Thermal decomposition of hydrazinium aluminium sulfate hydrate and hydrazinate

As a part of our research programme on hydrazine derivatives [I-4]. we have prepared a number of hydrazinium metal sulfates [ 1.S] (N2 H5), M(SO4)2, where M = Mn, Fe, Co, Ni, Cu. Zn, Cd and Mg and their hydrazine adducts [2] of the type (N2H5)2M(SO4)2 . 3 N2H4. where M = Fe, Co and Ni, as well as N2H5AI(SO4)2 . 6N2H4. Recently, we reported [5.6] the thermal analysis of these compounds. Our .literature survey on the thermal analysis of alums [7] and aluminium salts [8] indicated that, although the preparation of hydrazinium aluminium sulfate dodecahydrate, N2H5Al(SO4)2 . 12 H2O, has been reported [9], there appears to be no report on its thermal analysis. Here, we report the results df the thermal analysis of N2H5Al(SO4)2 . 12 H2O and N2H5Al(SO4)2 . 2N2H4.

Iron(II, III) complexes with N, N'-DI(2-)Pyridyl Thiourea. Moumlssbauer and other spectroscopic studies

Several iron(II, III) complexes of N, N'-di(2-)pyridyl thiourea have been synthesized. The preparation of the complexes from iron(III) salts proceeds through a reduction of iron(III) to iron(II) followed by a subsequent reoxidation. The Moumlssbauer, electronic and infrared spectra of these complexes have been measured. The results are concordant with the coordination of pyridine nitrogens and thiocarbonyl sulfur yielding polymeric complexes. A variable temperature NMR study of the free ligand shows that two conformation are accessible for it in solution at subambient temperatures.

Studies on nucleotidases in plants : Reversible denaturation of the crystalline mung bean nucleotide pyrophosphatase and the effect of adenylates on the native and renatured enzyme

The crystalline mung bean nucleotide pyrophosphatase was inhibited nonlinearly by AMP, one of the products of the reaction. The partially inactive enzyme was specifically reactivated by ADP, and V at maximal activation was the same as that of the native enzyme. ATP was a linear, noncompetitive inhibitor. The kinetic evidence suggested that ADP and ATP might not be reacting at the same site as AMP. The electrophoretic mobility of the enzyme was increased by AMP, whereas ADP and ATP were without effect. The enzyme was denatured on treatment with urea or guanidine hydrochloride. The renatured and the native enzyme had the same pH (9.4) and temperature (49 °C) optimum. The Km (0.2 mImage ) and V (3.2) of the native enzyme increased on renaturation to 1.8 mImage and 8.0, respectively. In addition, renaturation resulted in desensitization of the enzyme to inhibition by low concentrations of AMP. Renaturation did not affect the reactivation of the apoenzyme by Zn2+.

Synthesis and Characterisation of Metal Hydrazine Nitrate, Azide and Perchlorate Complexes

Metal hydrazine nitrate complexes of the type M(N2H4)Nn (NO3)2 where M = Mg, n = 2; M = Mn, Fe, Co, Ni, Zn and Cd and n = 3; metal dihydrazine azide complexes of the type M(N2H4)2 (N3)2 where M = Mg, Co, Ni and Zn; and Mg(N2H4)2 (C1O4)2 have been prepared by dissolving the respective metal powders in the solution of corresponding ammonium salts (NO3, N3 and C1O4) in hydrazine hydrate. These hydrazine complexes were also prepared by the conventional method involving the addition of alcoholic hydrazine hydrate to the aqueous solution of metal salts. The hydrazine complexes have been characterised by chemical analysis, infrared spectra and differential thermal analysis (DTA). Impact sensitivities of hydrazine complexes were determined by the drop weight method. The reactivity of these hydrazine complexes does not change with the method of preparation.

Studies on nucleotidases in plants - Reversible denaturation of the crystalline mung bean nucleotide pyrophosphatase and the effect of adenylates on the native and renatured enzyme

The crystalline mung bean nucleotide pyrophosphatase was inhibited nonlinearly by AMP, one of the products of the reaction. The partially inactive enzyme was specifically reactivated by ADP, and V at maximal activation was the same as that of the native enzyme. ATP was a linear, noncompetitive inhibitor. The kinetic evidence suggested that ADP and ATP might not be reacting at the same site as AMP. The electrophoretic mobility of the enzyme was increased by AMP, whereas ADP and ATP were without effect. The enzyme was denatured on treatment with urea or guanidine hydrochloride. The renatured and the native enzyme had the same pH (9.4) and temperature (49 °C) optimum. The Km (0.2 m ) and V (3.2) of the native enzyme increased on renaturation to 1.8 m and 8.0, respectively. In addition, renaturation resulted in desensitization of the enzyme to inhibition by low concentrations of AMP. Renaturation did not affect the reactivation of the apoenzyme by Zn2+.

