Rapid and Scalable Access to Sequence-Controlled DHDM Multiblock Copolymers by FLP Polymerization

An immortal N-(diphenylphosphanyl)-1,3-diisopropyl-4,5-dimethyl-1,3-dihydro-2H-imidazol-2-imine/diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum (P(NIⁱPr)Ph₂/(BHT)AlⁱBu₂)-based frustrated Lewis pair (FLP) polymerization strategy is presented for rapid and scalable synthesis of the sequence-controlled multiblock copolymers at room temperature. Without addition of extra initiator or catalyst and complex synthetic procedure, this method enabled a tripentacontablock copolymer (n=53, k=4, dp_n=50) to be achieved with the highest reported block number (n=53) and molecular weight (M_n=310 kg mol⁻¹) within 30 min. More importantly, this FLP polymerization strategy provided access to the multiblock copolymers with tailored properties by precisely adjusting the monomer sequence and block numbers.     

An Arbitrarily Regulated Monomer Sequence in Multi-Block Copolymer Synthesis by Frustrated Lewis Pairs

Rapid access to sequence-controlled multi-block copolymers (multi-BCPs) remains as a challenging task in the polymer synthesis. Here we employ a Lewis pair (LP) composed of organophosphorus superbase and bulky organoaluminum to effectively copolymerize the mixture of methacrylate, cyclic acrylate, and two acrylates, into well-defined di-, tri-, tetra- and even a hepta-BCP in one-pot one-step manner. The combined livingness, dual-initiation and CSC feature of Lewis pair polymerization enable us to achieve not only a trihexaconta-BCP with the highest record in 8 steps by using four-component monomer mixture as building blocks, but also the arbitrarily-regulated monomer sequence in multi-BCP, simply by changing the composition and adding order of the monomer mixtures, thus demonstrating the powerful capability of our strategy in improving the efficiency and enriching the composition of multi-BCP synthesis.     

Determination of Sunset Yellow using a carbon paste electrode modified with a nanostructured resorcinol-formaldehyde resin

This article describes an electrochemical sensor for the dye additive Sunset Yellow (SY). It consists of a carbon paste electrode modified with nanostructured resorcinol-formaldehyde (RF) resin. The RF resin warrants strong signal enhancement and a strongly increased oxidation peak currents of SY at 0.66 V (vs. SCE). The effects of pH value, amount of RF polymer, accumulation potential and time were optimized. The sensor has a linear response to SY in the 0.3 to 125 nM concentration range, and the limit of detection is 0.09 nM after a 2-min accumulation time. The electrode was applied to the analysis of samples of wastewater and drinks, and the results are consistent with those obtained by HPLC.

Nanostructured resorcinol-formaldehyde (RF) resin was prepared and used as a material for electrochemical determination of Sunset Yellow.

     

Electrochemical DNA hybridization assay for the FMV 35S gene sequence using PbS nanoparticles as a label

Microchimica Acta - An electrochemical DNA detection method was developed for the 35S promoter from Figwort mosaic virus (FMV 35S) gene sequence by using a microplate hybridization assay with PbS...     

Morphological transformations of nonequilibrium assemblies of amphiphilic diblock copolymer

Amphiphilic diblock copolymer polystyrene-block-poly(ethylene oxide) (PS-PEO) assembled into nonequilibrium bicontinuous structures or mixture of vesicles, bilayers and nanorods upon rapid micellization induced by rapid addition of selective solvent (water) into the PS-PEO solutions in a common solvent (dimethyl formamide) with different concentrations. These kinetically trapped assemblies were unstable and slowly evolved into thermodynamically favorable spheres and vesicles. The addition of non-ionic surfactant Pluronic P123 upon rapid micellization generated novel nanocages and flower-like vesicles. The nanocages spontaneously transformed into tubules capped with vesicles. These novel assemblies are beyond the classic phase diagram of block copolymer self-assemblies, especially for those primarily based on thermodynamics.     

Transient analysis of an M/G/1 retrial queue subject to disasters and server failures

An M/G/1 retrial queueing system with disasters and unreliable server is investigated in this paper. Primary customers arrive in the system according to a Poisson process, and they receive service immediately if the server is available upon their arrivals. Otherwise, they will enter a retrial orbit and try their luck after a random time interval. We assume the catastrophes occur following a Poisson stream, and if a catastrophe occurs, all customers in the system are deleted immediately and it also causes the server’s breakdown. Besides, the server has an exponential lifetime in addition to the catastrophe process. Whenever the server breaks down, it is sent for repair immediately. It is assumed that the service time and two kinds of repair time of the server are all arbitrarily distributed. By applying the supplementary variables method, we obtain the Laplace transforms of the transient solutions and also the steady-state solutions for both queueing measures and reliability quantities of interest. Finally, numerical inversion of Laplace transforms is carried out for the blocking probability of the system, and the effects of several system parameters on the blocking probability are illustrated by numerical inversion results.     

Synthesis of tungsten carbide nanocrystals and their electrochemical properties

Tungsten carbide (WC) nanocrystals have been prepared by a solvothermal method with Mg as the reductant and WO₃ and anhydrous ethanol as the precursors. The effects of time and temperature on the synthesis of WC were investigated and a probable formation mechanism was discussed. The obtained WC nanocrystals were characterized by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy and electrochemical methods. Hexagonal closepacked WC was successfully synthesized when the temperature was as low as 500°C. The content of carbon was more than that of W, indicating that the composition of the treated sample was C and WC only. The diameters of WC nanocrystals were ranged from 40 nm to 70 nm and the nanocrystals were dispersed on carbon films. The electrochemical measurements reveal that WC nanocrystals obviously promote Pt/C electrocatalytic ability for the oxygen reduction reaction. __________ Translated from Chinese Journal of Catalysis, 2008, 29(7) (in Chinese)     

A Mann type iterative scheme for variational inequalities in noncompact subsets of Banach spaces

In this paper, we study the existence of solutions and approximation of the solutions by using a Mann type iterative scheme for variational inequalities in noncompact subsets of Banach spaces. The results presented in this paper generalize the corresponding results of J. Li [J. Li, On the existence of solutions of variational inequalities in Banach spaces, J. Math. Anal. Appl. 295 (2004) 115-126].     

Fe(acac)3-Al(i-Bu)3-CCl4催化马来酸酐与降冰片烯共聚

 研究了Fe(acac)3-Al(i-Bu)3-CCl4(acac=乙酰丙酮)催化体系对马来酸酐(MA)与降冰片烯(NBE)交替聚合反应的催化性能. 用元素分析、核磁共振和红外光谱研究了共聚物的结构,在单体比为1∶1时,共聚物中MA和NBE的含量分别为52.2%和47.8%. 凝胶渗透色谱结果表明共聚物分子量分布窄. 动力学研究结果表明, MA与NBE共聚对单体浓度呈一级反应,其表观活化能为74.3 kJ/mol.