Diverse redox-active molecules bearing O-, S-, or Se-terminated tethers for attachment to silicon in studies of molecular information storage

A molecular approach to information storage employs redox-active molecules tethered to an electroactive surface. Attachment of the molecules to electroactive surfaces requires control over the nature of the tether (linker and surface attachment group). We have synthesized a collection of redox-active molecules bearing different linkers and surface anchor groups in free or protected form (hydroxy, mercapto, S-acetylthio, and Se-acetylseleno) for attachment to surfaces such as silicon, germanium, and gold. The molecules exhibit a number of cationic oxidation states, including one (ferrocene), two [zinc(II)porphyrin], three [cobalt(II)porphyrin], or four (lanthanide triple-decker sandwich compound). Electrochemical studies of monolayers of a variety of the redox-active molecules attached to Si(100) electrodes indicate that molecules exhibit a regular mode of attachment (via a Si-X bond, X = O, S, or Se), relatively homogeneous surface organization, and robust reversible electrochemical behavior. The acetyl protecting group undergoes cleavage during the surface deposition process, enabling attachment to silicon via thio or seleno groups without handling free thiols or selenols.     

含铈不锈钢的抗菌性能

以00Cr18Ni9不锈钢成分为基础,添加0～5%的稀土元素铈（Ce）.利用电子探针分析了加铈（Ce）不锈钢中Ce的分布;用化学分析法测定了含铈不锈钢中铈（Ce）和碳（C）的含量;用X射线衍射方法测试了含铈（Ce）不锈钢中铈（Ce）的析出相成分;采用贴膜法测试了含Ce不锈钢对大肠杆菌ATCC 8099、金黄色葡萄球菌ATCC 6538的抗菌性能.结果表明： 含Ce不锈钢具有优异的抗菌性能,与含Cu抗菌不锈钢相比,含Ce不锈钢无需时效热处理就具有优异的抗菌性能.并讨论了含Ce不锈钢的抗菌机制.     

Fe3O4-LiMo3Se3 nanoparticle clusters as superparamagnetic nanocompasses

A scaleable chemical approach to functional nanoscale analogues of the magnetic compasses in magnetotactic bacteria is described. LiMo(3)Se(3)-Fe(3)O(4) nanowire-nanoparticle composites were synthesized by a reaction of 3-iodopropionic acid treated LiMo(3)Se(3) nanowire bundles with oleic acid-stabilized Fe(3)O(4) nanoparticles of 2.8, 5.3, and 12.5 nm size in tetrahydrofuran. Transmission electron micrographs show that the composite consists of Fe(3)O(4) nanoparticles attached to the surfaces of the 4-6 nm thick nanowire bundles. UV/vis spectra reveal absorptions from the nanowire (506 nm) and magnetite components (280-450 nm), and IR spectra show characteristic bands for the propionic acid linkers and for the residual oleic acid ligands on the magnetite particles. In the presence of excess oleic acid, the nanocomposites undergo rapid disassembly, suggesting that Fe(3)O(4) nanoparticles are bonded to nanowires via carboxylate groups from the linkers. Ultrasonication of a dispersion of the composite in THF produces individual LiMo(3)Se(3)-Fe(3)O(4) clusters, which are 340 +/- 107 nm long and 20 +/- 5 nm thick, depending on the sonication time and Fe(3)O(4) nanoparticle size. Field cooled and zero-field cooled magnetization measurements reveal that the blocking temperature (T(B) = 100 K) of the clusters with 5.3 nm Fe(3)O(4) is increased as compared to the free nanoparticles (T(B) = 30 K). Directional dipolar interactions in the clusters lead to magnetic anisotropy, which makes it possible to align the clusters in a magnetic field (900 Oe).     

An ionic liquid-type carbon paste electrode and its polyoxometalate-modified properties

The replacement of a non-conductive organic binder with a conductive room temperature ionic liquid in fabricating carbon paste electrode has been made. This new electrode due to its enhanced conductivity presented very large current response from electroactive substrates. The novel carbon paste electrode was bulk-modified via the uniform dispersion of Keggin-type phospho polyoxomolybdate (PMo₁₂) in bulky carbons, which possessed excellent electrocatalytic activity for the reduction of nitrite. The pronounced multi-electron catalytic ability was ascribed to the used hydrophobic ionic liquid which constructed an excellent charge-transfer bridge in the bulk of carbon paste electrode, thus facilitated the intake of electrons from reduced PMo₁₂ mediators. In view of their prominent properties, the carbon paste electrode using ionic liquid binder and its bulk-modified electrode take on good prospects of the application in physical chemistry and electroanalytical chemistry fields.     

