Synthesis, crystal structures and protease activity of amino acid Schiff base iron(III) complexes

Iron(III) complexes, (NHEt3)[Fe(III)(sal-met)(2)] and (NHEt3)[Fe(III)(sal-phe)(2)], of amino acid Schiffbase ligands, viz., N-salicylidene-L-methionine and N-salicylidene L-phenylalanine, have been prepared and their binding to bovine serum albumin (BSA) and photo-induced BSA cleavage activity have been investigated. The complexes are structurally characterized by single crystal X-ray crystallography. The crystal Structures of the discrete mononuclear rnonoanionic complexes show FeN2O4 octahedral coordination geometry in which the tridentate dianionic amino acid Schiff base ligand binds through phenolate and carboxylate oxygen and imine nitrogen atoms. The imine nitrogen atoms are trans to each other. The Fe-O and Fe-N bond distances range between 1.9 and 2.1 angstrom. The sal-met complex has two pendant thiomethyl groups. The high-spin iron(III) complexes (mu(eff) similar to 5.9 mu(B)) exhibit quasi-reversible Fe(III)/Fe(II) redox process near -0.6 V vs. SCE in water. These complexes display a visible electronic hand near 480 nm in tris-HCl buffer assignable to the phenolate-to-iron(III) charge transfer transition. The water soluble complexes bind to BSA giving binding constant values of similar to 10(5) M-1. The Complexes show non-specific oxidative cleavage of BSA protein on photo-irradiation with UV-A light of 365 nm.

Adsorption isotherms for neutral organic compounds-A hierarchy in modelling: Part III

A simple three-state model permitting two different configurational states for the solvent, together with one for the organic adsorbate, is analysed to derive the adsorption isotherm. The implications of this model regarding pseudo-two-state and pseudo-Frumkin adsorption isotherms are indicated. A critique of the earlier theory of Bockris, Devanathan and Müller is presented in brief.

Effect of chelating anions on metal-crown interaction. Part III. X-ray structure of potassium picrate complex of benzo-15-crown-5

The cr~¢stal structure of [potassium(benzo-15-crown-5)](picrate) shows that in the complex the metal is sandwiched between two crowns andhas no interaction with plcrate.

Gustaf III inför sina undersåtar : Konsten att härska och politikens kulturhistoria

The dissertation analyses the political culture of Sweden during the reign of King Gustav III (1771-1792). This period commonly referred to as the Gustavian era followed the so-called Age of Liberty ending half a century of strong parliamentary rule in Sweden. The question at the heart of this study engages with the practice of monarchical rule under Gustav III, its ideological origins and power-political objectives as well as its symbolic expression. The study thereby addresses the very nature of kingship. In concrete terms, why did Gustav III, his court, and his civil service vigorously pursue projects that contemporaneous political opponents and, in particular, subsequent historiography have variously pictured as irrelevant, superficial, or as products of pure vanity? The answer, the study argues, is to be found in patterns of political practice as developed and exercised by Gustav III and his administration, which formed a significant part of the political culture of Gustavian Sweden. The dissertation is divided into three parts. The first traces the use and development of royal graces chivalric orders, medals, titles, privileges, and other gifts issued by the king. The practice of royal reward is illustrated through two case studies: the 1772 coup d état that established Gustav III s rule, and the birth and baptism of the crown prince, Gustav Adolf, in 1778. The second part deals with the establishment of the Court of Appeal in Vasa in 1776. The formation of the Appeals Court was accompanied by a host of ceremonial, rhetorical, emblematic, and architectural features solidifying its importance as one of Gustav III s most symbolic administrative reform projects and hence portraying the king as an enlightened monarch par excellence. The third and final part of the thesis engages with war as a cultural phenomenon and focuses on the Russo-Swedish War of 1788-1790. In this study, the war against Russia is primarily seen as an arena for the king and other players to stage, create and re-create as well as articulate themselves through scenes and roles adhering to a particular cultural idiom. Its codes and symbolic forms, then, were communicated by means of theatre, literature, art, history, and classical mythology. The dissertation makes use of a host of sources: protocols, speeches, letters, diaries, newspapers, poetry, art, medals, architecture, inscriptions and registers. Traditional political source material and literary and art sources are studied as totalities, not as separate entities. Also it is argued that political and non-fictional sources cannot be understood properly without acknowledging the context of genre, literary conventions, and artistic modes. The study critically views the futile, but nonetheless almost habitual juxtaposition of the reality of images, ideas, and metaphors, and the reality of supposedly factual historical events. Significantly, the thesis presumes the symbolic dimension to be a constitutive element of reality, not its cooked up misrepresentation. This presumption is reflected in a discussion of the concept of role , which should not be anachronistically understood as roles in which the king cast himself at different times and in different situations. Neither Gustav III nor other European sovereigns of this period played the roles as rulers or majesties. Rather, they were monarchs both in their own eyes and in the eyes of their contemporaries as well as in all relations and contexts. Key words: Eighteenth-Century, Gustav III, Cultural History, Monarchs, Royal Graces, the Vasa Court of Appeal, the Russo-Swedish War 1788–1790.

