Chirality control in optically active polysilane aggregates

A novel strategy for controlling the higher order chirality of aggregates prepared from enantiopure polysilanes is experimentally probed and discussed. Structurally similar poly[n-alkyl(aryl)]silanes were synthesized in which one side chain comprised the chiral (S)-2-methylbutyl group and the other an achiral m- or p-alkyl-substituted phenyl ring. In solution the polymers adopt helical conformations with the same induced preferential screw sense chirality, as evidenced by circular dichroism (CD) spectroscopy. Aggregates, however, formed by addition of a nonsolvent to a polymer solution, show oppositely signed CD spectra. Consistent results were obtained for another series of poly[p-n-alkyl(aryl)]silanes where alkyl is butyl, propyl, and ethyl. The sense of the aggregate higher order chirality is dependent on the chemical composition and environment and is coarse-tunable by adjusting the length of the achiral side chain and fine-tunable by adjusting the good/poor solvent ratio. The origin of these effects is discussed with reference to a simple model.     

A comparison between the SBR vulcanizates reinforced by magnesium methacrylate added directly or prepared in situ

The styrene-butadiene rubber (SBR) cured by dicumyl peroxide was reinforced by magnesium methacrylate [Mg(MAA)₂], which was added into SBR directly or prepared in situ in SBR through the neutralization of magnesium oxide (MgO) and methacrylic acid (MAA). The experimental results show that the SBR vulcanizates reinforced by Mg(MAA)₂ prepared in situ have better mechanical properties than those reinforced by Mg(MAA)₂ added directly. The SBR vulcanizates with Mg(MAA)₂ prepared in situ are semi-transparent, but those with Mg(MAA)₂ added directly are opaque. The Fourier transform infrared analysis shows that the polymerization conversion of Mg(MAA)₂ in the SBR vulcanizates with Mg(MAA)₂ prepared in situ is much higher than that in the SBR vulcanizates with Mg(MAA)₂ added directly. The scan probe microscopy photographs show that the particles in the SBR vulcanizates with Mg(MAA)₂ prepared in situ are much finer and disperse more evenly than that in the SBR vulcanizates with Mg(MAA)₂ added directly.     

Systematic investigation of the hydrothermal syntheses of Pr(III)-PDA (PDA = pyridine-2,6-dicarboxylate anion) metal-organic frameworks

A series of novel two-dimensional (2D) and three-dimensional (3D) praseodymium coordination polymers, namely, {[Pr3(PDA)4(HPDA)(H2O)8] x 8H2O}n (2), {[Pr2(PDA)3(H2O)3] x H2O}n (3), {[Pr(PDA)(H2O)4] x ClO4}n (4), and { [Pr2(PDA)2(H2O)5SO4] x 2H2O}n (5) (PDA = pyridine-2,6-dicarboxylic anion), was designed and synthesized under hydrothermal conditions. Complexes 1-3 (chainlike polymer, {[Pr(PDA)(HPDA)(H2O)2] x 4H2O}n (1) was also obtained independently by us, although it has been reported recently by Ghosh et al.) were fabricated successfully by simply tuning the Pr/PDA ratio and exhibited various and intriguing topological structures from a 1D chain to a 3D network. While the synthetic strategy of 5 was triggered and further performed only after 1 was structurally characterized. The complexes were characterized by X-ray single-crystal determination, spectroscopic, and variable-temperature magnetic susceptibility analyses. In complex 2 an unusual nanosized square motif as a building block constructed by eight Pr ions was further assembled into a highly ordered 2D grid compound. In complex 3 the decanuclear Pr metal-based structure as a repeat unit interpenetrated to form a novel 3D polymer. Complex 4 was a 3D network polymer fabricated through a hexanuclear Pr ring as a building block, and ClO4- anions as guests were trapped in the cavity. In complex 5 six Pr atoms, two SO4(2-) anions, and carboxylic oxygen bridges constructed an intriguing rectangle structure as a repeat unit in the grid to form a 2D coordination polymer in which the unique bi-bidentate coordination mode of SO4(2-) anion was observed.     

Chemical Constituents from Cynoglossum gansuense

Two new alkaloids, i.e., (2,3‐dihydro‐1‐oxo‐1H‐pyrrolo[1,2‐a]pyrrol‐7‐yl)methyl (2S*,3S*)‐3‐[(β‐D ‐glucopyranosyl)oxy]‐2‐hydroxy‐2‐(1‐methylethyl)butanoate ( 1 ) and 1,2‐dihydro‐8‐methoxy‐2‐oxoquinoline‐4‐carboxylic acid ( 2 ), were isolated from the alcoholic extract of the whole plant of Cynoglossum gansuense, together with twelve known compounds Their structures were characterized by means of spectroscopic methods, especially by ¹H‐, ¹³C‐, and 2D‐NMR, as well as by HR‐MS experiments and comparison with literature data.     

