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61.
A library of cold shock protein B mutant variants was employed to examine differences in protein binding behavior in ion exchange and multimodal chromatography. Single site mutations introduced at charged amino acids on the protein surface resulted in a homologous protein set with varying charge density and distribution. The retention times of the mutants varied significantly during linear gradient chromatography in both systems. The majority of the proteins were more strongly retained on the multimodal cation exchange resin as compared to the traditional cation exchanger. Further, the elution order of the mutants on the multimodal resin was different from that obtained with the ion exchanger. Quantitative structure–property relationship models generated using a support vector regression technique were shown to provide good predictions for the retention times of protein mutants on the multimodal resin. A coarse-grained ligand docking package was employed to examine the various interactions between the proteins and ligands in free solution. The multimodal ligand was shown to utilize multiple interaction types to achieve stronger retention on the protein surface. The use of this protein library in concert with the qualitative and quantitative analyses presented in this paper provides an improved understanding of protein behavior in multimodal chromatographic systems.  相似文献   
62.
The Shanno-Toint Procedure for Updating Sparse Symmetric Matrices   总被引:1,自引:0,他引:1  
Two recent methods (Shanno, 1978; Toint, 1980) for revisingestimates of sparse second derivative matrices in quasi-Newtonoptimization algorithms reduce to variable metric formulae whenthere are no sparsity conditions. It is proved that these methodsare equivalent. Further, some examples are given to show thatthe procedure may make the second derivative approximationsworse when the objective function is quadratic. Therefore theconvergence properties of the procedure are sometimes less goodthan the convergence properties of other published methods forrevising sparse second derivative approximations.  相似文献   
63.
Our lab has developed a new series of self‐immolative MR agents for the rapid detection of enzyme activity in mouse models expressing β‐galactosidase (β‐gal). We investigated two molecular architectures to create agents that detect β‐gal activity by modulating the coordination of water to GdIII. The first is an intermolecular approach, wherein we designed several structural isomers to maximize coordination of endogenous carbonate ions. The second involves an intramolecular mechanism for q modulation. We incorporated a pendant coordinating carboxylate ligand with a 2, 4, 6, or 8 carbon linker to saturate ligand coordination to the GdIII ion. This renders the agent ineffective. We show that one agent in particular (6‐C pendant carboxylate) is an extremely effective MR reporter for the detection of enzyme activity in a mouse model expressing β‐gal.  相似文献   
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Within the context of the linearized theory of elasticity, weconsider homogeneous crystals, which have orthorhombic, tetragonal,hexagonal symmetry or cubic symmetry (‘RTHC’ crystals).When such a crystal is subjected to a simple tension (or compression)of amount T in the direction n, there will be three, generallydifferent, extensional strains along the three mutually perpendiculardirections corresponding to the principal axes of strain. Thepurpose of this paper is to present a simple procedure to placebounds, upper and lower, on the possible extensional strainsin the crystal, both in the case when n is fixed in directionand in the case when n is arbitrary. The procedure allows usto determine whether the bounds are attained or not.  相似文献   
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In this paper, we briefly summarize the main conclusions of the Mössbauer analysis of [L2Fe2(-OH)3] (ClO4)2·2CH3OH·2H2O with L=N,N',N"-trimethyl-1,4,7-triazacyclononane, a novel dimeric iron compound, which possesses a central exchange-coupled delocalized-valence Fe(II/III) unit. The complete delocalization of the excess electron in the dimeric iron center is concluded from the indistinguishability of the two iron sites in Mössbauer spectroscopy. The magnetic Mössbauer spectra imply a system spinS t=9/2 for the dimer in its ground state. The values for hyperfine and spin-Hamiltonian parameters, obtained from simulations of the Mössbauer spectra, are =0.74 mms–1, E Q=–2.14 mms–1,A =–10.6 T,A =–13.5 T andD=1.8 cm–1. The system spinS t=9/2 is interpreted to be a consequence of double-exchange coupling.  相似文献   
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The I2‐sorption and ‐retention properties of several existing zeolitic imidazolate frameworks (ZIF‐4, ‐8, ‐69) and a novel framework, ZIF‐mnIm ([Zn(mnIm)2]; mnIm=4‐methyl‐5‐nitroimidazolate), have been characterised using microanalysis, thermogravimetric analysis and X‐ray diffraction. The topologically identical ZIF‐8 ([Zn(mIm)2]; mIm=2‐methylimidazolate) and ZIF‐mnIm display similar sorption abilities, though strikingly different guest‐retention behaviour upon heating. We discover that this guest retention is greatly enhanced upon facile amorphisation by ball milling, particularly in the case of ZIF‐mnIm, for which I2 loss is retarded by as much as 200 °C. It is anticipated that this general approach should be applicable to the wide range of available metal–organic framework‐type materials for the permanent storage of harmful guest species.  相似文献   
70.
Titanium dioxide is a common food additive of increasing interest in dietary intake studies and dietary exclusion studies. Food labelling for titanium dioxide is imprecise so a method was developed for its rapid determination in foods using acid digestion and inductively coupled plasma optical emission spectrometry (ICPOES). Twenty-five foods thought to contain titanium dioxide were obtained. Based on preliminary digestion studies, samples (500 mg) were digested in 18 mol l-1 H2SO4 at 250 degrees C for 1 h and then diluted to 5.9 mol l-1 H2SO4 before determination of titanium by ICPOES at 336.121 nm. Emission intensity was suppressed by H2SO4 so standards were matched for acid concentration. Titanium dioxide embedded in gelatine was used to assess accuracy. A standard reference material of known titanium concentration and six foods of known titanium dioxide content were used as external reference materials. Limits of detection were 2-7.5 ppb, depending on spectral integration times, and the signal was linear up to 5 ppm. Results for all control samples were in good agreement with the expected values. Twelve of the foods contained detectable titanium, ranging from 0.001 to 0.782% by weight, but only eight indicated this on their labels, four being exempt under food labelling regulations. Based on food portion sizes, an individual's daily intake of titanium dioxide could exceed 200 mg from just one of these products. This method may facilitate future studies on titanium dioxide intake, given the present limitations of food labelling.  相似文献   
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