A DNMR study on the ring inversion of oxazolidines

Ring inversion of eight substituted 2-phenyl-4, 4-dimethyloxazolidines in o-dichlorobenzene-d₄ was studied by ¹H DNMR. Very high inversion barriers (ΔG_o^≠ = 86.7–93.4 kJ·mol^?1) were found for these oxazolidine rings. The magnitude of the inversion barrier is dependent on the polarity of the substituent on the phenyl group. A linear correlation is present between the ΔG_o^≠ of the inversion and the substituent constant, σ+, of the substituent.     

Optical properties of flower‐like CdS prepared by a hydrothermal method with SDBS as surfactant

In this article, flower‐like CdS structures have been prepared by a hydrothermal method with SDBS as surfactant. The influences of different experimental conditions on the morphologies, UV‐Vis and fluorescence properties of CdS have been investigated. The performances of CdS have been analyzed by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), ultraviolet‐visible (UV–Vis) and room‐temperature photoluminescence (PL). The XRD result indicates that the flower‐like CdS structures are of hexagonal phase. The FESEM results indicate that the main role of SDBS is to make the CdS crystals assemble together to form the flower‐like structures. The UV–Vis results show CdS has a strong absorption in the ultraviolet region and visible‐light region. The PL results show CdS has two emission peaks, respectively at 461 nm and 553 nm. The growth mechanism for the formation of flower‐like CdS structures is also described.     

Synthesis of plant arabinogalactans

Plant arabinogalactans consisting of a β-(1→6)-linked D-galactopyranosyl oligosaccharide back-bone with α-(1→2)-L-arabinofuranosyl branches are synthesized based on the 1,2-anhydro galactopyranose technique, orthogonal (methoxydimethyl)methyl (MIP) and (2-naphthyl)methyl (NAP) protection strategy, and selective acylation or glycosylation method. The third method is the most simple and effective and it is also used for the synthesis of arabinogalactans composed of a β-(1→6)-linked D-galactopyranosyl oligosaccharide backbone with α-(1→3)-L-arabinofuranosyl branches.     

Coupled Chromatography for Assay of the Venom Proteome of the Snake Agkistrodon acutus: An Effective Strategy for Discovery of Active Components

Two-dimensional liquid chromatography (2D-LC) is an attractive option for proteome profiling because of its advantages in separation and analysis of proteins and peptides of extreme pH and molecular weight. Proteomics, regarded as a promising and high-throughput method for discovery of new active natural products, calls for technical progress in comprehensive separation, especially for peptides, glycoproteins, and hydrophobic proteins, etc. Here, an optimized off-line IEX-RP LC system has been used for separation of all the components of the venom of the five-pace snake (Agkistrodon acutus). Seventy-nine different natural venom components were obtained by use of this system, more than were obtained by two dimensional electrophoresis of the venom. An automated on-line IEX-RP LC system was also developed for heart-cut separation of components of interest. As a result, we discovered a new tripeptide (PGlu-Asn-Trp, MW 429.1) in the venom. This emphasizes the role of 2D-LC in drug discovery.     

Multiple expansions of real numbers with digits set $$\left\{ 0,1,q\right\} $$ 0 , 1 , q

Mathematische Zeitschrift - For $$q>1$$ we consider expansions in base q with digits set $$\left\{ 0,1,q\right\} $$ . Let $${{\mathcal {U}}}_q$$ be the set of points which have a unique...     

Reinvestigation of the Structure of Protonated Lysine Dimer

To better understand inconsistencies between the predicted infrared (IR) spectra of previously suggested isomers of Lys₂H⁺ reported by Wu et al. (J. Am. Soc. Mass Spectrom. 22:1651–1659, 18) and the experimental IR photon dissociation (IRPD) spectrum obtained by Oh et al. (J. Am. Chem. Soc. 127:4076–4083, 4), the structure of Lys₂H⁺ was reinvestigated using IRPD spectroscopy in the extended region 2700–3700 cm^?1 and theoretical calculations. The new experimental IRPD spectrum is in good agreement with Oh’s spectrum in the corresponding wavelength range. Based on calculations at the MP2/6-311++G(d,p)//B3LYP/6-311++G(d,p) and MP2/6-31?+?G(d,p)//MP2/6-31?+?G(d,p) levels, a new salt-bridged isomer, ZW1, was found to be the most stable isomer; it is more energetically favored than the previously suggested charge-solvated isomer LL-CS01 by 10 or 26 kJ mol^?1. Although the calculated IR spectrum of ZW1 is in good agreement with the experimental one in the range 2700–3700 cm^?1, it is in poor agreement with the previous IRPD spectrum in the range 1000–1900 cm^?1. This investigation shows that the intermolecular interactions inside the dimer are more complex than previously supposed. It is possible that both salt-bridged and charge-solvated isomers of Lys₂H⁺ are stable in the gas phase, and the isomers generated during ionization are sensitive to the experimental conditions.

