Probing the role of the C-H center dot center dot center dot O hydrogen bond stabilized polypeptide chain reversal at the C-terminus of designed peptide helices. Structural characterization of three decapeptides

The structural characterization in crystals of three designed decapeptides containing a double D-segment at the C-terminus is described. The crystal structures of the peptides Boc-Leu-Aib-Val-Xxx-Leu-Aib-Val- (D)Ala-(D)Leu-Aib-OMe, (Xxx = Gly 2, (D)Ala 3, Aib 4) have been determined and compared with those reported earlier for peptide 1 (Xxx = Ala) and the all L analogue Boc-Leu-Aib-Val-Ala-Leu-Aib-Val-Ala-Leu-Aib-OMe, which yielded a perfect right-handed a-helical structure. Peptides 1 and 2 reveal a right-handed helical segment spanning residues 1 to 7, ending in a Schellman motif with Ala(8) functioning as the terminating residue. Polypeptide chain reversal occurs at residue 9, a novel feature that appears to be the consequence of a C-(HO)-O-... hydrogen bond between residue 4 (CH)-H-alpha and residue 9 CO groups. The structures of peptides 3 and 4, which lack the pro R hydrogen at the C-alpha atom of residue 4, are dramatically different. Peptide 3 adopts a right-handed helical conformation over the 1 to 7 segment. Residues 8 and 9 adopt at conformations forming a C-terminus type I' beta-turn, corresponding to an incipient left-handed twist of the polypeptide chain. In peptide 4, helix termination occurs at Aib(6), with residues 6 to 9 forming a left-handed helix, resulting in a structure that accommodates direct fusion of two helical segments of opposite twist. Peptides 3 and 4 provide examples of chiral residues occurring in the less favored sense of helical twist; (D)Ala(4) in peptide 3 adopts an alpha(R) conformation, while (L)Val(7) in 4 adopts an alpha(L) conformation. The structural comparison of the decapeptides reported here provides evidence for the role of specific C-(HO)-O-... hydrogen bonds in stabilizing chain reversals at helix termini, which may be relevant in aligning contiguous helical and strand segments in polypeptide structures.

Micromechanics Of Fatigue Crack-Growth At Low Stress Intensities In A High-Strength Steel

An attempt to systematically investigate the effects of microstructural parameters in influencing the resistance to fatigue crack growth (FCG) in the near-threshold region under three different temper levels has been made for a high strength low alloy steel to observe in general, widely different trends in the dependence of both the total threshold stress intensity range, DELTA-K(th) and the intrinsic or effective threshold stress intensity range, DELTA-K(eff-th) on the prior austenitic grain size (PAGS). While a low strain hardening microstructure obtained by tempering at high temperatures exhibited strong dependence of DELTA-K(th) on the PAGS by virtue of strong interactions of crack tip slip with the grain boundary, a high strength, high strain hardening microstructure as a result of tempering at low temperature exhibited a weak dependence. The lack of a systematic variation of the near-threshold parameters with respect to grain size in temper embrittled structures appears to be related to the wide variations in the amount of intergranular fracture near threshold. Crack closure, to some extent provides a basis on which the increases in DELTA-K(th) at larger grain sizes can be rationalised. This study, in addition, provides a wide perspective on the relative roles of slip behaviour embrittlement and environment that result in the different trends observed in the grain size dependence of near-threshold fatigue parameters, based on which the inconsistency in the results reported in the literature can be clearly understood. Assessment of fracture modes through extensive fractography revealed that prior austenitic grain boundaries are effective barriers to cyclic crack growth compared to martensitic packet boundaries, especially at low stress intensities. Fracture morphologies comprising of low energy flat transgranular fracture can occur close to threshold depending on the combinations of strain hardening behaviour, yield strength and embrittlement effects. A detailed consideration is given to the discussion of cyclic stress strain behaviour, embrittlement and environmental effects and the implications of these phenomena on the crack growth behaviour near threshold.

MNDO study of coupled strained hydrocarbons: Additivity of exocyclic C---C bond contraction induced by different ring systems

MNDO geometry optimizations were carried out on a series of symmetrically and unsymmetrically coupled strained ring hydrocarbons, R1-R1 and R1–R2 (R1=methyl, cyclopropyl, 1-bicyclo[1.1.0]butyl, 1-bicyclo[1.1.1]pentyl, prismyl, cubyl, 6-tricyclo [3.1.1.03,6]heptyl, and tetrahedryl groups; R2=methyl and cyclopropyl). The remarkable contraction of the C---C bond connecting the strained rings found experimentally in a few cases was reproduced correctly by the calculations. A linear correlation was found between the bond length shortening and the bond angle widening at the corresponding carbon atoms for all the structures considered. The reduction in C---C bond lengths due to various ring systems is additive. The additivity indicates that inter-ring interactions which effect the central bond length are absent and confirms the common electronic origin of bond contraction in these systems, viz. enhanced s-character in the exocyclic bonds of strained rings.

Stress-strain characteristics of Tress-strain characteristics of reinforcing steel bars under cyclic loading

This paper presents test results for 22 high strength deformed bars and nine mild steel bars subjected to monotonic repeated and reversed axial loading to determine the stress-strain behavior. Equations have been proposed for the stress-strain curves and have been compared with test results. Satisfactory agreement was obtained.

Stress-Strain Characteristics of Reinforcing Steel Bars Under Cyclic Loading

This paper presents test results for 22 high strength deformed bars and nine mild steel bars subjected to monotonic repeated and reversed axial loading to determine the stress-strain behavior. Equations have been proposed for the stress-strain curves and have been compared with test results. Satisfactory agreement was obtained.

