Cationic polymerization of isobutylene at room temperature

This review highlights recent approaches toward polyisobutylene (PIB) by an energy efficient room temperature cationic polymerization. Special focus is laid on our own work using modified Lewis acids and nitrile‐ligated metal complexes associated with weakly coordinating anions. In both cases, suitable conditions have been found for efficient production of PIB characterized by medium to low molar masses and a high content of exo double bonds as end groups—the typical features of highly reactive PIB, an important commercial intermediate toward oil and gasoline additives. These and other approaches demonstrate that the cationic polymerization of isobutylene is still not fully explored, and new innovative catalyst systems can lead to surprising results of high commercial interest. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Copper(0)-mediated radical polymerization of styrene at room temperature

The “living’/controlled radical polymerization (LRP) of styrene (St) at room temperature is rarely reported. In this work, copper(0) (Cu(0))-mediated radical polymerization of St at room temperature was investigated in detail. Dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF) as well as a binary solvent, tetrahydrofuran/1,1,1,3,3,3-hexafluoro-2-propanol were used as the solvents, respectively. Methyl-2-bromopropionate and ethyl 2-bromoisobutyrate were used as the initiators, respectively. The polymerization proceeded smoothly with moderate conversions at room temperature. It was found that DMF was a good solvent with the essential features of LRP, while DMSO was a poor solvent with uncontrollable molecular weights. Besides, the match among the initiator, solvent and molar ratios of reactants can modulate the livingness of the polymerization, and the proper selection of ligand was also crucial to a controlled process. This work provided a first example of Cu(0)-mediated radical polymerization of St at room temperature, which would enrich and strength the LRP technique.     

基于室温离子液体的有序多孔金膜葡萄糖传感器

将1-丁基-3-甲基咪唑四氟硼酸盐（[BMIm][BF4]）、N,N-二甲基甲酰胺（DMF）与葡萄糖氧化酶（GOD）的混合物修饰于三维有序大孔（3DOM）金膜电极上,构建了一种新型的葡萄糖传感器．固定的GOD在pH7．0的磷酸缓冲液（PBS）中展现出一对可逆性好的氧化还原峰,这归因于GOD的活性中心黄素腺嘌呤二核苷酸（FAD）的直接电化学行为．研究表明,离子液体（IL）、DMF以及3DOM金膜对GOD的直接电化学都起到了重要的作用．3DOM金膜修饰电极作为基底提高了酶的负载量,加速了GOD与电极表面的电子传递;IL的应用增加了固定GOD的电化学活性;DMF与IL、GOD的协同作用更好地保持了GOD的生物活性．固定在电极表面的GOD对葡萄糖显示出良好的催化性能,其检测线性范围为10～125nmol／L,检测限为3．3nmol／L（S／N=3）,酶催化反应的表观米氏常数Km为0．018mmol／L．     

Preparation of the glucose sensor based on three-dimensional ordered macroporous gold film and room temperature ionic liquid

A novel type of glucose sensor was fabricated based on a glucose oxidase (GOD)-N,N-dimethtylformamide (DMF)-[BMIm][BF₄] composites modified three-dimensional ordered macroporous (3DOM) gold film electrode. The immobilized GOD exhibits a pair of well-defined reversible peaks in 50 mM pH 7.0 phosphate buffer solutions (PBS), which could be attributed to the redox of flavin adenine dinucleotide (FAD) in GOD. The research results show that ionic liquid ([BMIm][BF₄]), DMF and 3DOM gold film are crucial for GOD to exhibit a pair of stable and reversible peaks. It is believed that the large active area of 3DOM gold film can increase the amount of immobilized GOD. Simultaneously, the application of IL enhances the stability of GOD and facilitates the electron transfer between GOD and the electrode. The synergetic effect of DMF can help the GOD to maintain its bioactivity better. GOD immobilized on the electrode exhibits the favorable electrocatalytic property to glucose, and the prepared sensor has a linear range from 10 to 125 nM with a detection limit of 3.3 nM at a signal-to-noise ratio of 3σ. The apparent K _m (Michaelis- Menten constant) for the enzymatic reaction is 0.018 mM.     

