离子交换树脂固载金属纳米粒子:可持续化学的有效、多功能催化剂平台（英文）

This paper reviews the recent achievements in the immobilization of metal nanoparticles on ion-exchange resins and the related catalytic application. The focus is on the production processes for fine and commodity chemicals for which a low environmental impact has been demonstrated. The most significant papers that appeared in the literature from January 2010 to July 2014 have been covered. Their uses in unselective processes, bulk chemicals production, fuel cells components, as well as the use of metal-free ion-exchange resins in acid / base-catalysed reactions, were not included.     

Metal nanoparticles immobilized on ion-exchange resins:A versatile and effective catalyst platform for sustainable chemistry

This paper reviews the recent achievements in the immobilization of metal nanoparticles on ion-exchange resins and the related catalytic application. The focus is on the production processes for fine and commodity chemicals for which a low environmental impact has been demonstrated. The most significant papers that appeared in the literature from January 2010 to July 2014 have been covered. Their uses in unselective processes, bulk chemicals production, fuel cells compo-nents, as well as the use of metal-free ion-exchange resins in acid/base-catalysed reactions, were not included.     

Decontamination of spent ion-exchange resins contaminated with cesium radionuclides

Possible causes of the occurrence of radioactive contamination irremovable by acid–base regeneration of ion-exchange resins used in treatment of process media and liquid radioactive waste have been studied. It has been found that most of the irremovable cesium radionuclides are bound to inorganic deposits on the surface and in the bulk of ion-exchange resin granules. The nature of inorganic inclusions has been investigated on real and model spent ion-exchange resins (SIER). A method has been proposed for decontaminating SIER using resorcinol–formaldehyde resins selective to cesium radionuclides. Such an approach has been shown to be promising for deep decontamination of SIER.     

Uricase-like catalytic activity of ion-exchange resins modified with metalloporphyrins

The uricase-like catalytic activity of the ion-exchange resins modified with metalloporphyrins has been investigated through the oxidation of uric acid. The anion-exchange resins modified with Mn(3+)-tetrakis(sulfophenyl)porphine and the cation-exchange resin modified with Mn(3+)-tetrakis(1-methylpyridinium-4-yl)porphine exhibited the highest uricase-like activity among the modified resins tested. The fact that these resins accelerated the oxidation of uric acid even after ten cycles of use indicates that the modified resins act as catalysts in the reaction catalysed by uricase. Some of the modified resins may be effectively used for the determination of uric acid in place of uricase.     

Synthesis of Hindered Phenolic Esters over Ion-Exchange Resins

The esterification of 3,5-di-tert-butyl-4-hydroxybenzoic acid with 1-hexadecanol over a series of ion-exchange resins was investigated, in which resin D072 exhibited excellent catalytic performance. The influence of water on the reaction was also investigated, and it was found that water could improve the selectivity and increase the yield of the target product. Treatment of resins with aqueous sodium hydroxide could improve the selectivity of the target product but remarkably decreased the conversion of 3,5-di-tert-butyl-4-hydroxybenzoic acid. This result indicated that strong Brønsted acid sites played an important role in the reaction. Furthermore, D072 was efficiently recycled four runs by simple treatment with mineral acid. Finally, a series of hindered phenolic esters were successfully synthesized under the optimal reaction conditions. Therefore, a simple and versatile method for the synthesis of hindered phenolic esters has been established over ion-exchange resins and the target products were obtained in good yields.     

Etherification of glycerol with tert-butyl alcohol catalysed by ion-exchange resins

The reaction of glycerol with tert-butyl alcohol in the liquid phase on acid Amberlyst-type ion-exchange resins was studied. The influence of temperature, mole ratio n(TBA)/n(G), water and swelling of gel, and macroreticular type of polymer catalysts on etherification reaction was investigated. The most favourable reaction temperature is 75°C. The conversion of glycerol and yield of glycerol tert-butyl ethers has increased with the mole ratio n(TBA)/n(G). Dry form of macroreticular catalysts provided the best results. Etherification reaction of glycerol with isobutylene in non-aqueous conditions gives the highest yield of desired ethers. The influence of water was studied. The gel forms of ion-exchange resins have very low catalytic activity. It can be concluded that water has an inhibition effect on ion-exchange resins. By comparing the gel and macroreticular forms of Amberlyst ion-exchange resins it can be concluded that very acid forms of macroreticular ion-exchange resins with a high degree of crosslinking are more active catalysts for the studied reaction due to their pores which are sufficiently large so that the voluminous tert-butyl ethers of glycerol can be formed. It was estimated that tert-butyl alcohol as tert-butylation agent is not suitable for etherification of glycerol with the formation of di-and triethers.     

