Synthesis, structure and solution chemistry of quaternary oxovanadium(V) complexes incorporating hydrazone ligands

[VIVO(acac)(2)] reacts with an equimolar amount of benzoyl hydrazone of 2-hydroxyacetophenone (H2L1) or 5-chloro-2-hydroxyacetophenone (H2L2) in the presence of excess pyridine (py) in methanol to produce the quaternary [(VO)-O-V(L-1)(OCH3)(py)] (1) and [(VO)-O-V(L-2)(OCH3)(py)] (2) complexes, respectively, while under similar condition, the benzoyl hydrazones of 2-hydroxy-5-methylacetophenone (H2L3) and 2-hydroxy-5-methoxyacetophenone (H2L4) afforded only the methoxy bridged dimeric [(VO)-O-V(L-3/L-4)(OCH3)](2) complexes. The X-ray structural analysis of 1 and 2 indicates that the geometry around the metal is distorted octahedral where the three equatorial positions are occupied by the phenolate-O, enolate-O and the imine-N of the fully deprotonated hydrazone ligand in its enolic form and the fourth one by a methoxide-O atom. An oxo-O and a pyridine-N atom occupy two axial positions. Quaternary complexes exhibit one quasi-reversible one-electron reduction peak near 0.25 V versus SCE in CH2Cl2 and they decompose appreciably to the corresponding methoxy bridged dimeric complex in CDCl3 solution as indicated by their H-1 NMR spectra. These quaternary VO3+ complexes are converted to the corresponding V2O34+-complexes simply on refluxing them in acetone and to the VO2+-complexes on reaction with KOH in methanol. An equimolar amount of 8-hydroxyquinoline (Hhq) converts these quaternary complexes to the ternary [(VO)-O-V(L)(hq)] complexes in CHCl3. (C) 2009 Elsevier B. V. All rights reserved.

Synthesis, structure and solution chemistry of a family of dinuclear hydrazonato-vanadium(V) complexes with [OV(mu-O)VO](4+) core

Dinuclear trioxidic [{VOL}(2)mu-O] (1-4) complexes were synthesized from the reaction of [(VO)-O-IV(acac)(2)] with an equimolar amount of H2L [H2L is the general abbreviation of hydrazone ligands (H2L1-4) derived from the condensation of benzoyl hydrazine with either 2-hydroxyacetophenone or its para substituted derivatives] in acetone or CH2Cl2 or acetonitrile. These V2O3L2 complexes were also obtained from the reaction of VOSO4 with H2L in the presence of two equivalents sodium acetate in aqueous-methanolic (50% V/V) medium and also from the decomposition of [(VO)-O-IV(L)(bipy/phen)] complexes in CH2Cl2 Solution. Black monoclinic crystals of 2 and 4 with C2/c space group were obtained from the reaction of [(VO)-O-IV(acac)(2)], respectively, with H2L2 and H2L4 in acetone in which the respective ligands are bonded meridionally to vanadium in their fully deprotonated enol forms. The V-O bond lengths follow the order: V-O(oxo) < V-O(oxo-bridged) < V-O(phenolate) < V-O(enolate). Complexes (1-4) are diamagnetic exhibiting LMCT transition band near 380 nm in CH2Cl2 solution and they are electroactive displaying a quasi-reversible reduction peak in the 0.14-0.30 V versus SCE region. The and the reduction peak potential (E-p(c)) values show linear relationships with the Hammett constant (sigma) of the substituents in the hydrazone ligands. These dinuclear complexes are converted to the corresponding mononuclear cis dioxo complexes K(H2O)(+)[(VO2)-O-V(L)](-) (5-8) and mixed-ligand [(VO)-O-V(L)(hq)] complexes on reaction, respectively, with two equivalents KOH in methanol and two equivalents 8-hydroxyquinoline (Hhq) in CHCl3. Ascorbic acid reduces the dioxovanadium(V) complexes reversibly under aerobic condition. (C) 2008 Elsevier Ltd. All rights reserved.

