Synthesis of Y-shaped poly(solketal acrylate)-containing block copolymers and study on the thermoresponsive behavior for micellar aggregates

One novel type of Y-shaped amphiphilic copolymers with two hydrophobic poly(solketal acrylate) (PSA) branches and one hydrophilic monomethoxy poly(ethylene glycol) (MPEG) block was synthesized by atom transfer radical polymerization (ATRP). These Y-shaped polymers can disperse in aqueous media to self-assemble into micellar aggregates with a spherical core-shell structure. The aqueous copolymer solutions exhibited transmittancy transition in the temperature range of 30-60 °C via optical transmittance measurements. An interesting thermo-dependent size of the micellar aggregates was observed by dynamic light scattering techniques and transmission electron microscopy, which showed that the micelle diameters were decreased with temperature increasing. The nile red release from the micelles at 25 °C and 37 °C under various pHs showed that temperature has great influence on release behavior. With good biocompatibility, the micellar aggregates formed from MPEG-block-(PSA)(2) may serve as one promising thermosensitive nanovehicle for targeted drug delivery.     

Preparation of anionic phosphine ligands in situ for the palladium-catalyzed Buchwald/Hartwig amination reactions of aryl halides

2-Phenylindenyl phosphine ligand can be changed into anionic phosphine ligand in situ and utilized in the palladium-catalyzed Buchwald/Hartwig amination reactions in DME, providing good to excellent yields of amination products from aryl chlorides, bromides and iodides. ³¹P NMR studies show that the resonance for the anionic phosphine appeared between those of the (2-phenylindenyl)-dicyclohexyl phosphonium salt and (2-phenylindenyl)dicyclohexylphosphine. The calculated results were consistent with the experimental results.     

An easy compartment-less biofuel cell construction based on the physical co-inclusion of enzyme and mediator redox within pressed graphite discs

We report on the easy and fast immobilization of glucose oxidase (GOD) and laccase by mechanical compression with graphite particles to form disc electrodes. The electrical wiring of GOD and laccase was efficiently carried out by their co-inclusion with ferrocene (Fc) and 2,2′-azinobis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS) respectively. A glucose/air compartment-less biofuel cell was constructed based on the association of GOD-ferrocene-graphite disc and laccase-ABTS – graphite disc electrodes as bioanode and biocathode respectively. Such biofuel cell yielded a power density of 23 μW cm^?2 at 0.33 V as well as an open-circuit voltage and a short-circuit current of 0.63 V and 166 μA, respectively.     

Synthesis, structure and electrochemical property of diphenylacetypene-substituted diiron azadithiolates as active site of Fe-only hydrogenases

The model complexes 1-3 of functionalized azadithiolate (ADT)-bridged Fe-only hydrogenases, [Fe₂(Co)₆(μ-ADT)C₆H₄CCR] [R = C₆H₄NO₂-4 (1), C₆H₅ (2), C₆H₄OCH₃-4 (3)] have been synthesized in high yields under mild conditions by using Sonogashira reaction. Spectroscopic study and X-ray crystal structural analysis of 1 demonstrate that the model complexes retain the butterfly structure of 2Fe2S model analogues. The intermolecular C-H?O, C-H?π hydrogen bonding and π-π interactions play important roles in molecular packing of 1. In the presence of HOAc, complex 1 features the catalytic electrochemical proton reduction.     

Mesoporous tungsten titanate as matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis of biomolecules

In this paper, mesoporous tungsten titanate (WTiO) with different nano-pore structures was utilized as matrix for the analysis of short peptides by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). Effect of characteristic features of mesoporous matrices on laser desorption/ionization process was investigated. Experiments showed that the ordered two-dimensional and three-dimensional mesoporous matrices were superior in performance to the non-ordered WTiO matrix. The dramatic enhancement of signal sensitivity by the ordered mesoporous matrices can be reasonably attributed to the ordered structure, which facilitated the understanding on structure-function relationship in mesoporous cavity for laser desorption process of adsorbed biomolecules. With the ordered mesoporous matrix, the short peptides are successfully detected. The presence of trace alkali metal salt effectively increased the analyte ion yields and the MALDI-TOFMS using the inorganic mesoporous matrices displayed a high salt tolerance. The developed technique also showed a satisfactory performance in peptide-mapping and amino-acid sequencing analysis.     

