Synthesis, X-ray structure and catalytic properties of a copper(II) Schiff base complex modeling the activity of the Cu-B site of dopamine beta-hydroxylase

The copper(II) complex [Cu(salgly) (bpy)] . 4H(2)O (1), where salgly is a tridentate glycinatosalicylaldimine Schiffbase Ligand, is prepared and structurally characterized. The complex is found to be catalytically active in the oxidation of ascorbic acid by dioxygen and the process is also effective in the presence of benzylamine giving benzaldehyde as a product, thus modeling the activity of the Cu-B site of dopamine beta-hydroxylase. (C) 2000 Elsevier Science S.A. All rights reserved.

High-Resolution Magic Angle Spinning Nmr-Studies Of P-31 And B-11 In Fast Ion Conducting Agi-Ag2o-P2o5 And Agi-Ag2o-B2o3 Glasses

Silver iodide-based fast ion conducting glasses containing silver phosphate and silver borate have been studied. An attempt is made to identify the interaction between anions by studying the chemical shifts of31P and11B atoms in high resolution (HR) magic angle spinning (MAS) NMR spectra. Variation in the chemical shifts of31P or11B has been observed which is attributed to the change in the partial charge on the31P or11B. This is indicative of the change in the electronegativity of the anion matrix as a whole. This in turn is interpreted as due to significant interaction among anions. The significance of such interaction to the concept of structural unpinning of silver ions in fast ion conducting glasses is discussed.

Structural alteration from non-B to B-form could reflect DNase I hypersensitivity

Preferential cleavage of active genes by DNase I has been correlated with a structurally altered conformation of DNA at the hypersensitive site in chromatin. To have a better understanding of the structural requirements for gene activation as probed by DNase I action, digestability by DNase I of synthetic polynucleotides having the ability to adopt B and non-B conformation (like Z-form) was studied which indicated a marked higher digestability of the B-form of DNA. Left handed Z form present within a natural sequence in supercoiled plasmid also showed marked resistance towards DNase I digestion. We show that alternating purine-pyrimidine sequences adopting Z-conformation exhibit DNAse I foot printing even in a protein free system. The logical deductions from the results indicate that 1) altered structure like Z-DNA is not a favourable substrate for DNase I, 2) both the ends of the alternating purine-pyrimidine insert showed hypersensitivity, 3) B-form with a minor groove of 12-13 A is a more favourable substrate for DNase I than an altered structure, 4) any structure of DNA deviating largely from B form with a capacity to flip over to the B-form are potential targets for the DNase I enzymic probes in naked DNA.

Diffusion Studies in A(3)B Compounds with A15 Structure

There is a constant effort to understand the defect structure and diffusion behavior in intermetallic compounds with the A15 structure. Diffusion of elements in intermetallic compounds depends mainly on antisites and vacancies on different sublattices. In this article, we shall discuss the diffusion of elements in A(3)B compounds with the A15 structure.

Design of a Non-glycosylated Outer Domain-derived HIV-1 gp120 Immunogen That Binds to CD4 and Induces Neutralizing Antibodies

The outer domain (OD) of the HIV-1 envelope glycoprotein gp120 is an important target for vaccine design as it contains a number of conserved epitopes, including a large fraction of the CD4 binding site.Attempts to design OD-based immunogens in the past have met with little success. We report the design and characterization of an Escherichia coli-expressed OD-based immunogen (ODEC), based on the sequence of the HxBc2 strain. The ODEC-designed immunogen lacks the variable loops V1V2 and V3 and incorporates 11 designed mutations at the interface of the inner and the outer domains of gp120. Biophysical studies showed that ODEC is folded and protease-resistant, whereas ODEC lacking the designed mutations is highly aggregation-prone. In contrast to previously characterized OD constructs, ODEC bound CD4 and the broadly neutralizing antibody b12 but not the non-neutralizing antibodies b6 and F105. Upon immunization in rabbits, ODEC was highly immunogenic,and the sera showed measurable neutralization for four subtype B and one subtype C virus including two b12-resistant viruses. In contrast,sera from rabbits immunized with gp120 did not neutralize any of the viruses. ODEC is the first example of a gp120 fragment-based immunogen that yields significant neutralizing antibodies.