Solvothermal syntheses, crystal structures and properties of five new thloantimonates(III) containing the [Sb4S7](2-) anion

Five new thioantimonates have been synthesized in the presence of organic amines under solvothermal conditions and their structures determined by single-crystal X-ray diffraction. All of the compounds are layered and contain antimony-sulphide anions of stoichiometry [Sb4S7](2-), but the structure of the anion formed is dependent on the amine used in synthesis. (H3N(CH2)(4)NH3)[Sb4S7] (1) contains [Sb4S7](2-) double chains directed along [010]. Weak interchain Sb-S interactions between neighbouring chains cause the double chains to pack into layers in the ab plane. In the [001] direction, the layers of double chains alternate with doubly protonated diaminobutane molecules to which the chains are hydrogen bonded. Compounds of general formula (TH)(2)[Sb4S7] (T= CH3(CH2)(2)NH2 (2), (CH3)(2)CHNH2 (3), CH3(CH2)(3)NH2 (4) and CH3(CH2)(4)NH2 (5)) adopt a more complex structure in which [Sb3S8](7-) units are linked by Sb-3(3-) pyramids to form chains, which in turn are bridged by sulphur atoms to create sheets containing large heterorings. Pairs of such sheets form double layers of four atoms thickness that are stacked along [001]. Protonated amine molecules are located between anionic antimony-sulphide layers to which they are hydrogen bonded. Thermal analysis reveals that the decomposition temperature of materials containing [Sb4S7](2-) anions is dependent both on the structure of the anion, the lowest decomposition temperature being that of the low-dimensional phase (1) and on the identity of the amine, the decomposition temperature decreasing with an increasing number of carbon atoms and decreasing density. (c) 2005 Elsevier Inc. All rights reserved.

Redox chemistry and electronic properties of 2,3,5,6-tetrakis(2-pyridyl)pyrazine-bridged diruthenium complexes controlled by N,C,N '-biscyclometalated ligands

To investigate the consequences of cyclometalation for electronic communication in dinuclear ruthenium complexes, a series of 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) bridged diruthenium complexes was prepared and studied. These complexes have a central tppz ligand bridging via nitrogen-to-ruthenium coordination bonds, while each ruthenium atom also binds either a monoanionic, N,C,N'-terdentate 2,6-bis(2'-pyridyl)phenyl (R-N boolean AND C boolean AND N) ligand or a 2,2':6',2 ''-terpyridine (tpy) ligand. The N,C,N'-, that is, biscyclometalation, instead of the latter N,N', N ''-bonding motif significantly changes the electronic properties of the resulting complexes. Starting from well-known [{Ru(tpy)}(2)(mu-tppz)](4+) (tpy = 2,2':2 '',6-terpyridine) ([3](4+)) as a model compound, the complexes [{Ru(R-N boolean AND C boolean AND N)}(mu-tppz){Ru(tpy)}](3+) (R-N boolean AND C(H)boolean AND N = 4-R-1,3-dipyridylbenzene, R = H ([4a](3+)), CO2Me ([4b](3+))), and [{Ru(R-N boolean AND C boolean AND N)}(2)(mu-tppz)](2+), (R = H ([5a](2+)), CO2Me ([5b](2+))) were prepared with one or two N,C,N'-cyclometalated terminal ligands. The oxidation and reduction potentials of cyclometalated [4](3+) and [5](2+) are shifted negatively compared to non-cyclometalated [3](4+), the oxidation processes being affected more significantly. Compared to [3](4+), the electronic spectra of [5](2+) display large bathochromic shifts of the main MLCT transitions in the visible spectral region with low-energy absorptions tailing down to the NIR region. One-electron oxidation of [3](4+) and [5](2+) gives rise to low-energy absorption bands. The comproportionation constants and NIR band shape correspond to delocalized Robin-Day class III compounds. Complexes [4a](3+) (R = H) and [4b](3+) (R = CO2Me) also exhibit strong electronic communication, and notwithstanding the large redox-asymmetry the visible metal-to-ligand charge-transfer absorption is assigned to originate from both metal centers. The potential of the first, ruthenium-based, reversible oxidation process is strongly negatively shifted. On the contrary, the second oxidation is irreversible and cyclometalated ligand-based. Upon one-electron oxidation, a weak and low-energy absorption arises.

In-service and pre-service teachers' opinion on the use of models in teaching chemistry

The presented study examined the opinion of in-service and prospective chemistry teachers about the importance of usage of molecular and crystal models in secondary-level school practice, and investigated some of the reasons for their (non-) usage. The majority of participants stated that the use of models plays an important role in chemistry education and that they would use them more often if the circumstances were more favourable. Many teachers claimed that three-dimensional (3d) models are still not available in sufficient number at their schools; they also pointed to the lack of available computer facilities during chemistry lessons. The research revealed that, besides the inadequate material circumstances, less than one third of participants are able to use simple (freeware) computer programs for drawing molecular structures and their presentation in virtual space; however both groups of teachers expressed the willingness to improve their knowledge in the subject area. The investigation points to several actions which could be undertaken to improve the current situation.

