Preparation of Macroporous Poly(vinyl alcohol-co-triallyl isocyanurate)Beads Bearing Aminocarboxylic Acid as Functional Groups by Suspension Polymerization

Macroporous poly(vinyl acetate-co-triallyl isocyanurate)beads were prepared with suspension polymerization method.The copolymer beads were then transformed into poly(vinyl alcohol-co-triallyl isocyanurate)by ester exchange reaction.Aminocarboxylic acids were immobilized on the copolymer beads by the esterification of hydroxyl groups with diethyl-lenetriaminepentaacetic bisanhydride,The weak acid exchange capacities,specific surface areas and mean pore diameters of the rsultant resin beads were measured.     

高亲水性强阳离子交换色谱填料的制备及其在蛋白质分析中的应用

以具有双孔结构的聚甲基丙烯酸环氧丙酯(PGMA)微球为基质,以葡萄糖进行表面亲水改性,制备了强阳离子交换色谱填料,并将其用于复杂生命体系中生物大分子的快速而高效的分离、分析与纯化。葡萄糖亲水改性增进了填料的生物相容性,提高了蛋白质样品的回收率;双孔结构及较高的比表面积赋予填料良好的柱渗透性和样品负载量。以标准蛋白质为样品,考察了该填料对生物样品的分离性能。以100 mm×4.6 mm的色谱柱分离4种蛋白质,在6 min内实现了基线分离;以溶菌酶为样品,填料的吸附容量为39.5 g/L,在蛋白质快速分离纯化分析中显示了良好的应用前景。     

树脂吸附法纯化赤霉素

对比了几种大孔吸附树脂对赤霉素发酵液的吸附、解吸性能,实验发现,自制R4树脂的动态饱和吸附容量高达58.38mg/g干树脂,自制R5树脂的动态饱和吸附容量高达96.46mg/g干树脂,R5树脂的吸附容量明显高于R4,这与树脂的比表面积一致.50%(VIV)甲醇水溶液具有较好的解吸性能,收率高达95%以上,经过树脂一步吸附-解吸,赤霉素的浓度可平均提高5倍以上,集中收集最高可提高15倍以上,这对于工业化生产中,赤霉素的进一步结晶析出具有重要意义.     

Simple tools for resin distribution

Two simple instruments allowing uniform distribution of resin beads for solid-phase synthesis are described. The first tool simplifies distribution of resin into microtiterplates. The second tool was designed for distribution of a variable amount of resin beads into any number of reaction vessels, and the technique is applicable to resin beads with a wide range of physical properties (density).     

ULTRAMINE: a high-capacity polyethylene-imine-based polymer and its application as a scavenger resin

The synthesis of a novel high-loading polyethylene-imine resin (ULTRAMINE) is described, and its application as a scavenger resin in various acylation reactions is demonstrated. The inverse suspension polymerization technique was used for the synthesis of well-defined spherical polymer beads. Polymer beads with different cross-linking densities were synthesized according to the degree of acryloylation of the polyethylene-imine polymer. The resin was characterized by various spectroscopic techniques. The size, shape, and morphological features of the resin were demonstrated by microscopy. The resin showed excellent swelling properties in both polar and nonpolar solvents. The chemical stability of the resin in various reagents and solvents was investigated and monitored by IR spectroscopy. The mechanical stability of the beads was determined by a single-bead compressive experiment. The ULTRAMINE beads can be used as an excellent scavenger for excess acylating reagent, as demonstrated for a variety of reactions. ULTRAMINE-red resin was derived from ULTRAMINE through exhaustive reduction of the amide carbonyl groups to yield an all-amine resin.     

Micro solid phase spectrophotometry in a sequential injection lab-on-valve platform for cadmium,zinc, and copper determination in freshwaters

This work describes the development of a solid phase spectrophotometry method in a μSI-LOV system for cadmium, zinc, and copper determination in freshwaters. NTA (Nitrilotriacetic acid) beads with 60–160 μm diameter were packed in the flow cell of the LOV for a μSPE column of 1 cm length. The spectrophotometric determination is based on the colourimetric reaction between dithizone and the target metals, previously retained on NTA resin. The absorbance of the coloured product formed is measured, at 550 nm, on the surface of the NTA resin beads in a solid phase spectrophotometry approach.     

