Synthesis,Characterization of a Novel 1,2,4‐Thiotriazine Derivative (CAMTTO), and Copper(I) and Silver(I) Complexes thereof (CAMTTO = {(4‐[(4‐Chlorobenzylidene)‐amino]‐6‐methyl‐3‐thioxo‐[1,2,4]‐triazin‐3,4‐dihydro(2H)‐5‐one)}

The reaction of 4‐amino‐6‐methyl‐1,2,4‐triazin‐thione‐5‐one (H₂AMTTO, 1 ) with 4‐chlorobenzaldhyde led to the corresponding iminic compound {(4‐[(4‐chloro‐benzylidene)‐amino]‐6‐methyl‐3‐thioxo[1,2,4]‐triazin‐3,4‐dihydro(2H)‐5‐one), CAMTTO ( 2 ). Treatment of 2 with copper(I) chloride in chloroform gave the dimeric complex [{(CAMTTO)₂CuCl}₂]·2CHCl₃ ( 3 ). Treatment of 2 with copper(I) chloride and silver(I) nitrate in the presence of the co‐ligand triphenylphophane gave the complexes [(CAMTTO)CuCl(PPh₃)₂] ( 4 ) and [(CAMTTO)Ag(PPh₃)₂]NO₃·2CHCl₃ ( 5 ). All compounds have been characterized by elemental analyses, ¹H NMR spectroscopy, IR spectroscopy, and partly by mass spectrometry and X‐ray diffraction studies. In addition 4 and 5 have been characterized by ³¹P{¹H} NMR spectroscopy. Crystal data for 2 at ?80 °C: monoclinic, space group P2₁/c, a = 1370.3(1), b = 767.8(1), c = 1268.7(1) pm, β = 107.12(1)°, Z = 4, R₁ = 0.0379; for 3 at ?80 °C: monoclinic, space group P2₁/c, a = 1442.6(2), b = 878.8(1), c = 2558.7(3) pm, β = 95.31(1)°, Z = 2, R₁ = 0.0746; for 4 at ?80 °C: triclinic, space group , a = 1287.9(1), b = 1291.7(1), c = 1359.5(1) pm, α = 90.44(1)°, β = 94.81(1)°, γ = 107.54(1)°, Z = 2, R₁ = 0.0359 and for 5 at ?80 °C: triclinic, space group , a = 1060.5(1), b = 1578.2(2), c = 1689.6(2) pm, α = 87.70(1)°, β = 86.66(1)°, γ = 76.84(1)°, Z = 2, R₁ = 0.0487.     

Flexural behavior of unidirectional polyethylene–glass fiber–PMMA hybrid composites

Unidirectional hybrid laminates based on glass fibers (GF) and high performance polyethylene fibers (PEF) were prepared with a partially polymerized methyl methacrylate (MMA) matrix at room temperature followed by heating at 55°C for the stipulated time (well below the softening point of PEF). The ultimate flexural strength (UFS), flexural modulus (FM) and interlaminar shear strength (ILSS) of the composites were determined and analyzed. An interesting observation of the study was the change in flexural behavior, which was largely dependent on the position of GF and PEF ply/plies in the compression and tension sides. When the ply/plies of PEF were at the tension side, the UFS and FM showed a higher value than that when GF plies were in the tension side of the hybrid composites. The ILSS also follows the same trend regarding the position of the GF and PEF plies.     

Thermal investigations of the calcium salts of monocarboxylic aliphatic fatty acids

Calcium salts of acetic and mono, di and trichloroacetic acids were investigated with respect to their dehydration and decarboxylation, using a derivatograph. A phase transition was noticed only in the case of calcium acetate. Effects of crucible and diluent on the thermal behaviour of the above salts were also studied. The decomposition products were investigated qualitatively, and from these gaseous products and also from the residue after pyrolysis the probable mechanisms of decompositions have been suggested. Activation energies for the decarboxylation processes were evaluated from the TG curves.

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Zusammenfassung Die Calciumsalze von EssigsÄure sowie von Mono-, Di- und TrichloressigsÄure wurden mittels eines Derivatographen hinsichtlich ihrer Dehydratisierung und Decarboxylierung untersucht. Ein Phasenübergang wurde nur im Falle des Calciumacetats beobachtet. Der Effekt des Tiegels und des Verdünners auf das thermische Verhalten obiger Salze wurde ebenfalls untersucht. Die Zersetzungsprodukte wurden qualitativ geprüft und aus diesen gasförmigen Produkten sowie aus ihren Pyrolyseresten wurde ein wahrscheinlicher Zersetzungsmechanismus vorgeschlagen. Die Aktivierungsenergien der DecarboxylierungsvorgÄnge wurden aus den TG-Kurven ermittelt.