Preparation and characterization of polyvinyl alcohol-capped CdSe nanoparticles at room temperature

Polyvinyl alcohol (PVA)-capped CdSe nanoparticles were successfully prepared by a one-step solution growth technique at room temperature and ambient pressure. X-ray diffraction, transmission electron microscopy, infrared spectra, and X-ray photoelectron spectra were used to characterize the final product. The as-prepared CdSe nanocrystals were well dispersed and uniform in shape and the diameter of the particles was confined within 8 nm. Ultraviolet-visible absorption spectra were used to study the confined growth process of PVA-capped CdSe nanoparticles. Photoluminescence measurement showed the near band-edge luminescence of the final product.     

Preparation of two-dimensional molybdenum disulfide for NO2 detection at room temperature

In this work, the two-dimensional MoS₂ film was prepared by sulfuring the molybdenum atomic layer on SiO₂/Si substrate. The reaction temperature, heating rate, holding time and carrier gas flow rate were investigated comprehensively. The quality of MoS₂ film was characterized by optical microscopy, atomic force microscopy, Raman and photoluminescence spectroscopy. The characterization results showed that the optimum synthesis parameters were heating rate of 25 °C/min, reaction temperature of 750 °C, holding time of 30 min and carrier gas velocity of 100 sccm. The MoS₂ gas sensor was fabricated and its gas sensing performance was tested. The test results indicated that the sensor had a good response to both reducing gas (NH₃) and oxidizing gas (NO₂) at room temperature. The sensitivity to 100 ppm of NO₂ was 31.3%, and the response/recovery times were 4 s and 5 s, respectively. In addition, the limit of detection could be as low as 1 ppm. This work helps us to develop low power and integrable room temperature NO₂ sensors.     

Promoting organic room temperature phosphorescence through in situ polymerization

Organic room temperature phosphorescence materials (RTP) have attracted much attention for their wide application in organic light-emitting diodes, anti-counterfeiting, and sensors. In this work, a series of organic luminogens containing carbonyl and aromatics were fixed in a three-dimensional polymethyl methacrylate (PMMA) network by in situ polymerization. All organic luminogens-doped in situ PMMA (s-PMMA) columns achieved longer RTP lifetimes than those of doped commercial PMMA (c-PMMA) films, especially, the RTP lifetime of NMP2O in these PMMA matrixes increased from 1.82 ms to 156.34 ms by about 86 times. It is mainly due to the restriction of molecular motions by highly entangled polymer chains and rigid environments to efficiently inhibit the non-radiative transitions. Also, the excellent shielding effect toward oxygen by the in situ polymerization process can avoid possible quenching effects on triplet excited states, beneficial to RTP emission. Thus, it affords an efficient approach to achieving persistent RTP for three-dimensional displaying applications.     

Synthesis and characterization of CePO_4 nanowires via microemulsion method at room temperature

Uniform CePO_4 nanowires with diameter of about 25 nm were synthesized by the water-in-oil microemulsion method at room temperature from cerous chloride,sodium orthophosphate,sodium chloride,cyclohexane,Triton X-100 and cetyltrimethyl ammonium bromide(CTAB).The crystal structure and morphology of the nanowires were characterized by XRD and TEM, respectively.The UV-vis absorption was detected by UV-vis spectrophotometer techniques.The results showed that as-prepared nanowires with the hexagonal phase have...     

