Polymer pendant ligand chemistry, 4. Recovery of precious metal ions from strongly acidic solution with a polymer-supported o-phenylenediamine hydrochloride ligand

We report on the synthesis and reactivity of a polymer-supported o-phenylenediamine hydrochloride ligand, PS-PDHC, using macroporous 6% crosslinked polystyrene-divinylbenzene beads. The PS-PDHC ligand was found to be highly selective to AuCl₄⁻ ions in strongly acidic solutions in the presence of other precious metal ions, PdCl₄²⁻, PtCl₄²⁻, RhCl₆³⁻, and RuCl₅²⁻ (selectivity values: 2.5, Au/Pd; 7.5, Au/Pt; 7, Au/Rh; 2.2, Au/Ru) as well as other transition metal ions, Fe ³⁺, Cr³⁺, CU²⁺, Nit+, and Mn²⁺. The sorption capacity, selectivity, kinetics of removal and recovery, and solution isotherms have been determined for AuCl₄⁻ ions in competition with the above-mentioned metal ions. The relative ease of formation of the anionic complex in 0.5 M HCI, AuCl₄⁻ was thought to be the primary reason for its selective ability to bind to the PS-PDHC ligand by an anion-exchange mechanism. Therefore, the effect of the HCI concentration on the kinetics of AuCl₄⁻ ion removal from solution was also investigated to clearly show that raising the pH from 0 to 5 caused a dramatic decrease in rate. The AuCl₄⁻ ion can be recovered quantitatively from the PS-PDHC beads using a 5% thiourea solution in 0.1 M HCl, allowing the polymer-supported ligand to be reused.     

大孔强酸树脂吸附硫脲金

研究了D072大孔强酸性阳离子交换树脂从硫脲[Tu=CS(NH2)2]浸金液中吸附Au(Tu)2+的性能和机理. 结果表明，pH=2.0时，树脂对Au(Tu)2+有优良的吸附性能，金的交换容量为78.95 mg/g (Au/干树脂)，吸附的硫脲金可用乙醇-硫酸水溶液洗脱，洗脱率可达96.5%. D072树脂对Au(Tu)2+的吸附符合Langmuir吸附模型.     

高浓度盐对氰化物和金属铜的解吸研究

从提金废液中回收氰化物和金属铜一直具有重要的经济价值和环保意义。文中研究了用离子交换法处理含氰废水工艺中的解吸过程，针对试验使用的离子交换树脂寻找了一种简单有效的解吸剂；探索了解吸过程的温度、质量浓度和时间等影响因素，确定了解吸的优化条件。研究表明：高浓度的NaCl溶液能有效地将离子交换树脂上的金属分离解吸下来：该解吸剂尤其适合于高浓度的含铜废液，用20倍床层体积的解吸液对总氰的解吸率达到90％以上，对铜的解吸率达到85％以上，基本不解吸锌；解吸后的溶液可用传统的AVR（酸化、挥发、中和）法或电解．法回收铜和氰。该解吸工艺使解吸过程变得简单、有效，而且解吸剂价格低廉，解吸中无有毒物质产生，同时解决了离子交换树脂再生困难的问题。     

柚皮提取物不同级分的抗氧化活性研究

为柚皮资源的精细化利用提供参考依据，采用弱极性的DM130大孔吸附树脂为吸附剂、以不同浓度的乙醇溶液对柚皮提取物进行梯度洗脱，得到5种洗脱级分。采用二苯代苦肼自由基法和硫氰酸铁盐比色法对该5种级分的抗氧化活性进行了测定。结果显示：5种洗脱级分表现出不同程度的清除DPPH自由基和抗亚油酸过氧化活性，其作用大小依次为：水级分、20％乙醇级分、40％乙醇级分、60％乙醇级分和80％乙醇级分，5种洗脱级分的抗氢化活性均高干柚皮苷，但均低于二丁基羟基甲苯。柚皮提取物不同洗脱级分具有不同的抗氧化活性。     

Selective elution of tea catechins and caffeine from polyvinylpolypyrrolidone

Desorption of catechins and caffeine from polyvinylpolypyrrolidone (PVPP) was comprehensively investigated. The result showed that caffeine could easily be desorbed from PVPP by the tested solvents except n‐hexane, while catechins could only be thoroughly done by dimethyl sulphoxide (DMSO) and N, N‐dimethylformamide (DMF). Excellent desorption efficiency of DMSO and DMF might be attributed to their high dipole moments and H‐bond potentials. Addition of ethanol was recommended considering the elution efficiency and fluidity, but ethanol volume should be <40% (v/v) for DMSO or 20% (v/v) for DMF. Desorption would get to equilibrium within 1 h and followed the pseudo‐second‐order model. Caffeine and catechins could be separately desorbed through two‐stage elution procedure, that is, water or 20% aqueous ethanol for desorbing caffeine and part of nongalloylated catechins and DMSO/ethanol (8/2, v/v) for eluting the remaining catechins. Highly purified catechins (~95%) with high level (~70%) galloylated catechins would be achieved when the desorption procedure was applied in column chromatograph.     