Resonance Rayleigh scattering method for direct determination of polyacrylamide in water samples using basic phenothiazine dyes

Binding polyacrylamide (PAM) with some basic phenothiazine dyes such as methylene blue (MB), toluidine blue (TB) or Azure B (AB) etc. can result in a significant enhancement of resonance Rayleigh scattering (RRS). The maximum RRS wavelengths (λ_max) appear at 348, 340 and 342 nm for MB, TB, and AB systems, respectively. Accordingly, a new RRS method for the direct determination of PAM at nanogram levels has been established. The optimum conditions of these reactions, the influencing factors have been investigated. The RRS intensity is directly proportional to the concentration of PAM in the range of 0.040–5.0 μg/mL for three systems. The methods exhibit high sensitivities, and the detection limits are 15.9 ng/mL for MB system, 44.0 ng/mL for TB system, and 59.8 ng/mL for AB system. The selectivity of the method is investigated by using MB system owing to the highest sensitivity. Concentrations of PAM in tap water, synthetic water and practical waste water samples are determined satisfactorily. The reaction mechanism and RRS enhancement reasons are discussed.     

KF promoted mesoporous γ-Al2O3 with strong basicity: Preparation,characterization and catalytic activitiy for transesterification to biodiesel

The present paper describes the preparation of KF/M-γ-Al₂O₃, efficient mesoporous solid bases. The procedure involves loading KF into a crystalline mesoporous γ-Al₂O₃ that was synthesized by the self-assembly of poly-4-vinylpyridine (P4VP) with Al³⁺ species. The synthesis is based on the strong acid-base interaction, hydrothermal treatment at 180°C and calcination at 550°C. Characterizations using XRD analysis and low temperature N₂ adsorption indicated that different amounts of KF could be introduced into crystalline mesoporous γ-Al₂O₃ to obtain catalysts with high BET surface areas, large pore volumes and uniform pore size distribution. Based on SEM images, KF/M-γ-Al₂O₃ catalysts have rough surface character and a large nanopore volume. CO₂-TPD curves registered for KF/M-γ-Al₂O₃ contain high temperature peaks, indicating strong basicity of the catalysts. Under the same reaction conditions KF/M-γ-Al₂O₃ catalysts exhibit much better activities for transesterification to biodiesel than KOH, NaOH, H₂SO₄, hydrotalcite and CaO. Enhanced activities appear to arise from strong basisity and large BET surface areas.     

Fingerprint image enhancement using multi-scale DDFB based diffusion filters and modified Hong filters

The main task of a fingerprint image enhancement is to enhance the image in such a way that it not only remove the noise but also enhance the reliable minutiae points. For this purpose, in this paper we propose a multi-scale decimation-free directional filter bank method for reliable orientation estimation. This reliable orientation is used in coherence enhancement diffusion and in Gabor filter based enhancement, which overcomes the drawbacks of these two methods. Experimental results show that the proposed method not only enhances the images but also facilitates the minutiae algorithm, by enhancing the true minutiae points.     

Segregation of alloying atoms at a tilt symmetric grain boundary in tungsten and their strengthening and embrittling effects

We investigate the segregation behavior of alloying atoms （Sr, Th, In, Cd, Ag, Sc, Au, Zn, Cu, Mn, Cr, and Ti） near Z3 （ 111 ） [1]-0] tilt symmetric grain boundary （GB） in tungsten and their effects on the intergranular embrittlement by performing first-principles calculations. The calculated segregation energies suggest that Ag, Au, Cd, In, Sc, Sr, Th, and Ti prefer to occupy the site in the mirror plane of the GB, while Cu, Cr, Mn, and Zn intend to locate at the first layer nearby the GB core. The calculated strengthening energies predict Sr, Th, In, Cd, Ag, Sc, Au, Ti, and Zn act as embrittlers while Cu, Cr, and Mn act as cohesion enhancers. The correlation of the alloying atom＇s metal radius with strengthening energy is strong enough to predict the strengthening and embrittling behavior of alloying atoms; that is, the alloying atom with larger metal radius than W acts as an embrittler and the one with smaller metal radius acts as a cohesion enhancer.