Differential expression of the skeletal muscle proteome in mdx mice at different ages

The mdx mouse is the most commonly used animal model for Duchenne muscular dystrophy (DMD), a disease caused by the absence of dystrophin. Although much has been done to elucidate the structure and function of dystrophin and the dystrophin-associated glycoprotein complex (DGC), little is known about the cascade of molecular events triggered by the absence of dystrophin that lead to muscle degeneration. To study the molecular basis of DMD, we decided to systematically study the skeletal muscle proteome in mdx mice at different ages. By using two-dimensional (2-D) gel electrophoresis, we defined changes in the protein expression pattern between mdx and control muscles. Approximately 46 differentially expressed proteins from the cytosolic fraction of mdx hindlimb muscles at three months of age were detected by 2-D gel analysis, of which 24 were identified by matrix assisted laser desorption/ionization- mass spectrometry. Most of the proteins fell into five groups of functionally related proteins. These functional categories are (i) metabolism and energy production, (ii) serine protease inhibitor family, (iii) growth and differentiation, (iv) calcium homeostasis, and (v) cytoskeletal reorganization and biogenesis. The potential roles of the differentially expressed proteins are discussed in the context of the mdx phenotype. Finally, we analyzed alterations of protein expression in mdx mice at one and six months of age to determine how protein expression changes with disease progression.     

Probing the molecular-scale lipid bilayer response to shear flow using nonequilibrium molecular dynamics

A nonequilibrium molecular dynamics simulation of the response of dimyristoylphosphatidylcholine (DMPC) bilayers to a solvent shear flow is presented. Application of shear flow to planar, stationary DMPC bilayers results in a redistribution of the membrane density profile along the bilayer normal due to the alignment of the lipids in the direction of flow and an increase in average lipid chain length. An increase in the intermolecular and intramolecular order of the lipids in response to the shear flow is also observed. This study provides groundwork for understanding the mechanism of the full response of lipid bilayers to externally imposed solvent shear flows, beginning with the response in the absence of collective lipid motions such as undulations and bilayer flow.     

Infrared and Raman spectral interpretations of the ferroelectric phases of NaH3(SeO3)2 and NaD3(SeO3)2

The infrared and Raman spectra of NaH₃(SeO₃)₂ and NaD₃(SeO₃)₂ have been recorded from 24 to 300°K. The interpretation, assignments, and analysis of the spectral studies are presented on the paraelectric α phase (proton disordered), ferroelectric β phase (proton ordered) and ferroelectric γ phase (proton ordered). A discussion of a newly proposed proton-triggered phase transition mechanism and a possible origin of the hydrogen-bonded OH stretching region of KH₂PO₄-type ferroelectrics is given.     

Copper(I) iodide-catalysed arylation of acetoacetate to yield 2-arylacetic acid esters

The C-C coupling reaction between ethyl acetoacetate and aryl halides in the presence of CuI is described. The effects of solvent, ligands such as vicinal diamines and amino acids, base and temperature are reported. The arylated acetoacetate ester is deacylated under the reaction conditions resulting in the generation of 2-arylacetic acid esters, constituting a mild alternative to direct arylation of carboxylate esters.     

Interaction of tetraphenyl-porphyrin derivatives with DPPC-liposomes: an EPR study

The effect of the symmetry and polarity of the porphyrin molecules on their membrane localization and interaction with membrane lipids were investigated by electron paramagnetic resonance (EPR). For this purpose, two glycoconjugated tetraphenyl porphyrin derivatives were selected, respectively, symmetrically and asymmetrically substituted. Small unilamellar liposomes composed of dipalmitoylphosphatidylcholine (DPPC) and spin labeled stearic acids were prepared. The spin probe was located at the 5th or 7th or 12th or 16th position of the hydrocarbon chain in order to monitor various regions of the lipid bilayer. EPR spectra of porphyrin-free and porphyrin-bound liposomes were recorded at various temperatures below and above the phase transition temperature of DPPC. The effect on membrane fluidity proved to be stronger with the asymmetrical porphyrin derivative than with the symmetrical one. The rigidity increased when the spin label was near lipid head groups. The difference observed between control and porphyrin-treated samples when measured below the main lipid transition temperature disappeared at higher temperature. When the spin label was near the end of the hydrophobic tails, the symmetrical porphyrin derivative caused increase in fluidity, while the asymmetrical one slightly decreased it. To explain this phenomenon we propose that the asymmetrical derivative exerts a stronger ordering effect caused by its fluorophenyl group located at the level of the lipid heads, which is attenuated to the hydrophobic tails. The perturbing effect of the symmetric derivative could not lead to similar extent of ordering at the head groups and looses the hydrocarbon chains deeper in the membrane.     

