Mechanistic studies on the action of ammonium phosphate on polymer fire retardancy

The mechanism of fire retardant action of mono- and diammonium phosphates on polystyrene has been investigated. Ignition delay and mass burning rate studies reveal that the phosphates bring down both parameters considerably though to different extents. This has been adequately explained on the basis of the existing combustion models and physicochemical behavior of the material. Similar to their action on cellulosic materials, phosphates bring about fire retardancy in polystyrene via char formation. This is suggested to occur through a series of processes consisting of initial peroxide formation, decomposition to alcohols and aldehydes, formation of alkyl-phosphate esters, dehydration and subsequent char formation. Infrared and mass spectral studies support this mechanism.

Studies on diglycine sulphate

Both diglycine sulphate (DGS) and diglycine sulphate monohydrate (DGS.H2O) are reported to crystallize from solution with pH < 1(1,2). DGS.H2O (point group 2/m; Z = 4) shows a dielectric anomaly at 72°C suggestive of antiferroelectric transition(1). The crystals obtained by us from solution with pH < 0.5 at 20-25°C were always DGS (point group mmm; Z = 8) as confirmed by X-ray studies. The measurement of its dielectric constant along [100], [010] and [001] did not indicate any phase transition in the range 5-400°K. Thus DGS is a normal dielectric unlike TGS. The polarized Raman spectra and the infrared spectra were recorded to examine the configuration of glycine in DGS(3). The vibration spectra reveals that both the glycines in DGS exist as NH3+CH2COOH, thus precluding the hydrogen bond of the type N+-H…O- which exists between two glycine units in TGS. This seems to be a good reason for the difference in the dielectric behaviour of these two glycine sulphates.

Studies on Thermal Polymerization of Acrylamide

Thermal polymerization of acrylamide has been followed by the DSC technique, and the activation energy (E) values at different stages of the fraction polymerized (a) have been determined from the exotherm of the thermograms obtained. The trend of variation of E with agr shows that E remains constant up to agr = 0.5 and decreases with a further increase in agr. A close look at the composite nature of the exotherms, agr-t, and agr-T curves shows that the polymerization of acrylamide involves two processes. The first process is the formation of linear polyacrylamide and the second is the simultaneous cross-linking of the linear chains together with the formation of linear polyacrylamide. Experiments such as NH3 detection by differential thermal analysis techniques and annealing studies have been made to shed further light on the polymerization process.

Photo-Electron Spectroscopic Studies Of The Adsorption Of Organic-Molecules With Lone Pair Orbitals On Transition-Metal Surfaces

Ultraviolet and x-ray photoelectron spectroscopy have been employed to investigate the adsorption of methanol, ethanol, diethylether, acetaldehyde, acetone, methyl acetate and methylamine on surfaces of Fe, Ni and Cu. All these molecules adsorb molecularly at low temperatures (≤100 K). Lone pair orbitals of these molecules are stabilized on these metal surfaces (by 0·4–1·0eV) due to molecular chemisorption. The molecules generally undergo transformations as the temperature is raised to 120 K or above. The new species produced seems to depend on the metal surface. Some of the product species identified are methoxy species, formaldehyde and carbon monoxide in the case of methanol and methyl acetate, ethoxy species in the case of ethanol and 2-propanol in the case of acetone.

Interfacial structure and crystallographic studies of transformations in betat' and beta Cu---Zn alloys-II. martensitic formation of alpha1' plates in beta'

A TEM study of the interphase boundary structure of 9R orthorhombic alpha1' martensite formed in beta' Cu---Zn alloys shows that it consists of a single array of dislocations with Burgers vector parallel to left angle bracket110right-pointing angle beta and spaced about 3.5 nm apart. This Burgers vector lies out of the interface plane; hence the interface dislocations are glissile. Unexpectedly, though, the Burgers vectors of these dislocations are not parallel when referenced to the matrix and the martensite lattices. This finding is rationalized on published hard sphere models as a consequence of relaxation of a resultant of the Bain strain and lattice invariant shear displacements within the matrix phase.

