Selective ion binding by protein probed with the statistical mechanical integral equation theory

Selective ion binding by human lysozyme and its mutants is probed with the three-dimensional interaction site model theory which is the statistical mechanical integral equation theory. Preliminary and partial results of the study have been already published (Yoshida, N. et al. J. Am. Chem. Soc. 2006, 128, 12042-12043). The calculation was carried out for aqueous solutions of three different electrolytes, CaCl2, NaCl, and KCl, and for four different mutants of the human lysozyme: wild type, Q86D, A92D, and Q86D/A92D, which have been studied experimentally. The discussion of this article focuses on the cleft that consists of amino acid residues from Q86 to A92. For the wild type of protein in the aqueous solutions of all the electrolytes studied, there are no distributions observed for the ions inside the cleft. The Q86D mutant shows essentially the same behavior with that of the wild type. The A92D mutant shows strong binding ability to Na+ in the recognition site, which is in accord with the experimental results. There are two isomers of the Q86D/A92D mutant, e.g., apo-Q86D/A92D and holo-Q86D/A92D. Although both isomers exhibit the binding ability to the Na+ and Ca2+ ions, the holo isomer shows much greater affinity compared with the apo isomer. Regarding the selective ion binding of the holo-Q86D/A92D mutant, it shows greater affinity to Ca2+ than to Na+, which is also consistent with the experimental observation.     

A crack emanating from the tip of bonded dissimilar materials

1.IntroductionBondedstructurescanbewidelyfoundindifferentareas,suchasweldedpressurevessels,reinforcedconcretemembers,groutingsoftfoundationandsolidrocketpropellants.etc.Thestudy'ofthesingularityofbondedstructuresisespeciallyimp6rtantnotonlyforsafedesignbutalsoforconstruction.DeinpseyandSinclairl61studiedthegeneraleaseofN-materialcompositewedges,andprovedthat'ingeneralthereexistsstresssingularitynearthetipofthewedges,andtheorderofthesingularitydependsontheelasticconstantsandthelocalgeometry.Fo…     

Enhancement of electroluminescence intensity in poly(3-alkylthiophene) with different alkyl side-chain length by doping of fluorescent dye

Electroluminescent diodes utilizing poly(3-alkylthiophene) (PAT) containing fluorescent dyes have been fabricated and their unique enhancement of emission characteristics have been studied. Remarkable enhancement of the electroluminescence efficiency has been observed for diodes with PAT doped with oxadiazole derivative (2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole; PBD) and perylene derivative (N,N′ - Bis(2,5 - di - tert - butylphenyl) - 3,4,9,10 - perylenedi- carboximide; BPPC). The mechanism of emission enhancement by doping of PBD into PAT has been discussed with different alkyl side-chain lengths. © 1997 John Wiley & Sons, Ltd.     

Oxidation of Benzyl Alcohol with CuII and ZnII Complexes of the Phenoxyl Radical as a Model of the Reaction of Galactose Oxidase

Profound insights into the catalytic mechanism of galactose oxidase (GO) are offered by new models of the active form of the metalloenzyme. The important role of the Cu^II center in the oxidation of benzyl alcohol to benzaldehyde by the Cu^II–phenoxyl radical complex of ligand 1 has been revealed by comparison with the reactivity of the corresponding Zn^II–phenoxyl radical complex; py=2-pyridyl.     

NO2 sensing properties of YSZ-based sensor using NiO and Cr-doped NiO sensing electrodes at high temperature

Nickel oxide and chromium-doped nickel oxide (Ni_0.95Cr_0.03O_1−δ ) were prepared by thermal decomposition of nitrates. The obtained NiO and Ni_0.95Cr_0.03O_1−δ samples were utilized as sensing electrodes (SEs) in yttria-stabilized zirconia (YSZ)-based sensors for detection of NO₂ at 800 °C under wet condition (5 vol.% H₂O). While the mixed-potential-type planar sensor attached with NiO-SE gave rather large NO₂ sensitivity, the sensor attached with Ni_0.95Cr_0.03O_1−δ -SE exhibited fast recovery rate with an acceptable sensitivity. The Δemf (electromotive force) of the sensors varied linearly with NO₂ concentration in the examined range of 50–400 ppm on a logarithmic scale. Based on the results of measurements for polarization, complex impedance and gas phase catalysis, the fast recovery was attributable to the high rate for the anodic reaction of O₂ at the Ni_0.95Cr_0.03O_1−δ /YSZ interface, and the lower NO₂ sensitivity was caused by both the high rate for the anodic reaction of O₂ and the high degree for the gas phase conversion of NO₂ to NO.     

8-Endo selective Friedel-Crafts cyclization of vinyloxiranes with Co2(CO)6-complexed acetylene

An 8-endo selective Friedel-Crafts cyclization of vinyloxirane 8 with Co₂(CO)₆-complexed benzeneacetylene was found to give poly-functional eight-membered cyclic compound 9 in high yields.     

A chiral bidentate phosphoramidite (Me-BIPAM) for Rh-catalyzed asymmetric hydrogenation of α-dehydroamino esters, enamides, and dimethyl itaconate

High performance of Me-BIPAM for enantioselective hydrogenation of α-dehydroamino esters, enamides, and dimethyl itaconate was demonstrated. [Rh(Me-BIPAM)(diene)]X (diene = cod, nbd; X = BF₄, PF₆, SbF₆) gave optically active β-aryl α-amino esters up to 99% ee, 1-arylethylamines up to 97% ee, methyl 2-acetylaminobutanoate with 90% ee, and dimethyl 2-methylsuccinate with 97% ee under 0.3−0.8 MPa dihydrogen with 0.1−1 mol % catalyst loading.     

In situ ATR-IR investigation of L-lysine adsorption on montmorillonite

The adsorption behavior of lysine on montmorillonite in aqueous solution was investigated by in situ attenuated total reflectance infrared (ATR-IR) spectroscopy. To distinguish the protonation states of α-amino group, side-chain amino group and carboxyl group in lysine structure using ATR-IR spectra (i.e., NH₂ versus and COO⁻ versus COOH), pH-induced spectral changes of dissolved lysine were firstly measured and correlated with the thermodynamically calculated dissociation states of lysine (di-cationic, cationic, zwitterionic and anionic states). The obtained result was applied to interpret the ATR-IR spectra of lysine adsorbed on montmorillonite. We found that the adsorbed lysine was dominantly present as cationic state over the whole range of tested pH (pH = 4.9–9.7). This indicates that the adsorption is mainly driven by electrostatic interaction between the negatively charged montmorillonite surface and positively charged cationic lysine. We also found that lysine interacts with montmorillonite surface through the protonated side-chain amino group. This result suggests that lysine has a preferred vertical orientation, with the side-chain amino group pointing toward the surface.