用氯化三烷基甲基铵-甲基异丁基酮从大量铁、铝、钙、镁、钾、钠中分离富集痕量元素的研究

在 KI-Vc-HCl 介质中,用10%氯化三烷基甲基铵-甲基异丁基酮萃取方法可同时富集岩矿土壤中痕量的 Pb、Zn、Cu、Cd、Mo、Bi、Sn,将主量元素 Si、Fe、Al、Ca、Mg、K、Na 分离,确定富集分离的最佳条件,讨论 HNO_3、CH_3COOH-H_2O_2,H_2SO_4-H_2O_2三个反萃体系对痕量元素的反萃作用,探讨萃取及反萃机理。     

质子辐照对有机硅树脂增强甲基硅橡胶的性能损伤及机理

硅橡胶具有优良的电绝缘性以及耐高低温、耐电晕、耐化学腐蚀、耐大气老化、耐臭氧和耐辐射等性能，近年来在航天领域得到了广泛应用．在宇宙空间的带电粒子如质子、电子等的辐照作用下，硅橡胶会发生性能退化，其质损率上升，产生析气现象，从而直接影响航天器的可靠性和寿命．自80年代以来，人们就对不同辐照源及不同粒子注量对硅橡胶材料的影响进行了研究，但直到近几年才将研究热点转向辐照场中硅橡胶的性能退化及微观结构的演变规律，其辐照环境大多集中于γ射线、Si^＋和F^＋离子、He^2＋离子等．对于空间环境下带电粒子辐照对硅橡胶材料的影响，国外由于相应的研究工作保密性强，报道甚少；国内哈尔滨工业大学则对我国自行研制的白炭黑增强空间级甲基硅橡胶质子辐照作用后的性能与微观结构的变化做了较为深入的研究。     

Free-radical copolymerization of methyl methacrylate with styrene in the presence of 2-mercaptoethanol II. Influence of methyl methacrylate/styrene ratio

The free-radical copolymerization of methyl methacrylate (MMA) with styrene (St) in the presence of 2-mercaptoethanol (ME) was investigated in order to obtain ω-hydroxy oligomers with random copolymer-type chains of various compositions and molecular weights. Polymerizations at three different MMA/St molar ratios were carried out, while keeping constant the ME/monomer ratio. Monomer mixtures richer in MMA than in St were employed in order to attempt preparing lower polydispersity oligomers with monomodal molecular weight distribution (MWD). The molecular weights of the resulting oligomers increased with both conversion and MMA fraction in the feed, while polydispersities increased with conversion and decreased with MMA concentration in the initial monomer mixture. For the lower MMA fractions in the monomer feed, bimodal MWDs resulted beyond a certain conversion due to the faster relative consumption of ME than of monomer. Based on the pseudo-kinetic rate constant method, apparent chain transfer constants corresponding to the three different compositions of the monomer feed were estimated. The values obtained were in good agreement with the evolution of molecular weights and polydispersities with conversion and MMA fraction in the monomer feed. The co-oligomers prepared displayed functionalities around unity, making them suitable for the synthesis of macromonomers.     

包覆型磁性二氧化钛的制备及其光催化性能的研究

采用表面改性的方法分别制备了两种核-壳和核-壳-壳式结构的TiO2/γ-Fe2O3,TiO2/S iO2/γ-Fe2O3包覆型磁性二氧化钛.用XRD、TG-DTA、TEM、BET、和IR等手段对样品进行了结构表征,并研究了它们在紫外光照射下对甲基橙的降解性能.结果表明,在紫外光的照射下,包覆型磁性二氧化钛可有效地降解甲基橙;TiO2/S iO2/γ-Fe2O3的光催化活性优于TiO2/γ-Fe2O3,前者在循环使用三次后降解率仍不低于95%.     

Selective adsorption of the cationic dye rhodamine-6G from aqueous solution by phosphotungstic acid@MOF-199 composites