Mechanistic studies on polymer flame retardancy Effect of Tribromoaniline

Abstract is not available.

Electronic Structure of some Substituted azolidines.CNDO/2, NMR and vibratational spectoroscopic studies

The 1H and 13C chemical shifts, characteristic vibrational frequencies and force constants for some substituted azolidines are correlated with the results of the CNDO/2 calculations. The influence of the exo and endo heteroatoms on the electronic structure of the heterocyclic ring are discussed.

Studies on follicular atresia: role of tropic hormone and steroids in regulating cathepsin-D activity of preantral follicles of the immature rat

The ovary of the immature female rat is comprised of primary and medium-sized preantral follicles. Upon stimulation with FSH or PMSG, the cathepsin-D activity, a representative lysosomal enzyme of granulosa cells, is reduced by 50% (P < 0.01). 17β-Estradiol at the doses tried was unable to mimic this effect. Blockade of steroidogenesis with cyanoketone also had no effect on the cathepsin-D activity of isolated granulosa cells. Dihydrotestosterone (DHT), however, at a dose of 1 mg/rat was able to inhibit PMSG's tropic action. It brought about an increase in cathepsin-D activity and reduction in steroidogenic activity of isolated granulosa cells. The atretogenic activity of DHT could be relieved by supplementation with exogenous FSH. DHT was observed to significantly reduce (P < 0.01) endogenous FSH and LH levels within 12–18 h of its injection suggesting that its atretic effect was due to its action at the pituitary rather than the gonad. In addition to the above the ability of 15 IU of PMSG to reduce cathepsin-D activity of granulosa cells was also significantly reduced (P < 0.01) if endogenous FSH was neutralized by a specific FSH antiserum. The present study suggests that as far as small and medium-sized primary and preantral follicles are concerned, FSH lack is the essential signal for onset of atresia.

Studies on the effects of in vitro methyiation on aminoacylation of transfer RNA

In vitro methyiation of Escherichia coli transfer ribonucleic acid by cell free extracts of Mycobacterium smegmatis leads exclusively to the formation of 1-methyl adenine [Vani, B. R., Ramakrishnan, T., Taya, Y., Noguchi, S., Yamaiuzumi, Z. and Nishimura, S.(1978) J. Bact., 137,1085]. We have studied the effect of this modification on aminoacylation of Escherichia coli tRNA by mycobacterial enzymes. Aminoacylation with total algal protein hydrolysate as well as several individual aminoacids like methionine, valine, tyrosine, aspartic acid and lysine were monitored. In all the cases methyiation had a positive effect on the extent of aminoacylation by mycobacterial enzymes. Decreased aminoacylation in vitro was observed when hypomethylated transfer RNA from ethionine treated cells was used as the substrate for aminoacylation.

Photoelastic studies on progress of separation in interference fits

Interference fits are used extensively in aircraft structural joints because of their improved fatigue performance. Recent advances in analysis of these joints have increased understanding of the nonlinear load-contact and load-interfacial slip variations in these joints. Experimental work in these problems is lacking due to difficulties in determining partial contact and partial slip along the pin-hole interface. In this paper, an experimental procedure is enumerated for determining load-contact relations in interference/clearance fits, using photoelastic models and applying a technique for detecting progress of separation/contact up to predetermined locations. The study incorporates a detailed procedure for model making, controlling interference, locating break of contact up to known locations around the interface, estimating optically the degree of interference, determining interfacial friction and evaluating stresses in the sheet. Experiments, simulating joints in large sheets, were carried out under both pin and plate loads. The present studies provide load-separation behavior in interference joint with finite interfacial friction.

