含三乙烯二胺强弱碱功能基阴离子交换树脂的制备及其吸附性能

含三乙烯二胺强弱碱功能基阴离子交换树脂的制备及其吸附性能;三乙烯二胺; 强弱碱基阴离子交换树脂; 滴定曲线; 苯甲酸; 吸附性能     

Voltammetric oxidation and determination of cinnarizine at glassy carbon electrode modified with multi-walled carbon nanotubes

We discovered a novel method to prepare a protein-based hydrogel, that is, a “Three-Dimensional Nanostructured Protein Hydrogel (3D NPH)”, which is composed of protein–polymer hybrid nanoparticles. In this study, we propose a novel protein microarray whose 3D NPH spots were prepared by dispensing a small volume of the solution of protein–polymer mixture on a substrate. The dispensed solution had a short time for cross-linking before its drying-up and the resulting 3D NPH had loosely cross-linked, thin spongy structure. Therefore, the reaction ratio between ligands and analytes was drastically improved in this system compared with the large volume system for Surface Plasmon Resonance (SPR) protein microarray.     

树脂基球状活性炭的制备及对二氧化碳吸附性能的研究

以四种离子交换树脂（两种强碱性树脂D201和D280、两种弱碱性树脂D301G和D301R）为原料,经过磺化、炭化、活化处理制备了树脂基球状活性炭。采用TG、SEM、N₂吸附等对球状活性炭的收率、表面形貌、比表面积进行了表征,研究了所制球状活性炭对CO₂的吸附性能。结果表明,磺化处理有助提高树脂球的炭化收率;得到的四种球状活性炭对CO₂吸附性能良好,强碱性树脂球原料比弱碱性树脂球更具有优势,其中,由强碱性树脂球D201制得的树脂球状活性炭在30 ℃下对CO₂的吸附量可达2.57 mmol/g;十次循环吸附之后,树脂球仍能保持很好的CO₂吸附性能。     

新型树脂基水合锰氧化物对水体中磺胺嘧啶的降解去除

以大孔强碱阴离子交换树脂D201为载体, 采用离子交换和氧化还原方法制备了一种新型树脂基水合锰氧化物材料HMO-201. 考察了不同pH、 离子强度和溶解性有机质(DOM)含量条件下, 该材料对水体中磺胺嘧啶(SD)的去除能力. HPLC-MS分析表明, SD的高效去除是通过HMO-201的降解而非吸附方式实现的. 实验结果表明, pH为1.0时HMO-201在120 min内对0.01 mmol/L SD的去除效率为99.9%, 反应符合表观一级动力学模型; 体系的离子强度和DOM含量变化对SD的去除效率均无显著影响. 模拟环境离子强度和DOM浓度, 连续10批次实验中SD废水的去除效率在240 min内均大于99%; HMO-201的柱动态降解装置连续处理SD溶液2000床体积, 依然未检出SD. 表明HMO-201材料具有较稳定的重复利用性, 对环境中普遍存在的磺胺类抗生素药物具有着高效的降解去除效果, 具有广泛的应用前景.     

硫酸氢季铵盐催化环氧化物和氮杂环丙烷的醇解反应

利用四丁基硫酸氢铵(TBAHS)和大孔树脂(D201型)支载的硫酸氢季铵盐(D201-HSO4), 分别催化环氧化合物或氮杂环丙烷与甲醇的开环反应, 以高产率得到β-甲氧基醇或β-甲氧基胺. 两种催化剂对该反应都很有效, 但大孔树脂支载的硫酸氢季铵盐(D201-HSO4)易于制备, 并可以重复使用.     

Preparation of polymer-supported hydrated ferric oxide based on Donnan membrane effect and its application for arsenic removal

In the present study a novel technique was proposed to prepare a polymer-supported hydrated ferric oxide (D201-HFO) based on Donnan membrane effect by using a strongly basic anion exchanger D201 as the host material and FeCl3-HCl-NaCl solution as the reaction environment. D201-HFO was found to exhibit higher capacity for arsenic removal than a commercial sorbent Purolite ArsenX. Furthermore, it presents favorable adsorption selectivity for arsenic removal from aqueous solution, as well as satis- factory kinetics. Fixed-bed column experiments showed that arsenic sorption on D201-HFO could re- sult in concentration of this toxic metalloid element below 10 μg/L, which was the new maximum con- centration limit set recently by the European Commission and imposed by the US EPA and China. Also, the spent D201-HFO is amenable to efficient regeneration by NaOH-NaCl solution.     