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Résumé La déhydratation et la décarboxylation des sels de calcium des acides acétique, mono, di et trichloroacétique ont été étudiées à l'aide d'un Derivatograph. Seul l'acétate de calcium présente une transition de phase. Les effets respectifs du creuset et du diluant sur le comportement thermique de ces sels ont également été suivis. Les produits de décomposition ont été analysés qualitativement. D'après la nature des gaz émis et celle des résidus de pyrolyse, un mécanisme est proposé pour ces décompositions. Les énergies d'activation des réactions de décarboxylation sont calculées à partir des courbes TG.

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The authors express their most grateful thanks to the Council of Scientific and Industrial Research, New Delhi, for financial assistance.     

Self-consistent mean-field model based on molecular dynamics: application to lipid-cholesterol bilayers

We have developed a dynamic self-consistent mean-field model, based on molecular-dynamics simulations, to study lipid-cholesterol bilayers. In this model the lipid bilayer is represented as a two-dimensional lattice field in the lipid chain order parameters, while cholesterol molecules are represented by hard rods. The motion of rods in the system is continuous and is not confined to lattice cells. The statistical mechanics of chain ordering is described by a mean field derived from an extension of a model due to Marcelja. The time evolution of the system is governed by stochastic equations. The ensemble of chain configurations required in partition sums, and the energies of interaction, are taken from atomistic level molecular-dynamics simulations of lipid bilayers. The model allows us to simulate systems 500 nm in lateral size for 20 micros time scales, or greater. We have applied the model to dipalmitoyl-phosphatidylcholine-cholesterol (Chol) bilayers at 50 degrees C for Chol concentrations between 2% and 33%. At low concentrations of Chol (2%-4%), the model predicts the formation of isolated clusters of Chol surrounded by relatively ordered lipid chains, randomly dispersed in the disordered bilayer. With increasing Chol composition, regions of Chol-induced order begin to overlap. Starting from about 11% Chol this ordering effect becomes system wide and regions unaffected by Chol are no longer detectable. From the analysis of properties of the model we conclude that the change in lipid chain order with increasing Chol concentration is continuous over the 20-mus scale of the simulations. We also conclude that at 50 degrees C no large-scale Chol-rich and Chol-depleted coexisting phase-separated regions form at any concentration. At no point in any of the simulations do we observe a higher degree of lateral organization, such as Chol-based superlattice structures.     

A potential role for protein tyrosine phosphatase inhibition by a RuIII-edta complex (edta = ethylenediaminetetraacetate) in its biological activity

[RuIII(edta)(OH2/OH)]1-/2- (edta = ethylenediaminetetraacetate) inhibits protein tyrosine phosphatase (PTP) at physiological pH values in a mechanism that involves binding of the Cys residue of the catalytic domain of the enzyme and similar interactions may be important in the anti-cancer properties of the active forms of many Ru pro-drugs.     

Synthesis,Characterization, and Crystal Structure of the New Schiff‐Bases derived from 1,2,4‐Triazole and the Structure of [(PPh3)2Cu(AMTT)]NO3·EtOH (AMTT = 4‐Amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione)

The reactions of 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione (AMTT, L1 ) with 2‐thiophen carbaldehyde, salicylaldehyde and 2‐nitrobenzaldehyde in methanol led to the corresponding Schiff‐bases ( L1a‐c ). The reaction of L1 with [(PPh₃)₂Cu]NO₃ in ethanol gave the ionic complex [(PPh₃)₂Cu(L1)]NO₃·EtOH ( 2 ) All compounds were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for L1a at 20 °C: space group P2₁/n with a = 439.6(2), b = 2074.0(9), c = 1112.8(4) pm, β = 93.51(3)°, Z = 4, R₁ = 0.0406, L1b at ?80 °C: space group P2₁/n with a = 1268.9(2), b = 739.3(1), c = 1272.5(1) pm, β = 117.97(1)°, Z = 4, R₁ = 0.0361, L1c at ?80 °C: space group P2₁/n with a = 847.8(1), b = 1502.9(2), c = 981.5(2) pm, β = 110.34(1)°, Z = 4, R₁ = 0.0376 and for 2 at ?80 °C: space group with a = 1247.8(1), b = 1270.3(1), c = 1387.5(1) pm, α = 84.32(1)°, β = 84.71(1)°, γ = 63.12(1)°, Z = 2, R₁ = 0.0539.