Many-body effects in electrochemisorption : Part III. Beyond mean field and hartree-fock

Several channels provided by many-body couplings — both fermion-fermion and fermion-boson — for the evolution of the chemisorption system are discussed. This provides an opportunity of a systematic study of the effects of correlations reflected through the intricate pole structure of the absorbate Green functions. The results of Newns, Anda and others in the context of chemisorption are generalized.

Photo-induced double-strand DNA and site-specific protein cleavage activity of L-histidine (mu-oxo)diiron(III) complexes of heterocyclic bases

Three oxo-bridged diiron(III) complexes of L-histidine and heterocyclic bases [Fe-2(mu-O)(L-his)(2)(B)(2)](ClO4)(2) (1-3), where B is 2,2'-bipyridine (bpy),1,10-phenanthroline (phen), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq), were prepared and characterized. The bpy complex 1 was structurally characterized by X-ray crystallography. The molecular structure showed a {Fe-2(mu-O)} core in which iron(III) in a FeN4O2 coordination is bound to tridentate monoanionic L-histidine and bidentate bpy ligands. The Fe center dot center dot center dot Fe distance is similar to 3.5 angstrom. The Fe-O-Fe unit is essentially linear, giving a bond angle of similar to 172 degrees. The complexes showed irreversible cyclic voltammetric cathodic response near -0.1 V vs. SCE in H2O-0.1 M KCl. The binuclear units displayed antiferromagnetic interaction between two high-spin (S = 5/2) iron(III) centers giving a -J value of -110 cm(-1). The complexes showed good DNA binding propensity giving a binding constant value of similar to 10(5) M-1. Isothermal titration calorimetric data indicated single binding mode to the DNA. The binding was found to be driven by negative free energy change and enthalpy. The dpq complex 3 showed oxidative double-strand DNA cleavage on exposure to UV-A and visible light. The phen complex 2 displayed single-strand photocleavage of DNA. The DNA double-strand breaks were rationalized from theoretical molecular docking calculations. Mechanistic investigations showed formation of hydroxyl radicals as the reactive species through photodecarboxylation of the L-histidine ligand. The complexes exhibited good binding propensity to bovine serum albumin (BSA) protein in Tris-HCl/NaCl buffer medium. The dpq complex 3 showed UV-A light-induced site-specific oxidative BSA cleavage forming fragments of similar to 45 kDa and similar to 20 kDa molecular weights via SOH pathway.

A Magnetic Susceptibility Study of Spin-state Transitions in Rare-earth TrioxocobaItates( III)

Rare-earth trioxocobaltates(lll), Ln[CoO,], with Ln = Pr, Nd, Tb, Dy. and Yb exhibit low-spin to high-spin transitions of cobalt characterised by a maximum in the Ax-l against temperature plots where Ax is the cobalt contribution to the magnetic susceptibility. The susceptibility behaviour is distinct from that of La[CoO,] which shows a plateau in the x-I-T curve accompanied by a structural transition. The temperature at which the AX- I-T curve shows a maximum increases with the decrease in the size of the rare-earth ion. The susceptibility behavior of solid solutions of La,,Nd,CoO, has been investigated to see how the behaviour characteristic of Nd[CoO,] changes to that of La[CoO,].

Synthesis and physico-chemical properties of diruthenium(III, II) tetra-aryl carboxylato compounds

Monochloro-tetra-μ-aryl-carboxylatodiruthenium(III, II) compounds Ru2Cl (O2CAr)4 (Ar = -C6H5; -C6H4-p-OCH3), are prepared and characterized. The compounds have magnetic moments that correspond to three unpaired spins per dimer. The Rusingle bondRu bond order is 2.5 and the ground electronic configuration is σ2π4δ2(δ*π*)3. The visible spectral band is observed at ca 450 nm along with a shoulder near 580 nm in DMF solution. The compounds undergo a one-electron Ru(III)Ru(II) → Ru(II)Ru(II) quasi-reversible reduction in DMF near 0.0 V vs sce.

Leading Sheep III

Leading Sheep is a framework for supporting decision-making about technologies and practices to increase the profitability and productivity of the Queensland Sheep Businesses. Leading Sheep aims to achieve a high level of engagement with sheep businesses in Queensland to support their ongoing decision making processes about productivity and profitability.

Biodegradation of gelatin graft copolymers. III

Gelatin-g-poly(methyl acrylate) and gelatin-g-poly(acrylonitrile) copolymers were prepared in an aqueous medium using K2S2O8 initiator. A plausible mechanism has been put forward for the observed grafting behavior of monomers. Gelatin-g-PAN showed a greater resistance to mixed bacterial inolucum compared to gelatin-g-PMA samples. The rate of degradation decreased with the increase in grafting efficiency. A parallel set of experiments carried out by employing the samples as the only source of both carbon and nitrogen showed a marginal but definite increase in the utilization of the polymer. The nitrogen analysis also showed the utilization of the polymer. Scanning electron micographs of the polymer films do show extensive pitting after microbiological testing.

