Anionic-cationic switchable amphoteric monodisperse mesoporous silica nanoparticles

Anionic-cationic switchable monodisperse mesoporous silica nanoparticles were synthesized by one-pot amino and carboxylic acid bifunctionalization based on the self-assembly of the surfactant, two types of co-structure-directing agents containing amino and carboxylic groups, and silica sources. These nanoparticles revealed properties of dispersity and reversibility, with the advantage of the pH-responsive anionic-cationic/acid-base switchability. It was demonstrated that the extracted materials achieved reutilization and controllable dispersity in aqueous solution by adjusting the static electric power among the particles during the switching process.     

Production of a biomimetic Fe(I)-S phase on pyrite by atomic hydrogen beam surface reactive scattering

Molecular beam surface scattering and X-ray absorption spectroscopic experiments were employed to study the reaction of deuterium atoms with a pyrite, FeS(2) (100), surface and to investigate the electronic and geometric structures of the resulting Fe-S phases. Incident D atoms, produced by a radiofrequency plasma and expanded in an effusive beam, were directed at a pyrite surface held at various temperatures from ambient up to 200 °C. During exposure to the D-atom beam, D(2)S products were released with a thermal distribution of molecular speeds, indicating that the D atoms likely reacted in thermal equilibrium with the surface. The yield of D(2)S from the surface decreased approximately exponentially with exposure duration, suggesting that the surface accessible sulfur atoms were depleted, thus leaving an iron-rich surface. This conclusion is consistent with X-ray absorption measurements of the exposed surfaces, which indicated the formation of a layered structure, with elemental iron as the outermost layer on top of a formally Fe((I))-S phase as an intermediate layer and a formally Fe((II))-S(2) bulk pyrite layer at lower depths. The reduced Fe((I))-S phase is particularly remarkable because of its similarity to the catalytically active sites of small molecule metalloenzymes, such as FeFe-hydrogenases and MoFe-nitrogenases.     

Electroactive SWNT/PEGDA hybrid hydrogel coating for bio-electrode interface

Electric interface between neural tissue and electrode plays a significant role in the development of implanted devices for continuous monitoring and functional stimulation of central nervous system in terms of electroactivity, biocompatibility and long-term stability. To engineer an interface that possesses these merits, a polymeric hydrogel based on poly(ethylene glycol) diacrylate (PEGDA) and single-walled carbon nanotubes (SWNTs) were employed to fabricate a hybrid hydrogel via covalent anchoring strategy, i.e., self-assembly of cysteamine (Cys) followed by Michael addition between Cys and PEGDA. XPS characterization proves that the Cys molecules are linked to gold surface via the strong S-Au bond and that the PEGDA macromers are covalently bonded to Cys. FTIR spectra indicate the formation of hybrid hydrogel coating during photopolymerization. Electrochemical measurements using cyclic voltammetry (CV) and impedance spectrum clearly show the enhancement of electric properties to the hydrogel by the SWNTs. The charge transfer of the hybrid hydrogel-based electrode is quasi-reversible and charge transfer resistance decreases to the tenth of that of the pure hydrogel due to electron hopping along the SWNTs. Additionally, this hybrid hydrogel provides a favorable biomimetic microenvironment for cell attachment and growth due to its inherent biocompatibility. Combination of these merits yields hybrid hydrogels that can be good candidates for application to biosensors and biomedical devices. More importantly, the hybrid hydrogel coatings fabricated via the current strategy have good adhesion to the electrode substrate which is highly desired for chronically implantable devices.     