Environmentally benign chemical fixation of CO2 catalyzed by the functionalized ion-exchange resins

Basic ion-exchange resins, one kind of polystyryl-supported tertiary amine, were demonstrated to be highly efficient and recyclable catalysts for the fixation of carbon dioxide with aziridines under mild conditions, leading to the formation of 5-aryl-2-oxazolidinone with excellent regio-selectivities. Notably, neither solvents nor any additives were required, and the catalyst could be recovered by simple filtration and directly reused at least five times without significant loss of catalytic activity and selectivity. The present protocol has been applied to reactions of epoxides/propargyl amines with CO₂/CS₂. This solvent-free process thus represents environmentally friendly catalytic conversion of CO₂ into value-added chemicals and may have potential in various continuous flow reactors in industry.     

Local structures of ions at ion-exchange resin/solution interface

The local structures of Cl- and Br- in anion-exchange resins have been studied by X-ray absorption fine structure (XAFS), and separation selectivity is discussed on the basis of results. When two different anion-exchange resins having trimethylammonium and dimethylammonium groups as anion-exchange groups are employed for ion-exchange experiments, slightly higher Br- selectivity has been obtained with the former. XAFS has indicated that the average hydration numbers for a given anion is not affected by the structure of the ion-exchange group, but that the extent of ion-association between the anion and the ion-exchange groups depends on the type of the ion-exchange group. Shorter interaction distance (and in turn stronger ion-association) has been confirmed for the dimethylammonium-type resin, and is consistent with lower Br- selectivity of this resin.     

Kinetics of esterification of palmitic acid with isobutyl alcohol on ion-exchange resin pellets

Cylindrical pellets were made by mixing ion-exchange resin particles with binding powders and heating to 140°C. To compare catalytic activities of these resin pellets with those of resin particles and sulfuric acid, the esterification of palmitic acid with isobutyl alcohol was carried out in a batch reactor. The rate equation for sulfuric acid could be applied to ion-exchange resins although the values of parameters were different.     

14C in spent ion-exchange resins and process water from nuclear reactors: A method for quantitative determination of organic and inorganic fractions

A method of separately quantifying organic and inorganic ¹⁴C compounds present in spent ion-exchange resins and process water from nuclear power reactors has been developed. Extraction of carbon compounds is accomplished by means of acid stripping (inorganic ¹⁴C) and subsequent wet oxidation (organic ¹⁴C) or by N₂ purging in combination with a catalytic furnace (oxidized and reduced gaseous compounds) with organic and inorganic ¹⁴C species collected separately. Recovery experiments on simulated samples spiked with ¹⁴C-labeled sodium carbonate, sodium acetate and sodium formate, showed extraction yields of 94–98%. The sample-specific procedures were also tested on authentic samples of spent resins and reactor water with good results. Validation and reliability of the procedures are presented and the method is compared to previous methods reported in the literature.     

Efficient utilization of nanospace of layered transition metal oxide HNbMoO6 as a strong, water-tolerant solid acid catalyst

Layered HNbMoO6 was found to function as a strong solid acid catalyst, exceeding the activity of zeolites and ion-exchange resins for Friedel-Crafts alkylation. HNbMoO6 also exhibited high catalytic activity for esterification of hydrocarboxylic acid and hydration. The catalytic performance of layered HNbMoO6 is attributed to the intercalation of reactants into the interlayer and the development of strong acidity.     

Some chelating ion-exchange resins containing ketoiminocarboxyclic acids as functional groups

A series of ion-exchange resins containing -COCH(2)N[(CH(2))(m)COOH(2)](2) groups has been synthesized. Additional analogues were prepared by means of the reaction of the carbonyl group with phosphorus trichloride or thioglycollic acid. The properties of these resins and the selectivity for different metal ions have also been investigated.     

