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111.
Beth A. Dykerman Erin M. McCarvill Natasha D. Doiron Hillary A. Jenkins Kevin M. Smith 《Journal of organometallic chemistry》2007,692(15):3183-3190
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. 相似文献
112.
Dr. Samir Das Dr. Arundhati Nag JingXin Liang Dr. David N. Bunck Dr. Aiko Umeda Blake Farrow Matthew B. Coppock Deborah A. Sarkes Amethist S. Finch Heather D. Agnew Suresh Pitram Bert Lai Mary Beth Yu Dr. A. Katrine Museth Dr. Kaycie M. Deyle Bianca Lepe Frances P. Rodriguez‐Rivera Amy McCarthy Belen Alvarez‐Villalonga Ann Chen John Heath Dimitra N. Stratis‐Cullum Prof. James R. Heath 《Angewandte Chemie (International ed. in English)》2015,54(45):13219-13224
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. 相似文献
113.
Beth Anne V. Bennett Zhongxian Cheng∗∗ Robert W. Pitz Mitchell D. Smooke 《Combustion Theory and Modelling》2013,17(3):497-527
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. 相似文献
114.
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. 相似文献
115.
Mfuh AM Mahindaratne MP Quintero MV Lakner FJ Bao A Goins BA Phillips WT Negrete GR 《Langmuir : the ACS journal of surfaces and colloids》2011,27(8):4447-4455
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. 相似文献
116.
Li J Armstrong BL Kiggans J Daniel C Wood DL 《Langmuir : the ACS journal of surfaces and colloids》2012,28(8):3783-3790
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. 相似文献
117.
de Vargas BA Argenta DF Borghetti G Koester LS Bassani VL Teixeira HF 《Journal of chromatographic science》2012,50(2):114-118
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. 相似文献
118.
The heart is a complex integrated system that leverages mechanoelectrical signals to synchronize cardiomyocyte contraction and push blood throughout the body. The correct magnitude, timing, and distribution of these signals is critical for proper functioning of the heart; aberrant signals can lead to acute incidents, long-term pathologies, and even death. Due to the heart's limited regenerative capacity and the wide variety of pathologies, heart disease is often studied in vitro. However, it is difficult to accurately replicate the cardiac environment outside of the body. Studying the biophysiology of the heart in vitro typically consists of studying single cells in a tightly controlled static environment or whole tissues in a complex dynamic environment. Micro-electromechanical systems (MEMS) allow us to bridge these two extremes by providing increasing complexity for cell culture without having to use a whole tissue. Here, we carefully describe the electromechanical environment of the heart and discuss MEMS specifically designed to replicate these stimulation modes. Strengths, limitations and future directions of various designs are discussed for a variety of applications. 相似文献
119.
Beth Allen 《The Journal of mathematical sociology》2013,37(2):265-281
Two important generalizations of information diffusion models are the presence of stochastic effects and the possibility of arbitrary patterns of influence among individuals. A Markov random fields model includes both of these features. Under very weak assumptions, there is a unique equilibrium distribution of information patterns for given stochastic (local) interactions among a finite population. This has implications for policies to influence the transmission of information. The dynamic behavior of a special and simple case of the model tends to approximate the standard (logistic) diffusion curve. For an infinite population, uniqueness of equilibrium distributions may fail; some sufficient conditions to ensure uniqueness are given. 相似文献
120.
An operator convex function on (0,∞) which satisfies the symmetry condition k(x−1)=xk(x) can be used to define a type of non-commutative multiplication by a positive definite matrix (or its inverse) using the primitive concepts of left and right multiplication and the functional calculus. The operators for the inverse can be used to define quadratic forms associated with Riemannian metrics which contract under the action of completely positive trace-preserving maps. 相似文献