Theoretical-Studies On The Conformations Of Acyclic Alditols

The conformational analysis by energy calculation is described for some acyclic sugars such as D-glucitol, D-mannitol and galactitol. Planar Zig-zag conformation is the most favoured conformation for the three alditols. However, the energy difference between the ‘bent-chain’ and ‘straight-chain’ conformation is less in the case of D-glucitol (0.9 Kcal Mole-1)compared to those of D-mannitol (~2.4 Kcal mole-1)and galactitol (~2.5 Kcal Mole-1).The solvent accessibility studies favour bent –chain conformation for D-glucitol and straight-chain conformation for D-mannitol and glactitol. These conformations, arrived at by theorticle analysis are compared with those abseverd in the solid state determined by X=ray differaction techinique and their acetylated derivatives in solution by NMR technique. These studies suggest that, when the energy difference between straight and bent conformations is small, latticc energy (in the case of solids) and solvent (in the case of solutions) do play a dominant role on the favoured conformations.

Synthesis of Azo Coupled Crown Ethers Containing Transition Metal and other Chromophoric Environments and Their Ion Complexation Properties

The crown ethers, 2,3-benzo-1,4,7,10,13-pentaoxa-cyclopentadeca-2-ene and 2,3, ll,12-dibenzo-l,4,7,10,13,16-hexaoxscyclooctadeca-2,11-diene are incorporated into H,N'-ethylenebis(acetylacetoneimino) nickel(II) and copper(II), phenol, and β-naphthol by diazo coupling reactions. The selective nature of the coupling reaction has-been demonstrated by the isolation of both asymmetric mono- and symmetric bis(glyoxalarylcrownhydrazoneimino) metal(II) complexes. An interesting binuclear complex containing two intramolecularly rearranged (glyoxal-hydrazonearylimino) metal(II) groups joined by 18-crown-6 result8 when bis(arenediazonium)-18-crown-6 is coupled with the metal(I1) Schiff bases. The substituted ethers form cationic salts with NaClO4, KCNS, NH4CNS, 14g(CNS)2 and Ca(CNS)2. All the synthesised ethers exhibit ion selectivity sequence as K+ > Na+ and Ca2+ > Mg2+.

Theoretical studies on Beta-lactam antibiotics VI: Conformational analysis and structure-activity relationships of penicillin sulfoxides and cephalosporins

Conformational energy calculations were carried out on penicillin α-and Β-sulfoxides and δ2- and δ3-cephalosporins, in order to identify the structural features governing their biological activity. Results on penicillin Β-sulfoxide indicated that in its favoured conformation, the orientation of the aminoacyl group was different from the one required for biological activity. Penicillin α sulfoxide, like penicillin sulfide, favoured two conformations of nearly equal energies, but separated by a much higher energy barrier. The reduced activity of the sulfoxides despite the nonplanarity of their lactam peptide indicated that the orientations of the aminoacyl and carboxyl groups might also govern biological activity. δ3-cephalosporins favoured two conformations of nearly equal energies, whereas δ2-cephalosporins favoured only one conformation. The lactam peptide was moderately nonplanÄr in the former, but nearly planar in the latter. The differences in the.preferred orientations of the carboxyl group between penicillins and cephalosporins were correlated with the resistance of cephalosporins to penicillinases.

Studies involving electrostatic potential of valinomycin

The electrostatic potential of valinomycin in various conformations as obtained by the crystal structures (uncomplexed, complexed) and theoretical considerations have been evaluated and compared. The potential energy profiles along the æ axis of the bracelet-like structures show a systematic variation from the uncomplexed to the complexed structure. This type of conformational change and the potential variation are probably associated with different states of ion transport, like the capture and release of ions by the ionophore. Also, the asymmetry of the molecule due to D-HyIV on one side and L-Lac on the other side is reflected in the potential values along the Z-axis, the magnitude of which, is considerable in the uncomplexed structure. The evaluation of the potential at the ab-initio level on smaller fragments indicate that the order of liganding capacity of oxygen is amide ether ester. Also, the inductive effects due to alkyl substitution is negligible as evidenced by the potential studies on the substituted amides and esters.