Three-component one-pot total syntheses of glyantrypine, fumiquinazoline F, and fiscalin B promoted by microwave irradiation

A microwave-promoted three-component one-pot reaction has been developed to provide access to the core pyrazino[2,1-b]quinazoline-3,6-dione (1) scaffold, which is common to several families of alkaloids with significant biological activities. By adapting this synthetic strategy through the use of selected Boc-amino acids and amino acid esters, we have accomplished highly efficient and concise total syntheses of glyantrypine (2), fumiquinazoline F (3), and fiscalin B (5), achieving overall yields of 55, 39, and 20%, respectively.     

Crystalline Morphology and Polymorphic Phase Transitions in Electrospun Nylon 6 Nanofibers

Uniform nylon 6 nanofibers with diameters around 200 nm were prepared by electrospinning. Polymorphic phase transitions and crystal orientation of nylon 6 in unconfined (i.e., as-electrospun) and a high T(g) (340 degrees C) polyimide confined nanofibers were studied. Similar to melt-spun nylon 6 fibers, electrospun nylon 6 nanofibers also exhibited predominant, meta-stable gamma crystalline form, and the gamma-crystal (chain) axes preferentially oriented parallel to the fiber axis. Upon annealing above 150 degrees C, gamma-form crystals gradually melted and recrystallized into the thermodynamically stable alpha-form crystals, which ultimately melted at 220 degrees C. Release of surface tension accompanied this melt-recrystallization process, as revealed by differential scanning calorimetry. For confined nanofibers, both the melt-recrystallization and surface tension release processes were substantially depressed; gamma-form crystals did not melt and recrystallize into alpha-form crystals until 210 degrees C, only 10 degrees C below the T(m) at 220 degrees C. After complete melting of nano-confined crystals at 240 degrees C and recrystallization at 100 degrees C, only alpha-form crystals oriented perpendicular to the nanofiber axis were obtained. In the polyimide-confined nanofibers, the Brill transition (from the monoclinic alpha-form to a high temperature monoclinic form) was observed at 180-190 degrees C, which was at least 20 degrees C higher than that in unconfined nylon 6 at approximately 160 degrees C. This, again, was attributed to the confinement effect.     

锚联膦,胺配体对胶体钯的配位俘获及其负载催化剂的催化性能

本文继采用含硫配体(-SH,-SR)对高分子保护金属胶体的配位俘获之后,采用锚联在SiO_2表面的较含硫配体配位能力弱的P,N配体分别与聚乙烯吡咯烷酮(PVP)保护的胶体钯在室温下反应,在P/Pd大于3.5,N/Pd大于7时,可以实施对保护金属胶体的配位俘获,证实了配位俘获法是一种具有普遍意义的方法,经原子吸收光谱分析,溶液中残留的金属钯的量小于0.36 ppm(P/Pd=3.5)。经电子能谱证实,锚联膦胺配体与金属钯之间存在配位作用,这是实施保护胶体负载化的关键。透射电镜分析表明,在整个配位俘获的过程中,无论是在载体上或是在溶液中,胶体钯的颗粒大小与分布均保持不变。因此,配位俘获法是一种能控制多相催化剂中金属颗粒大小与分布的有效方法。由此合成的钯催化剂具有很高的催化活性,良好的选择性和稳定性,在对Cis,Cis-1,3-环辛二烯的选择性加氢中,其活性仅比均相的PVP-Pd胶体催化剂稍低,选择性达100％。在周转数达12,000次/个钯原子后,其催化活性仍保持不变,随着P/Pd比的增大,催化活性迅速下降。     

镧系元素杂多钼磷酸钾的合成与性质研究

本文首次报道了K_(17)[Ln(P_2Mo_(17)O_(61))_2]·xH_2O(Ln=La~(3+),Ce~(3+),pr~(3+),Nd~(3+),Sm~(3+),Eu~(3+),Gd~(3+),Tb~(3+),Yb~(3+))的合成方法,取测定结果表明,与(?)系离子配位的配体P_2Mo_(17)O♂♀~-为α_2-型,Ln的配位数为8,推测其结构类似于K_(16)[Ce(Ⅳ)(α_2-P_2W_(17)O_(61))_2]·xH_2O,还进行了UV光谱、CV、极谱、TG-DTA及磁化率等性质的研究。     

Separation and concentration of molybdenum(VI) and tungsten(VI) with chelating ion-exchange resins containing sulphur ligands

Three chelating ion-exchange resins based on macroreticular polyacrylonitrile-divinylbenzene copolymers with thioglycollic acid and cysteine as functional groups have been tested for separation of molybdenum(VI) and tungsten(VI). On a short column of the thioglycollic acid resin, molybdenum(VI) and tungsten(VI) can be selectively sorbed from pH-4.3 acetate buffer and eluted with 2M hydrochloric acid and a mixture of 0.1M sodium hydroxide and 0.1M sodium chloride, respectively, with quantitative recovery even at very low concentrations. Simulated sea-water samples have been analysed.