Conformation of di-n-propylglycine residues (Dpg) in peptides: crystal structures of a type I 'beta-turn forming tetrapeptide and an alpha-helical tetradecapeptide

The crystal structures of two oligopeptides containing di-n-propylglycine (Dpg) residues, Boc-Gly-Dpg-Gly-Leu-OMe (1) and Boc-Val-Ala-Leu-Dpg-Val-Ala-Leu-Val-Ala-Leu-Dpg-Val-Ala-Leu-OMe (2) are presented. Peptide 1 adopts a type I' beta-turn conformation with Dpg(2)-Gly(3) at the corner positions. The 14-residue peptide 2 crystallizes with two molecules in the asymmetric unit, both of which adopt alpha-helical conformations stabilized by 11 successive 5 -> 1 hydrogen bonds. In addition, a single 4 -> 1 hydrogen bond is also observed at the N-terminus. All live Dpg residues adopt backbone torsion angles (phi, psi) in the helical region of conformational space. Evaluation of the available structural data on Dpg peptides confirm the correlation between backbone bond angle N-C-alpha-C' (tau) and the observed backbone phi,psi values. For tau > 106 degrees, helices are observed, while fully extended structures are characterized by tau < 106 degrees. The mean r values for extended and folded conformations for the Dpg residue are 103.6 degrees +/- 1.7 degrees and 109.9 degrees +/- 2.6 degrees, respectively. Copyright (C) 2007 European Peptide Society and John Wiley & Sons, Ltd.

The syntheses, characterizations, X-ray crystal structures and properties of Cu(I) complexes of a bis-bidentate schiff base ligand

Bis-bidentate Schiff base ligand L and its two mononuclear complexes [CuL(CH3CN)(2)]ClO4 (1)and [CuL(PPh3)(2)]ClO4 (2)have been prepared and thoroughly characterized by elemental analyses, IR, UV-Vis, NMR spectroscopy and X-ray diffraction analysis. In both the complexes the metal ion auxiliaries adopt tetrahedral coordination environment. Their reactivity, electrochemical and photophysical behavior have been studied. Complex 1 shows reversible Cu-II/I couple with potential 0.74 V versus Ag/AgCl in CH2Cl2. At room temperature L is weakly fluorescent in CH2Cl2, however in Cu(I)complexes 1 and 2 the emission in quenched. (C) 2009 Elsevier B. V. All rights reserved.

Structural plasticity and enzyme action: Crystal structures of Mycobacterium tuberculosis peptidyl-tRNA hydrolase

Peptidyl-tRNA hydrolase cleaves the ester bond between tRNA and the attached peptide in peptidyl-tRNA in order to avoid the toxicity resulting from its accumulation and to free the tRNA available for further rounds in protein synthesis. The structure of the enzyme from Mycobacteritan tuberculosis has been determined in three crystal forms. This structure and the structure of the enzyme frorn Escherichia coli in its crystal differ substantially on account of the binding of the C terminus of the E. coli enzyme to the peptide-binding site of a neighboring molecule in the crystal. A detailed examination of this difference led to an elucidation of the plasticity of the binding site of the enzyme. The peptide-binding site of the enzyme is a cleft between the body, of the molecule and a polypepticle Y stretch involving a loop and a helix. This stretch is in the open conformation when the enzyme is in the free state as in the crystals of M. tuberculosis peptidyl-tRNA hydrolase. Furthermore, there is no physical continuity between the tRNA and the peptide-binding sites. The molecule in the E. coli crystal mimics the peptide-bound enzyme molecule. The peptide stretch referred to earlier now closes on the bound peptide. Concurrently, a channel connecting the tRNA and the peptide-binding site opens primarily through the concerted movement of two residues. Thus, the crystal structure of M. tuberculosis peptidyl-tRNA hydrolase when compared with the crystal structure of the E. coli enzyme, leads to a model of structural changes associated with enzyme action on the basis of the plasticity of the molecule. (c) 2007 Elsevier Ltd. All rights reserved.

Solution structures of conformationally equilibrium forms of holo-acyl carrier protein (PfACP) from Plasmodium falciparum provides insight into the mechanism of activation of ACPs