Intermolecular Interactions of Noble-Gas-Containing Species

The importance of intermolecular interactions to chemistry, physics, and biology is difficult to overestimate. Without intermolecular forces, condensed phase matter could not form. The simplest way to categorize different types of intermolecular interactions is to describe them using van der Waals and hydrogen bonded (H-bonded) interactions. In the H-bond, the intermolecular interaction appears between a positively charged hydrogen atom and electronegative fragments and it originates from strong electrostatic interactions. H-bonding is important when considering the properties of condensed phase water and in many biological systems including the structure of DNA and proteins. Vibrational spectroscopy is a useful tool for studying complexes and the solvation of molecules. Vibrational frequency shift has been used to characterize complex formation. In an H-bonded system A∙∙∙H-X (A and X are acceptor and donor species, respectively), the vibrational frequency of the H-X stretching vibration usually decreases from its value in free H-X (red-shift). This frequency shift has been used as evidence for H-bond formation and the magnitude of the shift has been used as an indicator of the H-bonding strength. In contrast to this normal behavior are the blue-shifting H-bonds, in which the H-X vibrational frequency increases upon complex formation. In the last decade, there has been active discussion regarding these blue-shifting H-bonds. Noble-gases have been considered inert due to their limited reactivity with other elements. In the early 1930 s, Pauling predicted the stable noble-gas compounds XeF6 and KrF6. It was not until three decades later Neil Bartlett synthesized the first noble-gas compound, XePtF6, in 1962. A renaissance of noble-gas chemistry began in 1995 with the discovery of noble-gas hydride molecules at the University of Helsinki. The first hydrides were HXeCl, HXeBr, HXeI, HKrCl, and HXeH. These molecules have the general formula of HNgY, where H is a hydrogen atom, Ng is a noble-gas atom (Ar, Kr, or Xe), and Y is an electronegative fragment. At present, this class of molecules comprises 23 members including both inorganic and organic compounds. The first and only argon-containing neutral chemical compound HArF was synthesized in 2000 and its properties have since been investigated in a number of studies. A helium-containing chemical compound, HHeF, was predicted computationally, but its lifetime has been predicted to be severely limited by hydrogen tunneling. Helium and neon are the only elements in the periodic table that do not form neutral, ground state molecules. A noble-gas matrix is a useful medium in which to study unstable and reactive species including ions. A solvated proton forms a centrosymmetric NgHNg+ (Ng = Ar, Kr, and Xe) structure in a noble-gas matrix and this is probably the simplest example of a solvated proton. Interestingly, the hypothetical NeHNe+ cation is isoelectronic with the water-solvated proton H5O2+ (Zundel-ion). In addition to the NgHNg+ cations, the isoelectronic YHY- (Y = halogen atom or pseudohalogen fragment) anions have been studied with the matrix-isolation technique. These species have been known to exist in alkali metal salts (YHY)-M+ (M = alkali metal e.g. K or Na) for more than 80 years. Hydrated HF forms the FHF- structure in aqueous solutions, and these ions participate in several important chemical processes. In this thesis, studies of the intermolecular interactions of HNgY molecules and centrosymmetric ions with various species are presented. The HNgY complexes show unusual spectral features, e.g. large blue-shifts of the H-Ng stretching vibration upon complexation. It is suggested that the blue-shift is a normal effect for these molecules, and that originates from the enhanced (HNg)+Y- ion-pair character upon complexation. It is also found that the HNgY molecules are energetically stabilized in the complexed form, and this effect is computationally demonstrated for the HHeF molecule. The NgHNg+ and YHY- ions also show blue-shifts in their asymmetric stretching vibration upon complexation with nitrogen. Additionally, the matrix site structure and hindered rotation (libration) of the HNgY molecules were studied. The librational motion is a much-discussed solid state phenomenon, and the HNgY molecules embedded in noble-gas matrices are good model systems to study this effect. The formation mechanisms of the HNgY molecules and the decay mechanism of NgHNg+ cations are discussed. A new electron tunneling model for the decay of NgHNg+ absorptions in noble-gas matrices is proposed. Studies of the NgHNg+∙∙∙N2 complexes support this electron tunneling mechanism.