Reactions of Mixed-Valent Palladium (IV,II) Complexes of Tetradentate Schiff-Bases Involving Bond Isomerization

Reactions of [PdIVB-(AI)2]++ [PdIICl4]-- (i) B-(AI)2 = dianion of N,N'-ethylene-/i-propylene-/n-propylene-bis(acetyl-acetoneimine) with some π-acceptor ligands, aliphatic primary amines and nitrosating reagents have been investigated. In all these reactions except nitrosation, 1:1 adducts having the formula, [PdIVB-(AI)2.X] [PdIICl4] [X = triphenylphosphine (TPP), triphenylarsine (TPA), pyridine (Py), methylamine (CH3NH2) or ethylamine (C2H5NH2)] are obtained. The formation of these complexes is associated with a bond isomerization - from Pd-Cxo-π -allylic bond prevailing in [PdIVB-(AI)2]2+ to PdIV-O bonding.Reaction of (i) with nitrosating reagents reduces PdIV to PdII and subsequently transform the γ-CH group, into an ambidentate isonitroso group (°C = NOH). The latter enters into coordination with PdII by dislodging the already coordinated carbonyl group. Further, selective nitrosation (mono- and dinitrosation) has been carried out by controlling the amount of the nitrosating reagent and the reaction time. The complexes have been characterized by elemental analyses, electrical conductivity, magnetic susceptibility and ir spectral data.

The influence of lone-pair repulsions on C–C bond lengths: a critical evaluation of the experimental and theoretical evidence

X-Ray structural data, as well as semiempirical and ab initio molecular orbital calculations, reveal no systematic and substantial difference between the C–C bond lengths of cis and trans 1,2-diketones. Additional results on various conformations of 1,2-diimines and 1,2-dithiones follow the same pattern. Therefore, lone-pair repulsions cannot be implicated in the observed lengthening of C–C bonds in isatin and several related molecules. Conjugation in these systems occurs peripherally avoiding the participation of the central C–C bond. Negative hyperconjugative interaction between the oxygen lone pairs and the adjacent C–C σ* orbital is suggested to be the principal reason for the relatively long C–C bond in diketones. This effect is found in both the cis and trans conformations.

A numerical study of projectile impact on mild steel armour plates

The present article deals with the development of a finite element modelling approach for the prediction of residual velocities of hard core ogival-nose projectiles following normal impact on mild steel target plates causing perforation. The impact velocities for the cases analysed are in the range 818–866.3 m/s. Assessment of finite element modelling and analysis includes a comprehensive mesh convergence study using shell elements for representing target plates and solid elements for jacketed projectiles with a copper sheath and a rigid core. Dynamic analyses were carried out with the explicit contact-impact LS-DYNA 970 solver. It has been shown that proper choice of element size and strain rate-based material modelling of target plate are crucial for obtaining test-based residual velocity.The present modelling procedure also leads to realistic representation of target plate failure and projectile sheath erosion during perforation, and confirms earlier observations that thermal effects are not significant for impact problems within the ordnance range. To the best of our knowledge, any aspect of projectile failure or degradation obtained in simulation has not been reported earlier in the literature. The validated simulation approach was applied to compute the ballistic limits and to study the effects of plate thickness and projectile diameter on residual velocity, and trends consistent with experimental data for similar situations were obtained.

Macroscopic model of city traffic using bond graph modelling

Modelling of city traffic involves capturing of all the dynamics that exist in real-time traffic. Probabilistic models and queuing theory have been used for mathematical representation of the traffic system. This paper proposes the concept of modelling the traffic system using bond graphs wherein traffic flow is based on energy conservation. The proposed modelling approach uses switched junctions to model complex traffic networks. This paper presents the modelling, simulation and experimental validation aspects.

A2MoTiO7−x (Atriple bond; length as m-dashrare earth or Y): a new series of oxide pyrochlores prepared by topochemical reduction of A2MoTiO8 scheelites

A series of anion-deficient pyrochlore oxides of the formula A2MoTiO7−x (xless-than-or-equals, slant0.5), where Atriple bond; length as m-dashSm, Gd, Tb, Dy, Ho, Er, Lu and Y, has been prepared by reduction of A2MoTiO8 scheelites. The scheelite-to-pyrochlore conversion is reversible, indicating that the reaction is likely to be topochemical. The oxidation states of molybdenum and titanium are most probably Mo(III) and Ti(IV) for the limiting composition of the pyrochlores A2MoTiO6.5. The new pyrochlores are non-metallic and paramagnetic as expected.

Advances in the analysis and design of concrete structures, metal containments and liner plate for extreme loads

The material presented in this paper summarizes the progress that has been made in the analysis, design, and testing of concrete structures. The material is summarized in the following documents: 1. Part I - Containment Design Criteria and Loading Combinations - J.D. Stevenson (Stevenson and Associates, Cleveland, Ohio, USA) 2. Part II - Reinforced and Prestressed Concrete Behavior - J. Eibl and M. Curbach (Karlsruhe University, Karlsruhe, Germany) 3. Part III - Concrete Containment Analysis, Design and Related Testing - T.E. Johnson and M.A. Daye (Bechtel Power Corporation, Gaithersburg, Maryland USA) 4. Part IV - Impact and Impulse Loading and Response Prediction - J.D. Riera (School of Engineering - UFRGS, Porto Alegre, RS, Brazil) 5. Part V - Metal Containments and Liner Plate Systems - N.J. Krutzik (Siemens AG, Offenbach Am Main, Germany) 6. Part VI - Prestressed Reactor Vessel Design, Testing and Analysis - J. Nemet (Austrian Research Center, Seibersdorf, Austria) and K.T.S. Iyengar (Indian Institute of Science, Bangalore, India).