Acyl Carrier Protein (ACP) from the malaria parasite, Plasmodium falciparum (PfACP) in its holo form is found to exist in two conformational states in solution. Unique 3D solution structures of holo-PfACP have been determined for both equilibrium conformations, using high-resolution NMR methods. Twenty high-resolution solution structures for each of the two forms of holo-PfACP have been determined on the basis of 1226 and 1218 unambiguously assigned NOEs (including NOEs between 4 '-phosphopantetheine prosthetic group (4 '-PP) and protein), 55 backbone dihedral angles and 26 hydrogen bonds. The atomic rmsd values of the determined structures of two equilibrium forms, about the mean coordinates of the backbone and heavy atoms, are 0.48 +/- 0.09 and 0.92 +/- 0.10 and 0.49 +/- 0.08 and 0.97 +/- 0.11 angstrom, respectively. The interaction of 4 '-PP with the polypeptide backbone is reported here for the first time for any of the ACPs. The structures of holo-PfACP consist of three well-defined helices that are tightly packed. The structured regions of the molecule are stabilized by extensive hydrophobic interactions. The difference between the two forms arises from a reorientation of the 4 '-PP group. The enthalpy difference between the two forms, although small, implies that a conformational switch is essential for the activation of holo-ACP. Sequence and structures of holo-PfACP have been compared with those of the ACPs from type I and type II fatty acid biosynthesis pathways (FAS), in particular with the ACP from rat and the butyryl-ACP from E. coli. The PfACP structure, thus determined has several novel features hitherto not seen in other ACPs.

Study of (Ba3MMWO9)-M-II-W-IV (M-II = Ca, Zn; M-IV = Ti, Zr) perovskite oxides: Competition between 3C and 6H perovskite structures

We describe an investigation of (Ba3MMWO9)-M-II-W-IV oxides for M-II = Ca, Zn, and other divalent metals and M-IV = Ti, Zr. In general, a 1:2-ordered 6H (hexagonal, P6(3)/mmc) perovskite structure is stabilized at high temperatures (1300 degrees C) for all of the (Ba3MTiWO9)-Ti-II oxides investigated. An intermediate phase possessing a partially ordered 1:1 double perovskite (3C) structure with the cation distribution, Ba-2(Zn2/3Ti1/3)(W2/3Ti1/3)O-6, is obtained at 1200 degrees C for Ba3ZnTiWO9. Sr substitution for Ba in the latter stabilizes the cubic 3C structure instead of the 6H structure. A metastable Ba3CaZrWO9 that adopts the 3C (cubic, Fm (3) over barm) structure has also been synthesized by a low-temperature metathesis route. Besides yielding several new perovskite oxides that may be useful as dielectric ceramics, the present investigation provides new insights into the complex interplay of crystal chemistry (tolerance factor) and chemical bonding (anion polarization and d(0)-induced distortion of metal-oxygen octahedra) in the stabilization of 6H versus 3C perovskite structures for the (Ba3MMWO9)-M-II-W-IV series.

Identification of carbohydrate structures as receptors for localised adherent enteropathogenic Escherichia coli

Enteropathogenic Escherichia coli strains of diffused adherent (DA) and localised adherent (LA) phenotypes were tested for their ability to bind to glycolipids. DA strains did not bind to the glycolipids tested, while LA strains bound to asialo GM1, asialo GM2, globoside and lacto-N-neotetraose in decreasing order of avidity. The minimum common sequence among the four glycolipids could be delineated as GalNac β 1–4 Gal as the binding epitope with GalNac β 1–3 Gal and GlcNac β 1–3 Gal serving as relatively weaker binders. The binding was not inhibited by a variety of free oligosaccharides or by the neoglycoproteins tested. Adhesion-negative mutants of an enteropathogenic LA strain showed a markedly reduced binding to asialo GM1 indicating that the recognition of GalNac β 1–4 Gal was correlated with the ability to adhere to HeLa cells. Thus recognition and binding to glycolipids could play an important role in colonisation through adherence to intestinal surfaces.

Note on the locally product and almost locally product structures

This paper is concerned with a study of some of the properties of locally product and almost locally product structures on a differentiable manifold X n of class C k . Every locally product space has certain almost locally product structures which transform the local tangent space to X n at an arbitrary point P in a set fashion: this is studied in Theorem (2.2). Theorem (2.3) considers the nature of transformations that exist between two co-ordinate systems at a point whenever an almost locally product structure has the same local representation in each of these co-ordinate systems. A necessary and sufficient condition for X n to be a locally product manifold is obtained in terms of the pseudo-group of co-ordinate transformations on X n and the subpseudo-groups [cf., Theoren (2.1)]. Section 3 is entirely devoted to the study of integrable almost locally product structures.

Molecular model for localised modes in zincblende structures

A molecular model for substitutional defects in a zincblende lattice has been worked out. The infrared absorption due to A1 in InSb and Li in GaAs are interpreted on the basis of this model.