Optimization of polyacrylonitrile-cysteine resin synthesis and its selective removal of Cu(Ⅱ) in aqueous solutions

Polyacrylonitrile beads(PAN) cysteine(CS) was synthesized from polyacrylonitrile beads(PAN) and cysteine(CS).The content of the functional group and the percentage conversion of the functional group of PAN-CS prepared under the optimum condition using response surface methodology(RSM) for the first attempt were 3.22 mmol/g and 35.78%.The structure was characterized by ET-IR and elemental analysis.The adsorption properties of the resin for Cu(Ⅱ) were investigated by batch and column experiments.Batch adsorption results suggested that PAN-CS had higher adsorption capability for Cu(Ⅱ)than other metal ions and maximum saturated adsorption capacity was 184.7 mg/g.The resin and its metal complexes were studied by FT-IR.Furthermore,the resin can be eluted easily using 1 mol/L HC1.PAN-CS can provide a potential application for selective removal of copper from waste solution.     

Vibrational spectroscopic analysis of an amber necklace—a forensic historical study

The vibrational infrared spectroscopic analysis of an important historical necklace of 102 beads that are purported to be made of amber indicated strong signal characteristics of cellulose nitrate with dark green-coloured areas of a naphthylamine dye. Confocal Raman depth-profiling spectroscopy using a 785-nm laser excitation, a novel application first applied here for the analysis of inclusions in amber resin, confirmed that the beads were amber resin and that residues of cellulose nitrate, camphor plasticiser and a naphthylamine dyestuff were present in surface cracks and inclusions in the bead matrix. The bead stringing material was confirmed as cellulose, which was stained green in part with the dyestuff. Comparison of the Raman spectra of the amber beads with a resin database suggested that the amber was sourced from Northern England. The scientific evidence supports the stylistic opinion that the necklace is an important example that could date from the 19th Century and that efforts had been made to coat it with a synthetic dyed polymer; this provides a rather unusual example of the chemical masking of a genuine article—a procedure that renders the article of particular interest.     

Exploiting the bead injection concept for sequential determination of copper and mercury ions in river-water samples

A procedure involving bead-injection concept and sequential determination of copper and mercury ions in river-water samples is proposed. The method is based on the solid-phase extraction of both metal ions on the same beads surface (Chelex 100 resin) and in their subsequent reaction with the colorimetric reagents (APDC and Dithizone for copper and mercury ions, respectively). For this task, a resin mini-column is established in the optical path by the selection, introduction and trapping of a defined volume of the Chelex-100 resin beads suspension in the flow system. The passage of the sample solution through the resin mini-column promotes the sorption of Cu(II) ions and, making the APDC colorimetric reagent flows through the beads, the formation of the coloured complex on the solid phase surface occurs. The absorbance of the formed APDC-Cu complex is then monitored at 436 nm and the spent beads are discarded. Packing another resin mini-column in the flow cell and repeating the concentration step it is possible to carried out the mercury determination by using Dithizone as reagent. The absorbance of the Dithizone-Hg complex is monitored at 500 nm. After each measurement, the spent beads are wasted and a new portion of fresh one is trapped in the system, letting it ready for the next measurement. The bead injection system is versatile and can be used to concentrate different sample volumes, which permits the determination of a wide range of copper and mercury ions concentrations. When the sample-selected volumes are 100 and 1000 μl the analytical ranges were 5.0 up to 500.0 μg l⁻¹ and 2.5 up to 30.0 μg l⁻¹ for Cu(II) and Hg(II) ions, respectively. Under these conditions, the detection limit was estimated as 0.63 and 0.25 μg l⁻¹ for copper and mercury ions determination. The system consumes 2 mg of Chelex 100 resin beads, 0.20 mg of APDC or 1.25 mg of Dithizone per determination and the traditional organic solvent extraction methodology, normally used in connection with APDC and Dithizone reagents, is not used here which permits to classify the present method as green.     