Aminopropyl-grafted various silica mesostructures for adsorption of molybdenum ions from Re-containing effluent

Four different silica mesostructures, SBA-15 with mesopore size (8.5 nm), SBA-15 with mesopore size (10.3 nm), mesocellular foam (MCF) with uniform cell size (33.2 nm), and MCF with bimodal mesoporosity, were grafted with aminopropyl groups and used for selective recovery of Mo(VI) from Re(VII)-containing effluent. Adsorption isotherms and mechanism of Mo(VI) adsorption on these materials were studied. The adsorbed complexes of Mo(VI) could be formed by ion exchange process or/and by chelation reaction. This study shows a new approach for fractional recovery and separation of Mo(VI) from Re(VII) by using amino-modified SBA-15-type mesoporous silica.     

Secondary succession and its effects on soil moisture and nutrition in abandoned old-fields of hilly region of Loess Plateau, China

Floristic composition, community structure and soil moisture and nutrient contents in abandoned fields of different ages were analyzed to clarify the regenerative aspects of succession as a tool for vegetation restoration. The results indicated that secondary succession in this region can be interpreted as an auto-succession: there are main changes in species-relative abundance and species turnover. Annual or biennial species (e.g. Artemisia scoparia), acted as pioneers and strongly dominated the early stages. Then, they underwent a progressive decline, while forbs (e.g. Artemisia sacrorum) and grasses (e.g. Xanthium sibiricum) had their peak abundance at intermediate stages. Dwarf shrubs (e.g. Lespedeza dahurica) and short rhizome grass (e.g. Bothriochloa ischaemum) appeared at mid-succession stage and gradually increased in abundance during succession, becoming dominant at late stages. The first axis of detrended correspondence canonical analysis arranged the sites according to their fallow time, indicating a successional sere. The second axis, associated with diverging pathways of regeneration, correlated with topographic factors and soil moisture and nutrition. Structural divergence between plots increased as succession went on, attained the highest at the mid-succession stage, decreased at the late stage.

Soil moisture and available phosphorus content decreased steadily with field age after their abandonment, whereas pools of organic matter, total and available nitrogen, potassium and total phosphorus increased with field age. The pace and direction of recovery of native vegetation and natural soil properties in these abandoned fields resembled classic old-field succession, which is a form of secondary succession that often serves as a template for guiding restoration efforts. Interface between the abandoned field soil and plant system was crucial to the above process. Our current study supported the generally accepted hypothesis in the succession literature.     

A New β-Carboline Alkaloid and a New Derivate of Isoferulic Acid from Anemone altaica

A new β-carboline alkaloid, 4-（9H-β-carbolin-1-yl）-4-oxobutyric acid and a new derivate of isoferulic acid, （E）-3-（3-hydroxy-4-methoxyphenyl）acrylic acid carboxymethyl ester, were isolated from the roots of Anemone altaica. Their structures were determined on the basis of spectral data.     

Two New Acetylenic Compounds from Asparagus gobicus

Two new acetylenic compounds were isolated from the roots of Asparagus gobicus. Their structures were elucidated by spectroscopic methods including 2D NMR techniques.     

A New Diterpene Acid from the Flowers of Heteropappus altaicus

A new compound, named heteraltaic acid was isolated from the flowers of Heteropappus altaicus (willd) Novopokr. The compound was elucidated as (5R, 6S, 8aS) -5-[2-(3-furyl) ethyl-5, 6, 8a-trimethyl-4a, 5, 6, 7, 8, 8a -hexahydro-l-naphthalenecarboxylic acid] by the combination of 1D and 2D NMR techniques (HSQC, HMBC) and X-ray analysis.