Pulse radiolysis studies of functionally substituted imidazolium-based ionic liquids

The reactions of imidazolium-based ionic liquids having different substituent groups on the ring with hydrated electrons (eaq-),hydroxyl radicals (·OH),and sulfate anion radicals (SO4·-) were investigated using nanosecond pulse radiolysis techniques.The spectra of these ionic liquids on reaction with eaq-all exhibited a similar peak at about 320 nm,and a typical peak for eaq-in aqueous ionic liquid solutions.The reaction rate constants for 1,3-disubstituted imidazolium-based ionic liquid hexafluorophosphates (BMIPF 6) with eaq-were deduced to be 10 10 L mol-1s-1,however the values were lower for trisubstituted ionic liquids.For example,the rate constant for 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BMMIBF 4) was 5.5×10 9 L mol-1s-1.Imidazolium-based ionic liquids reacted with hydroxyl radicals via adducts to produce a mixture of isomeric OH adducts,and the pk a value of the OH adducts was deduced to be 8.4±0.4 for 1-butyl-3-methylimdazolium tetrafluoroborate (BMIBF 4).Moreover,imidazolium cations were also oxidized by SO4·-to produce bivalent cation radicals,which exhibit a peak at 320 nm,and these rate constants are of the same order of magnitude,i.e.,10 9 L mol-1s-1,except that for 1-(2-hydroxyethyl)-3-methylimdazolium tetrafluoroborate with SO4·-(k=2.8×10 8 L mol-1 s-1).Theoretical calculations were carried out to estimate the structures of the products of reduction by eaq- and the results were related to the experimental data.     

Studies on kinetics of reactions between phycobiliproteins and hydroxyl radicals by a pulse radiolytic technique

Scavenging of hydroxyl radical (· OH) by phycobiliproteins (C-phycocyanin, Allophycocyanin and R-phycoerythrin) was studied by competitive kinetics methods. Hydroxyl radicals were generated from pulse radiolysis of aqueous systems saturated with nitrous oxide (N₂O). The experimental results indicated that the three types of phycobiliproteins are all strong scavengers of · OH, the rate constants are around (2.8-5.6)×10⁹ L · mol^-1 · s^-1.     

Electrochemical properties of room temperature ionic liquids incorporating BF4^- and TFSI^- anions as green electrolytes

Two series of room temperature ionic liquids, 1-alkyl-3-methylimidazolium tetrafluoroborate and 1-alkyl- 3-methylimidazolium bis（trifluoromethylsulfonyl）imide （n = 2--4） as electrolytes were prepared and fundamental electrochemical properties of the neat ionic liquids and those mixed with an organic solvent （EC-DMC-DEC, 1 ： 1 ： 1, mass ratio） were investigated. It was found that the Arrhenius equation is approximately fit for the relationship between conductivity and temperature for neat ionic liquids within lower temperature range （298--323 K）. The VTF interpretation describes the conductivity temperature dependence for the ionic liquids containing tetrafluoroborate anion more accurately than those containing bis（trifluoromethylsulfonyl）imide anion within wider temperature range. The potential windows are approximately 4.0 V for all these ionic liquids. Conductivities of the mixed electrolytes show a maximum value as the solution concentrations increase.     

Electrochemical behavior of a series of azobenzene self-assembled monolayers on gold

Conclusion This work shows that the structures of C_n AzoC₂ (n = 1, 2, 3, 4) SAMs are significantly different and influence the observed electrochemical behavior of these novel azobenzene systems. The sluggish electron-transfer kinetics of azobenzene SAMs were explained by the alkyl spacer between azobenzene and electrode, the spatial inhibition for structural change in the redox process of azobenzene, as well as the ion-transportation barriers. For decrease of the apparent electrontransfer rate constants with increasing the length of end-groups, and the electrochemical inaccessibility of C₄AzoC₂ SAMs, the spatial inhibition for structure conformational change and ion-transportation was considered as the predominant factor.     