Preparation of Designer Resins via Living Free Radical Polymerization of Functional Monomers on Solid Support

Merrifield resin is converted to a solid-supported free radical initiator by reacting with the TEMPO-Na. Heating TEMPO-methyl resin with a variety of functionalized styrene and acrylate monomers gives larger resin beads via living free radical polymerization. We have coined the term Rasta resin to describe resin beads prepared in this fashion. The process can be described as a solvent-free suspension polymerization. It is particularly well suited for preparation of resin beads from monomers which contain electrophilic groups that would be destroyed upon suspension polymerization in water. Rasta resins have a novel macromolecular architecture wherein long straight chain polymers bearing reactive functional groups emanate from the phenyl groups of a cross-linked polystyrene core. With judicious choice of co-monomers and polymerization strategy, the solvent affinity, loading capacity, and distance of functionality from the cross-linked core may be controlled giving beads with properties that are tailored to specific uses as synthesis supports and scavenging resins.     

Large uniform-sized polymer beads for use as solid-phase supports prepared by ascension polymerization

Large uniform-sized polymer beads are desirable for "one-bead-one-compound" applications in the combinatorial synthesis of compound libraries. We have developed a technique for the preparation of large polymer spheres with narrow size distributions. Uniform-sized poly(styrene-co-divinylbenzene) beads with diameters in excess of 1 mm have been prepared by free radical polymerization in an ascension process through a heated column. The size of the beads can be adjusted by the diameter of the injection needle and the injection speed. The resin beads can be made porous by the incorporation of a porogen during the preparation; they reach a specific surface area in excess of 200 m(2)/g. The mechanical properties of the spheres and their use in organic synthesis have been studied.     

Specific binding of a biotinylated,metallocarbonyl‐labelled dendrimer to immobilized avidin detected by diffuse‐reflectance infrared Fourier transform spectroscopy

Molecular recognition between avidin covalently immobilized at the surface of acrylic resin beads and a transition metallocarbonyl tracer of the biotin ligand was detected using diffuse reflectance infrared Fourier transform spectroscopy. Copyright © 2004 John Wiley & Sons, Ltd.     

Catalysts for Hydration of Cyclohexene to Cyclohexanol

The hydration of cyclohexene was determined in a stirred tank of 100 mL in a batch mode in the presence of modified or unmodified resin as catalyst. The ion-exchange sulfonate resin was modified with alkyl secondary amine. At an optimum amination rate of 15%, the conversion of cyclohexene reached to 22% and the selectivity of cyclohexanol was 95.6%. In a temperature range of 90―150 ℃, the activity and selectivity of the modified resin ca-talyst were much higher than those of the unmodified resin catalyst, which was attributed to the inclusion formed between cyclohexene and alkyl chain and also the quasi-lipophilic phase formed around the outer surface of resin beads. The formed quasi-lipophilic phase formed enhanced the conversion of cyclohexene and depressed the formation of by-products.     

Dielectric properties of quaternary ammonium ion-exchange beads dispersed in aqueous phases

Dielectric measurements were carried out for dense sediments of quaternary ammonium type anion-exchange resin beads dispersed in deionized water over a frequency range of 30 Hz to 130 MHz. According to a method proposed in previous studies the relative permittivities and electrical conductivities of ion-exchange beads were evaluated from the relaxation data observed in a megahertz region on the basis of a theory of interfacial polarization. The permittivities of the ion-exchange beads were found to be unchanged irrespectively of the salt form and somewhat lower than that of a continuous medium, while the conductivities of the ion-exchange beads were characteristic of the salt form. The equivalent ionic conductances of different counter anions in the beads were estimated from the conductivities of the ion-exchange beads. These results indicate an ion-binding effect in the resin beads.     

Bead-injection determination of total mercury in river water samples.

