Electronic structure of the azide group in 3′-Azido-3′- deoxythymidine (AZT) compared to small azide compounds

Theoretical calculations for some structural and electronic properties of the azide moiety in the nucleoside reverse transcriptase (RT) inhibitor 3′-azido-3′- deoxythymidine (AZT) are reported. These properties, which include geometrical properties in three dimensional space, Hirshfeld charges, electrostatic potential (MEP), vibrational frequencies, and core and valence ionization spectra, are employed to study how the azide group is affected by the presence of a larger fragment. For this purpose, two small but important organic azides, hydrazoic acid and methyl azide, are also considered. The general features of trans Cs configuration for RNNN fragments[1] is distorted in the large AZT bio-molecule. Hirshfeld charge analysis shows charges are reallocated more evenly on azide when the donor group R is not a single atom. Infrared and photoelectron spectra reveal different aspects of the compounds. In conclusion, the electronic structural properties of the compounds depend on the specific property, the local structure and chemical environment of a species.

π-Selective stationary phases: (II) Adsorption behaviour of substituted aromatic compounds on n-alkyl-phenyl stationary phases

The frontal analysis method was used to measure the adsorption isotherms of phenol, 4-chlorophenol, p-cresol, 4-methoxyphenol and caffeine on a series of columns packed with home-made alkyl-phenyl bonded silica particles. These ligands consist of a phenyl ring tethered to the silica support via a carbon chain of length ranging from 0 to 4 atoms. The adsorption isotherm models that fit best to the data account for solute–solute interactions that are likely caused by π–π interactions occurring between aromatic compounds and the phenyl group of the ligand. These interactions are the dominant factor responsible for the separation of low molecular weight aromatic compounds on these phenyl-type stationary phases. The saturation capacities depend on whether the spacer of the ligands have an even or an odd number of carbon atoms, with the even alkyl chain lengths having a greater saturation capacity than the odd alkyl chain lengths. The trends in the adsorption equilibrium constant are also significantly different for the even and the odd chain length ligands.

π-Selective stationary phases: (III) Influence of the propyl phenyl ligand density on the aromatic and methylene selectivity of aromatic compounds in reversed phase liquid chromatography

The retention characteristics of phenyl type stationary phases for reversed phase high performance liquid chromatography are still largely unknown. This paper explores the retention process of these types of stationary phases by examining the retention behaviour of linear PAHs and n-alkylbenzenes on a series of propyl phenyl stationary phases that have changes in their ligand density (1.23, 1.31, 1.97, 2.50 μmol m⁻²). The aromatic and methylene selectivities increased with increasing ligand density until a point where a plateau was observed, overall the propyl phenyl phases had a higher degree of aromatic selectivity than methylene selectivity indicating that these columns are suitable for separations involving aromatic compounds. Also, retention characteristics relating to the size of the solute molecule were observed to be influenced by the ligand density. It is likely that the changing retention characteristics are caused by the different topologies of the stationary phases at different ligand densities. At high ligand densities, the partition coefficient became constant.

π-Selective stationary phases: (I) Influence of the spacer chain length of phenyl type phases on the aromatic and methylene selectivity of aromatic compounds in reversed phase high performance liquid chromatography

Phenyl type stationary phases of increasing spacer chain length (phenyl, methyl phenyl, ethyl phenyl, propyl phenyl and butyl phenyl, with 0–4 carbon atoms in the spacer chain, respectively) were synthesised and packed in house to determine the impact that the spacer chain length has on the retention process. Two trends in the aromatic selectivity, q_aromatic, were observed, depending on whether the number of carbon atoms in the spacer chain is even or odd. Linear log k′ vs ϕ plots were obtained for each stationary phase and the S coefficient was determined from the gradient of these plots. For the phenyl type phases, the S vs n_c plots of the retention factors of linear polycyclic aromatic hydrocarbons vs the number of rings exhibit a distinct discontinuity that between 3 and 4 rings, which increases with increasing spacer chain length for even phases but decreases for odd phases. Accordingly, we suggest that the retention factors depend differently on the number of carbon atoms in the spacer chain depending on whether this number is even or odd and that this effect is caused by different orientations of the aromatic ring relative to the silica surface.

