Push-pull ethylenes: the structures of 3-(2-imidazolidinylidene)-2,4-pentanedione (I), C8H12N2O2, and 3-(1,3-dimethyl-2-imidazolidinylidene)-2,4-pentanedione trihydrate (II), C10H16N2O2.3H2O

(I): Mr= 168, triclinic, P1, Z=2, a= 5.596 (2), b = 6.938 (3), c = 10.852 (4) A, ~t= 75.64 (3), fl= 93.44 (3), ),= 95.47 (3) °, V= 406.0A 3, Din= 1.35 (by flotation using carbon tetrachloride and n-hexane), D x= 1.374 Mg m -3, g(Mo Kct, 2 = 0.7107 A) = 1.08 cm -l, _F(000) = 180, T= 293 K. (II): Mr= 250, triclinic, P1, Z= 2, a = 7.731(2), b=8.580(2), c=11.033(3)A, a= 97-66 (2), fl= 98.86 (2), y= 101.78 (2) °, V= 697.5 A 3, D m = 1.18 (by flotation using KI solution), Dx= 1.190Mgm -3, g(MoKa, 2=0.7107A)= 1.02 cm -1, F(000) = 272, T= 293 K. Both structures were solved by direct methods and refined to R = 4.4% for 901 reflexions for (I) and 5.7% for 2001 reflexions for (II). The C=C bond distances are 1.451 (3) A in (I) and 1.468 (3)A in (II), quite significantly longer than the C=C bond in ethylene [1.336 (2).~; Bartell, Roth, Hollowell, Kuchitsu & Young (1965). J. Chem. Phys. 42, 2683-2686]. The twist angle about the C=C bond in (II) is 72.9 (5) ° but molecule (I) is essentially planar, the twist angle being only 4.9 (5) ° .

Elastic analysis of pin joints in plates under some combined pin and plate loads

Joints are primary sources of weakness in structures. Pin joints are very common and are used where periodic disassembly of components is needed. A circular pin in a circular hole in an infinitely large plate is an abstraction of such a pin joint. A two-dimensional plane-stress analysis of such a configuration is carried out, here, subjected to pin-bearing and/or biaxial-plate loading. The pin is assumed to be rigid compared to the plate material. For pin load the reactive stresses at the edges of the infinite plate tend to zero though their integral over the external boundary equals to the pin load. The pin-hole interface is unbonded and so beyond some load levels the plate separates from the pin and the extent of separation is a non-linear function of load level. The problem is solved by inverse technique where the extent of contact is specified and the causative loads are evaluated directly. In the situations where combined load is acting the separation-contact zone specification generally needs two parameters (angles) to be specified. The present report deals with analysing such a situation in metallic (or isotropic) plates. Numerical results are provided for parametric representation and the methodology is demonstrated.

The structures of the ammonium halides

A comparison with the alkali halides suggests that all the ammonium halides should occur in the NaCl centre-of-mass structure. Experimentally, at room temperature and atmospheric pressure, only NH4I crystallizes in this structure, while NH4F is found in the ZnO structure, and NH4C1 and NH4Br occur in the CsCl structure. We show that a distributed charge on the NH4+ ion can explain these structures. Taking charges of + 0.2e on each of the five atoms in NH4+, as suggested by other studies, we have recomputed the Madelung energy in the cases of interest. A full ionic theory including electrostatic, van der Waals and repulsive interactions then explains the centre-of-mass structures of all the four ammonium halides. The thermal and pressure transitions are also explained reasonably well. The calculated phase diagram of NH4F compares well with experiment. Barring the poorly understood NH4F(II) phase, which is beyond the scope of this work, the other features are in qualitative agreement. In particular, the theory correctly predicts a pressure transition at room temperature from the ZnO structure directly to the CsCl structure without an intermediate NaCl phase. A feature of our approach is that we do not need to invoke hydrogen bonding in NH4F.

Pin-Loaded Holes in Large Orthotropic Plates

Pin-loaded holes commonly occur in engineering structures. However, accurate analysis of such holes presents formidable difficulties because of the load-dependent contact of the pin with the plate. Significant progress has recently been achieved in the analysis of holes in isotropic plates. This paper develops a simple and accurate method for the partial contact analysis of pin-loaded holes in composites. The method is based on an inverse formulation that seeks to determine loads in a given contact-separation configuration. A unified approach for all types of fit was used. Continuum solutions were obtained for infinitely large plates of various typical orthotropic properties with holes loaded by smooth rigid pins. These solutions were then compared with those for isotropic plates. The effects of orthotropy and the type of fit were studied through load-contact relationships, distribution of stresses and displacements, and their variation with load. The results are of direct relevance to the analysis and design of pin joints in composite plates.

A large orthotropic plate with misfit pin under arbitrarily oriented biaxial loading

The problem of misfit (interference or clearance) pin in a large orthotropic plate was solved earlier by the authors for biaxial loading in the principal directions of orthotropy. Here, a more general case of arbitrarily oriented loading is considered. The most important aspect of the problem studied is the partial contact at the pin-hole interface. The solution is obtained by extending the use of ‘inverse technique’ which was successfully applied earlier by the authors to problems of pins in isotropic and orthotropic domains. The loss of symmetry because of the arbitrary orientation of loading makes the problem more complex. Additional parameters are then involved in the inversion of the problem for the solution. Numerical results are presented primarily for a smooth interference fit pin in a typical orthotropic plate.