阴离子交换树脂回收水相中有机磷酸萃取剂

研究了阴离子交换树脂对水相中有机磷酸萃取剂的吸附。 通过比较不同的离子交换树脂对水相中2-乙基己基膦酸-单-2-乙基己基酯(P507)的去除率,发现大孔强碱性阴离子交换树脂(D201-OH)从水溶液中去除P507的能力最强,去除率可达99.24%。 而且当溶液在pH=1.0时,D201-OH对P507的吸附主要是分子吸附,其吸附等温线更适用于Langmuir模型;当溶液在pH=5.0时,阴离子交换反应占主导地位,其吸附等温线更适用于Freundlich模型。 研究还表明,D201-OH对P507的吸附在20 min内即达到吸附平衡时99.8%的吸附量。 通过动力学研究表明,拟一级动力学模型(R²>0.99)更适用于描述实验数据,并且吸附速率主要受膜扩散控制。 此外,吸附-解吸附循环8次后,D201-OH的吸附能力仍然保持在93%以上。 综上所述,D201-OH是有机磷酸类萃取剂的良好吸附剂,其吸附性能高效,循环过程稳定,因此可用于实际生产过程中回收有机磷酸萃取剂。     

Preparation and catalytic activity of titanium silicalite-1 zeolite membrane with TPABr as template

The preparation of the supported titanium silicalite-1 (TS-1) zeolite membrane with inexpensive tetrapropylammonium bromide (TPABr)/weak base synthesis system was studied by three methods, and the catalytic activity of the obtained TS-1 zeolite membrane was evaluated with the oxidation of 2-propanol (IPA) under pervaporation condition. It was found that TS-1 zeolite membrane could be successfully prepared with “seeding” or “seeding in situ” method, but could not be achieved with “in situ” method. Adding a little amount of promoter ions of PO₄³⁻ into the synthesis gel was of benefit to the catalytic activity of the prepared TS-1 zeolite membrane, but had no obvious effect on the membrane layer formation on the mullite porous support. For “seeding” method, the membrane prepared with the synthesis gel having molar composition of SiO₂:0.1TPABr:0.9Et₂NH:0.03TiO₂:80H₂O:0.06H₃PO₄ at 150 °C for 48 h showed the highest oxidation conversion of IPA of 72% accompanied by a flux of 0.35 kg/m² h. Further more, much higher IPA oxidation conversion of 76% accompanied by a flux of 0.65 kg/m² h was obtained for the TS-1 zeolite membrane prepared with the same synthesis gel by “seeding in situ” method at 150 °C for 72 h.     

耐高温阴离子交换树脂的合成及在环氧乙烷催化水合反应中的应用

我们合成了一种新型结构的季铵型阴离子交换树脂催化剂(NC-1),并将其转型为碳酸氢根型应用于环氧乙烷(EO)催化水合反应.并用NC-1、D201树脂催化EO水合反应进行了考察.NC-1型离子交换树脂催化剂,因具有较好的热稳定性,其使用寿命比D201树脂提高到数十倍.同时,还设计了一种“二步法”新型水合工艺,与传统水合工艺相比,这种工艺有效地抑制了树脂催化剂的膨胀.在使用105h后,催化剂的膨胀率由原来的76%下降到5%左右.     

Amine groups functionalized gel-type resin supported Pd catalysts: Physicochemical and catalytic properties in hydrogenation of alkynes

Palladium catalysts (0.125–0.5 wt.% Pd) supported by amine groups—functionalized gel-type resin (FCN) were studied in the hydrogenation of alkynes reagents, 2-butyne-1,4-diol and phenylacetylene. The catalysts were prepared by two routes. The first, “OAc” is based on the immobilization of Pd-precursor in the pre-swollen resin from THF solution of Pd(OAc)₂, followed by chemical reduction of the Pd-centers. This method produces Pd particles of size in nano-scale. The second procedure, “aq” implies the deposition of Pd-species on dry resin beads using aqueous solution of PdCl₂. Reduction of these Pd-species gives relatively large Pd particles, dominating are 30–50 nm in size. The SEM studies performed over the cross-section of catalysts grains showed location of Pd in outer shell of polymer beads in both “OAc” and “aq” catalysts; however, thinner layer of Pd appears in “aq” series catalysts. In the presence of all catalysts, prepared by “OAc” and “aq” methods the selectivity towards alkenes is high, above 90%. The catalysts of “aq’ series are much more active and more selective than “OAc” analogues giving selectivity to alkene ca. 94% at almost complete conversion of alkynes. Moreover, catalytic performance of “aq’ series catalyst is unchanged under recycling use. The catalyst was recovered and reused 4 times, maintaining its catalytic efficiency.     

