Facile regio- and stereoselective hydrometalation of alkynes with a combination of carboxylic acids and group 10 transition metal complexes: selective hydrogenation of alkynes with formic acid

A facile, highly stereo- and regioselective hydrometalation of alkynes generating alkenylmetal complex is disclosed for the first time from a reaction of alkyne, carboxylic acid, and a zerovalent group 10 transition metal complex M(PEt(3))(4) (M = Ni, Pd, Pt). A mechanistic study showed that the hydrometalation does not proceed via the reaction of alkyne with a hydridometal generated by the protonation of a carboxylic acid with Pt(PEt(3))(4), but proceeds via a reaction of an alkyne coordinate metal complex with the acid. This finding clarifies the long proposed reaction mechanism that operates via the generation of an alkenylpalladium intermediate and subsequent transformation of this complex in a variety of reactions catalyzed by a combination of Br?nsted acid and Pd(0) complex. This finding also leads to the disclosure of an unprecedented reduction of alkynes with formic acid that can selectively produce cis-, trans-alkenes and alkanes by slightly tuning the conditions.     

Study on the temperature-induced sol–gel transition of cellulose/silk fibroin blends in 1-butyl-3-methylimidazolium chloride via rheological behavior

Temperature-induced sol–gel transition of cellulose/silk fibroin/1-butyl-3-methylimidazolium chloride ([BMIM]Cl) was studied from the viscosity and dynamic modulus of the mixtures. The shear thinning behavior of the mixture solution was very obvious with a decrease in temperature. The curves of storage modulus G′ and loss modulus G″ were parallel when the temperature was below 20 °C, indicating that a gel structure exists in the system. The sol–gel transition process was described according to Winter and Chambon’s theory. The gel structure of the mixture system was loosened with the increase of silk fibroin concentration.     

Rheological behavior of cellulose/silk fibroin blend solutions with ionic liquid as solvent

The rheological behavior of cellulose and silk fibroin blend in 1-butyl-3-methylimidazolium chloride was studied. The data from the rheological results was analyzed to understand the microstructure of the blend solutions. The viscosity and dynamic modulus of the blend solution decreased with increasing ratio of silk fibroin. While comparing the experimental results with the calculated data from the log-additivity rule, it is revealed that zero-shear viscosity, dynamic modulus show positive–negative deviations and a typical continuous–discrete type of morphology could be imaged. At lower shear rate, the change of phase morphology took place at the ratio of about 0.5 volume fraction of cellulose. However, the blend solution showed positive deviations for all cellulose/silk fibroin blend ratios at high shear rate, which indicates that the dispersion of cellulose and silk fibroin was improved under shear stress. The properties of cellulose/silk fibroin blends observed by Fourier transform infrared spectroscopy and scanning electron microcopy agreed with the result from rheology.     

Synthesis and properties of cocotriethoxylpropanediamine oxide

A new kind of amine oxide surfactant – cocotriethoxylpropanediamine oxide (CTPDAO) – was synthesized by a two-step process. The molecular structure was characterized by FTIR spectra and ¹H NMR. The new surfactant showed high surface activity in aqueous solution in the surface tension measurement. Emulsifying capacity and wetting ability were studied in comparison to dodecyldimethylamine oxide (DDMAO). The results indicate that this new surfactant could reach the lowest surface tension of 30.4?mN?m^?1 in aqueous solution with a critical micelle concentration (CMC) of 0.23?mmol L^?1. The wetting ability of DDMAO is better than that of CTPDAO. Compared with CTPDAO, DDMAO shows a greater capacity to emulsify soybean oil, although CTPDAO is a better emulsifying agent for liquid paraffin. The foaming properties and thickening function of DDMAO and CTPDAO mixed with alcohol ether sulfate (AES) and dodecylbenzene sulfonate (LAS) were also investigated. The results show that CTPDAO is a superior foam stabilizer than DDMAO while CTPDAO and DDMAO both have excellent thickening functions.     