Xenon porometry at room temperature

Xenon porometry is a method in which porous material is immersed in a medium and the properties of the material are studied by means of 129Xe nuclear magnetic resonance (NMR) of xenon gas dissolved in the medium. For instance, the chemical shift of a particular signal (referred to as signal D) arising from xenon inside small pockets formed in the pores during the freezing of the confined medium is highly sensitive to the pore size. In the present study, we show that when naphthalene is used as the medium the pore size distribution of the material can be determined by measuring a single one-dimensional spectrum near room temperature and converting the chemical shift scale of signal D to the pore radius scale by using an experimentally determined correlation. A model has been developed that explains the curious behavior of the chemical shift of signal D as a function of pore radius. The other signals of the spectra measured at different temperatures have also been identified, and the influence of xenon pressure on the spectra has been studied. For comparison, 129Xe NMR spectra of pure xenon gas adsorbed to porous materials have been measured and analyzed.     

Aqueous room temperature metal-catalyzed living radical polymerization of vinyl chloride

This paper describes the room-temperature living radical polymerization (LRP) of vinyl chloride in H2O/THF in the presence of Cu0 or CuI salts as catalysts, tren or PEI as ligands, and iodoform as initiator. The disproportionation reaction 2CuI + L --> Cu0 + CuII(L) is the crucial step, as it continuously provides the active species for both the initiation (Cu0) and the reversible termination step (CuII). Mn was found to increase linearly with conversion and is in good agreement with Mth, with the Mw/Mn being approximately 1.5.     

Silyl‐protected hydroxystyrenes: Living anionic polymerization at room temperature and selective desilylation

Both 4‐ and 3‐(tert‐butyldimethylsilyl)oxystyrene (MSOST) undergo living anionic polymerization at room temperature with sec‐butyllithium (sBuLi) in cyclohexane or methylcyclohexane upon injection of a small amount of tetrahydrofuran. Desilylation can be conveniently afforded with hydrogen chloride or tetra(alkyl)ammonium fluoride to provide poly(hydroxystyrene) (PHOST) with a narrow molecular weight distribution, which could be further transformed to other polystyrene derivatives. ¹³C NMR spectra of poly(tert‐butyldimethylsilyloxystyrene) (PMSOST) and PHOST prepared under different conditions (tetrahydrofuran vs. cyclohexane, −78 °C vs. 20 °C) have indicated that the room temperature living polymerization in the hydrocarbon‐rich solvent produces polymers with high syndiotacticity. Similarly, 4‐(tert‐butyldiphenylsilyl)oxystyrene (PhSOST), a new monomer, provides living anionic polymerization at room temperature. Desilylation of this polymer can be achieved using tetra(n‐butyl)ammonium or tetraethylammonium fluoride. Inertness of the phenylsilyl ether to HCl allows selective desilylation of the dimethylsilyl ether with HCl in the presence of the phenylsilyl ether group, providing a new route to interesting macromolecules. Application of the selective desilylation technique to the synthesis of a block copolymer of HOST and 4‐tert‐butoxycarbonyloxystyrene (BOCST) is described. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2415–2427, 2000     

Effect of temperature on the radiation-induced polymerization of ethylene in various media

The effects of temperature on the radiation-induced polymerization of ethylene in bulk and in the presence of ethyl alcohol, n-butyl alcohol, tert-butyl alcohol, cyclohexane, 2,2,4-trimethylpentane, and 2,2,5-trimethylhexane were studied. The changes of the amounts of polymerized monomer with the reaction temperature were different from each other in these reaction systems, especially in the range lower than 60–80°C. At temperatures lower than 60–80°C, as the reaction temperature increases, the amount of polymerized monomer decreased in bulk and in the presence of tert-butyl alcohol. The amount was almost constant in the presence of ethyl alcohol and 2,2,4-trimethylpentane, and it increased in the presence of n-butyl alcohol, cyclohexane, and 2,2,5-trimethylhexane. However, in the temperature range higher than 60–80°C, the amount of polymerized monomer increased with increasing temperature in every reaction system except for bulk polymerization. The molecular weight of polymer decreased with increasing temperature in every reaction system except at temperatures lower than 25°C. The molecular weight of polymer formed in bulk, in tert-butyl alcohol, and also in 2,2,4-trimethylpentane were relatively higher than that in other reaction systems. A bimodal molecular weight distribution was observed for the polymer formed in bulk and in tert-butyl alcohol at 40–60°C. These results are discussed in connection with the heterogeneity of the reaction system. The differences due to temperature in each reaction system are explained as due to the difference in affinity of the reaction system for the propagating chain and in the facility of chain transfer to the medium.     