HSO3-functionalized Brønsted acidic ionic liquids promote esterification of aromatic acid

Esterification of aromatic acid can be promoted via HSO3-functionalized Br nsted acidic ionic liquids (ILs). Under the optimum conditions, using 1-(3-sulfonic acid) propyl-3-methylimidazolium hydrogen sulfate ([MimC3SO3H][HSO4]) and 1-(4-sulfonic acid) butyl-3-methylimidazolium hydrogen sulfate ([MimC 4 SO 3 H][HSO4 ]) as dual solvent-catalysts, the conversion of esterification of aromatic acid was determined to be more than 90%, indicating that HSO3-functionalized ILs show much better catalytic ability than those of non-functionalized ionic liquids. The separation of desired product was easily performed by extraction with diethyl ether and these HSO3-functionalized ILs could be reused 7 times after vacuum drying. Our data represent an environmentally friendly method for the preparation of aromatic esters.     

含氮手性离子液体的合成及应用研究进展

综述咪唑鎓盐、季铵盐和吡啶鎓盐等含氮手性离子液体的合成及其在不对称催化反应中的应用研究进展.研究成果表明,手性离子液体的制备既可以直接使用手性源(如氨基酸、氨基醇、或生物碱等),也可以利用不对称合成.含氮手性离子液体手性中心的构建、固载化方法以及构效关系将是今后研究工作的重点.     

Excited-state solvation dynamics of meso-tetrakis(4-sulfonatophenyl) porphyrin in solid imidazolium-sulfonate-based ionic liquids

The steady-state absorption and fluorescence emission positions of diprotonated meso-tetrakis(4-sulfonatophenyl) porphyrin (H₄TPPS^2?) are dependent on the polarity of the selected two solid ionic liquids (ILs) and are red-shifted with the increase of cation size. The solvation dynamics process of H₄TPPS^2? in these ILs occurs on two well-separated time scales. The short components with 121.2–128.6 ps arise from the local motion of the ion-pairs in close proximity to the porphine core, and the long components with 1056.6–1261.8 ps are due to the collective translation motions of the ion-pairs. The dynamic Stokes shifts and the relaxation times increase with the increasing cation size of the ILs.     

八马来酰亚胺基苯基POSS/BT树脂固化行为

合成了八马来酰亚胺基苯基POSS(OMPS),并对产物进行了测试表征。将OMPS与4,4′-双马来酰亚胺基二苯甲烷(BMI)/双酚A型氰酸酯(BCE)(BT树脂)进行共混,差示量热扫描仪(DSC)和傅立叶红外光谱仪(FT-IR)测试结果表明,在220℃左右,OMPS/BT树脂固化反应能充分进行;在140～220℃范围内分段固化,动态粘弹分析仪(DMA)测试结果显示固化后树脂的T_g不高,250℃下固化1h后,DMA测试结果显示T_g有明显提高。OMPS/BT树脂复合材料的介电测试结果显示,加入适量的OMPS能明显降低BT树脂的介电常数。     

Properties improvement of SPEEK based proton exchange membranes by doping of ionic liquids and Y2O3

The membranes of sulfonated poly(etheretherketone) with 65％ sulfonation degree were prepared by doping of Y2O3 and ionic liquids,such as 1-ethyl-3-methylimidazole tetrafluoroborate (EB) or 1-butyl-3-me...     

Phase equilibria, diffusion growth and diffusivities in Ni-Al-Pt system using Pt/β -NiAl diffusion couples

The phase equilibria,diffusion growth and diffusivities in the Ni-Al-Pt system at 1 150,1 200 and 1 250℃were studied using Pt/β-NiAl diffusion couples.Based on the measured concentration profiles coupled with the local equilibrium hypothesis,the tie-lines between neighboring phases were determined.Two intermediate phases,Pt_3Al andα-NiPt(Al),are found to develop between the Pt andβ-NiAl couples.The thicknesses of Pt_3Al andα-NiPt(Al) layers varies linearly with the square of annealing time, indicating th...     