Spectrophotometric and thermoanalytical study of cypermethrin/cyclodextrin complexes

Cypermethrin/β-CD complexes were prepared at 1:2 cypermethrin/β-CD molar ratio by different complexation methods: conventional coprecipitation, suspension and kneading methods as well as “melting in solution” technique, which was developed in our laboratory. The complexes were investigated by UV-spectrophotometry and thermal analysis. It was found that complexes made by coprecipitation, suspension and kneading methods contained cypermethrin not only in complexed but also in uncomplexed form. The guest molecule in the complex prepared by “melting in solution” technique showed to be completely complexed, so it was the most effective complexation method studied.Investigating the solubility of cypermethrin with different cyclodextrins (CDs), it was established that the increase of solubility of cypermethrin was the highest in case of methylated cyclodextrins. The equilibrium constants were calculated from solubility isotherms. On the basis of these results, the heptakis(2,6-di-O-methyl)-β-cyclodextrin (DIMEB) complex was the more stable. By UV-irradiation measurements it was found that the photodegradation of cypermethrin was inhibited by methylated β-CDs.     

An experimental study on the “sequential order” rules in generalized two-dimensional correlation spectroscopy

Following our theoretical analysis on the “sequential order” rules in generalized two-dimensional (2D) correlation spectroscopy (H. Huang, Anal. Chem. 79 (2007) 8281–8292), an experimental study was conducted to test the “sequential order” rules using the FT-NIR data of poly(3-hydroxybutyrate) (PHB)/poly(l-lactic acid) (PLA) blends under uniaxial elongation and parallel polarization. The local sequential order concept proposed for the generalized two-dimensional (2D) correlation spectroscopy is now more clearly stated; “the intensity change at ν1 occurs predominantly before ν2” means that the starting time of the intensity change at ν1 is prior to that at ν2. It is this local sequential order which reflects the real and intuitive sequential order between two events in generalized situations. It has been found that the integrated/overall sequential order results obtained from the 2D correlation analysis may be contradictory to the intuitive local sequential order. In addition, different integrated/overall sequential orders could be obtained by selection of different sampling intervals from a certain set of experimental data, or choosing different number of the contours for the same sampling interval. These new experimental findings are a perfect reinforcement to our previous theoretical study and have further demonstrated the uncertainty of applying the “sequential order” rules in generalized 2D correlation spectroscopy.     

离子交换分离钨钼及微波诱导树脂再生的研究

本文研究了不同型号的树脂和硫化条件对离子交换分离钨钼的影响。探讨了用D201树脂交换除钼及其树脂再生的机理。实验结果表明：碱性钨酸铵（AT）溶液经硫化转型后,可用阴离子交换柱除去其微量钼;该除钼树脂经微波场辐照诱导-减性食盐水协同再生处理,可基本恢复其除相交换容量。     

钯-高分子载体催化剂对糠醛加氢液相反应的研究

以弱碱性苯乙烯系阴离子交换树脂[D392,-NH₂,D382,-NHCH₃,D301R,-NH(CH₃)₂],强碱性苯乙烯系阴离子交换树脂[201×7DVB,-NH⁺(CH₃)₃]和弱碱性环氧系阴离子交换树脂(701,-NH₂)为载体制备了3种钯-高分子载体催化剂.考察了反应条件、高分子载体的种类、钯含量和催化剂用量对糠醛催化加氢生成四氢糠醇反应及催化性能的影响.在体积分数为50%的乙醇-水溶液和水中对糠醛常压液相加氢反应,钯-高分子载体(阴离子交换树脂D392,-NH₂,D382,-NHCH₃)催化剂均可使糠醛的加氢反应转化率达100%,生成四氢糠醇的选择性达98%以上,而用金属钯为催化剂的转化率达70%以上,选择性达97%以上.同时用XPS分析了高分子载体催化剂的结构与催化加氢反应性能的关系.     