Two New Xanthone Glycosides from Polygala tenuifolia

Two new xanthone glycosides,polygalaxanthone IV and V were isolated from the roots of Polygala tenuifolia Willd. Their structures were established as 6-O-[α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranosyl]-1-hydroxy-3,7-dimethoxyxanthone(polygalaxanthone IV), and 6-O-[α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranosyl]-1,3-dihydroxyl-7-methoxyxanthone (polyga-laxanthone V),respectively, on the basis of chemical and spectral evidence.     

Determination of atrazine, desethyl atrazine and desisopropyl atrazine in environmental water samples using hollow fiber-protected liquid-phase microextraction and high performance liquid chromatography

A new method based on hollow fiber-protected liquid-phase microextraction (LPME) was developed for the simultaneous determination of atrazine, desethyl atrazine and desisopropyl atrazine in environmental water samples. In LPME, analytes were extracted into 1-octanol immobilized in the micropores of a poly(vinylidene fluoride) porous hollow fiber membrane, and back extracted into the acceptor (4 M HCl) filled in the lumen of the hollow fiber. After LPME, the analytes trapped in the acceptor were analyzed with high-performance liquid chromatography after neutralization. The effect of extraction factors such as sample pH, acceptor pH, salinity, extraction time, stirring rate, and humic acid were studied. Under the optimized conditions, the limits of detection and relative standard deviations were respectively in the range of 0.5–1.0 μg L⁻¹ and 3.9–4.7% (n = 5). The proposed method was applied to determine atrazine, desethyl atrazine and desisopropyl atrazine in wastewater and groundwater samples. The three analytes were below the limits of detection, but good relative spiked recoveries over 90.1 ± 5.9% at 5 μg L⁻¹ spiked level were obtained.     

Adsorption, desorption and activities of acid phosphatase on various colloidal particles from an Ultisol

Adsorption, desorption and activity of acid phosphatase on various soil colloidal particles and pure clay minerals were studied. Higher adsorption amounts and low percentage of desorption of acid phosphatase were found on fine soil clays (<0.2 μm). Electrostatic force and ligand exchange are the major driving forces that are involved in the adsorption of enzymes on soil clays. More enzyme molecules were adsorbed on soil clays in the presence of organic components. However, enzymes on organic clays were more easily released. One-third of the enzyme on goethite was adsorbed via ligand exchange process. Some other interactions, such as van der Waals force, hydrophobic force and hydrogen bonding may be more important in the adsorption of enzyme on kaolinite and the enzyme in this system cannot be easily removed. Coarse clays (0.2–2 μm) and inorganic soil clays had higher affinities for enzyme molecules than fine clays and organic clays, respectively. The activity of enzyme bound on soil clays was inhibited and the thermal stability was increased in the presence of organic matter. Data obtained in this study are helpful for a better understanding of the interactions of enzymes with inorganic and organic constituents in soil and associated environments.     

Controlling the agglomeration of anisotropic Ru nanoparticles by the microwave-polyol process

A rapid polyol process for the synthesis of ruthenium nanoparticles was developed using microwave irradiation. A colloidal solution of monodispersed anisotropic Ru metal nanoparticles (mean particle size 2-6 nm) with different aspect ratios was obtained first. Particles with different degrees of agglomeration have also been synthesized using monodisperse particles as seeds and PVP (poly-N-vinyl-2-pyrrolidone) as the stabilization reagent. The stabilization mechanisms of different protective reagents were studied by UV-vis spectra. The HRTEM images indicated that dendritic particles formed by controlling agglomeration consisted of single-crystal domains with a random crystalline orientation.     

Coriatone and corianlactone, two novel sesquiterpenes from Coriaria nepalensis

Both coriatone (1). a novel highly oxygenated picrotoxane-type sesquiterpene, and corianlactone (2). with an unprecedented sesquiterpene basic skeleton, named coriane, were isolated from Coriaria nepalensis Wall. The structures of 1 and 2 were determined by analysis of their two-dimensional NMR data, and the structure of 2 was confirmed by X-ray analysis. Compounds 1 and 2 showed no remarkable inhibitory activity toward K(562) cells. They are cytotoxic with IC(50) > 50 microg/mL (cis-platinim: IC(50) = 0.49 microg/mL).     

RE（Ⅲ）—ADP,RE（Ⅲ）—AMP配合物的合成及物性研究

首次合成了具有生物活性的系列配合物RE(Ⅲ)-ADP(稀土-腺苷二磷酸)和RE(Ⅲ)-AMP(稀土-腺苷-磷酸)(RE=Y,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu),根据红外、紫外、荧光、X射线衍射、元素分析、络合滴定等分析结果,研究了[RE(Ⅲ)(ADP)(H_2O)_3]和[RE(Ⅲ)(AMP)_2(H_2O)_4]H两个系列配合物的化学组成和性质。