Molecular conformations and relative stabilities can be as demanding of the electronic structure method as intermolecular calculations

We have performed a variety of high-level electronic structure calculations on two moderately sized organic molecules and found considerable sensitivity of the intramolecular potential energy surface to the method employed. The gas-phase structure of tyrosine-glycine varies qualitatively between B3LYP and MP2 optimizations, producing different close contacts between the tyrosine ring and the glycine moiety. The relative energies of the 2-(acetylamino)benzamide conformations found in its two polymorphs can vary by over 20 kJ mol-1 between MP2 and B3LYP calculations, using the same basis set. It is shown by a novel analysis that the intramolecular equivalent of basis set superposition error competes with the errors in the intramolecular dispersion in causing this sensitivity.     

Formation of the C-S-H Layer during early hydration of tricalcium silicate grains with different sizes

Portland cement is a mixture of solid phases which all react with water. Tricalcium silicate (Ca3SiO5) is its main component and is often used in model systems to study cement hydration. It is generally recognized that setting and hardening of cement are due to the formation, by a dissolution-precipitation process, of a calcium silicate hydrate (C-S-H) on anhydrous grains during Ca3SiO5 hydration. The purpose of this paper is to study the effect of Ca3SiO5 particle size on the nucleation-growth process of C-S-H. An experimental study of the rate of hydration by using different grain sizes under controlled conditions has been performed. The experimental data have been compared with results obtained by numerical simulation based on a particles-aggregation model. The thickness of the C-S-H layer when the reaction becomes limited by diffusion has been then estimated.     

Ca2+ indicators based on computationally redesigned calmodulin-peptide pairs

The binding interface of calmodulin and a calmodulin binding peptide were reengineered by computationally designing complementary bumps and holes. This redesign led to the development of sensitive and specific pairs of mutant proteins used to sense Ca(2+) in a second generation of genetically encoded Ca(2+) indicators (cameleons). These cameleons are no longer perturbed by large excesses of native calmodulin, and they display Ca(2+) sensitivities tuned over a 100-fold range (0.6-160 microM). Incorporation of circularly permuted Venus in place of Citrine results in a 3- to 5-fold increase in the dynamic range. These redesigned cameleons show significant improvements over previous versions in the ability to monitor Ca(2+) in the cytoplasm as well as distinct subcellular localizations, such as the plasma membrane of neurons and the mitochondria.     

A fluorescent broad-spectrum proteasome inhibitor for labeling proteasomes in vitro and in vivo

The proteasome is an essential evolutionary conserved protease involved in many regulatory systems. Here, we describe the synthesis and characterization of the activity-based, fluorescent, and cell-permeable inhibitor Bodipy TMR-Ahx(3)L(3)VS (MV151), which specifically targets all active subunits of the proteasome and immunoproteasome in living cells, allowing for rapid and sensitive in-gel detection. The inhibition profile of a panel of commonly used proteasome inhibitors could be readily determined by MV151 labeling. Administration of MV151 to mice allowed for in vivo labeling of proteasomes, which correlated with inhibition of proteasomal degradation in the affected tissues. This probe can be used for many applications ranging from clinical profiling of proteasome activity, to biochemical analysis of subunit specificity of inhibitors, and to cell biological analysis of the proteasome function and dynamics in living cells.     

Embedding operators into strongly continuous semigroups

We study linear operators T on Banach spaces for which there exists a C₀-semigroup (T(t))_t≥0 such that T = T(1). We present a necessary condition in terms of the spectral value 0 and give classes of examples for which such a C₀-semigroup does or does not exist. Received: 22 December 2008, Revised: 7 April 2009     

Dynamic NanoSIMS ion imaging of unicellular freshwater algae exposed to copper

This work demonstrates the capabilities of nanoscale secondary-ion mass spectrometry, using the Cameca NanoSIMS50 ion microprobe, to detect and image the copper-ion distribution in microalgal cells exposed to nanomolar and micromolar copper concentrations. In parallel to ⁶³Cu⁻ secondary-ion maps, images of ¹²C⁻, ¹²C¹⁴N⁻, and ³¹P⁻ secondary ions were collected and analysed. A correlation of ⁶³Cu⁻ secondary-ion maps with those found for ¹²C¹⁴N⁻ and ³¹P⁻ demonstrated the possible association of Cu with cell components rich in proteins and phosphorus. The results highlighted the potential of NanoSIMS for intracellular tracking of essential trace elements such as Cu in single cells of the microalga Chlorella kesslerii. Figure  ¹²C¹⁴N^-, ⁶³Cu^- secondary-ion distributions in algal cell     

Entropic Contributions to Sodium Solvation and Solvent Stabilization upon Electrochemical Sodium Deposition from Diglyme and Propylene Carbonate Electrolytes

The formation of an appropriate solid electrolyte interphase (SEI) at the anode of a sodium battery is crucially dependent on the electrochemical stability of solvent and electrolyte at the redox potential of Na/Na⁺ in the respective system. In order to determine entropic contributions to the relative stability of the electrolyte solution, we measure the reaction entropy of Na metal deposition for diglyme (DG) and propylene carbonate (PC) based electrolyte solutions by electrochemical microcalorimetry at single electrodes. We found a large positive reaction entropy for Na⁺ deposition in DG of Δ_R 234 J mol⁻¹ K⁻¹ (c.f.: Δ_R 83 J mol⁻¹ K⁻¹), which signals substantial entropic destabilization of Na⁺ in DG by about 0.73 eV, thus increasing the stability of solvent and electrolyte relative to Na⁺ reduction. We attribute this strong entropic destabilization to a highly negative solvation entropy of Na⁺, due to the low dielectric constant and high freezing entropy of DG.     

New organic supports for metallocene catalysts applied in olefin polymerizations

Nano-sized latex particles as organic supports for metallocenes applied in olefin polymerizations are introduced. The particles are functionalized with nucleophilic surfaces such as polyethylenoxide (PEO), polypropyleneoxide (PPO) or pyridine units allowing an immobilization of the metallocene catalysts via a non-covalent immobilization process. The latices are obtained by emulsion or miniemulsion polymerization with styrene, divinylbenzene as the crosslinker, and either PEO or PPO functionalized styrene or 4-vinylpyridine for surface functionalization. The supported catalysts, e.g. [Me₂Si(2MeBenzInd)₂ZrCl₂/MAO] on PPO containing latices or Cp₂ZrMe₂/([Ph₃C][B(C₆F₅)₄]) on pyridine functionalized materials were tested in ethylene polymerizations. Remarkably, high activities and excellent product morphologies were obtained. The influence of the degree of surface functionalization on activity and productivity was investigated. Furthermore, the fragmentation of the catalyst was studied by electron microscopy using bismuth-labeled latex particles or by fluorescence and confocal fluorescence microscopy using dye-labeled supports. Finally, a self-immobilizing catalyst/monomer system is presented. It is demonstrated that by using PEO-functionalized olefins, the metallocenes were immobilized on the monomers. Subjecting these mixtures to an ethylene copolymerization, again high activities and productivities as well as polyolefin beads with high bulk densities are observed, indicating that an extra supporting process for controlling the product size and shape of the polyolefins is not necessary for these monomers.     

ChemInform Abstract: Electronic Properties of the Two Rutiles TiO2 and VF2: A Comparative Study.

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