Dipole patterns in the structures of some ferroelectrics and antiferroelectrics

The dipole patterns in the ferroelectric and antiferroelectric structures are drawn according to experimentally determined symmetry changes in the ferroelectrics and antiferroelectrics. For the ferroelectrics the dipoles of the unit cells for one domain are oriented in parallel and the directions of the polarisation in the adjacent domains are at definite angles to each other. It is assumed for the antiferroelectrics, that the superstructural unit cell is formed by the adjacent cells of the paraelectrical modification; the subcells having the antiparallel directions of the polarisation. It is these superstructural cells of the antiferroelectrics that are determined during the experimental investigations of the antiferroelectrics. The superstructural cells of the adjacent domains are different. In one case, the difference is that in the adjacent domains, the directions of the polarisation in the subcells form an angle (e.g., in PbZrO3). In other cases the superstructural cells have not only different directions of the polarisation in the subcells but different signs of the enantiomorphism (e.g., NH4H2PO4). In the third case, the only difference is that the superstructural unit cells in the adjacent domains are turned by an angle to each other round the direction of the subcell polarisation [e.g., (NH4)2H3IO6], etc.

Analysis of Ridge-Loaded Folded-Waveguide Slow-Wave Structures for Broadband Traveling-Wave Tubes

An E-plane serpentine folded-waveguide slow-wave structure with ridge loading on one of its broad walls is proposed for broadband traveling-wave tubes (TWTs) and studied using a simple quasi-transverse-electromagnetic analysis for the dispersion and interaction impedance characteristics, including the effects of the beam-hole discontinuity. The results are validated against cold test measurements, an approximate transmission-line parametric analysis, an equivalent circuit analysis, and 3-D electromagnetic modeling using CST Microwave Studio. The effect of the structure parameters on widening the bandwidth of a TWT is also studied.

Cytosines, but Not Purines, Determine Recombination Activating Gene (RAG)-induced Breaks on Heteroduplex DNA Structures

The sequence specificity of the recombination activating gene (RAG) complex during V(D)J recombination has been well studied. RAGs can also act as structure-specific nuclease; however, little is known about the mechanism of its action. Here, we show that in addition to DNA structure, sequence dictates the pattern and efficiency of RAG cleavage on altered DNA structures. Cytosine nucleotides are preferentially nicked by RAGs when present at single-stranded regions of heteroduplex DNA. Although unpaired thymine nucleotides are also nicked, the efficiency is many fold weaker. Induction of single- or double-strand breaks by RAGs depends on the position of cytosines and whether it is present on one or both of the strands. Interestingly, RAGs are unable to induce breaks when adenine or guanine nucleotides are present at single-strand regions. The nucleotide present immediately next to the bubble sequence could also affect RAG cleavage. Hence, we propose “C(d)C(S)C(S)” (d, double-stranded; s, single-stranded) as a consensus sequence for RAG-induced breaks at single-/double-strand DNA transitions. Such a consensus sequence motif is useful for explaining RAG cleavage on other types of DNA structures described in the literature. Therefore, the mechanism of RAG cleavage described here could explain facets of chromosomal rearrangements specific to lymphoid tissues leading to genomic instability.

Large-scale structures in turbulent and reverse-transitional sink flow boundary layers

Aspects of large-scale organized structures in sink flow turbulent and reverse-transitional boundary layers are studied experimentally using hot-wire anemometry. Each of the present sink flow boundary layers is in a state of 'perfect equilibrium' or 'exact self-preservation' in the sense of Townsend (The Structure of Turbulent Shear Flow, 1st and 2nd edns, 1956, 1976, Cambridge University Press) and Rotta (Progr. Aeronaut. Sci., vol. 2, 1962, pp. 1-220) and conforms to the notion of 'pure wall-flow' (Coles, J. Aerosp. Sci., vol. 24, 1957, pp. 495-506), at least for the turbulent cases. It is found that the characteristic inclination angle of the structure undergoes a systematic decrease with the increase in strength of the streamwise favourable pressure gradient. Detectable wall-normal extent of the structure is found to be typically half of the boundary layer thickness. Streamwise extent of the structure shows marked increase as the favourable pressure gradient is made progressively severe. Proposals for the typical eddy forms in sink flow turbulent and reverse-transitional flows are presented, and the possibility of structural self-organization (i.e. individual hairpin vortices forming streamwise coherent hairpin packets) in these flows is also discussed. It is further indicated that these structural ideas may be used to explain, from a structural viewpoint, the phenomenon of soft relaminarization or reverse transition of turbulent boundary layers when subjected to strong streamwise favourable pressure gradients. Taylor's 'frozen turbulence' hypothesis is experimentally shown to be valid for flows in the present study even though large streamwise accelerations are involved, the flow being even reverse transitional in some cases. Possible conditions, which are required to be satisfied for the safe use of Taylor's hypothesis in pressure-gradient-driven flows, are also outlined. Measured convection velocities are found to be fairly close to the local mean velocities (typically 90% or more) suggesting that the structure gets convected downstream almost along with the mean flow.