富勒烯(C60/C70)与 N,N,N′,N′-四-(对甲基苯)-4,4′-二胺-1,1′-二苯碲醚电荷转移复合物的特征

用激光光解方法研究了富勒烯(C60 / C70)与N,N,N′,N′-四-(对甲基苯)-4,4′-二胺-1,1′-二苯碲醚电荷转移复合物的特征. 通过观察在近红外区瞬间吸收带,富勒烯(C60 / C70)激发三线态,富勒烯(C60 / C70)阴离子自由基和N,N,N′,N′-四-(对甲基苯)-4,4′-二胺-1,1′-二苯碲醚阳离子自由基的出现,测定了在苯腈溶液中从N,N,N′,N′-四-(对甲基苯)-4,4′-二胺-1,1′-二苯碲醚到富勒烯(C60 / C70)激发三线态的量子转化产率和电子转移常数.     

醇胺盐酸类离子液体的性质研究

用酸碱中和法合成了二乙醇胺盐酸[DEA]Cl、三乙醇胺盐酸[TEA]Cl两种离子液体,测定了两种离子液体在不同浓度水和乙醇溶液中的电导率,二乙醇胺盐酸离子液体乙醇溶液的电导率呈较好的正态分布.用微量热法测定了温度为310 K下不同浓度二乙醇胺盐酸、三乙醇胺盐酸离子液体存在下,大肠杆菌生长代谢的热功率-时间曲线,用Logistic方程求出细菌生长的速率常数,结果表明二乙醇胺盐酸、三乙醇胺盐酸离子液体对大肠杆菌的生长具有抑制作用,且抑菌作用的大小与离子液体阳离子结构有关.该研究对离子液体的环境风险评价和工业化应用进程有一定的指导意义.     

硫酸氢根吡啶催化制备乙酸正丁酯的酯化反应精馏过程模拟

采用离子液体硫酸氢根吡啶（[Hpy][HSO4]）作为催化剂,对乙酸和正丁醇在反应精馏塔中进行酯化反应生成乙酸正丁酯的过程进行模拟研究。在缺乏实验数据的情况下,使用真实溶剂似导体屏蔽模型(COSMO-RS)方法预测了离子液体与其他物质的汽液相平衡,得到了离子液体与反应体系的二元交互参数。基于共沸精馏概念设计了带有分相器的反应精馏塔,实现了离子液体的循环利用。分析了反应精馏塔总塔板数、进料模式、进料塔板位置、再沸器热值和塔板持液量对于产品质量和乙酸转化率的影响,结果表明,当反应精馏塔塔板总数为28,反应物从第4块塔板同时进料,离子液体从第2块塔板进料,且塔板持液量为0.05m3时,乙酸正丁酯纯度和乙酸转化率均可达99.9%。     

Synthesis of 2,4-diisopropyl-5,5-dimethyl-1,3-dioxane catalyzed by Br?nsted acidic ionic liquids

The acetalization reactions of isobutyraldehyde with 2,2,4-trimethyl-1,3-pentanediol （TMPD） for the synthesis of 2,4-diisopropyl-5,5-dimethyl-1,3-dioxsne were carried out under mild reaction conditions using four water-stable Brenstad-acidic task-specific ionic liquids （[HMIM]BF4, -SO3H funcUonalized acidic ionic liquid, -COOH functionalized acidic ionic liquid, [NMP][HSO4]） as environmentally benign catalysts for the first time. The process is highly effective and very selective. The -COOH functionalized Brensted acidic ionic liquid with the two acid sites （IL-3） exhibited the most excellent catalytic performance under mild reactlon conditions. The -COOH functionalized Brensted acidic ionic liquid could be conveniently separated from the product and easily recycled in subsequent runs.     

