Pd (II)‐catalyzed vinyl addition polymerization of novel functionalized norbornene bearing dimethyl carboxylate groups

Three novel functionalized polynorbornenes (PNB) with pendant dimethyl carboxylate group (carboxylates—acetate, propionate, and butyrate) are synthesized as a vinyl‐type with a palladium (II) catalyst in high yield. The effects of size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of exo‐norbornene dimethyl propionate were systematically investigated. The low molar ratio and temperature, as well as high polarity of solvent, and long reaction time, are favorable for the enhancement of the monomer conversion, especially, the solvent have an obvious effect on the catalyst activity. The resulting poly(cis‐norbornene‐exo‐2,3‐dimethyl carboxylates) (PNB‐dimethyl carboxylates) show good solubility in common organic solvent and high thermal stability up to 360 °C. The glass transition temperature was detected by DMA at 331, 324, and 318 °C for acetate, propionate, and butyrate, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3391–3399, 2007     

Ethylene–propylene copolymerization with bis(β‐enaminoketonato) titanium complexes activated with modified methylaluminoxane

Ethylene–propylene copolymerization, using [(Ph)NC(R₂)CHC(R₁)O]₂TiCl₂ (R₁ = CF₃, Ph, or t‐Bu; R₂ = CH₃ or CF₃) titanium complexes activated with modified methylaluminoxane as a cocatalyst, was investigated. High‐molecular‐weight ethylene–propylene copolymers with relatively narrow molecular weight distributions and a broad range of chemical compositions were obtained. Substituents R₁ and R₂ influenced the copolymerization behavior, including the copolymerization activity, methylene sequence distribution, molecular weight, and polydispersity. With small steric hindrance at R₁ and R₂, one complex (R₁ = CF₃; R₂ = CH₃) displayed high catalytic activity and produced copolymers with high propylene incorporation but low molecular weight. The microstructures of the copolymers were analyzed with ¹³C NMR to determine the methylene sequence distribution and number‐average sequence lengths of uninterrupted methylene carbons. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5846–5854, 2006     

Chemically modified proton‐conducting membranes based on sulfonated polyimides: Improved water stability and fuel‐cell performance

A series of branched/crosslinked sulfonated polyimide (B/C‐SPI) membranes were prepared and evaluated as proton‐conducting ionomers based on the new concept of in situ crosslinking from sulfonated polyimide (SPI) oligomers and triamine monomers. Chemical branching and crosslinking in SPI oligomers with 1,3,5‐tris(4‐aminophenoxy)benzene as a crosslinker gave the polymer membranes very good water stability and mechanical properties under an accelerated aging treatment in water at 130 °C, despite their high ion‐exchange capacity (2.2–2.6 mequiv g^?1). The resulting polymer electrolytes displayed high proton conductivities of 0.2–0.3 S cm^?1 at 120 °C in water and reasonably high conductivities of 0.02–0.03 S cm^?1 at 50% relative humidity. In a single H₂/O₂ fuel‐cell system at 90 °C, they exhibited high fuel‐cell performances comparable to those of Nafion 112. The B/C‐SPI membranes also displayed good performances in a direct methanol fuel cell with methanol concentrations as high as 50 wt % that were superior to those of Nafion 112. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3751–3762, 2006     

Synthesis and application as polymer electrolyte of hyperbranched polyether made by cationic ring‐opening polymerization of 3‐{2‐[2‐(2‐hydroxyethoxy)ethoxy]ethoxymethyl}‐3′‐methyl‐oxetane

A novel cyclic ether monomer 3‐{2‐[2‐(2‐hydroxyethoxy)ethoxy]ethoxy‐methyl}‐3′‐methyloxetane (HEMO) was prepared from the reaction of 3‐hydroxymethyl‐3′‐methyloxetane tosylate with triethylene glycol. The corresponding hyperbranched polyether (PHEMO) was synthesized using BF₃·Et₂O as initiator through cationic ring‐opening polymerization. The evidence from ¹H and ¹³C NMR analyses revealed that the hyperbranched structure is constructed by the competition between two chain propagation mechanisms, i.e. active chain end and activated monomer mechanism. The terminal structure of PHEMO with a cyclic fragment was definitely detected by MALDI‐TOF measurement. A DSC test implied that the resulting polyether has excellent segment motion performance potentially beneficial for the ion transport of polymer electrolytes. Moreover, a TGA assay showed that this hyperbranched polymer possesses high thermostability as compared to its liquid counterpart. The ion conductivity was measured to reach 5.6 × 10^?5 S/cm at room temperature and 6.3 × 10^?4 S/cm at 80 °C after doped with LiTFSI at a ratio of Li:O = 0.05, presenting the promise to meet the practical requirement of lithium ion batteries for polymer electrolytes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3650–3665, 2006     

Automated method, based on micro-sequential injection, for the study of enzyme kinetics and inhibition.