Deriving structural information from non-coding ribonucleic acids by mass spectrometry

The purpose of this study is to describe the development of application of mass spectrometry for the structural analyses of non-coding ribonucleic acids during past decade. Mass spectrometric methods are compared of traditional gel electrophoretic methods, the characteristics of performance of mass spectrometric, analyses are studied and the future trends of mass spectrometry of ribonucleic acids are discussed. Non-coding ribonucleic acids are short polymeric biomolecules which are not translated to proteins, but which may affect the gene expression in all organisms. Regulatory ribonucleic acids act through transient interactions with key molecules in signal transduction pathways. Interactions are mediated through specific secondary and tertiary structures. Posttranscriptional modifications in the structures of molecules may introduce new properties to the organism, such as adaptation to environmental changes or development of resistance to antibiotics. In the scope of this study, the structural studies include i) determination of the sequence of nucleobases in the polymer chain, ii) characterisation and localisation of posttranscriptional modifications in nucleobases and in the backbone structure, iii) identification of ribonucleic acid-binding molecules and iv) probing of higher order structures in the ribonucleic acid molecule. Bacteria, archaea, viruses and HeLa cancer cells have been used as target organisms. Synthesised ribonucleic acids consisting of structural regions of interest have been frequently used. Electrospray ionisation (ESI) and matrix-assisted laser desorption ionisation (MALDI) have been used for ionisation of ribonucleic analytes. Ammonium acetate and 2-propanol are common solvents for ESI. Trihydroxyacetophenone is the optimal MALDI matrix for ionisation of ribonucleic acids and peptides. Ammonium salts are used in ESI buffers and MALDI matrices as additives to remove cation adducts. Reverse phase high performance liquid chromatography has been used for desalting and fractionation of analytes either off-line of on-line, coupled with ESI source. Triethylamine and triethylammonium bicarbonate are used as ion pair reagents almost exclusively. Fourier transform ion cyclotron resonance analyser using ESI coupled with liquid chromatography is the platform of choice for all forms of structural analyses. Time-of-flight (TOF) analyser using MALDI may offer sensitive, easy-to-use and economical solution for simple sequencing of longer oligonucleotides and analyses of analyte mixtures without prior fractionation. Special analysis software is used for computer-aided interpretation of mass spectra. With mass spectrometry, sequences of 20-30 nucleotides of length may be determined unambiguously. Sequencing may be applied to quality control of short synthetic oligomers for analytical purposes. Sequencing in conjunction with other structural studies enables accurate localisation and characterisation of posttranscriptional modifications and identification of nucleobases and amino acids at the sites of interaction. High throughput screening methods for RNA-binding ligands have been developed. Probing of the higher order structures has provided supportive data for computer-generated three dimensional models of viral pseudoknots. In conclusion. mass spectrometric methods are well suited for structural analyses of small species of ribonucleic acids, such as short non-coding ribonucleic acids in the molecular size region of 20-30 nucleotides. Structural information not attainable with other methods of analyses, such as nuclear magnetic resonance and X-ray crystallography, may be obtained with the use of mass spectrometry. Sequencing may be applied to quality control of short synthetic oligomers for analytical purposes. Ligand screening may be used in the search of possible new therapeutic agents. Demanding assay design and challenging interpretation of data requires multidisclipinary knowledge. The implement of mass spectrometry to structural studies of ribonucleic acids is probably most efficiently conducted in specialist groups consisting of researchers from various fields of science.

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+.

Ni(II)chelates of 4,9-dimethyl-5,8-dizadodeca-4,8-diene-2,11-dione-3,10-diphenyl hydrazone and related molecules

Syntheses and structural characterization of Ni(II) chelates of a new series of symmetric and unsymmetric tetradentate linear ligands are described. Preparative routes involve either the direct reaction between a metal complex and arene diazonium diazonium salts or a simple metal incorporation into the independently synthesized ligands. Recent X-ray structure determination of 4,9-dimethyl-5,8-diazadodeca-4,8-diene-2,11-dione-3,10-di(4′-methyl phenyl) hydrazonatonickel(II) complex reveals the geometry around the Ni(II) to be very close to square planar. The expected distortion because of the disposition of bulky aromatic groups on the neighbouring nitrogens is minimized by their projection in the opposite directions from the plane. PMP, IR and electronic spectral data for the complexes are quite in agreement with this structure.

Thermal decomposition of alkali metal perchlorates

The effect of past mechanical history on the subsequent thermal decomposition kinetics of sodium, potassium, rubidium and caesium perchlorates, has been investigated. At low temperatures the decomposition of all these salts is significantly sensitized by pre-compression. At high temperatures, however, prior compression results in a lowered decomposition rate in the case of potassium, rubidium and caesium perchlorates and in an increase in the thermal reactivity of sodium perchlorate. The high temperature behaviour is shown to be an indirect consequence of the low temperature behaviour. The difference in behaviour between sodium perchlorate and the other alkali metal perchlorates is explained on the basis of the stability of the respective chlorates, formed during the low temperature decomposition. This is substantiated by experiments which show that the addition of sodium chlorate to sodium perchlorate brings about a sensitization while potassium perchlorate admixed with potassium chlorate results in a desensitization at high temperatures.

