Synthesis of chromium(III) bis(benzamidinate) complexes via single electron oxidation

Single-electron oxidation of the known Cr(II) bis(amidinate) Cr[(Me₃SiN)₂CPh]₂ (1) provides synthetic access to neutral Cr(III) complexes. The complexes Cr[(Me₃SiN)₂CPh]₂X were prepared by reaction of 1 with AgO₂CPh (X = O₂CPh, 2), of 1 with iodine in THF (X = I/THF, 3), or of 1 with iodine in pentane, followed by addition of 2-adamantanone (X = I/2-adamantanone, 4). Treatment of 2 or 3 with C₃H₅MgCl resulted in the thermally stable allyl complex (X = η³-C₃H₅, 5). A preliminary kinetics study of the reaction of 1 with excess allyl benzoate and allyl acetate was performed. The molecular structures of 2, 3 and 5 were confirmed by single crystal X-ray diffraction.     

A General Synthetic Approach for Designing Epitope Targeted Macrocyclic Peptide Ligands

We describe a general synthetic strategy for developing high‐affinity peptide binders against specific epitopes of challenging protein biomarkers. The epitope of interest is synthesized as a polypeptide, with a detection biotin tag and a strategically placed azide (or alkyne) presenting amino acid. This synthetic epitope (SynEp) is incubated with a library of complementary alkyne or azide presenting peptides. Library elements that bind the SynEp in the correct orientation undergo the Huisgen cycloaddition, and are covalently linked to the SynEp. Hit peptides are tested against the full‐length protein to identify the best binder. We describe development of epitope‐targeted linear or macrocycle peptide ligands against 12 different diagnostic or therapeutic analytes. The general epitope targeting capability for these low molecular weight synthetic ligands enables a range of therapeutic and diagnostic applications, similar to those of monoclonal antibodies.     

Computational and experimental study of oxygen-enhanced axisymmetric laminar methane flames

Three axisymmetric laminar coflow diffusion flames, one of which is a nitrogen-diluted methane/air flame (the ‘base case’) and the other two of which consist of nitrogen-diluted methane vs. pure oxygen, are examined both computationally and experimentally. Computationally, the local rectangular refinement method is used to solve the fully coupled nonlinear conservation equations on solution-adaptive grids. The model includes C2 chemistry (GRI 2.11 and GRI 3.0 chemical mechanisms), detailed transport, and optically thin radiation. Because two of the flames are attached to the burner, thermal boundary conditions at the burner surface are constructed from smoothed functional fits to temperature measurements. Experimentally, Raman scattering is used to measure temperature and major species concentrations as functions of the radial coordinate at various axial positions. As compared to the base case flame, which is lifted, the two oxygen-enhanced flames are shorter, hotter, and attached to the burner. Computational and experimental flame lengths show excellent agreement, as do the maximum centreline temperatures. For each flame, radial profiles of temperature and major species also show excellent agreement between computations and experiments, when plotted at fixed values of a dimensionless axial coordinate. Computational results indicate peak NO levels in the oxygen-enhanced flames to be very high. The majority of the NO in these flames is shown to be produced via the thermal route, whereas prompt NO dominates for the base case flame.     

Microscopic Symmetry Imposed by Rotational Symmetry Boundary Conditions in Molecular Dynamics Simulation

A large number of viral capsids, as well as other macromolecular assemblies, have icosahedral structure or structures with other rotational symmetries. This symmetry can be exploited during molecular dynamics (MD) to model in effect the full viral capsid using only a subset of primary atoms plus copies of image atoms generated from rotational symmetry boundary conditions (RSBC). A pure rotational symmetry operation results in both primary and image atoms at short range, and within nonbonded interaction distance of each other, so that nonbonded interactions can not be specified by the minimum image convention and explicit treatment of image atoms is required. As such an unavoidable consequence of RSBC is that the enumeration of nonbonded interactions in regions surrounding certain rotational axes must include both a primary atom and its copied image atom, thereby imposing microscopic symmetry for some forces. We examined the possibility of artifacts arising from this imposed microscopic symmetry of RSBC using two simulation systems: a water shell and human rhinovirus 14 (HRV14) capsid with explicit water. The primary unit was a pentamer of the icosahedron, which has the advantage of direct comparison of icosahedrally equivalent spatial regions, for example regions near a 2-fold symmetry axis with imposed symmetry and a 2-fold axis without imposed symmetry. Analysis of structural and dynamic properties of water molecules and protein atoms found similar behavior near symmetry axes with imposed symmetry and where the minimum image convention fails compared with that in other regions in the simulation system, even though an excluded volume effect was detected for water molecules near the axes with imposed symmetry. These results validate the use of RSBC for icosahedral viral capsids or other rotationally symmetric systems.     