A bead-injection system is proposed for total mercury determination in river-water samples. The procedure is based on the introduction of a defined quantity of a resin suspension in the flow system. The selected beads are packed inside of a flow cell and the formed resin mini-column constitutes the optical path. The sample volume is then selected, and its passage by the mini-column allows retention of the mercury ions on the surfaces of the beads. The introduction of a spectrophotometric reagent in the flow system leads to the formation of a colored Hg-dithizone complex on the surface of the bead, which is spectrophotometricaly monitored. The spent beads are directed to waste, allowing the system to become ready to process another sample. The proposed system handles about 20 measurements per hour, consuming 1000 microl of the sample, 1 mg of Chelex 100 resin and 1.25 microg of Dithizone per determination. When 1000 microl of the sample is injected, a linear analytical curve is obtained (A = 0.0052[Hg] + 0.1028, from 0 up to 30 microg l(-1), R2 = 0.995); the detection limit is estimated to be 0.9 microg l(-1). The results are precise, r.s.d. < 9%; spiked sample recoveries within 91.2 and 109% are found.     

氯化硫酰-甲缩醛法合成强碱型阴离子交换树脂

<正> 氯甲基苯乙烯-二乙烯苯共聚体(简称氯甲基共聚珠体)的合成,当采用传统的氯甲醚法时,由于混杂有容易致癌的二氯甲醚而不甚妥善.不直接使用氯甲醚的氯甲基化方法,虽已有些专利报道,但并不具体.本文研究氯化硫酰-甲缩醛法制备氯甲基共聚珠体,可在氯化硫酰、甲缩醛、催化剂无水氯化锌用量甚低的情况下,得到氯甲基共聚珠体含氯量稳定在16—17.7％,合成的强碱型阴离子交换树脂的交换当量稳定在3.3—3.5毫克当量/克(干树脂),而且发现甲缩醛中少量甲醇或水的存在对氯甲基化反应影响甚微.     

大孔聚丙烯醛-呋喃-2-硫代酰腙螯合树脂的合成及其性能的初步研究

合成了一新型高分子骨架，大孔内烯醛－苯乙烯－二乙烯苯三元共聚物树脂骨架，通过其含有的活泼醛基与呋喃－2－硫代酰肼螯合剂进行高分子反应，制备了一种含氮、硫配位原子的螯合树脂，聚丙烯醛－呋喃－2－硫代酰腙。对其与贵金属离子的吸附性能进行了初步研究，结果表明，该树脂对金、钯及铂具有选择性吸附作用，吸附容量分别为1.20mmol/g干树脂，0.37mmol/g干树脂及0.28mmol/g干树脂。     

Vibrational spectroscopic encoding of polystyrene-based resin beads: converting the encoding peaks into barcodes

A detailed approach is described for the vibrational spectroscopic encoding of polystyrene-based resin beads by converting the infrared absorption peaks suitable for encoding (encoding peaks) into barcodes. Based on combining the FT-IR measurements and the quantum-chemical computations, the vibrational characteristics of p-tert-butylstyrene monomer, polystyrene and poly(p-tert-butylstyrene) resin beads are analyzed, which are helpful for the selection of encoding peaks. The vibrational spectroscopic encoding of polystyrene-based resin beads could be obtained by converting the wavenumber, intensity and full width at half maximum (FWHM) of the encoding peaks into barcodes automatically through a computer program designed in our laboratory.     

Investigation of the Molecular Recognition of Amino Acids by Cyclopeptides with Reflectometric Interference Spectroscopy

IR spectroscopic mapping of resin beads allows destruction-free characterization of polymer-bound combinatorial compound libraries. By choice of different absorptions for IR reconstruction, resin beads with common structural elements can be “fished out” of a library and statistically investigated.     

Palladium cluster catalysts supported on chelate resin-metal complexes

The dry beads of chelate resin-metal complexes have been prepared from metal ions and the chelate resin containing iminodiacetic acid moieties. The surface area of the chelate resin can be increased both by washing with an organic solvent miscible with water and by complexing with multi-valent cations. Palladium clusters are supported on the chelate resin-metal complexes by two methods, in which the order is reversed between “complexing of metal ions” and “supporting of palladium clusters”. The supported palladium clusters catalyze the hydrogenation of C=C bonds, and the catalytic activity greatly depends on the metal ions used for the complexation. In the case of typical metal ions, the complexing of metal ions after supporting of palladium clusters makes the surface area of the resin increase, but makes the catalytic activity decrease compared with the reverse order. In the case of lanthanoid ions, on the other hand, the same order makes both the surface area and the catalytic activity increase.