Arsenicicoccus bolidensis a novel arsenic reducing actinomycete in contaminated sediments near the Adak mine (northern Sweden): impact on water chemistry

Weathering of mine tailings in Adak results in high As concentrations in surface and ground water, sediments, and soil. In spite of the oxic conditions, As-rich surface and ground, water samples indicate As(III) species predominantly (up to 83%). Several microorganisms were isolated from the enrichment cultures that were involved in As cycling. Amongst them was Arsenicicoccus bolidensis - a novel gram-positive, facultatively anaerobic, coccus-shaped actinomycete, which actively reduced As(V) to As(III) in aqueous media. A. bolidensis reduced 0.06-0.20 mM day(-1) As(V). As(V) reduction displays a direct correlation between the initial As(V) concentration, growth rate, and biomass yield. (c) 2006 Elsevier B.V. All rights reserved.

Interaction of sulphur-containing aroma compounds with proteins in both model systems and real food systems

Irreversible binding of key flavour disulphides to ovalbumin has been shown previously to occur in model systems. The extent of binding is determined by the availability of the sulphydryl groups to participate in disulphide exchange, influenced either by pH, or the state of the protein (native or heat-denatured). In this study, two further proteins, one with sulphydryl groups available in the native state (beta-lactoglobulin) and one with no sulphydryl groups in the native state (lysozyme) were used to confirm this hypothesis. When the investigation was extended to real food systems, a similar effect was shown when a commercial meat flavouring containing disulphides was added to heat-denatured ovalbumin. Furthermore, comparison of the volatiles generated from onions, cooked either alone, or in the presence of meat, showed a significant reduction of key onion-derived disulphides when cooked in the presence of meat, and an even greater reduction of trisulphides. These findings may have implications for consumer acceptance of food products; where these compounds are used as flavourings or where they occur naturally.

Recent highlights in modified oligonucleotide chemistry

The synthesis of modified nucleic acids has been the subject of much study ever since the structure of DNA was elucidated by Watson and Crick at Cambridge and Wilkins and Franklin at King's College over half a century ago. This review describes recent developments in the synthesis and application of these artificial nucleic acids, predominantly the phosphoramidites which allow for easy inclusion into oligonucleotides, and is divided into three separate sections. Firstly, modi. cations to the base portion will be discussed followed secondly by modi. cations to the sugar portion. Finally, changes in the type of nucleic acid linker will be discussed in the third section. Peptide Nucleic Acids ( PNAs) are not discussed in this review as they represent a separate and large area of nucleic acid mimics.

Increased temperature sensitivity of net DOC production from ombrotrophic peat due to water table draw-down.

The production and release of dissolved organic carbon (DOC) from peat soils is thought to be sensitive to changes in climate, specifically changes in temperature and rainfall. However, little is known about the actual rates of net DOC production in response to temperature and water table draw-down, particularly in comparison to carbon dioxide (CO2) fluxes. To explore these relationships, we carried out a laboratory experiment on intact peat soil cores under controlled temperature and water table conditions to determine the impact and interaction of each of these climatic factors on net DOC production. We found a significant interaction (P < 0.001) between temperature, water table draw-down and net DOC production across the whole soil core (0 to −55 cm depth). This corresponded to an increase in the Q10 (i.e. rise in the rate of net DOC production over a 10 °C range) from 1.84 under high water tables and anaerobic conditions to 3.53 under water table draw-down and aerobic conditions between −10 and − 40 cm depth. However, increases in net DOC production were only seen after water tables recovered to the surface as secondary changes in soil water chemistry driven by sulphur redox reactions decreased DOC solubility, and therefore DOC concentrations, during periods of water table draw-down. Furthermore, net microbial consumption of DOC was also apparent at − 1 cm depth and was an additional cause of declining DOC concentrations during dry periods. Therefore, although increased temperature and decreased rainfall could have a significant effect on net DOC release from peatlands, these climatic effects could be masked by other factors controlling the biological consumption of DOC in addition to soil water chemistry and DOC solubility. These findings highlight both the sensitivity of DOC release from ombrotrophic peat to episodic changes in water table draw-down, and the need to disentangle complex and interacting controls on DOC dynamics to fully understand the impact of environmental change on this system.

Flux difference splitting for inviscid, real gases with non-equilibrium chemistry

A flux-difference splitting method is presented for the inviscid terms of the compressible flow equations for chemical non-equilibrium gases