Interruptions of (CG)n sequences by GG, TG and CA need not prevent B to Z transition in solution

Oligonucleotides containing alternating purines-pyrimidines with AT base pairs have been shown to exist in the Z-form preferably in solid state. We report that oligodeoxyribonucleotides with GG, TG and CA interruptions in their alternating CG sequences can undergo B to Z transition in solution in the absence of any chemical modification or topological constraint. The sequences, d(CGCGCGGCGCGC) and d(CGTGCGCACG) have been synthesised and shown to adopt Z- conformation in presence of millimolar concentrations of Ni2+ under low water activity conditions. Significance of GG, TG and CA interruptions in the B to Z transition is discussed.

Theoretical studies on alpha-helix--DNA interactions

The interaction energies between (Ala)10 and alpha-helix fragment and different nucleotide sequences in right-handed B-form have been optimized using semi-empirical potential energy functions. The energies are calculated for two different orientations of the alpha-helix, viz., when the alpha-helix axis taken in the N----C direction is (i) parallel and (ii) antiparallel to the 5'-3' ascending strand of DNA, proximal to it. When both the DNA molecule as well as the alpha-helix are treated as rigid molecules it is found that a polyalanine alpha-helix has slightly more favourable contacts when it is in the proximity of a four nucleotide sequence of 5'-(N-A-T-N)-3' type, where N is either a purine or a pyrimidine. However, when the two interacting molecules are allowed to undergo local structural variations then the interaction energy appears to be independent of the base sequence confirming the non-specific nature of these interactions.

Thermodynamic measurements of b.c.c. Cr-Mn solid solutions at 1373 K

Thermodynamics of Cr-Mn alloys have been studied by Eremenko et al (l) using a fused salt e.m.f.technique. Their results indicate positive deviations from ideality at 1023 K. Kaufman (2) has independently estimated negative enthaipy and excess entropy for the b.c.c. Cr-Mn alloys, such that at high temperatures, the entropy term predominates over the enthalpy term giving positive deviations from ideality. Recently the thermodynamic properties of the alloys have been measured by 3acob (3) using a Knudsen cell technique in the temperature range of 1200 to 1500 K. The results indicate mild negative deviations from ideality over the entire composition range. Because of the differences in the reported results and Mn being a volatile component in the alloys which leads to surface depletion under a dynamic set up, an isopiestic technique is used to measure the properties of the alloys.

Total syntheses of the fungal metabolites (+/-)-acremines A, B and I

A concise and diversity-oriented approach, incorporating elements of regio- and stereocontrol, to the recently isolated bioactive polyoxygenated cyclohexanoid natural products acremines A. B and I. from commercially accessible building blocks, is outlined. (c) 2010 Elsevier Ltd. All rights reserved.

Synthetic studies toward the PPAP natural products, prolifenones A and B and hyperforin: an Effenberger cyclization approach

A synthetic approach toward the geranylated PPAP natural products, prolifenones A and B. employing Effenberger cyclization as the key step, is delineated. The efficacy of this approach is further expanded through access to an advanced precursor of hyperforin. (C) 2010 Elsevier Ltd. All rights reserved.

