Structural studies of the allelic wheat glutenin subunits 1Bx7 and 1Bx20 by matrix-assisted laser desorption/ionization mass spectrometry and high-performance liquid chromatography/electrospray ionization mass spectrometry

Structural studies of the high molecular mass (HMM) glutenin subunits 1Bx7 (from cvs Hereward and Galatea) and 1Bx20 (from cv. Bidi17) of bread wheat were conducted using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) and reversed-phase high-performance liquid chromatography/electrospray ionization mass spectrometry (RP-HPLC/ESI-MS). For all three proteins, MALDI-TOFMS analysis showed that the isolated fractions contained a second component with a mass about 650 Da lower than the major component. The testing and correction of the gene-derived amino acid sequences of the three proteins were performed by direct MALDI-TOFMS analysis of their tryptic peptide mixture. Analysis of the digest was performed by recording several MALDI mass spectra of the mixture at low, medium and high mass ranges, optimizing the matrix and the acquisition parameters for each mass range. Complementary data were obtained by RP-HPLC/ESI-MS analysis of the tryptic digest. This resulted in coverage of about 98% of the sequences. In contrast to the gene-derived data, the results obtained demonstrate the insertion of the sequence QPGQGQ between Trp716 and Gln717 of subunit 1Bx7 (cv. Galatea) and a possible single amino acid substitution within the T20 peptide of subunit 1Bx20. Moreover, the mass spectrometric data demonstrated that the lower mass components present in all the fractions correspond to the major components but lack about six amino acid residues, which are probably lost from the protein C-terminus. Finally, the results obtained provide evidence for the lack of glycosylation or other post-translational modifications of these subunits.     

CAST/CNMR: highly accurate C NMR chemical shift prediction system considering stereochemistry

Accurate, practical prediction of ¹³C NMR chemical shifts has been achieved with a new system, CAST/CNMR, taking account of stereochemistry. The CAST/CNMR system has solved the critical problem of the accurate distinction of differences and similarities in stereochemical structures around a specific carbon, which has not yet been achieved by any other database-oriented system for prediction of ¹³C NMR chemical shifts. CAST/CNMR uses a three-dimensional structural database together with a ¹³C NMR spectral database. Absolute/relative configurational and conformational structural information are described by the CAST (CAnonical-representation of STereochemistry) coding method. This paper provides an overview of the CAST/CNMR system, and describes its application to two natural products as examples.     

Precise and accurate quantitative C NMR with reduced experimental time

In order to detect small variations in ¹³C isotopomers concentrations, high sensitivity, accuracy and precision have to be achieved. To assess such criteria, when using ¹³C NMR, ¹³C bi-labelled ethanol has been proposed as a molecular probe. Advantage has been taken of the pre-established structural relationship between the peak areas of the ¹³C NMR spectrum of this molecule, i.e. the ratio of signal areas is set to a fixed value. It is shown that the quality performance, required by quantitative ¹³C NMR spectroscopy, is not affected by a large reduction of the repetition delay using relaxation reagents.     

Tunable electronic Raman laser at 16 μm

6s–9s electronic Raman scattering in caesium vapour is used to generate tunable 16m radiation. Output energies in excess of 8 J were obtained, with peak powers in the kilowatt range.     

Simultaneous determination of C1−C8 n-alkyl acetates and corresponding mono-, di- and trichloroacetates on glass capillary columns with programmed temperature rise

Summary Gas chromatography of mixtures of aliphaticn-alkyl acetates (CH₃–COOR), chloroacetates (CHCl₂–COOR), dichloroacetates (CHCl₂–COOR) and trichloroacetates (CCl₃–COOR), where the alcohol chain length (R) varied between 1 and 8, has been studied on SE-30, Carbowax 20M and OV-351 glass capillary columns with programmed temperatures from 50°C at 2, 4, 6, 8 and 10°C/min. Compounds in the homologous series are eluted in the direct order from methyl ton-octyl acetate. The isomeric chloro esters are eluted on SE-30 according to their boiling points in the order: mono-, di- and trichloro isomer, whereas on polar columns di- and trichloro esters are eluted in the reverse order. The complete separation of all 32 individual components from the mixture could not be reached by any single column, the best separation occurred on SE-30. The mixture can, however, be separated by using columns with polar and non-polar stationary phases. The relative retention times for the compounds are given and the retention order discussed.     