Recent developments in corrosion inhibitors based on rare earth metal compounds

Rare earth organic compounds can provide an environmentally safe and non-toxic alternative to chromates as corrosion inhibitors for some steel and aluminium applications. For steel lanthanum 4-hydroxy cinnamate offers corrosion protection and reduces the susceptibility to hydrogen embrittlement. Recent work has also indicated that it inhibits the corrosion of steel in environments containing high levels of carbon dioxide. For aluminium alloys, cerium diphenyl phosphate provides excellent corrosion inhibition in chloride environments, and reduces susceptibly to stress corrosion cracking. Furthermore, for both steel and aluminium alloys filiform corrosion can be suppressed when rare earth inhibitor compounds are added as pigments to polymer coatings. The levels of inhibition observed are thought to be due to synergistic effects between the rare earth and organic parts of these novel compounds, and are related to the various species that may be present in the complex chemical conditions that develop in solution close to a metal surface. This paper reviews some of the published research conducted by the group at Deakin University over recent years.

Inhibiting localized corrosion of aluminum and aluminum alloy by rare earth metal compounds : behaviors and characteristics observed using an electrochemically integrated multi-electrode array

An electrochemically integrated multi-electrode array namely the wire beam electrode (WBE) has been used to characterize the behavior of cerium chloride (CeCl3) and lanthanum chloride (LaCl3) in inhibiting localized corrosion of AA2024-T3 and AA1100. CeCl3 has been found to inhibit AA2024-T3 corrosion in 0.005 M sodium chloride (NaCl) solution by suppressing galvanic corrosion activities and by creating a large number of insignificant anodes. It has also been shown to inhibit localized corrosion of AA1100 in 0.5 M NaCl solution by promoting the random distribution of minor anodes. LaCl3 has been found to inhibit localized corrosion of AA2024-T3 at 1000 ppm, although its efficiency dropped significantly when its concentration decreased to 500 ppm. The addition of CeCl3 and LaCl3 to corrosion testing cells at later stages was unable to effectively suppress existing corrosion anodes.

Chemiluminescence detection of piperazine designer drugs and related compounds using tris(2,2?-bipyridine)ruthenium(III)

 An exploration of the chemiluminescence from reactions of a large number of benzyl and phenylpiperazine analytes with tris(2,2’-bipyridyl)ruthenium(III) was carried out providing information towards the emission intensity of this chemiluminescent reagent and the structure of analytes it interacts with.

Detection of nitro-explosive compounds using derivatization and tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence

This thesis describes a novel approach towards the trace level detection of nitramine explosives, by exploring various reduction strategies and utilising ruthenium chemiluminescence. Synthesis of novel chemiluminescence compounds has been achieved, as well as the development of a detection method for determining the shelf life of ammunition.

New Compounds Bearing [M(S2O7)3]2– Anions (M = Si, Ge, Sn): Syntheses and Characterization of A2[Si(S2O7)3] (A = Na, K, Rb), A2[Ge(S2O7)3] (A = Li, Na, K, Rb, Cs), A2[Sn(S2O7)3] (A = Na, K), and the Unique Germanate Hg2[Ge(S2O7)3]Cl2 with Cationic 1∞[

The reaction of the group 14 tetrachlorides MCl4 (M = Si, Ge, Sn) with oleum (65 % SO3) at elevated temperatures led to the unique anionic complexes [M(S2O7)3]2– that show the central M atoms in coordination of three chelating S2O72– groups. The mean distances M–O within the complexes increase from 175 pm (M = Si) via 186 pm (M = Ge) up to 200 pm (M = Sn). The charge balance for the [M(S2O7)3]2– anions is achieved by alkaline metal ions A+ (A = Li, Na, K, Rb, Cs) which were implemented in the syntheses in form of their sulfates. The size of the A+ ions, i.e. their coordination requirement causes the crystallographic differences in the crystal structures, while the structure of the complex [M(S2O7)3]2– anions remains essentially unaffected. Furthermore, we were able to characterize the unique germanate Hg2[Ge(S2O7)3]Cl2 which forms when HgCl2 is added as a source for the counter cation. The Hg2+ and the Cl– ions form infinite cationic chains according to 1∞[HgCl2/2]+ which take care for the charge compensation. For selected examples of the compounds the thermal behavior has been monitored by means of thermal analyses and X-ray powder diffraction. For A being an alkaline metal the decomposition product is a mixture of the sulfates A2SO4 and the dioxides MO2, whereas Hg2[Ge(S2O7)3]Cl2 shows a more complicated decomposition. The tris-(disulfato)-silicate Na2[Si(S2O7)3] has additionally been examined by solid state 29Si and 23Na NMR spectroscopic measurements.