Copper(0)‐mediated living radical polymerization of acrylonitrile at room temperature

The copper(0)‐catalyzed living radical polymerization of acrylonitrile (AN) was investigated using ethyl 2‐bromoisobutyrate as an initiator and 2,2′‐bipyridine as a ligand. The polymerization proceeded smoothly in dimethyl sulphoxide with higher than 90% conversion in 13 h at 25 °C. The polymerization kept the features of controlled radical polymerization. ¹H NMR spectra proved that the resultant polymer was end‐capped by ethyl 2‐bromoisobutyrate species. Such polymerization technique was also successfully introduced to conduct the copolymerization of styrene (St) and AN to obtain well‐controlled copolymers of St and AN at 25 °C, in which the monomer conversion of St could reach to higher than 90%. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

室温光致发光含钒硅胶的制备和研究

钒掺杂的硅胶显示出有广阔应用前景的催化和光催化特性,引起了人们在其催化机理和应用方面的研究热潮[1-6]。硅胶中氧化钒的微观分子结构和电子状态与它的催化特性密切相关,而荧光谱和磷光谱是研究分子结构,电子状态和光反应的重要工具,目前关于发光机制的研究已经取得巨大进展     

Cerium modified MCM-41 nanocomposite materials via a nonhydrothermal direct method at room temperature

Ce-containing MCM-41 materials were prepared via a direct, nonhydrothermal method at room temperature from tetra-ethoxysilane, n-hexadecyl trimethyl ammonium bromide, ammonia solution, and cerium(IV) ammonium nitrate precursors. Composite materials containing the nominated ratios of 5 and 10% (w/w) CeO2/MCM-41 were targeted. The obtained materials were investigated by TGA, DSC, FTIR, diffuse reflectance UV-vis, XRD, N2 adsorption/desorption isotherms, and SEM. Results indicated the insertion of cerium ions in tetrahedral environment in the framework of MCM-41. BET surface area amounting to 824 and 726 m2/g; total pore volume amounting to 0.427 and 0.515 cm3/g; and narrow pore size distribution maximizing at 22.5 and 23.7 A, respectively were obtained for the 5 and 10% CeO2/MCM-41 calcined composites. SEM showed a spherical type morphology for the composites which is rather similar to their blank MCM-41, and no clear ceria aggregates were observed on the external surfaces of composites spherical particles. Thus, the adopted method allows the persistence of MCM-41 texture with cerium inserts in the framework of MCM-41 and/or forms finely divided ceria nanoparticles on the wall of MCM-41 materials. Moreover, stabilization of any formed ceria nanoparticles was attributed to the short nonintersecting porous nature of MCM-41 matrix, which hinders their aggregation upon calcinations.     

Crystallization-induced phosphorescence of benzils at room temperature

Efficient room temperature phosphorescence (RTP) is rarely observed in pure organic luminogens. However, we have newly observed that benzil and its derivatives are nonluminescent in solvents and thin layer chromatography (TLC) plates, but become highly phosphorescent in crystal state at room temperature, exhibiting typical crystallization-induced phosphorescence (CIP) characteristics. The CIP phenomenon is ascribed to the restriction of intramolecular rotations in crystals owing to effective intermolecular interactions. Such intermolecular interactions greatly rigidify the molecular conformation and significantly decrease the nonradiative deactivation channels of the triplet excitons, thus giving boosted phosphorescent emission at room temperature.