X-ray Studies on Crystalline Complexes Involving Amino Acids and Peptides. XIII. Effect of Chirality on Molecular Aggregation: The Crystal Structures of L-Arginine D-Aspartate and L-Arginine D-Glutamate Trihydrate

The crystal structures of (1) L-arginine D-asparate, C6HIsN40~.C4H6NO4 [triclinic, P1, a=5.239(1), b=9.544(1), c=14.064(2)A, a=85"58(1), /3=88.73 (1), ~/=84.35 (1) °, Z=2] and (2) L-arginine D-glutamate trihydrate, C6H15N40~-.CsHsNO4.3H20 [monoclinic, P2~, a=9.968(2), b=4.652(1), c=19.930 (2) A, fl = 101.20 (1) °, Z = 2] have been determined using direct methods. They have been refined to R =0.042 and 0.048 for 2829 and 2035 unique reflections respectively [I>2cr(I)]. The conformations of the two arginine molecules in the aspartate complex are different from those observed so far in the crystal structures of arginine, its salts and complexes. In both complexes, the molecules are organized into double layers stacked along the longest axis. The core of each double layer consists of two parallel sheets made up of main-chain atoms, each involving both types of molecules. The hydrogen bonds within each sheet and those that interconnect the two sheets give rise to EL-, DD- and DE-type head-to-tail sequences. Adjacent double layers in (1) are held together by side-chain-side-chain interactions whereas those in (2) are interconnected through an extensive network of water molecules which interact with sidechain guanidyl and carboxylate groups. The aggregation pattern observed in the two LD complexes is fundamentally different from that found in the corresponding EL complexes.

Conformations Of Peptides Containing 1-Aminocyclohexane-Carboxylic Acid (Acc6) - Crystal-Structures Of 2 Model Peptides

The crystal structures of two peptides containing 1-aminocyclohexanecarboxylic acid (Acc6) are described. Boc-Aib-Acc6-NHMe · H2O adopts a β-turn conformation in the solid state, stabilized by an intramolecular 4 → 1 hydrogen bond between the Boc CO and methylamide NH groups. The backbone conformational angles (φAib = – 50.3°, ψAib = – 45.8°; φAcc6 = – 68.4°, ψAcc6 = – 15°) lie in between the values expected for ideal Type I or III β-turns. In Boc-Aib-Acc6-OMe, the Aib residue adopts a partially extended conformation (φAib = – 62.2°, ψAib = 143°) while the Acc6residue maintains a helical conformation (φAcc6 = 48°, ψAcc6= 42.6°). 1H n.m.r. studies in CDCl3 and (CD3)2SO suggest that Boc-Aib-Acc6-NHMe maintains the β-turn conformation in solution.

Development of special fastener elements

A special finite element (FASNEL) is developed for the analysis of a neat or misfit fastener in a two-dimensional metallic/composite (orthotropic) plate subjected to biaxial loading. The misfit fasteners could be of interference or clearance type. These fasteners, which are common in engineering structures, cause stress concentrations and are potential sources of failure. Such cases of stress concentration present considerable numerical problems for analysis with conventional finite elements. In FASNEL the shape functions for displacements are derived from series stress function solutions satisfying the governing difffferential equation of the plate and some of the boundary conditions on the hole boundary. The region of the plate outside FASNEL is filled with CST or quadrilateral elements. When a plate with a fastener is gradually loaded the fastener-plate interface exhibits a state of partial contact/separation above a certain load level. In misfit fastener, the extent of contact/separation changes with applied load, leading to a nonlinear moving boundary problem and this is handled by FASNEL using an inverse formulation. The analysis is developed at present for a filled hole in a finite elastic plate providing two axes of symmetry. Numerical studies are conducted on a smooth rigid fastener in a finite elastic plate subjected to uniaxial loading to demonstrate the capability of FASNEL.

Analysis of laminated shells of revolution with laminated stiffeners using a doubly curved quadrilateral finite element

A finite element analysis of laminated shells of revolution reinforced with laminated stifieners is described here-in. A doubly curved quadrilateral laminated anisotropic shell of revolution finite element of 48 d.o.f. is used in conjunction with two stiffener elements of 16 d.o.f. namely: (i) A laminated anisotropic parallel circle stiffener element (PCSE); (ii) A laminated anisotropic meridional stiffener element (MSE). These stifiener elements are formulated under line member assumptions as degenerate cases of the quadrilateral shell element to achieve compatibility all along the shell-stifiener junction lines. The solutions to the problem of a stiffened cantilever cylindrical shell are used to check the correctness of the present program while it's capability is shown through the prediction of the behavior of an eccentrically stiffened laminated hyperboloidal shell.