A micro-reactor system with continual spectrophotometric detection has been operated in Sequential Injection lab-on-valve (SI-LOV) mode and applied to enzyme kinetics and inhibition studies, using acetylcholinesterase (AChE) and angiotensin-converting enzyme (ACE) as model systems. With the advantages of automation, real-time kinetic measurement, and thorough mixing, the SI-LOV micro-reactor system allows for the monitoring of initial reaction rates and determination of reactant concentrations in the reaction mixture, both of which are essential for the determination of kinetic constants for enzymes and inhibitors. Enzyme, substrate, and inhibitor are precisely metered by the syringe pump and delivered to a stirred micro-reactor, followed by a reference scan that establishes the baseline for the following reaction rate measurement. Michaelis constants (Km) for AChE and ACE were determined to be 0.16 mM and 0.30 mM, respectively, which are consistent with literature values. The type of inhibition (competitive, uncompetitive, or mixed), the dissociation constants for the inhibitors, and the inhibitor dose-response curves were also determined.     

Chiral separation of synthetic vicinal diol compounds by capillary zone electrophoresis with borate buffer and beta-cyclodextrin as buffer additive.

The investigation on capillary electrophoretic enantioseparation of six synthetic compounds containing vicinal diol groups has been undertaken to acquire the optimum conditions using native beta-cyclodextrin (beta-CD) as chiral selector and borate as a background electrolyte. The separation was carried out in an uncoated capillary (58.5 cm x 75 microm i.d., effective length 48.5 cm) and the effects of several important factors were investigated in detail. The results showed that beta-CD as a chiral selector exhibited good enantioselectivity and that the enantioseparation was greatly influenced by the structure of the diols, the borate concentration and the buffer pH. The optimum performance was obtained for the chiral vicinal diols under the conditions of 200 mM borate buffer of pH 9.8 containing 1.7% beta-CD at an applied voltage of 15 kV and a capillary temperature of 20 degrees C. Under the conditions, four diols were baseline separated with fast analysis time and the good theoretical plate numbers (above 10 x 10(4)) and favorable migration-time reproducibilities (RSDs below 3.0%) were obtained. The separation results were satisfactory.     

A highly sensitive and rapid assay for protein determination in human urine and penicillin using a Rayleigh light-scattering technique with benzeneazo-8-acetylamino-1-naphthol-3,6-disulfonic acid sodium salt.

A simple and sensitive method was conducted for the determination of trace amounts of proteins with benzeneazo-8-acetylamino-1-naphthol-3,6-disulfonic acid sodium salt (azophloxine, AP) using a Rayleigh light-scattering (RLS) technique. At pH 2.60 and in the presence of an emulsifier OP microemulsion, the RLS of AP can be greatly enhanced by proteins, owing to the interaction between AP and protein. The enhanced intensity is proportional to the concentration of proteins. Four proteins, including bovine serum albumin (BSA), human serum albumin (HSA), lysozyme (Lys) and gamma globulin (gamma-G) have been tested. For example, the linear range of BSA was 0 - 0.06 microg mL(-1) with detection limits of 2.38 ng mL(-1). The method was applied to the analysis of protein in human urine and penicillin samples with satisfactory results. The relative standard deviation was in all instances less than 4.0%, and the recovery was in the range of 97.5 - 104%.     

Oxidation and Reduction Processes During NO x Removal with Corona-Induced Nonthermal Plasma

In this paper, the NO-to-NO ₂ conversion in various gaseous mixtures is experimentally investigated. Streamer coronas are produced with a dc-superimposed high-frequency ac power supply (10–60 kHz). According to NO _x removal experiments in N ₂ +NO _x and N ₂ +O ₂ +NO _x gaseous mixtures, it is supposed that the reverse reaction NO ₂ +ONO+O ₂ may not only limit NO ₂ production in N ₂ +NO _x mixtures, but also increase the energy cost for NO removal. Oxygen could significantly suppress reduction reactions and enhance oxidation processes. The reduction reactions, such as N+NON ₂ +O, induce negligible NO removal provided the O ₂ concentration is larger than 3.6%. With adding H ₂ O into the reactor, the produced NO ₂ per unit removed NO can be significantly reduced due to NO ₂ oxidation. NH ₃ injection could also significantly decrease the produced NO ₂ via NH and NH ₂ - related reduction reactions. Almost 100% of NO ₂ can be removed in gaseous mixtures of N ₂ +O ₂ +H ₂ O+NO ₂ with negligible NO production.     

Single Atom Alloy Preparation and Applications in Heterogeneous Catalysis

There have been remarkable progresses in manipulating heterogeneous catalysts' nanostructures in the past decade. The concept of single atom alloy (SAA) was firstly proposed in 2012 when researchers successfully stabilized single Pd atoms on the Cu(111) surface. However, earlier work in 2009, which focused on replacing one Au atom with a Pd atom in thiolate protected Au₂₅ nanoclusters, could also be considered as the pioneer work of single atom alloy. Both kinds of single atom alloys exhibited the potential of maximum utilization of scarce elements and attractive catalytic performances. The well‐defined structures of SAA catalysts make accurate modeling possible, which further realizes the rational design of single atom alloy catalysts. In this review, we summarize the research trajectory of single atom alloys as well as recent achievements in this field. We also introduce several commonly adopted characterization methods for SAA catalysts such as scanning tunneling microscopy (STM), temperature programmed reaction (TPR), extended X‐ray absorption fine structure (EXAFS) spectra, matrix assisted laser desorption/ionization mass spectrum (MALDI‐MS) and differential pulse voltammetry (DPV). Through discussing recent progresses in SAA catalysts, we propose that future researches in this filed should be focused on exploring new kinds of metal nanocrystals and controlling the nanostructure of SAA even more precisely.