Dynamics of the CH3 + OH reaction

We study dynamics of the CH₃ + OH reaction over the temperature range of 300–2500 K using a quasiclassical method for the potential energy composed of explicit forms of short‐range and long‐range interactions. The explicit potential energy used in the study gives minimum energy paths on potential energy surfaces showing barrier heights, channel energies, and van der Waals well, which are consistent with ab initio calculations. Approximately, 20% of CH₃ + OH collisions undergo OH dissociation in a direct‐mode mechanism on a subpicosecond scale (<50 fs) with the rate coefficient as high as ～10^?10 cm³ molecule^?1 s^?1. Less than 10% leads to the formation of excited intermediates CH₃OH? with excess vibrational energies in CO and OH bonds. CH₃OH? stabilizes to CH₃OH, redissociates back to reactants, or forms one of various products after intramolecular energy redistribution via bond dissociation and formation on the time scale of 50–200 fs. The principal product is ¹CH₂ (k being ～10^?11), whereas ks for CH₂OH, CH₂O, and CH₃O are ～10^?12. The minor products are HCOH and CH₄ (k～10^?13). The total rate coefficient for CH₃ + OH → CH₃OH? → products is ～10^?11 and is weakly dependent on temperature. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 455–466, 2011     

Novel asparagine-derived lipid enhances distearoylphosphatidylcholine bilayer resistance to acidic conditions

A novel asparagine-derived lipid analogue (ALA(11,17)) bearing a tetrahydropyrimidinone headgroup and two fatty chains (11 and 17 indicate the lengths of linear alkyl groups) was synthesized in high yield and purity. The thin film hydration of formulations containing 5 mol % or greater ALA(11,17) in distearoylphosphatidylcholine (DSPC) generated multilamellar vesicles (MLVs) that remained unaggregated according to optical microscopy, while those formed from DSPC only were highly clustered. The MLVs were processed into unilamellar liposomes via extrusion and were characterized by dynamic light scattering (DLS), zeta potential, turbidity, and scanning electron microscopy (SEM) analysis. Results show that the presence of ALA(11,17) in DSPC liposomes significantly alters the morphology, colloidal stability, and retention of encapsulated materials in both acidic and neutral conditions. The ability of ALA(11,17)-hybrid liposomes to encapsulate and retain inclusions under neutral and acidic conditions (pH < 2) was demonstrated by calcein dequenching experiments. DLS and SEM confirmed that ALA(11,17)/DSPC liposomes remained intact under these conditions. The bilayer integrity observed under neutral and acidic conditions and the likely biocompatibility of these fatty amino acid analogues suggest that ALA(11,17) is a promising additive for modulating phosphatidylcholine lipid bilayer properties.     

Enhancement of fluorescence and lasing properties of covalent bridged fluorescent dye in organic–inorganic hybrid materials

Fluorescent dye (DCM-OH) is covalently bridged to organic–inorganic hybrid material to prevent molecular stacking and to get high fluorescence efficiency and laser property. Novel DCM-OH is synthesized to have hydroxyl functional groups and is bridged to trialkoxysilane as a sol–gel precursor. It participates in sol–gel process to synthesize dye-bridged organic–inorganic hybrid material (dye-bridged hybrimer) and solid-state dye laser sample is ready through polymerization. Fluorescence property of dye-bridged hybrimer is compared with DCM-doped hybrimer that is simple mixture of DCM-OH and hybrimer matrix. The covalently bridged structure of hybrimer with DCM-OH prevented the stacking of fluorescent molecules and enhanced concentration stability. The dye-bridged hybrimer shows much higher fluorescence intensity and low color-shift until it reached high concentration in comparison with DCM-doped system. And the proper lasing property is observed in dye-bridged hybrimer samples.     

Optimization of LiFePO4 nanoparticle suspensions with polyethyleneimine for aqueous processing

Addition of dispersants to aqueous based lithium-ion battery electrode formulations containing LiFePO(4) is critical to obtaining a stable suspension. The resulting colloidal suspensions enable dramatically improved coating deposition when processing electrodes. This research examines the colloidal chemistry modifications based on polyethyleneimine (PEI) addition and dispersion characterization required to produce high quality electrode formulations and coatings for LiFePO(4) active cathode material. The isoelectric point, a key parameter in characterizing colloidal dispersion stability, of LiFePO(4) and super P C45 were determined to be pH = 4.3 and 3.4, respectively. PEI, a cationic surfactant, was found to be an effective dispersant. It is demonstrated that 1.0 wt % and 0.5 wt % PEI were required to stabilize the LiFePO(4) and super P C45 suspension, respectively. LiFePO(4) cathode suspensions with 1.5 wt % PEI demonstrated the best dispersibility of all components, as evidenced by viscosity and agglomerate size of the suspensions and elemental distribution within dry cathodes. The addition of PEI significantly improved the LiFePO(4) performance.     

Validation of an LC method to determine skin retention profile of genistein from nanoemulsions incorporated in hydrogels

Recent studies have shown the effect of soy isoflavones in preventing skin photoaging and photocarcinogenesis, especially for genistein (GEN). Nanoemulsions have been proposed as a delivery system for GEN administration due to the low water solubility of this isoflavone. This article describes the validation of an isocratic liquid chromatography method to determine GEN in porcine ear skin layers from nanoemulsions before and after incorporation into hydrogels. The analyses are performed on a reversed-phase C18 column using a mobile phase composed of methanol-water (70:30, v/v) under acid conditions (at pH 3.0) and UV detection at 270 nm. The method is linear in the range of 0.1-10 μg/mL (r(2) > 0.999) in the presence of skin extracts. The low limit of quantitation is estimated as 0.1 μg/mL. No interferences from formulation excipients or skin layer compounds are detected. The RSD values for intra- and inter-day precision are lower than 15%. Recovery ranged from approximately 90% to 110%. The method is applied to estimate GEN retention in the skin from formulations using Franz diffusion cells. The highest amount of GEN is detected in the epidermis (185 μg/cm(2)). In conclusion, the method proved to be specific, precise, and accurate in determining GEN amounts from formulations in skin retention studies.