Scope and regioselectivity of the 1,3-dipolar cycloaddition of azides with methyl 2-perfluoroalkynoates for an easy,metal-free route to perfluoroalkylated 1,2,3-triazoles

1,3-Dipolar cycloadditions of methyl 2-perfluoroalkynoates with various azides have been examined, leading to a simple metal-free synthetic protocol for the synthesis of perfluoroalkylated 1,2,3-triazoles. The regiochemical results demonstrated that the cycloaddition was controlled by FMO (the frontier molecular obitals) interaction and steric hindrance in transition states.     

IR laser absorption diagnostic for C2H4 in shock tube kinetics studies

An IR laser absorption diagnostic has been further developed for accurate and sensitive time‐resolved measurements of ethylene in shock tube kinetic experiments. The diagnostic utilizes the P14 line of a tunable CO₂ gas laser at 10.532 μm (the (0 0 1) → (1 0 0) vibrational band) and achieves improved signal‐to‐noise ratio by using IR photovoltaic detectors and accurate identification of the P14 line via an MIR wavemeter. Ethylene absorption cross sections were measured over 643–1959 K and 0.3–18.6 atm behind both incident and reflected shock waves, showing evident exponential decay with temperature. Very weak pressure dependence was observed over the pressure range of 1.2–18.6 atm. By measuring ethylene decomposition time histories at high‐temperature conditions (1519–1895 K, 2.0–2.8 atm) behind reflected shocks, the rate coefficient of the dominant elementary reaction C₂H₄ + M → C₂H₂ + H₂ + M was determined to be k₁ = (2.6 ± 0.5) × 10¹⁶exp(?34,130/T, K) cm³ mol^?1 s^?1 with low data scatter. Ethylene concentration time histories were also measured during the oxidation of 0.5% C₂H₄/O₂/Ar mixtures varying in equivalence ratio from 0.25 to 2. Initial reflected shock conditions ranged from 1267 to 1440 K and 2.95 to 3.45 atm. The measured time histories were compared to the modeled predictions of four ethylene oxidation mechanisms, showing excellent agreement with the Ranzi et al. mechanism (updated in 2011). This diagnostic scheme provides a promising tool for the study and validation of detailed hydrocarbon pyrolysis and oxidation mechanisms of fuel surrogates and realistic fuels. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 423–432, 2012     

Copper‐catalyzed Clauson–Kass pyrroles synthesis in aqueous media

An efficient and convenient copper‐catalyzed Clauson–Kass reaction of 2,5‐dimethoxytetrahydrofuran with amines in aqueous media has been developed, providing a wide range of N‐substituted pyrroles in good yields. It is noteworthy that the Clauson–Kass reaction of 2,5‐dimethoxytetrahydrofuran with p‐phenylenediamine or m‐phenylenediamine proceeds smoothly to afford the corresponding monopyrroles and bispyrroles with high selectivity in impressive yields. A plausible mechanism for the formation of N‐substituted pyrroles has been proposed. Copyright © 2012 John Wiley & Sons, Ltd.     

Turing structures and stability for the 1-D Lengyel–Epstein system

This paper continues the analysis on the Lengyel–Epstein reaction- diffusion system of the chlorite-iodide-malonic acid-starch (CIMA) reaction for the rich Turing structures. The steady state structures, especially the double bifurcation one, and their stability and multiplicity are studied by the use of Lyapunov–Schmidt reduction technique and singularity theory. Numerical simulations are presented to support our theoretical studies. The results show that the richer stationary Turing patterns heavily rely both on the size of the reactor and on the effective diffusion rate in the CIMA reaction.     

The preparation and adsorption properties of electrospun aramid nanofibers

The focus of this work is the preparation of aramid nanofibers via electrospinning technology and the study of their adsorption properties. In this article, aramid nanofibers were prepared by electrospinning aramid fibers solution with the addition of lithium chloride (LiCl). It showed a good adsorption capacity when methylene blue (MB) was used as the model target. There were much larger adsorption amounts and faster kinetics of uptaking target species of electrospun aramid nanofibers to MB than that of electrospun polyethersulfone (PES) nanofibers. Compared with activated carbon, aramid nanofibers also have a much faster adsorption rate to MB. Aramid nanofibers were subsequently used to effectively remove endocrine disruptors such as bisphenol A (BPA), phenol (Phe), and p‐hydroquinone (BPhe) from their aqueous solutions. Additionally, molecule imprinted technology enhances aramid nanofibers with much higher adsorption amounts and special adsorption property for endocrine disruptors. These results showed that aramid nanofibers have the potential to be used in environmental applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Sorption equilibria of CO2 on silica-gels in the presence of water

The sorption equilibria of carbon dioxide on three types of silica gel (SG) with different pore size distributions in the presence of water were studied experimentally using a volumetric method at 275?K with pressures from 0 to 3.7?MPa. Both the pore size distribution of the silica gel and the quantity of pre-sorbed water impact the formation of the CO₂ hydrates. For wet silicon gel A(SG-A) with water loading ratio of 0.75, the highest CO₂ sorption was about 2.5?mmol of CO₂ per gram of dry sorbent at 275?K. Similarly, the highest sorption was about 2.7?mmol for wet SG-B with R _w =0.81. However, CO₂ hydrate did not form on the wet surface of SG-C due to its large pore sizes.     

Synthesis of tetrasubstituted thiophenes from pyridinium 1,4-zwitterionic thiolates and modified activated alkynes

Pyridinium 1,4-zwitterionic thiolates were applied to a formal [3 + 2] annulation reaction with modified activated alkynes, affording various tetrasubstituted thiophenes with aryl, alkenyl, alkyl or silyl group at the special position. The structural modification of alkyne substrates enabled the synthesis of diverse thiophenes to be achieved using the pyridinium 1,4-zwitterionic thiolates as the sulfur-containing building blocks. This approach is metal-free and catalyst-free.     

中等规模多肽分子的2DNOESY实验问题

由于中等规模多肽在水溶液中运动的特殊性(ω₀τ_c≈1),2DNOESY谱上往往得不到相关讯息(采用合理的混合时间),而降低温度的余地也很小·本工作将少量氘代甲醇加到水溶液中,并将实验温度降到零下,实验取得成功。例如从一个九肽和一个十一肽的NOESY实验得到了很多残基内和残基间的NOESY相关讯息,足以作出归属并进一步计算质子间距离.