Demonstration and characterization of biomolecular enrichment on microfluidic aptamer-functionalized surfaces

This paper demonstrates and systematically characterizes the enrichment of biomolecular compounds using aptamer-functionalized surfaces within a microfluidic device. The device consists of a microchamber packed with aptamer-functionalized microbeads and integrated with a microheater and temperature sensor to enable thermally controlled binding and release of biomolecules by the aptamer. We first present an equilibrium binding-based analytical model to understand the enrichment process. The characteristics of the aptamer-analyte binding and enrichment are then experimentally studied, using adenosine monophosphate (AMP) and a specific RNA aptamer as a model system. The temporal process of AMP binding to the aptamer is found to be primarily determined by the aptamer-AMP binding kinetics. The temporal process of aptamer-AMP dissociation at varying temperatures is also obtained and observed to occur relatively rapidly (<2 s). The specificity of the enrichment is next confirmed by performing selective enrichment of AMP from a sample containing biomolecular impurities. Finally, we investigate the enrichment of AMP by either discrete or continuous introduction of a dilute sample into the microchamber, demonstrating enrichment factors ranging from 566 to 686×, which agree with predictions of the analytical model.     

硫脲浸出液活性炭负载洗脱研究

从硫脲浸出液中活性炭负载洗脱金是比较困难的,目前在这方面发表的文献并不很多。本文着重研究并讨论了从负载活性炭上洗脱金的不同方法,包括酸性硫脲有机溶液和非有机洗脱液。研究了丙酮、乙腈、丁醇、乙二醚和乙醇5种有机溶剂。研究了不同的硫脲、硫酸和有机溶剂的浓度和温度对洗脱的影响。试验表明了这5种有机溶剂对金的洗脱能力按如下顺序排列: 丁醇>乙腈>乙二醚>乙醇>丙酮当采用5%丁醇,50～100g/L硫脲和50～100g/L硫酸,温度40～60℃时,金的洗脱率可达98～99%,此时活性炭含金降至0.10mg/g以下。对于非有机洗脱液,像硫化钠和硫代硫酸钠,研究表明金的洗脱率主要取决于溶液的浓度和温度,在室温时,1～2mol的硫化钠溶液可以洗脱99%的金。如果溶液的浓度降低至0.5mol,则温度需升至80℃以上才可能获得相同的洗脱率。     

HPLC法同时测定化妆品中的12种防腐剂

建立了化妆品中12种常用防腐剂(甲基氯异噻唑啉酮、2-溴-2-硝基丙烷-1,3-二醇、甲基异噻唑啉酮、苯甲醇、苯氧乙醇、苯甲酸、4-羟基苯甲酸甲酯、4-羟基苯甲酸乙酯、4-羟基苯甲酸异丙酯、4-羟基苯甲酸丙酯、4-羟基苯甲酸异丁酯、4-羟基苯甲酸丁酯)的HPLC检测方法。采用Waters symmetry(250 mm×4.6 mm×5μm)色谱柱,流动相为乙腈-0.1%(体积分数)磷酸,梯度洗脱,柱温35℃,DAD检测器,以各物质的紫外光谱数据和保留时间定性。检测波长设定为:甲基氯异噻唑啉酮和甲基异噻唑啉酮在280 nm检测,其余成分在254 nm检测。结果发现,在所建立的方法下,12种防腐剂的分离度良好、线性范围广、准确度高。     

Studies of the comonomer distributions in low density polyethylenes using temperature rising elution fractionation and stepwise crystallization by DSC

The comonomer distributions of commercial linear low density polyethylenes (LLDPE) and linear very low density polyethylenes (VLDPE) produced with traditional high activity Ziegler–Natta (Z–N) catalysts were characterized by temperature rising elution fractionation (TREF). In order to develop faster characterization methods the polymers were also characterized using a segregation fractionation technique (SFT) based on a stepwise crystallization by differential scanning calorimetry (DSC). Comparative studies of SFT and TREF demonstrated that SFT provides an alternative tool for the relative qualitative analysis of the chemical composition distribution (CCD) and the technique is useful to characterize the heterogeneity in comonomer unit distribution. Lamellar thickness distributions can be calculated from the DSC endo-therms by applying the Thomson–Gibbs equation. The SFT technique was also applied to commercial single-site (metaliocene) LLDPE and VLDPE polymers. In spite of their more homogeneous structure compared with the Z–N copolymers, which contain many active sites, these single site copolymers also gave thermograms resolved into several peaks.     

离子色谱法测定玄参中的单糖和低聚寡糖

建立阴离子交换色谱-脉冲安培检测法测定玄参中的葡萄糖、蔗糖、果糖和水苏糖的方法。以METROSEPCARB1(150mm×4.0mm)阴离子交换柱为分离柱,脉冲安培检测,30mmol/LNaOH溶液为淋洗液等度洗脱,超声水提法提取玄参中的糖。峰面积的相对标准偏差为0.56%～9.01%,线性范围1～50mg/L,检出限为0.0452～0.0921mg/L,相关系数R为0.9931～0.9998,加标回收率在96.52%～109.56%之间。该方法预处理简单,准确度高,适用于快速测定玄参中的单糖和低聚寡糖。