Wash-free in-situ self-desalting and peptide enrichment by block copolymer analyzed with MALDI-TOFMS

A novel technique of simultaneous peptide enrichment and wash-free in-situ self-desalting for MALDI analysis is reported, where a newly synthesized block copolymer with a microphase-separated configuration is applied to embed salts with its hydrophilic domain of poly(ethylene oxide) and concentrate peptides with its hydrophobic domain of polysulfone.     

Two new diterpenoids from the buds of Wikstroemia chamaedaphne

Two new diterpenoids, wikstroelide Q (1) and prostratin Q (5), together with three known diterpenoids, pimelea factors P? (2), P? (3), and prostratin (4), and five known lignans, (+)-epipioresinol (6), (+)-isolariciresinol (7), (?)-lariciresinol (8), (+)-epi-sesaminone (9), and prestegane B (10), were isolated from the buds of Wikstroemia chamaedaphne Meissn. Their structures were elucidated by a combination of spectroscopic analyses. Compounds 1–10 were evaluated for their cytotoxicities against HL-60, SMMC-7721, A549, MCF-7, SW480, and BEAS-2B cell lines in vitro.     

基于高选择性氟液相传感膜的离子传感器

本文基于国外最新研究工作,系统总结了电位型传感器中的一种新型传感膜——氟液相传感膜。对构成氟液相传感膜的所有组分:氟溶剂、溶解在氟溶剂中的亲氟离子交换剂和亲氟离子载体以及对氟溶剂起支撑作用的惰性微孔支撑膜等进行了全面归纳,重点讨论了这4种因素对传感器性能的影响。指出目前使用的亲氟离子交换剂分子和亲氟离子载体分子均含有2—8根链长为6—10的全氟碳链。氟液相传感膜具有优于传统PVC膜的检测下限,其中通过三维有序大孔碳以固体接触方式构建的氟液相传感膜电位传感器对Ag⁺的探测下限可达3.8×10^-11 mol/L。氟液相传感膜还具有十分出色的选择性,无任何离子载体的空白氟液相传感膜的选择系数对数值log K_i,J^pot的跨越宽度达16—18,比无载体的PVC膜宽8个数量级。这类全新的氟液相传感膜构建的电位型离子传感器将以其独特的优势在环境监测、食品卫生,尤其是在医疗诊断、生物物质检测中展示出不可替代的作用。     

A novel time-division multiplexing fiber Bragg grating sensor interrogator for structural health monitoring

A novel fiber Bragg grating (FBG) sensor system for measurement of strain and temperature is proposed in this paper. The proposed sensor technique is based on time-division multiplexing (TDM). A semiconductor optical amplifier (SOA), connected in a ring cavity, is used to serve as a gain medium and switch. The SOA is driven by a pulse generator, which operates the SOA at different periods of time to select reflected pulses from a particular sensor. The FBG sensors have identical center wavelengths and can be deployed along the same fiber. This technique relieves the spectral bandwidth issue and permits the interrogation of up to 100 FBGs along a fiber, if the reflectivity of the individual sensors is sufficiently low to avoid shadowing effects. This system is particularly suitable for the application in structural health monitoring (SHM) where large numbers of sensors are required in wide measurement ranges.     

An Efficient and Environmentally Friendly Method for the Synthesis of Cellulose Carbamate by Microwave Heating

An efficient, solvent‐free, and catalyst‐free microwave synthesis of cellulose carbamate from a mixture of native cellulose and urea is reported. The structure of the samples are characterized by elemental analysis, FT‐IR spectroscopy, X‐ray diffraction, and NMR spectrometry. Cellulose carbamates with a nitrogen content of 0.651–2.427% are obtained by microwave heating at 255 W for 2–5 min. With the introduction of carbamate groups, the hydrogen bonding and crystalline structure of the native cellulose are partially destroyed. The products retain the cellulose I crystalline form of the native cellulose, and display good solubility in NaOH solutions.