Electrochemical behavior of 304 stainless steel with electrodeposited niobium as PEMFC bipolar plates

In order to enhance the corrosion resistance of 304 stainless steel, niobium was electrodeposited on its surface in air- and water-stable ionic liquids. The electrochemical behaviors of bare and niobium-coated 304 stainless steel were evaluated by electrochemical tests in a simulated proton exchange membrane fuel cell (PEMFC) environment. The results showed that niobium could be electrodeposited on the surface of 304 stainless steel from ionic liquids, and a smooth and strong chemical inert compound film was obtained on the surface of 304 stainless steel, which was mainly composed of NbO and Nb₂O₅. The thin composite film acted as a barrier and remarkably improved the corrosion resistance of 304 stainless steel in the PEMFC environment.     

Influence of FeCl3 on radiation stability of ionic liquid BmimCl

This study investigates the effect FeCl3 on the radiation stability of the ionic liquid,1-butyl-3-methylimidazolium chloride(BmimCl) over a wide dose range of 0 to 1000 kGy under γ-ray radiation.The ionic liquid species,BmimFeCl4,was formed by adding FeCl3 into BmimCl.The results showed that the presence of FeCl4-significantly improved the radiation resistance of BmimCl,wherein the effect was more pronounced at higher FeCl4-content.Meanwhile,under irradiation,Fe(II) was generated from Fe(III),which was reduced by solvated electron.In addition,the concentration of Fe(II) increased with low level of absorbed dose,but leveled off at higher doses.Moreover,the radiation yield of the solvated electrons of BmimCl was further estimated at approximately 0.358±0.01 μmol/J in BmimCl-7 mol% FeCl3 system.     

The impact of HS radicals on the measured rate constant of H<Subscript>2</Subscript>S with OH radicals

The rate constant for the reaction of OH radicals and hydrogen sulfide (H₂S) was studied in different bath gases (including N₂, air, O₂ and He) by using relative technique at 298 K. The small difference of the measured rate constants between N₂ and those with the presence of O₂ suggested possible influence of HS self reaction. Further experiments with NO_x presence for scavenging HS demonstrated this assumption. The rate constant of (5.48±0.12) ×10^–12 cm³ molecule^–1 s^–1 obtained with 4.09 ×10^–4 mol m₃ NO presence may be accurate for estimating the atmospheric lifetime of H2S. The results provided circumstantial evidence that the rapid reaction of HS with N₂O is suspected.     

离子液体与蛋白质相互作用的荧光光谱研究

在25,35和45℃测定了离子液体([C4mim]Br,[C6mim]Br,[C8mim]Br)对蛋白质(BSA、溶菌酶)的荧光猝灭光谱,分析了离子液体与蛋白质相互作用的荧光猝灭规律,计算了荧光猝灭过程的猝灭常数和热力学参数.结果表明:离子液体可以有规律地使蛋白质的荧光猝灭,猝灭是由离子液体与蛋白质的碰撞引起的,是一个动态猝灭过程.该过程的猝灭常数很小,说明离子液体与蛋白质之间的相互作用较弱.热力学研究表明,猝灭过程是一个熵驱动过程,疏水相互作用是其主要特征.     

Phase-field simulation on microstructure evolution of D0_(19) phase in γ/γ′structure of Co–Al–W superalloys

The morphological evolution and precipitation kinetics of γ′ and D0_(19)(Co_3 W) phase in Co–Al–W alloys at 900 °C have been studied by applying Phase-field method and experiment in order to understand the transformation process of γ′ phase and D0_(19) phase. The growth processes of D0_(19) phase and precipitation of γ′ phase under elastic fields were simulated through coupling with thermodynamics and dynamics databases. The simulation results indicate that the misfit δ≥ 0.53% has a greater impact on γ′ particle morphology in γ/γ′ structure.Co–Al–W alloy with low Al and high W is one of the factors to promote the precipitation of D0_(19) phase. Three stages during aging, namely the γ′ phase incubation stage, the γ′ phase fast nucleation and growth stage, and the transformation from γ′ phase to D0_(19) phase stage can be observed with the non-constant coarsening rate that varying with the decrease of γ′ phase. The particle size distribution(PSD) during the precipitation of D0_(19) phase is more in line with MLSW theory than LSW theory. This simulation results are in good agreement with the experiment results to help analyze microstructure evolution of Co–Al–W alloy.