Diterpene glycosides from Stevia rebaudiana

Three novel diterpene glycosides were isolated for the first time from the commercial extract of the leaves of Stevia rebaudiana, along with several known steviol glycosides, namely stevioside, rebaudiosides A-F, rubusoside and dulcoside A. The new compounds were identified as 13-[(2-O-β-D-glucopyranosyl-3-O-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy] ent-kaur-15-en-19-oic acid, 13-[(2-O-β-D-glucopyranosyl-3-O-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy]-16β-hydroxy-ent-kauran-19-oic acid and 13-methyl-16-oxo-17-nor-ent-kauran-19-oic acid-β-D-glucopyranosyl ester on the basis of extensive 2D NMR and MS spectroscopic data as well as chemical studies.     

Supramolecular polymerization from polypeptide-grafted comb polymers

The helical and tubular structures self-assembled from proteins have inspired scientists to design synthetic building blocks that can be "polymerized" into supramolecular polymers through coordinated noncovalent interactions. However, cooperative supramolecular polymerization from large, synthetic macromolecules remains a challenge because of the difficulty of controlling the structure and interactions of macromolecular monomers. Herein we report the synthesis of polypeptide-grafted comb polymers and the use of their tunable secondary interactions in solution to achieve controlled supramolecular polymerization. The resulting tubular supramolecular structures, with external diameters of hundreds of nanometers and lengths of tens of micrometers, are stable and resemble to some extent biological superstructures assembled from proteins. This study shows that highly specific intermolecular interactions between macromolecular monomers can enable the cooperative growth of supramolecular polymers. The general applicability of this strategy was demonstrated by carrying out supramolecular polymerization from gold nanoparticles grafted with the same polypeptides on the surface.     

A molecular dynamics study of the interaction of oleate and dodecylammonium chloride surfactants with complex aluminosilicate minerals

Surface characteristics of complex aluminosilicate minerals like spodumene [LiAl(SiO(3))(2)], jadeite [NaAl(SiO(3))(2)], feldspar [KAlSi(3)O(8)], and muscovite [K(2)Al(4)(Al(2)Si(6)O(20))(OH)(4)]) are modeled. Surface energies are computed for the cleavage planes of these minerals. Adsorption mechanisms of anionic chemisorbing type oleate and cationic physisorbing type dodecylammonium chloride molecules on two different crystal planes, that is (110) and (001), of spodumene and jadeite are studied in terms of the surface-surfactant interaction energies computed using molecular dynamics (MD) simulations. The conclusions drawn from purely theoretical computations match remarkably well with our experimental results.     

Interfacial regions governing internal cavities of dendrimers. Studies of poly(alkyl aryl ether) dendrimers constituted with linkers of varying alkyl chain length

This report deals with a study of the properties of internal cavities of dendritic macromolecules that are capable of encapsulating and mediating photoreactions of guest molecules. The internal cavity structures of dendrimers are determined by the interfacial regions between the aqueous exterior and hydrocarbon like interior constituted by the linkers that connect symmetrically sited branch points constituting the dendrimer and head groups that cap the dendrimers. Phloroglucinol-based poly(alkyl aryl ether) dendrimers constituted with a homologous series of alkyl linkers were undertaken for the current study. Twelve dendrimers within first, second, and third generations, having ethyl, n-propyl, n-butyl, and n-pentyl groups as the linkers and hydroxyl groups at peripheries in each generation, were synthesized. Encapsulation of pyrene and coumarins by aqueous basic solutions of dendrimers were monitored by UV-vis and fluorescence spectroscopies, which showed that a lower generation dendrimer with an optimal alkyl linker presented better encapsulation abilities than a higher generation dendrimer. Norrish type I photoreaction of dibenzyl ketone was carried out within the above series of dendrimers to probe their abilities to hold guests and reactive intermediate radical pairs within themselves. The extent of cage effect from the series of third generation dendrimers was observed to be higher with dendrimers having an n-pentyl group as the linker.     

Highly selective, sensitive and quantitative detection of Hg2+ in aqueous medium under broad pH range

Amidothiourea linked acridinedione derivatives selectively detect Hg(2+) in unbuffered aqueous solution under broad pH range with both single- and two-photon excitation. The observed linear fluorescence intensity change allows the quantitative detection of Hg(2+) in the concentration range of 22 nM-0.33 μM with the lower detection limit of 2 nM.     

Meso-diacylated calix[4]pyrrole: structural diversities and enhanced binding towards dihydrogenphosphate ion

Meso-diacylated calix[4]pyrrole was obtained via acid catalysed condensation of meso-acylated dipyrromethane with acetone. Selective presence of flexible substituents at the calix[4]pyrrole periphery led to interesting structural motifs in the solid state along with enhanced binding towards anions, especially dihydrogenphosphate ion via anchoring.     

A density functional theory approach to mushroom-like platinum clusters on palladium-shell over Au core nanoparticles for high electrocatalytic activity

Recently, it was found that Pt clusters deposited on Pd shell over Au core nanoparticles (Au@Pd@Pt NPs) exhibit unusually high electrocatalytic activity for the electro-oxidation of formic acid (P. P. Fang, S. Duan, et al., Chem. Sci., 2011, 2, 531-539). In an attempt to offer an explanation, we used here carbon monoxide (CO) as probed molecules, and applied density functional theory (DFT) to simulate the surface Raman spectra of CO at this core-shell-cluster NPs with a two monolayer thickness of Pd shell and various Pt cluster coverage. Our DFT results show that the calculated Pt coverage dependent spectra fit the experimental ones well only if the Pt clusters adopt a mushroom-like structure, while currently the island-like structure is the widely accepted model, which follows the Volmer-Weber growth mode. This result infers that there should be a new growth mode, i.e., the mushroom growth mode as proposed in the present work, for Au@Pd@Pt NPs. We suggest that such a mushroom-like structure may offer novel active sites, which accounts for the observed high electrocatalytic activity of Au@Pd@Pt NPs.     

NEA GaAs光电阴极激活工艺研究

本文报道了 GaAs 反射式光电阴极的激活工艺过程和结果.通过实验确定了 GaAs表面的热清洁温度,利用钼丝热辐射加热方法达到了比较理想的清洁效果,采用铯分子源和高纯氧作氧源获得了高于1000μA/1m 的激活积分灵敏度.     

Low temperature elastic behaviour of As-Sb-Se and Ge-Sb-Se glasses

The ternary glasses of arsenic and germanium with antimony and selenium can be prepared in large sizes for optical purposes. The elastic behaviour of eight compositions of each glass has been studied down to 4.2 K using a 10 MHz ultrasonic pulse echo interferometer. The glasses have a normal elastic behaviour, with the velocities gradually increasing as the temperature is lowered. An anharmonic solid model of Lakkad satisfactorily explains the temperature variations. The elastic moduli of Ge _x Sb₁₀Se_90?x glasses increase linearly as the Ge content is increased up to 25 at. % and beyond this the increase is nonlinear. (AsSb)₄₀Se₆₀ glasses show a linear increase in elastic moduli with increasing Sb content. The elastic moduli of As _x Sb₁₅Se_85?x glasses exhibit a drastic change near the stoichiometric composition As₂₅Sb₁₅Se₆₀. These behaviours have been qualitatively explained on the basis of the structural changes in glasses.