In this paper, H₃[ P(W₃O₁₀)₄]@MOF-199 composites ([email protected]) were successfully synthesized by a simple one-step reaction under solvothermal conditions and characterized by XRD, SEM, FT-IR and N₂ adsorption–desorption isotherms. Additionally, rhodamine-6G (Rh6G, a cationic dye) and methyl orange (MO, a anionic dye) as model dyes were employed to assess its adsorption performance. The adsorption capacity of MOF-199 towards Rh6G and MO were enhanced and weakened respectively after the introduction of PTA (from 8.6 mg/g to 41 mg/g; 11.4 mg/g to 2.6 mg/g) proving that the selective adsorption capacity for the cationic dye of porous MOF-199 could be improved through the modification of PTA. Moreover, in diverse initial concentrations of single Rh6G and MO aqueous solutions (10 mg/L, 25 mg/L, 50 mg/L and 100 mg/L), [email protected] exhibited much higher adsorbing capacity towards Rh6G (about 25, 30, 11 and 16 times higher than that of MO). In mixed dyes adsorption studies, the adsorption capacity of [email protected] towards Rh6G (2.871 mg) are nearly five times larger than that of MO (0.437 mg) even in a solution with a higher concentration of MO than Rh6G (5 mg/L of Rh6G and 10 mg/L of MO). The kinetic study indicated that the adsorption of the Rh6G and MO onto [email protected] followed the pseudo second-order model well. The isotherm obtained from experimental data fitted the Freundlich model (the linearly dependent coefficient are 0.99839 and 0.94845 for Rh6G and MO respectively) indicating multilayer adsorption mechanism. In summary, all these results implied that the as-prepared [email protected] is of great potential to be used as a cationic pollutants adsorbent with high efficiency and selectivity.     

Stereoselective dioxirane hydroxylations and the synthesis of tripod boronic acid esters

Methyl(trifluoromethyl)dioxirane (TFDO, 1b), a powerful yet selective oxidant, was employed to achieve in high yield the direct stereoselective hydroxylation at tert-CH of cis,cis-1,3,5-trimethylcyclohexane (4), yielding triol 7 bearing all-axial disposition of the three OH groups. Similarly, TFDO oxidation of 1,3- and of 1,4-dimethylcyclohexane gave the corresponding Z-diols 5 and 6, respectively. Triol 7 was a convenient starting material to synthesize a novel borate—that is, 1-bora-2,8,9-trioxa-3,5,7-trimethyladamantane (8)—having a peculiar cage-shaped ‘tripod’ structure. From triol 7, novel tripod arylboronic Brönsted-assisted Lewis acids (BLA) could be obtained, as exemplified by 10a and 10b.     

δ-MnO2对TiO2光催化降解甲基橙的抑制作用

采用动力学方法研究了在水悬浮液中δ-MnO2颗粒物对P-25 TiO2光催化降解甲基橙活性的影响, 并利用紫外-可见漫反射光谱(DRS)和光致发光光谱(PL)对受δ-MnO2污染前后的TiO2样品进行了表征. 动力学研究结果表明, 在3种不同初始pH值条件下, δ-MnO2对TiO2光催化剂都具有明显的致毒效应, 共存δ-MnO2的浓度越大, 致毒效应越明显. 表征结果表明, 由于δ-MnO2 与TiO2之间的界面接触, 使得TiO2吸收带边蓝移, 紫外光区的吸收强度降低, 光致发光信号(PL)明显减弱. 因此, δ-MnO2导致TiO2的禁带宽度增大, 光利用率降低, 并且是光生电子与空穴的复合中心.     

Enantiomeric purity of (+/-) -methyl jasmonate in fresh leaf samples and commercial fragrances

The enantiomeric purity of (+/-) -methyl jasmonate in fresh leaf material of Jasminum from different species and Rosmarinus officinalis was examined by solid-phase microextraction-GC-MS (SPME-GC-MS). For comparison with these natural products, commercial jasmine and rosemary fragrances were also studied. The extraction conditions were selected as a result of testing different values of temperature (40, 50, and 60 degrees C) and time (2, 15, 30, and 40 min). The results obtained in this work revealed a range of enantiomeric excesses for (+/-) -methyl jasmonate varying from 13 to 95% depending on the Jasminum specie considered. In contrast, (-) -methyl jasmonate always occurred as a pure enantiomer in all R. officinalis samples studied. This implies those Jasminum species in which the enantiomeric purity of (-) -methyl jasmonate is high enough and any R. officinalis sample might be used as natural sources of pure (-) -methyl jasmonate. Concerning the commercial fragrances, those of jasmine showed enantiomeric composition of (-) -methyl jasmonate ranging from 1 to 15% whereas those of rosemary exhibited practically the pure (-) -methyl jasmonate. This fact suggests the addition and nonaddition of the racemic mixture of methyl jasmonate to the commercial jasmine and rosemary samples, respectively.     

Separation and Assay of Cholecalciferol in Vitamin A + D Ointment

Summary. In this paper two methods are presented. One involves the separation of cholecalciferol from a topical ointment. The other involves the assay of cholecalciferol in this ointment. The study was performed with normal-phase high performance liquid chromatography using a NP-L3 column and UV detection. Applying a mobile phase mixture containing n-hexane:2-propanol (99:1) a total separation was achieved within 15 min. For isolation and assay of cholecalciferol from an ointment (vitamin A + D), dissolution in n-hexane gave the highest recovery (>95%). The isolation and assay process can be performed within 3.5 h.