Tissue-spray ionization mass spectrometry for raw herb analysis

Tissue-spray ionization mass spectrometry is developed for the in situ chemical analysis of raw herbs under ambient conditions. We demonstrated that analyte molecules could be directly sprayed and ionized from solvent-wetted ginseng tissues upon the application of high electrical voltage to the tissue sample. Abundant phytochemicals/ metabolites, including ginsenosides, amino acids and oligosaccharides, could be detected from ginseng tissues when the tissue-spray experiments were conducted in positive ion mode. Thermally labile and easily hydrolyzed malonyl-ginsenosides were also detected in negative ion mode. The tissue-spray ionization method enables the direct detection of analytes from raw herb samples and preserves the sample integrity for subsequent morphological and/ or microscopic examination. In addition, this method is simple and fast for chemical profiling of wild-type and cultivated-type American ginsengs with differentiation.     

高效液相色谱-加热电喷雾串联三重四级杆质谱法测定蔬菜中18种常用农药残留

建立了蔬菜中18种农药残留的高效液相色谱-加热电喷雾串联三重四级杆质谱测定方法.样品由乙腈提取,氨基柱净化,经C18液相色谱柱分离后,加热电喷雾离子源正负离子同时采集,在选择反应监测模式下进行测定.结果表明,该方法简便、快速、灵敏,方法的线性范围、回收率、精密度和检出限均符合农药残留分析的要求.     

Virgatolides A-C, benzannulated spiroketals from the plant endophytic fungus Pestalotiopsis virgatula

Virgatolides A-C (1-3), unique metabolites with a 3',4',5',6'-tetrahydrospiro[chroman-2,2'-pyran] core, were isolated from cultures of the plant endophytic fungus Pestalotiopsis virgatula. Compounds 1-3 possess two previously undescribed skeletons originating from a benzannulated 6,6-spiroketal and one (2 and 3) and two (1) γ-lactone units, respectively. The structure of 1 was secured by X-ray crystallography.     

Homopolar dihydrogen bonding in alkali-metal amidoboranes and its implications for hydrogen storage

The solid-state structures of LiNH(2)BH(3) and NaNH(2)BH(3) have been shown recently to exhibit intricate M(δ+)···(δ-)H-B and N-H(δ+)···(δ-)H-B interactions. However, closer inspection of these structures reveals additional homopolar H···H interactions, viz., B-H(δ-)···(δ-)H-B and N-H(δ+)···(δ+)H-N, which contribute to the relative stability of the extended structures of these crystalline materials. In addition, an NMR study of the isotopomer LiND(2)BH(3) shows that a significant quantity of H(2) is desorbed thermally along with HD, which can only arise from hydride-hydride interactions, either directly from B-H(δ-)···(δ-)H-B moieties or indirectly through the participation of Li-H intermediates.     

Evolution of packing parameters in the structural changes of silica mesoporous crystals: cage-type, 2D cylindrical, bicontinuous diamond and gyroid, and lamellar

Cage-type, two-dimensional (2D) cylindrical hexagonal (C), bicontinuous diamond (D), bicontinuous gyroid (G), and one-dimensional (1D) lamellar (L) structures of silica mesoporous crystals (SMCs) were obtained by using the anionic surfactant N-stearoyl-l-glutamic acid (C(18)GluA) as a template in the presence of the nonionic surfactant C(16)(EO)(10) (Brij-56). The mesostructures were controlled by the organic/inorganic interface curvature change induced by Brij-56. A synthesis-field diagram showed that the mesostructure changed in the sequence cage-type → C → intergrowth of C and D → intergrowth of C and G → D → G → L with increase of the amount of Brij-56. Mixed micelles were formed by the anionic and nonionic surfactants, the packing parameter g of which increased with increasing the addition amount of nonionic surfactant and the reaction temperature. The local g parameter was obtained from electron crystallography reconstruction results by calculating mean curvatures and Gaussian curvatures from the equi-electrostatic potential surface. The intergrowth of C and D and two kinds of intergrowth of C and G are also discussed.     