Large cryptic internal sequence repeats in protein structures from Homo sapiens

Amino acid sequences are known to constantly mutate and diverge unless there is a limiting condition that makes such a change deleterious. However, closer examination of the sequence and structure reveals that a few large, cryptic repeats are nevertheless sequentially conserved. This leads to the question of why only certain repeats are conserved at the sequence level. It would be interesting to find out if these sequences maintain their conservation at the three-dimensional structure level. They can play an active role in protein and nucleotide stability, thus not only ensring proper functioning but also potentiating malfunction and disease. Therefore, insights into any aspect of the repeats - be it structure, function or evolution - would prove to be of some importance. This study aims to address the relationship between protein sequence and its three-dimensional structure, by examining if large cryptic sequence repeats have the same structure.

Thermally Induced Acyl Migration in Salicylamides. 1. Structures of the Reactants, O-Acetylsalicylamide and O-Benzoylsalicylamide

O-Acetylsalicylamide (Ia), C9H9NO3, M r =179.18, monoclinic, P2Jc, a=8.155(5), b=8.571 (2), c= 13.092 (3)A, fl=99.54 (5) ° , V= 902.4(6)A 3, Z=4, Dm=l.31, Dx=l.319gcm -3, 2(Mo Ka) = 0.71069 A,/~ = 1.08 cm -1, F(000) = 376, T = 295 K, R = 0.076 for 1604 reflections. O-Benzoylsalicylamide (Ib), C14HtlNO 3, M,=241.2, monoclinic, P2t/e, a=9.423(1), b=5.116(1), e= 26.424 (2) A, fl= 103.97 (1)% V= 1236.2 (3)/~3, Z= 4, D~ = 1.28, D x = 1.296 gcm -3, ,;L(Cu Ks) = 1.5418 A, p = 7.71 cm-', F(000) = 504, T= 295 K, R =0.050 for 2115 reflections. The dihedral angles between the amide group and the benzene ring are 39.9 ° (Ia) and 37.9 ° (Ib), whereas between the acyl group and the benzene ring they are 78.1 ° (Ia) and 93.4 ° (Ib). The differences in the packing of the two structures are brought out in terms of the observed hydrogen-bonding patterns. Based on the crystallographic results, an intramolecular mechanism for the migration of the acyl group from the O to the N position is suggested in both compounds.

Indian developments in ultrasonics and acoustic emission methods

Fundamental investigations in ultrasonics in India date back to the early 20th century. But, fundamental and applied research in the field of nondestructive evaluation (NDE) came much later. In the last four decades it has grown steadily in academic institutions, national laboratories and industry. Currently, commensurate with rapid industrial growth and realisation of the benefits of NDE, the activity is becoming much stronger, deeper, broader and very wide spread. Acoustic Emission (AE) is a recent entry into the field of nondestructive evaluation. Pioneering efforts in India in AE were carried out at the Indian Institute of Science in the early 1970s. The nuclear industry was the first to utilise it. Current activity in AE in the country spans materials research, incipient failure detection, integrity evaluation of structures, fracture mechanics studies and rock mechanics. In this paper, we attempt to project the current scenario in ultrasonics and acoustic emission research in India.

Flexure of composite plates

A new higher order shear deformation theory of laminated composite plates is developed. The basic displacement variables in this theory are two partial normal displacements and two in-plane displacement parameters. The governing equations are presented in the form of four simultaneous partial differential equations. The shear deformation theories of Bhimareddy and Stevens, and of Reddy are special cases of this formulation. In their models, transverse shear strains will become zero at points in the plate where displacements are constrained to be zero such as those on fixed edges. This limitation has been overcome in the present formulation.

Macromechanical behaviour of composite laminates

An improved higher order transverse shear deformation theory is employed to arrive at modified constitutive relations which can be used in the flexural, buckling and vibration analysis of laminated plates and shells. The strain energy for such systems is then expressed in terms of the displacements and the rotations for ready reference and use. Numerical values of vibration frequencies are obtained using this formulation employing Ritz's method of analysis. The results are compared with those available in the literature to validate the analysis presented.

The structures of the ammonium halides

A comparison with the alkali halides suggests that all the ammonium halides should occur in the NaCl centre-of-mass structure. Experimentally, at room temperature and atmospheric pressure, only NH,1 crystallizes in this structure, while NH,F is found in the ZnO structure, and NH&I and NH,Br occur in the CsCl structure. We show that a distributed charge on the NH,+ ion can explain these structures. Taking charges of + 0.2e on each of the five atoms in NH,+, as suggested by other studies, we have recomputed the Madelung energy in the cases of interest. A full ionic theory including electrostatic, van der Waals and repulsive interactions then explains the centre-of-mass structures of all the four ammonium halides. The thermal and pressure transitions are also explained reasonably well. The calculated phase diagram of NH,F compares well with experiment. Barring the poorly understood NH,F(II) phase, which is beyond the scope of this work, the other features are in qualitative agreement. In particular, the theory correctly predicts a pressure transition at room temperature from the ZnO structure directly to the CsCl structure without an intermediate NaCl phase. A feature of our approach is that we do not need to invoke hydrogen bonding in NH,F.