Bridged and linear dilithioacetylenes - Two minima on the potential energy surface?

Vibrational frequency calculations at the 6–31G^*, 6–31G and STO-3G levels in addition to an STO-3G basis set with only a 1s orbital on lithium reveal that both bridged and linear dilithioacetylenes are minima on the potential energy surface.     

Thermally controlled preferential molecular aggregation state in a thiacarbocyanine dye

Herein we report the experimental and theoretical study of the temperature dependence of a thiacarbocyanine dye in its monomer, H- and J-aggregates states. We demonstrate the ability to control the ratio of monomer, H- and/or J-aggregates with heat. We link such a control to the conformation dependence of the molecule. An alternative way to gain access to the dominating species without changing the concentration as a complete switching mechanism between all the present species is proposed. The results presented in this work lead to a better understanding of thiacarbocyanine dye's behavior.     

Reversible Light‐Driven Polymerization of Polyoxometalate Tethered with Coumarin Molecules

A new photosensitive polyoxometalate (POM) organic–inorganic hybrid compound has been prepared by covalently tethering coumarin moieties onto a Mn–Anderson cluster. This compound has been fully characterized by ¹H NMR, ¹³C NMR, FTIR, and UV/Vis spectroscopy, and ESI‐MS. This organic–inorganic hybrid compound can undergo reversible light‐driven polymerization and this process has been characterized in detail.     

Toxicity of chemical mixtures: proteomic analysis of persisting liver and kidney protein alterations induced by repeated exposure of rats to JP-8 jet fuel vapor

Male Sprague-Dawley rats were exposed by whole body inhalation to 1000 mg/m3 +/- 10% JP-8 jet fuel vapor or room air control conditions for 6 h/day, 5 days/week for six consecutive weeks. Following a rest period of 82 days rats were sacrificed, and liver and kidney tissues examined by proteomic methods for both total protein abundance and protein charge modification. Kidney and lung samples were solubilized and separated via large scale, high resolution two-dimensional electrophoresis (2-DE) and gel patterns scanned, digitized and processed for statistical analysis. Through the use of peptide mass fingerprinting, confirmed by sequence tag analysis, three altered proteins were identified and quantified. Numerical, but not significantly different increases were found in total abundance of lamin A (NCBI Accession No. 1346413) in the liver, and of 10-formyltetrahydrofolate dehydrogenase (10-FTHF DH, #1346044) and glutathione-S-transferase (GST; #2393724) in the kidneys of vapor-exposed subjects. Protein charge modification index (CMI) analysis indicated significant alterations (P < 0.001) in expressed lamin A and 10-FTHF DH. These persisting changes in liver and kidney proteins are discussed in terms of possible alterations in the functional capacity of exposed subjects.     

Isolation of extendable transition metal incorporated polyoxometalate intermediates with structural control

Three discrete cobalt-substituted silicotungstates, [Co3(H2O)(B-beta-SiW9O34)(B-beta-SiW8O29(OH)2)]12- (1), [Co3(H2O)(B-alpha-SiW9O34)(B-beta-SiW8O31)]14- (2), and [Co9Cl2(OH)3(H2O)9(B-beta-SiW8O31)3]17- (3), have been synthesized using a synthetic approach involving Co(II) ions, the dilacunary [gamma-SiW10O36]8- polyanion and a bulky organic cation in basic media; all three compounds have been fully characterized and their position as structural intermediates in Co-containing silicotungstate chemistry is described.     

Improved controlled relative humidity dynamic mechanical analysis of artists’ acrylic emulsion paints

After improvements were made to a modified Polymer Labs MkIII DMTA instrument to facilitate repeatable controlled humidity (RH) experiments using isothermal and thermal scanning conditions, the viscoelastic properties of titanium white pigmented artists’ acrylic emulsion films were measured in tensile mode. The effects of temperature, relative humidity and accelerated ageing regimes on two brands of titanium white paints were explored. These paints are highly responsive to changes in temperature and relative humidity, formulation differences affect properties slightly, and while light ageing had a negligible effect, thermal ageing resulted in decreased storage modulus and increased film density.     

Transition from enantioselective high performance to ultra-high performance liquid chromatography: A case study of a brush-type chiral stationary phase based on sub-5-micron to sub-2-micron silica particles

Three brush-type chiral stationary phases (CSPs) differing in the particle size of the starting silica particles have been prepared by covalent grafting of the π-acidic bis-(3,5-dinitrobenzoyl)-derivative of trans-1,2-diaminocyclohexane (DACH-DNB). Starting silica particles of 4.3, 2.6 and 1.9 micron were used to generate the final CSPs using an improved, highly reproducible synthetic methodology, that allowed to assemble and surface-graft the whole chiral selector in only two steps. The different CSPs have been packed in columns of various length and diameters, and fully characterized in terms of flow permeability, kinetic performances and enantioselectivity using a set of test solutes. Very high speed and high resolution applications together with stereodynamic HPLC examples are demonstrated on the columns with reduced particle diameters, on which separations of several enantiomeric pairs are routinely obtained with analysis times in the 15–40 s range.     

Unsymmetrical surface modification of a heteropolyoxotungstate via in-situ generation of monomeric and dimeric copper(II) species

Unsymmetrical functionalization of a discrete alpha-{SiW12O40} Keggin with two heterometallic building blocks, a Cu(II) dimer and a Cu(II) monomer, results in the formation of [{Cu2(O2CMe)2(5,5'-dimethyl-2,2'-bipy)2}{Cu(5,5'-dimethyl-2,2'-bipy)2}SiW12O40] that displays interesting physical properties.