Ruthenium complexes of 1,4,7-trimethyl-1,4,7-triazacyclononane for atom and group transfer reactions

With support by macrocyclic tertiary amine ligand 1,4,7-trimethyl-1,4,7-triazacyclononane (Me₃tacn), a number of mononuclear metal–ligand multiple bonded complexes have been isolated. Starting with a brief summary of these complexes, the present review focuses on ruthenium-oxo and -imido complexes of Me₃tacn. A family of monooxoruthenium(IV) complexes [Ru^IV(Me₃tacn)O(N–N)]²⁺ (N–N = 2,2′-bipyridines) and a cis-dioxoruthenium(VI) complex cis-[Ru^VI(Me₃tacn)O₂(CF₃CO₂)]⁺ have been isolated, and the structures of [Ru^IV(Me₃tacn)O(bpy)](ClO₄)₂ (bpy = 2,2′-bipyridine) and cis-[Ru^VI(Me₃tacn)O₂(CF₃CO₂)]ClO₄ have been determined by X-ray crystallography. Oxidation of [Ru^III(Me₃tacn)(NHTs)₂(OH)] (Ts = p-toluenesulfonyl) with Ag⁺ and electrochemical oxidation of [Ru^III(Me₃tacn)(H₂L)](ClO₄)₂ (H₃L = α-(1-amino-1-methylethyl)-2-pyridinemethanol) are likely to generate ruthenium-imido complexes supported by Me₃tacn. DFT calculations on cis-[Ru^VI(Me₃tacn)O₂(CF₃CO₂)]⁺ and proposed ruthenium-imido complexes have been performed. Complexes [Ru^IV(Me₃tacn)O(N–N)]²⁺ are reactive toward alkene epoxidation, and cis-[Ru^VI(Me₃tacn)O₂(CF₃CO₂)]⁺ efficiently oxidizes various organic substrates including concerted [3+2] cycloaddition reactions with alkynes and alkenes to selectively afford α,β-diketones, cis-diols, or CC bond cleavage products. Related oxidation reactions catalyzed by ruthenium Me₃tacn complexes include epoxidation of alkenes, cis-dihydroxylation of alkenes, oxidation of alkanes, alcohols, aldehydes, and arenes, and oxidative cleavage of CC, CC, and C–C bonds, all of which exhibit high selectivity. Ruthenium Me₃tacn complexes are also active catalysts for amination of saturated C–H bonds.     

Bruceines K and L from the Ripe Fruits of Brucea javanica

Bruceine K ( 1 ), a pentacyclic C₂₀‐quassinoid bearing a unique 12,20‐epoxy moiety, and bruceine L ( 2 ), along with the ten known compounds (6S,7E)‐6,9,10‐trihydroxy‐ and (6S,7E)‐6,9‐dihydroxymegastigma‐4,7‐dien‐3‐one ( 3 and 4 , resp.), cleomiscosins A–C, luteoline, quercetine, bruceantinol, pinoresinol, and thevetiaflavone, were isolated from the ripe fruits of Brucea javanica. Bruceines K ( 1 ) and L ( 2 ) were determined to be (1β,2α,11β,12β,14ξ,15β)‐12,20‐epoxy‐1,2,11,13,14,15‐hexahydroxypicras‐3‐en‐16‐one and (1β,2α,11β,12β,15β)‐13,20‐epoxy‐1,2,11,12‐tetrahydroxy‐16‐oxo‐15‐(senecioyloxy)picras‐3‐en‐21‐oic acid methyl ester (senecioic acid=3‐methylbut‐2‐enoic acid), respectively, on the basis of NMR (¹H‐ and ¹³C‐NMR, DEPT, ¹H,¹H‐COSY, NOESY, HMQC, and HMBC) and ESI‐MS data. Among the known compounds, (6S,7E)‐6,9,10‐trihydroxy‐ and (6S,7E)‐6,9‐dihydroxymegastigma‐4,7‐dien‐3‐one ( 3 and 4 , resp.), cleomiscosin C, luteoline, quercetine, and thevetiaflavone were isolated for the first time from the Brucea plants.