Molecular structure and spectral properties of thionaphthalimides

The molecular structure and absorption spectra of monothio- and dithio-naphthalimides were compared to their naphthalimide analogues using AM1, PM3 and ZINDO/S semiempirical quantum chemical methods. The substitution of the 4R-naphthalimide oxygen atoms by sulphur atoms resulted in a red-shift of the absorption spectra by Δλ_max60-65 and 100-140 nm, respectively. The thionated naphthalimide derivatives do not show observable fluorescence due to intersystem crossing to the triplet -states localised at the CS groups. The -absorption bands of monothioimides are located at 525-580 nm (ε=60-80) and those for dithioimides at 535-560 nm (ε=140-390) and 628-686 nm (ε=34-68). None of these transitions are solvent sensitive. The -transitions of N-phenylthioimides have also a small contribution from -states due to a partial conjugation between CS group and π-electronic system of the N-phenyl ring. As a result, the bands of aromatic substituted N-phenylthioimides are red-shifted as compared to those of the aliphatic N-methyl-thioimides.     

Conditional solubility versus pO2− of cerium(III) oxide in molten equimolar NaCl+KCl at 727°C

Reactions between cerium trichloride and oxide ions were studied in NaCl+KCl (1/1) at 1000°K, by potentiometry with a calcia-stabilized zirconia membrane electrode. Titration curves clearly demonstrated the existence of soluble cerium oxychloride (CeO⁺) and precipitated cerium oxide (Ce₂O₃), with respective dissociation constants 10^?11 and 10^?30 (molality scale). The corresponding conditional solubility diagram {log S (Ce^III)=f(pO^2?)} is presented and discussed.     

New lipids from the soft corals of the Andaman Islands

Sphingolipids and glycolipids including previously unknown (2S,3S,4R)-1,3,4-trihydroxy-2-(2-(R)-hydroxyoctadecanoylamino)octadec-8E-ene, (2S,3R)-1,3-dihydroxy-2-octadecanoylamino-4E,8E-hexadecadiene, and (2-hydroxy-3-hexadecyloxypropyl)--L-fucopyranoside were isolated from soft corals collected on the shelf near the Andaman Islands (Indian Ocean). The structures of all compounds were established by spectroscopic methods and chemical analyses. The lipids possessed antibacterial activity against Bacillus subtilis, Bacillus pumilus, Escherichia coli, and Pseudomonas aeruginosa and antifungal activity against Aspergillus niger, Rhizopus oryzae, and Candida albicans.     

DFT and NMR parameterized conformation of valeranone

A Monte Carlo random search using molecular mechanics, followed by geometry optimization of each minimum energy structure employing density functional theory (DFT) calculations at the B3LYP/6-31G* level and a Boltzmann analysis of the total energies, generated accurate molecular models which describe the conformational behavior of the antispasmodic bicyclic sesquiterpene valeranone (1). The theoretical H-C-C-H dihedral angles gave the corresponding 1H, 1H vicinal coupling constants using a generalized Karplus-type equation. In turn, the 3J(H,H) values were used as initial input data for the spectral simulation of 1, which after iteration provided an excellent correlation with the experimental 1H NMR spectrum. The calculated 3J(H,H) values closely predicted the experimental values, excepting the coupling constant between the axial hydrogen alpha to the carbonyl group and the equatorial hydrogen beta to the carbonyl group (J(2beta, 3beta)). The difference is explained in terms of the electron density distribution found in the highest occupied molecular orbital (HOMO) of 1. The simulated spectrum, together with 2D NMR experiments, allowed the total assignment of the 1H and 13C NMR spectra of 1.