Electronic Raman spectroscopy of the vanadium(III) hexaaqua cation in guanidinium vanadium sulphate: Quintessential manifestation of the dynamical Jahn-Teller effect

Single-crystal Raman spectra are presented for the salt [C(NH2)3][V(OH2)6](SO4)2, displaying electronic transitions between the trigonal components of the vanadium(III) 3T1g(Oh) ground term. The 3A-->3E(C3) electronic Raman band is centered at approximately 2720 cm-1, and exhibits extensive structure, revealing the energies of the spinor components of the 3E(C3) term for the two crystallographically distinct [V(OH2)6]3+ cations. The data are interpreted in conjunction with parameters previously reported from an electron paramagnetic resonance study of the salt. A satisfactory reproduction of the electronic Raman profile and ground-state spin-Hamiltonian parameters is achieved by employing a (3A plus sign in circle3E)multiply sign in circle e vibronic coupling model, in which the spin-orbit splitting of the 3E(C3) is quenched significantly by the Ham effect, and the intensity of harmonics of the Jahn-Teller active vibration enhanced by their proximity to the electronic Raman bands. The model gives an excellent account of the intensities of the electronic Raman bands, which are shown to depend profoundly on both temperature and the selected component of the polarizability tensor. The electronic Raman profile changes notably upon deuteriation, a result that exposes deficiencies in the single-mode coupling model.     

Synthesis of ferrocenyl-1,2-diketones and related compounds: Crystal and molecular structures of 1,2-diferrocenylethanedione and 1-ferrocenyl-2-(4-biphenylyl) ethanedione

Ferrocenyl-1,2-diketones FcCOCOR, 3, [Fc = (C₅H₅)Fe(C₅H₄)] can be prepared by oxidation of acylferrocenes FcCOCH₂R or, more efficiently, by oxidation of the isomeric ketones FcCH₂COR, 2. The ketones 2 are in turn readily synthesized from the salt (FcCH₂PPh₃)⁺I⁻ via the acylated salts [FcCH(COR)PPh₃]⁺I⁻. The haloacylferocenes FcCOCCl_x H_3−x (x = 1, 2, 3, of which the x = 2 example is synthetically equivalent to a diketone) are synthesized by Friedel—Crafts acylation of ferrocene using CCl_xH_3−xCOCl/AlCl₃, but the reaction proceeds via two parallel pathways, one giving the normal acyl derivatives FcCOCCl_xH_3−x and the other giving the reduced products FcCOCCl_x−1H_4−x. Two diketones FcCOCOFc 3b and FcCOCOC₆H₄Ph 3c have been structurally characterised by single-crystal X-ray diffraction.     

Synthesis and characterization of water-soluble phenylene-vinylene-based singlet oxygen sensitizers for two-photon excitation

[reaction: see text] The synthesis and characterization of water-soluble singlet oxygen sensitizers with a phenylene-vinylene motif is presented. The principal motivation for this study was to better understand specific features of a water-soluble molecule that influence the photosensitized production of singlet oxygen upon nonlinear, two-photon excitation of that molecule. To achieve water solubility, sensitizers were synthesized with ionic as well as nonionic substituents. In the ionic approach, salts of N-methylated pyridine, benzothiazole, and 1-methyl-piperazine moieties were used, as were aryl-substituted sulfonic acid moieties. In the nonionic approach, aryl-substituted triethylene glycol moieties were used. Selected photophysical properties of the compounds synthesized were determined, including singlet oxygen quantum yields. Of the molecules examined, the most efficient singlet oxygen sensitizers had triethylene glycol units as the functional group that imparted water solubility. Molecules containing the ionic moieties did not make singlet oxygen in appreciable yield nor did they efficiently fluoresce. Rather, for these latter molecules, rapid charge-transfer-mediated non-radiative processes appear to dominate excited state deactivation.     

The stannylation of carbonyl-stabilised phosphorus ylids,and tin-assisted elimination reactions

The interaction of organotin halides with lithium salts of mono-substituted phosphorus ylids and also with disubstituted ylids is described.     

Trace level analysis of volatile and semi-volatile organic compounds in water using a membrane/jet separator interfaced to an ion trap mass spectrometer

An ion trap mass spectrometer, equipped with a membrane/jet separator interface, is used for the direct detection of volatile and semi-volatile organic compounds in aqueous solutions. Aqueous sample is passed through a capillary membrane, the outside surface of which is continuously purged by helium. The permeate is pneumatically transported to the mass spectrometer via a jet separator which acts as an additional enrichment device. The performance and response characteristics of non-porous silicone and microporous polytetrafluoroethylene (PTFE) membranes are studied. The microporous membrane allows sufficient water to pass for it to be used as a reagent gas for chemical ionization. Both types of membranes provide detection limits in the parts per trillion (pptr) to parts per billion (ppb) range with a linear dynamic range of 3 orders of magnitude for some volatile organic compounds. Results show that there is no detectable matrix effect on response in the selected cases examined. The use of microporous membranes to analyze more polar compounds, such as 5-hydroxymethyl furfuraldehyde and lactic acid, is also demonstrated. The effects of other experimental parameters, such as membrane temperature and length, on sensitivity are also investigated.