Preparation, characterisation and thermal properties of hydrazinium derivatives. Part III

Hydrazinium acetate, metavanadate, sulfite, sulphamate and thiocyanate have been prepared by the reaction of corresponding ammonium salts with hydrazine hydrate. The compounds were characterised by chemical analysis and infrared spectra. Thermal behaviour of these hydrazinium derivatives have been investigated using thermogravimetry and differential thermal analysis.

Risk assessment and preventive strategies for herbicide resistance in NR (phase III)

The threat and management of glyphosate# resistant weeds are major issues facing northern region growers. At present five weeds are confirmed glyphosate-resistant: barnyard grass, liverseed grass, windmill grass, annual ryegrass and flaxleaf fleabane. This project used 25 experiments to investigate the ecology of the grass weeds, plus new or improved chemical and non-chemical control tactics for them. The refined glyphosate resistance model developed in this project used the experiments' findings to predict the long-term impacts on evolution of resistance and on seed bank numbers of resistant weeds. These data led to revised management and resistance avoidance strategies, which were published in the Reporter newsletter, and via an on-line risk assessment tool. - See more at: http://finalreports.grdc.com.au/UQ00054#sthash.oTkCN4Sk.dpuf

Herbicide tolerance of barley and wheat cultivars in NR (phase III)

During the past 10 years, this project tested 23 barley and 51 wheat varieties with 19 and 34 registered herbicides, respectively. It concentrated on new varieties and herbicides. The research highlighted that Northern Region (NR) wheat and barley varieties differed considerably in their sensitivity to these herbicides. Overall, 9 per cent of wheat variety x herbicide combinations and 6 per cent of barley variety x herbicide combinations had significant yield losses (3 to 38%) from herbicides at recommended rates and crop stages. In addition, 21 to 23 per cent had significant yield losses from herbicides at double rates, indicating a narrow margin of crop safety.

Ternary metal complexes of anionic and neutral pyridoxine (vitamin B6) with 2,2'-bipyridine. Syntheses and x-ray structures of (pyridoxinato)bis(2,2'-bipyridyl)cobalt(III) perchlorate and chloro(2,2'-bipyridyl)(pyridoxine)copper(II) perchlorate hydrate

Ternary metal complexes involving vitamin B6 with formulas [CO",(PN-H)](anCdI [OC)'(bpy)(PN)Cl]C10(.bpHy 0 = 2,2'-bipyridine, PN = neutral pyridoxine, PN-H = anionic pyridoxine) have been prepared for the first time and characterized by means of magnetic and spectroscopic measurements. The crystal structures of the compounds have also been determined. [CO(PN-H)](CcryIsOta,l)lize s in the space group P2,/c with a = 18.900 (3) A, b = 8.764 (1) A, c = 20.041 (2) A,p = 116.05 (l)', and Z = 4 and [Cu(bpy)(PN)C1]C104-H20in the space group Pi with a = 12.136 (5) A, b = 13.283 (4) A,c = 7.195 (2) A, a = 96.91 (Z)', 0 = 91.25 (3)', y = 71.63 (3)', and Z = 2. The structures were solved by the heavy-atom method and refined by least-squares techniques to R values of 0.080 and 0.042 for 3401 and 2094 independent reflections, respectively. Both structures consist of monomeric units. The geometry around Co(II1) is octahedral and around Cu(I1) is distorted square pyramidal. In [CO(PN-H)]t(wCo IoxOy~ge)n~s ,fro m phenolic and 4-(hydroxymethyl) groups of PN-H and two nitrogens from each of two bpy's form the coordination sphere. In [Cu(bpy)(PN)C1]C104.H20o ne PN and one bpy, with the same donor sites, act as bidentate chelates in the basal plane, with a chloride ion occupying the apical position. In both structures PN and PN-H exist in the tautomeric form wherein pyridine N is protonated and phenolic 0 is deprotonated. However, a novel feature of the cobalt compound is that PN-H is anionic due to the deprotonation of the 4-(hydroxymethyl) group. The packing in both structures is governed by hydrogen bonds, and in the copper compound partial stacking of bpy's at a distance of -3.55 also adds to the stability of the system. Infrared, NMR, and ligand field spectroscopic results and magnetic measurements are interpreted in light of the structures.

Mixed ligand complexes in vinyl polymerization-II: [NN-ethylenebis(salicylideneiminato)] (benzoylacetonato)cobalt(III) as an initiator

The polymerization of methyl methacrylate initiated by a mixed ligand complex. [NN-ethylenebis(salicylideneiminato)](benzoylacetonato)cobalt(III) has been studied in bulk and in benzene at 70° and 80°. The rate of polymerization is proportional to (concentration of the chelate)Image and the monomer exponent is close to 1.5. The activation energy and the kinetic and transfer constants are evaluated. A free radical mechanism has been proposed.