Rule for structures of open metal surfaces

We present a clear and simple rule for determining the relaxation sequences on open (stepped, vicinal, or high-Miller-index) metal surfaces. At the bulk-truncated configuration of a surface, a surface slab is defined where the coordination of atoms is reduced from the bulk. The rule predicts that the interlayer spacings within this slab contract, while the interlayer spacing between this slab and the substrate expands. By first-principles calculations, we show that this rule is obeyed on all open Cu surfaces with interlayer spacings down to about 0.5 A. We also illustrate a direct relation of the relaxation sequences to the charge redistribution on these surfaces, which is demonstrated to be driving the multilayer relaxations. The applicability of the rule can be extended to other fcc and bcc metals, including unreconstructed and missing-row surfaces.     

Effects of silicone acrylate on morphology, kinetics, and surface composition of photopolymerized acrylate mixtures

Films (ca. 150 microm thick) of twelve acrylate mixtures, which contained various proportions of hydrocarbon acrylates [mainly oligo(ethylene glycol) diacrylate, (OEGDA)] and small amounts of a silicone hexaacrylate (in proportion of 5% or less), were cured on a nickel substrate, and X-ray photoelectron spectroscopy analysis of the nickel-side surface compositions showed that for formulations with and without the silicone hexaacrylate, this surface was enriched with OEGDA and saturated (up to 50%) with the silicone hexaacrylate, respectively. The silicone hexaacrylate phase-separated and formed micelles which migrated to the resin-nickel interface. Silicone hexaacrylate, inherently less reactive, also significantly slowed the photopolymerization of the mixtures. The sequential homopolymerization of OEGDA and silicone hexaacrylate in a formulation was elicited using real-time Fourier transform infrared spectroscopy. The design-of-experiment approach was used to quantify the influence of the components on gelation time and the nickel-side surface composition as well as provide the statistical models to predict these two properties for new compositions.     

A novel synthesis of 5-functionalized oxazolidin-2-ones from enantiomerically pure 2-substituted N-[(R)-(+)-alpha-methylbenzyl]aziridines

5-Funtionalized enantiomerically pure oxazolidin-2-ones were prepared in one pot from commercially available chiral aziridines bearing an electron-withdrawing group at C-2 with retention of the configuration in high yields by regioselective aziridine ring-opening followed by intramolecular cyclization.     

Structure of liquid water with ST2 model potentials in the temperature interval 273–373 K

Ufa Aviation Institute. Translated from Zhurnal Strukturnoi Khimii, Vol. 31, No. 4, pp. 69–73, July–August 1990.     

Changes in Isoflavone Profile from Soybean Seeds during Cheonggukjang Fermentation Based on High-Resolution UPLC-DAD-QToF/MS: New Succinylated and Phosphorylated Conjugates

In this study, thirty-eight isoflavone derivatives were comprehensively identified and quantified from the raw, steamed and fermented seeds of four selected soybean cultivars based on UPLC-DAD-QToF/MS results with reference to the previously reported LC-MS library and flavonoid database, and summarized by acylated group including glucosides (Glu), malonyl-glucosides (Mal-Glu), acetyl-glucosides (Ac-Glu), succinyl-glucosides (Suc-Glu) and phosphorylated conjugates (Phos) in addition to aglycones. Among them, Suc-Glu and Phos derivatives were newly generated due to fermentation by B. subtilis AFY-2 (cheonggukjang). In particular, Phos were characterized for the first time in fermented soy products using Bacillus species. From a proposed roadmap on isoflavone-based biotransformation, predominant Mal-Glu (77.5–84.2%, raw) decreased rapidly by decarboxylation and deesterification into Ac-Glu and Glu (3.5–8.1% and 50.0–72.2%) during steaming, respectively. As fermentation continued, the increased Glu were mainly succinylated and phosphorylated as well as gradually hydrolyzed into their corresponding aglycones. Thus, Suc-Glu and Phos (17.3–22.4% and 1.5–5.4%, 36 h) determined depending on cultivar type and incubation time, and can be considered as important biomarkers generated during cheonggukjang fermentation. Additionally, the changes of isoflavone profile can be used as a fundamental report in applied microbial science as well as bioavailability research from fermented soy foods.     