Catalyzed air oxidation for treatment of thiosalt effulents

Continuous slurry reactor runs of two to four weeks duration were carried out for catalyzed air oxidation of thiosalts under a variety of conditions using poly (4-vinylpyridine) - Cu (II) and quaternized poly (4-vinylpyridine) - Cu (II) catalysts. Results obtained indicate that these catalysts have high activity and relatively long-term catalyst stability for thiosalt waste streams of < 1000 ppm thiosalt level. Using 2% (w/w) slurries of the poly (4-vinylpyridine) Cu (II) catalyst, effective oxidation of 700 ppm S2O32− influent to an effluent of < 100 ppm total thio-salts can be carried out continuously for at least one month when operating at 20 to 30°C with solution flow rates of$˜1l/h and aeration of 1300 XXX/h using a two-stage reactor system comprised of 12 l reactors. At higher thiosalt influent levels (i.e. > 1600 ppm) increased reaction temperatures enable depletion to < 100 ppm thiosalt effluent levels for up to one week of continuous operation. The catalysts deactivate much more readily at these higher influent levels as a result of greater copper losses and appreciable adsorption of S2O32− and S4O62−. The behaviour of continuous slurry reactors employed in the experimental studies, by use of batch reaction data for the poly (4-vinylpyridine) Cu (II) catalyzed oxidation of thiosalts, can be modelled successfully. Quaternized poly (4-vinylpyridine) Cu (II) catalyst has good long-term stability and copper losses are very low. The poly (4-vinylpyridine) Cu (II) catalyst, however, is susceptible to appreciable oxidation of the polymer matrix on long-term usage. This oxidation of the polymer matrix results in a substantial loss in the activity of the regenerated catalyst.

Effect of pretreatment on the sublimation of ammonium perchlorate

The effects of pretreatments on the sublimation of pure ammonium perchlorate (AP) were studied by differential thermal analysis. The addition of inorganic salts (doping), or preheating, lead to desensitisation of the sublimation process, whereas it was sensitised by precompression. Sublimation increased with decrease in the particle size of the AP from 500 to 200 microns, but decreased with a further decrease in size from 200 to 100 microns. The results are interpreted in terms of gross imperfections and strain in the AP crystals.

The denaturation of β-lactoglobulin-A at pH 2

The denaturation of β-lactoglobulin-A by heat and guanidine hydrochloride at pH 2 has been investigated. The effect of ethylene glycol on the thermal denaturation at this pH has also been studied. The conditions of the experiments have been chosen so as to eliminate complications arising out of disulfide interchange, changes in the degree of association of the protein during denaturation, and intermolecular aggregation. The physical parameters characterizing the denatured states of the protein which are produced by heat and guanidine hydrochloride have been determined. The thermodynamic parameters for these transitions have been estimated using a two-state hypothesis in each case. Both the physical and thermodynamic parameters indicate that the heat-denatured state of β-lactoglobulin-A retains about 15-20% of residual structure which is destroyed on adding guanidine hydrochloride.

The role of lithium and magnesium perchlorate ammines in ammonium perchlorate decomposition

The preparation and thermal decomposition of lithium and magnesium perchlorate ammines have been investigated. The catalytic effect of these ammines on AP decomposition has been studied. The catalytic effect of lithium and magnesium salts on AP decomposition has been attributed to the formation of the metal perchlorate ammine intermediate. In the case of a magnesium salt: AP mixture, the melting of the magnesium perchlorate monoammine intermediate seems to play an important role in catalysing the decomposition.

Primary structure of a Thomsen-Friedenreich-antigen-specific lectin, jacalin [Artocarpus integrifolia (jack fruit) agglutinin]. Evidence for the presence of an internal repeat

Jacalin [Artocarpus integrifolia (jack fruit) agglutinin] is made up of two types of chains, heavy and light, with M(r) values of 16,200 +/- 1200 and 2090 +/- 300 respectively (on the basis of gel-permeation chromatography under denaturing conditions). Its complete amino acid sequence was determined by manual degradation using a 4-dimethylaminoazobenzene 4'-isothiocyanate double-coupling method. Peptide fragments for sequence analysis were obtained by chemical cleavages of the heavy chain with CNBr, hydroxylamine hydrochloride and iodosobenzoic acid and enzymic cleavage with Staphylococcus aureus proteinase. The peptides were purified by a combination gel-permeation and reverse-phase chromatography. The light chains, being only 20 residues long, could be sequenced without fragmentation. Amino acid analyses and carboxypeptidase-Y-digestion C-terminal analyses of the subunits provided supportive evidence for their sequence. Computer-assisted alignment of the jacalin heavy-chain sequence failed to show sequence similarity to that of any lectin for which the complete sequence is known. Analyses of the sequence showed the presence of an internal repeat spanning residues 7-64 and 76-130. The internal repeat was found to be statistically significant.