed. These studies resulted in the elaboration of efficient electrochemical versions of the known Michaelis-Becker, Wittig-Horner, and Perkin reactions; electrochemical analogs of homolytic aromatic substitution, alkylation, heterocyclization,etc. were developed. Based on CDA, convenient and promising methods for preparing variousN-, O-, P-, S-, andC-alkylated and arylated substances have been developed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1411–1422, August, 1995.The author is grateful to Professor V. A. Dorokhov, Professor V. P. Litvinov, and researchers from the laboratories of N. D. Zelinsky Institute of Organic Chemistry headed by them, who participated in joint studies.The work was carried out with financial support from the International Science Foundation (Grant No. MHYOO).