Ergodicity of scalar stochastic differential equations with Hölder continuous coefficients

It is well-known that for a one dimensional stochastic differential equation driven by Brownian noise, with coefficient functions satisfying the assumptions of the Yamada–Watanabe theorem (Yamada and Watanabe, 1971, [31,32]) and the Feller test for explosions (Feller, 1951, 1954), there exists a unique stationary distribution with respect to the Markov semigroup of transition probabilities. We consider systems on a restricted domain $D$ of the phase space $\mathbb{R}$ and study the rate of convergence to the stationary distribution. Using a geometrical approach that uses the so called free energy function on the density function space, we prove that the density functions, which are solutions of the Fokker–Planck equation, converge to the stationary density function exponentially under the Kullback–Leibler divergence, thus also in the total variation norm. The results show that there is a relation between the Bakry–Émery curvature dimension condition and the dissipativity condition of the transformed system under the Fisher–Lamperti transformation. Several applications are discussed, including the Cox–Ingersoll–Ross model and the Ait-Sahalia model in finance and the Wright–Fisher model in population genetics.     

Separation of D‐psicose and D‐fructose using simulated moving bed chromatography

Simulated moving bed (SMB) processes have been widely used in the sugar industries with ion‐exchange resin as a stationary phase. D ‐Psicose, a rare monosaccharide known as a valuable pharmaceutical substrate, was synthesized by the enzymatic conversion from D ‐fructose. The SMB process was adopted to separate D ‐psicose from D ‐fructose. Before the SMB experiment, the reaction mixture including D ‐psicose and D ‐fructose was treated by a deashing process to remove contaminants, such as buffers, proteins, and other organic materials. Four columns packed with Dowex 50WX4‐Ca²⁺ (200–400 mesh) ion‐exchange resins were used in the four‐zone SMB. Single‐step frontal analysis was performed to estimate the isotherm parameters of each monosaccharide. The operating conditions of the SMB process were determined based on the Equilibrium Theory. According to the simulation of the SMB process, the purity and yield of extract product (D ‐psicose) achieved were 99.04 and 97.46%, respectively and those of raffinate product (D ‐fructose) were 99.06 and 99.53%, respectively. Under the optimized operating condition, complete separation (extract purity = 99.36%, raffinate purity = 99.67%) was achieved experimentally.     

Sulfone coupling and double-elimination strategy for carotenoid synthesis

[Reaction: see text]. A highly efficient synthetic method of carotenoid compounds has been developed on the basis of the sulfone coupling and double-elimination strategy. This method highlighted the sulfone-mediated coupling with the novel C(10) dialdehyde, 2,7-dimethyl-4-octenedial, which was easily prepared and efficiently utilized in the synthesis of the conjugated polyene chains.     

Importance of supersuperexchange interactions in determining the dimensionality of magnetic properties. Determination of strongly interacting spin exchange paths in A(2)Cu(PO(4))(2) (A = Ba, Sr), ACuP(2)O(7) (Ba, Ca, Sr, Pb), CaCuGe(2)O(6), and Cu(2)UO(2)(PO(4))(2) on the basis of qualitative spin dimer analysis

The patterns of the Cu(2+) ion arrangements in the magnetic oxides A(2)Cu(PO(4))(2) (A = Ba, Sr), ACuP(2)O(7) (Ba, Ca, Sr, Pb), CaCuGe(2)O(6), and Cu(2)UO(2)(PO(4))(2) are quite different from the patterns of the strongly interacting spin exchange paths deduced from their magnetic properties. This apparently puzzling observation was explained by evaluating the strengths of the Cu-O-Cu superexchange and Cu-O...O-Cu supersuperexchange interactions of these oxides on the basis of qualitative spin dimer analysis. Supersuperexchange interactions are found to be crucial in determining the dimensionality of magnetic properties of these magnetic oxides.     

Fully integrated lab-on-a-disc for simultaneous analysis of biochemistry and immunoassay from whole blood

We report a fully integrated device that can perform both multiple biochemical analysis and sandwich type immunoassay simultaneously on a disc. The whole blood is applied directly to the disposable "lab-on-a-disc" containing different kinds of freeze-dried reagents for the blood chemistry analysis as well as reagents required for the immunoassay. The concentrations of different kinds of analytes are reported within 22 min by simply inserting a disc to a portable device. Using the innovative laser irradiated ferrowax microvalves together with the centrifugal microfluidics, the total process of plasma separation, metering, mixing, incubation, washing, and detection is fully automated. The analyzer is equipped with an optical detection module to measure absorbances at 10 different wavelengths to accommodate the various kinds of reaction protocols. Compared to the conventional blood analysis done in clinical laboratories, it is advantageous for point-of-care applications because it requires a smaller amount of blood (350 μL vs. 3 mL), takes less time (22 min vs. several days), does not require specially trained operators or expensive instruments to run biochemical analysis and immunoassay separately.