Peptide models for b-turns.A circular dichroism study

The circular dichroism spectra of four 0-turn model peptides, Z-Aib-Pro-Aib-Pro- OMe (l), Piv-Pro-Aib-NHMe (2), Piv-Pro-D-Ala-NHMe (3) and Piv-Pro-Val-NHMe (4) have been examined under a wide range of solvent conditions, using methanol, hexafluoroisopropanol and cyclohexane. Type I and Type I1 0-turns have been observed for peptides 1 and 2 respectively, in the solid state, while the Pro-D-Ala sequence adopts a Type I1 Sturn in a related peptide crystal structure. A class C spectrum is observed for 1 in various solvents, suggesting a variant of a Type I(II1) structure. The Type I1 f3-turn is characterized by a CD spectrum having two positive CD bands at - 230 nm and - 202 nm, a feature observed in Piv-Pro- D-Ala-NHMe in cyclohexane and methanol and for Piv-Pro-Aib-NHMe in methanol. Peptide 2 exhibits solvent dependent CD spectra, which may be rationalized by considering Type 11, I11 and V reverse turn structures. Piv-Pro- Val-NHMe adopts nonaturn structures in polar solvents, but exhibits a class B spectrum in cyclohexane suggesting a population of Type I &turns.

High-Temperature (1023 K to 1273 K 750 degrees C to 1000 degrees C]) Plastic Deformation Behavior of B-Modified Ti-6Al-4V Alloys: Temperature and Strain Rate Effects

A minor addition of B to the Ti-6Al-4V alloy, by similar to 0.1 wt pct, reduces its as-cast prior beta grain size by an order of magnitude, whereas higher B content leads to the presence of in situ formed TiB needles in significant amounts. An experimental investigation into the role played by these microstructural modifications on the high-temperature deformation behavior of Ti-6Al-4V-xB alloys, with x varying between 0 wt pct and 0.55 wt pct, was conducted. Uniaxial compression tests were performed in the temperature range of 1023 K to 1273 K (750 degrees C to 1000 degrees C) and in the strain rate range of 10(-3) to 10(+1) s(-1). True stress-true strain responses of all alloys exhibit flow softening at lower strain rates and oscillations at higher strain rates. The flow softening is aided by the occurrence of dynamic recrystallization through lath globularization in high temperature (1173 K to 1273 K 900 degrees C to 1000 degrees C]) and a lower strain rate (10(-2) to 10(-3) s(-1)) regime. The grain size refinement with the B addition to Ti64, despite being marked, had no significant effect on this. Oscillations in the flow curve at a higher strain rate (10(0) to 10(+1) s(-1)), however, are associated with microstructural instabilities such as bending of laths, breaking of lath boundaries, generation of cavities, and breakage of TiB needles. The presence of TiB needles affected the instability regime. Microstructural evidence suggests that the matrix cavitation is aided by the easy fracture of TiB needles.

b-Turn conformations in crystal structures of model peptides containing a,a-di-n-propylglycine (Dpg) and a,a-di-n-butyl-glycine (Dbg).

The crystal state conformations of three peptides containing the a,a-dialkylated residues, a,adi n-propylglycine (Dpg) and a,@-di-n-butylglycine (Dbg), have been established by x-ray diffraction. Boc-Ala-Dpg-Ala-OMe ( I ) and Boc-Ala-Dbg-Ala-OMe (III) adopt distorted type II @-turn conformations with Ala ( I ) and Dpg/Dbg (2) as the corner residues. In both peptides the conformational angles at the Dxg residue (I: 4 = 66.23 J/ = 19.3'; III: 4 = 66S0, J. = 21 .la)deviate appreciablyfrom ideal values for the i + 2 residue in a type II @-turn. In both peptides the observed(N. 0) distances between the Boc CO andAla(3) NHgroups are far too long (I:3.44 k; III: 3.63 k) for an intramolecular 4 + 1 hydrogen bond. Boc-Ala-Dpg-Ala-NHMe (II)crystallizes with two independent molecules in the asymmetric unit. Both molecules IIA and IIB adopt consecutive @-turn (type III-III in IIA and type III-I in IIB) or incipient 3,,,-helical structures, stabilized by two intramolecular 4 --t I hydrogen bonds. In all four molecules the bond angle N-C"-C' ( T ) at the Dxg residues are 2 1109 The observation of conformational angles in the helical region of 4,J/ space at these residues is consistent with theoretical predictions