Side chain dependence of intensity and wavenumber position of amide I' in IR and visible Raman spectra of XA and AX dipeptides

A series of AX and XA dipeptides in D2O have been investigated by FTIR, isotropic, and anisotropic Raman spectroscopy at acidic, neutral, and alkaline pD, to probe the influence of amino acid side chains on the amide I' band. We obtained a set of spectral parameters for each peptide, including intensities, wavenumbers, half-widths, and dipole moments, and found that these amide I' parameters are indeed dependent on the side chain. Side chains with similar characteristic properties were found to have similar effects on the amide I'. For example, dipeptides with aliphatic side chains were found to exhibit a downshift of the amide I' wavenumber, while those containing polar side chains experienced an increase in wavenumber. The N-terminal charge causes a substantial upshift of amide I', whereas the C-terminal charge causes a moderate decrease of the transition dipole moment. Density functional theory (DFT) calculations on the investigated dipeptides in vacuo yielded different correlations between theoretically and experimentally obtained wavenumbers for aliphatic/aromatic and polar/charged side chains, respectively. This might be indicative of a role of the hydration shell in transferring side chain-backbone interactions. For Raman bands, we found a correlation between amide I' depolarization ratio and wavenumber which reflects that some side chains (valine, histidine) have a significant influence on the Raman tensor. Altogether, the obtained data are of utmost importance for utilizing amide I as a tool for secondary structure analysis of polypeptides and proteins and providing an experimental basis for theoretical modeling of this important backbone mode. This is demonstrated by a rather accurate modeling for the amide I' band profiles of the IR, isotropic Raman, and anisotropic Raman spectra of the beta-amyloid fragment Abeta(1-82).     

The Behavior of 3,3-Diphenylindan-1,2-dione Towards Alkyl Phosphites

Summary. The reaction of 3,3-diphenylindan-1,2-dione with trimethyl phosphite in dry benzene at room temperature for about 15 h led to the formation of a mixture containing dimethyl (3,3-diphenyl-2-methoxy-1-indenyl)phosphate and dimethyl (3,3-diphenyl-1H-2-oxo-1-indanyl)phosphate, whereas with triisopropyl phosphite, diisopropyl (3,3-diphenyl-2-isopropoxy-1-indenyl)phosphate is the only product. Treatment of the dione with dialkyl phosphites under different experimental conditions gave dialkyl (3,3-diphenyl-1-hydroxy-2-oxo-1-indanyl)phosphates. Reaction mechanisms are presented which account for the experimental results. Structural assignments of the new compounds are based on the spectroscopic evidences and two examples were elucidated by X-ray crystallography.     

A computational investigation of the reactions of methylene, chlorocarbene, and dichlorocarbene with cyclopropane

The reactions of CH(2), CHCl, and CCl(2) with cyclopropane, 1, have been examined computationally. In all cases the lowest energy reaction between the carbene and 1 is predicted to be C-H insertion. In the reaction of CH(2) with 1, the transition state for C-C insertion leading to cyclobutane is 1.7 kcal/mol higher in enthalpy than the transition state for C-H insertion at the G3B3 level. A pathway higher in energy than C-H insertion in the reactions of CHCl and CCl(2) with 1 involves two-bond cleavages generating ethylene along with chloro and dichloroethylene, respectively.     

Polyphenolic Profile of Callistemon viminalis Aerial Parts: Antioxidant,Anticancer and In Silico 5-LOX Inhibitory Evaluations

Five new compounds viz kaempferol 3-O-(4″-galloyl)-β-d-glucopyranosyl-(1‴→6″)-O-β-d-glucopyranoside (1), kaempferol 3-O-β-d-mannuronopyranoside (2), kaempferol 3-O-β-d-mannopyranoside (3), quercetin 3-O-β-d-mannuronopyranoside (4), 2, 3 (S)- hexahydroxydiphenoyl]-d-glucose (5) along with fifteen known compounds were isolated from 80% aqueous methanol extract (AME) of C. viminalis. AME and compounds exerted similar or better antioxidant activity to ascorbic acid using DPPH, O₂⁻, and NO inhibition methods. In addition, compounds 16, 4, and 7 showed cytotoxic activity against MCF-7 cell lines while 3, 7 and 16 exhibited strong activity against HepG2. An in silico analysis using molecular docking for polyphenolic compounds 2, 3, 7, 16 and 17 against human stable 5-LOX was performed and compared to that of ascorbic acid and quercetin. The binding mode as well as the enzyme-inhibitor interactions were evaluated. All compounds occupied the 5-LOX active site and showed binding affinity greater than ascorbic acid or quercetin. The data herein suggest that AME, a source of polyphenols, could be used against oxidative-stress-related disorders.     

New combined polymer/chromium approach for investigating the phototransformations involved in hologram formation in dichromated poly(vinyl alcohol)

The photochemical behavior of dichromated poly(vinyl alcohol) films has been analyzed upon exposure at 365 nm in relationship with the performances of holograms recorded in such photosensitive materials. The evolution of both involved species, poly(vinyl alcohol) and chromium, has been quantified by the implementation of an innovative approach. This approach combines the monitoring of the structural modification of the polymeric matrix and the fate of the various chromium species. For the first time, it has been established that chromium(V) not only is an indicator of the hologram quality, as previously assessed, but also appears to be responsible for the crosslinking implied in the hologram formation. Actually, the crosslinking has been proved to proceed through coordination bonds around chromium(V), which acts as a bridge between the polymeric chains. The role played by the ammonium cations in the hologram quality has also been elucidated. The improvement brought by ammonium dichromate with respect to potassium dichromate involves amide groups resulting from poly(vinyl alcohol) phototransformation. These groups provide additional chelating sites for chromium(V), leading to an increase in the matrix crosslinking. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1317–1325, 2006     

A theorem of Jon F. Carlson on filtrations of modules

We give an alternative proof to a theorem of Carlson [J.F. Carlson, Cohomology and induction from elementary abelian subgroups, Quart. J. Math. 51 (2000) 169-181] which states that if G is a finite group and k is a field of characteristic p, then any kG-module is a direct summand of a module which has a filtration whose sections are induced from elementary abelian p-subgroups of G. We also prove two new theorems which are closely related to Carlson’s theorem.     

Perturbation of semi-Browder operators and stability of Browder's essential defect and approximate point spectrum

In the present paper we investigate the stability of closed densely defined semi-Browder operators under operator perturbations that belong to a perturbation class related to compact operators. Furthermore, we apply the obtained results to give a characterization and to study the stability of Browder's essential approximate point spectrum and Browder's essential defect spectrum.     

The Configuration of Naturally Occurring Iridoid Glucosides at C(6) and C(8): A Complementary Assignment Aid by 13C-NMR. Spectroscopy

Evidence is presented which demonstrates that ¹³C-NMR. spectroscopy can be used with confidence in evaluating the configuration of R¹R²CHOH centers at C(6) and C(8) of iridoid glucosides.     

A de Vries (SmC*) Phase in a Novel Series of Chiral Fluorinated Organosiloxane Liquid Crystals

The synthesis and characterization of a series of five chiral fluorinated low molar mass (bifurcated tail) organosiloxane materials is presented. The mesogenic moiety is similar to that in the TSiKN65F mesogen reported by Naciri et al., which displays a de Vries-type SmA* phase. The one parameter varied across the series reported herein is the length of the alkyl chain linking the mesogen's core to the bifurcated siloxane tail. One of the five materials displays a de Vries SmC* phase upon cooling from SmA*.