Impact of the structure of phospholipid dispersions on the stability of fluorocarbon/phospholipid emulsions for biomedical uses

The preparation of injectable fluorocarbon emulsions includes the dispersion of the phospholipids in the aqueous phase, then the admixing of the fluorocarbon to produce a crude premix; emulsification is then achieved using a high pressure mechanical procedure, followed by final heat-sterilization. In this work we report that, depending on the procedure used and energy applied, the dispersions of phospholipids consist of poorly organized unclosed “pre-liposomes”, multilamellar vesicles (MLV), or small unilamellar vesicles (SUV). This has a significant impact on the stability of the final fluorocarbon emulsions (90% (w/v) concentration), those prepared from “pre-liposomes” being more stable than those prepared from MLV or SUV. The first emulsion is shown to contain less fluorocarbon-free phospholipid vesicles than the other two. These free vesicles have previously been reported to have a detrimental effect on the stability of concentrated fluorocarbon emulsions.     

同时吸附油和六价铬离子复合材料的制备及性能

以亲油疏水型三元乙丙橡胶(EPDM)作为基体, 焙烧Fe2O3和阴离子交换树脂201Х7作为填料, 利用熔融共混的方法, 制备一种可以同时吸附油和六价铬离子的用于污水处理的复合材料, 这种材料能够悬浮于油水界面处. 当焙烧Fe2O3和阴离子交换树脂的用量比例不同时, 材料吸附性能变化很大. 实验结果表明, 在保证复合材料密度介于油水密度之间的前提下, 随着焙烧Fe2O3含量的增加, 材料的吸油性能不断增大; 随着阴离子交换树脂含量的增加, 材料对六价铬的吸附性能不断增加. 在油水共存体系中, 复合材料对两种污染物的吸附率同时达到最佳时, 两种填料的比例可以确定, 因油品的不同而不同. 在油水共存体系中, 复合材料对油和六价铬的总吸附能力要远大于复合材料分别在单一吸附介质中的吸附能力.     

Synthesis and photochromism of polymer-bound phenoxyquinone derivatives

Acrylate- and styrene-derived polymers having pendant phenoxyquinones for photochromism were prepared by 2,2′-azoisobutyronitrile (AIBN)-initiated radical polymerization. Synthesis of the monomers were straightforward and the polymers were obtained in high yields in spite of the quinone moieties presented in the monomers, which usually can function as radical scavengers and/or catalysts poison. Photo-induced rearrangement from the “trans”-quinone forms to the “ana”-quinone forms readily occurred when the polymer films were irradiated with UV light.     

Preparation of alpha-elastin nanoparticles by gamma irradiation

Nanoparticles were prepared by utilizing the thermosensitive aggregation of alpha-elastin and gamma ray crosslinking. Three different heating process, “Slow heating”, “Fast heating”, and “Heat shock”, were applied for the aggregation of the alpha-elastin and examined to yield nanoparticles by gamma rays crosslinking. As a result, only “Slow heating” process yielded nanoparticles with diameters of about ca. 300 nm above cloud point (CP) and about ca. 100 nm below CP, and a narrow size distribution above 1.0 mg/ml concentration (exclude 1.0 mg/ml).     

ITINERANT MAGNETISM IN ULTRATHIN METALLIC FILMS

This paper addresses the question: “How do we define a two-dimensional itinerant magnet?” Results are presented indicating a cross-over from three-dimensional (3D) to two-dimensional (2D) behavior at a finite-size film thickness. It is argued that quantization of the electronic states in ultrathin metallic films dictate this behavior. Data from a broad range of epitaxial ferromagnetic films grown on different metallic substrates suggest a cross-over into just two classes of 2D behavior, viz 2D Ising model in the presence of uniaxial surface anisotropy and finite-size lattice 2D XY model behavior in films in which the preferred direction of magnetization lies in-plane. In this ultrathin film 2D limit, the Curie temperature falls rapidly to zero as the thickness approaches a single monolayer due to the sudden onset of disordered microdomains.     

Comparison of chemometric methods for brand classification of cigarettes by near-infrared spectroscopy

The combinations of NIR spectroscopy and three classification algorithms, i.e., multi-class support vector machine (BSVM), k-nearest neighbor (KNN) and soft independent modeling of class analogies (SIMCA), for discriminating different brands of cigarettes, were explored. The influence of the training set size on the relative performance of each algorithm was also investigated. A NIR spectral dataset involving the classification of cigarettes of three brands was used for illustration. Three performance criteria based on “correctly classified rate (CCR)”, i.e., “Average CCR”, “95 percentile of CCR” and “S.D. of CCR”, were defined to compare different algorithms. It was revealed that BSVM is significantly better than KNN or SIMCA in the statistical sense, especially in cases where the training set is relatively small. The results suggest that NIR spectroscopy together with BSVM could be an alternative to traditional methods for discriminating different brands of cigarettes.