Electrocatalytic oxidation of hydrazine at poly(4,5-dihydroxy-1,3-benzenedisulfonic acid) multiwall carbon nanotubes modified-glassy carbon electrode: Improvement of the catalytic activity

A stable electroactive thin film of poly(4,5-dihydroxy-1,3-benzenedisulfonic acid) was electrochemically deposited at the surface of multiwall carbon nanotubes-glassy carbon electrode. The electrocatalytic oxidation of hydrazine has been studied at the surface of the modified electrode using cyclic voltammetry, chronoamperometry and linear sweep voltammetry as diagnostic techniques. The modified electrode exhibits good electrocatalytic activity for the oxidation of hydrazine with a good sensitivity. Linear calibration range was in the wide concentration range of 10–3540 μM hydrazine with a detection limit of 1.8 μM and a sensitivity of 85.3 nA/μM. A Tafel plot, derived from voltammograms, indicated a one-electron transfer process to be the rate-limiting step and the overall number of electrons involved in the catalytic oxidation of hydrazine was found to be four. The influences of potentially interfering substances were studied. The diffusion coefficient of hydrazine was also evaluated. Finally, the proposed modified electrode was used for the determination of hydrazine in spiked water samples.     

离子交换法从醋酸溶液中提取脯氨酸的研究

本文研究了脯氨酸在732,DO01,DH-8三种阳离子交换树脂上的静态吸附特性,发现732树脂的吸附容量最大,速度最快。并选用732树脂,研究了它从醋酸脯氨酸水溶液中吸附脯氨酸的动态过程。最后,以氨水为洗脱剂,考察了不同氨水浓度,洗脱速度对洗脱过程的影响。     

pH Neutralization while Succinic Acid Adsorption onto Anion-Exchange Resins

Succinic acid is a useful chemical and its purification from fermentation broth by ion-exchange resins has widely drawn attention. In this study, pH neutralization in the process of adsorption of succinic acid from model solutions and fermentation broth by anion-exchange resin NERCB 04 has been tested. Adsorption capacity of NERCB 04 was about 0.41 g succinic acid/g resin at concentrations of succinic acid in the range of 10–50 g/L in packed column. In the process of succinic acid removal, pH of the system could also be neutralized. The neutralizing ability of the resin as a neutralizing agent has also been studied in the model cycle system and in the real fermentation cycle process. It was found that NERCB 04 showed stable adsorption capacity and pH neutralization ability after each regeneration. A certain amount of anion-exchange resin could neutralize the low pH values (pH 2–5) and maintain the system around pH 7.0. This means the anion-exchange resins have the function of neutralizing reagent in the process of adsorbing succinic acid.     

Sulfoacylated poly(styrene-divinylbenzene) copolymers as resins for cation chromatography. Comparison with sulfonated, dynamically coated and silica gel cation exchangers

Most important properties of an ion chromatographic resin are influenced by the resin matrix, the type of functional group and the ion-exchange capacity. Highly crosslinked PS-DVB resins of 5 microm diameter have been functionalized by sulfoacylation, by sulfonation and by dynamic coating over a wide range of exchange capacities. These materials allow a study of the influence of different ion-exchange sites and capacities. The influence of the degree of functionalization on resin performance is completely reverse for sulfoacylated and sulfonated resins. The HETP values for all observed analytes (Cu, Pb, Zn, Ni, Co, Cd, Mn, Ca, Mg) in a tartaric acid elution system decrease for sulfoacylated resins with increasing capacity, for sulfonated resins with decreasing capacity. The performance of sulfoacylated exchangers is better than for dynamically coated ones and far better than for sulfonated resins. The performance of silica gel based cation-exchangers such as BioSil CAT is in most cases better than observed for sulfoacylated resins.     

Cross‐Coupling between Hydrazine and Aryl Halides with Hydroxide Base at Low Loadings of Palladium by Rate‐Determining Deprotonation of Bound Hydrazine

Reported here is the Pd‐catalyzed C–N coupling of hydrazine with (hetero)aryl chlorides and bromides to form aryl hydrazines with catalyst loadings as low as 100 ppm of Pd and KOH as base. Mechanistic studies revealed two catalyst resting states: an arylpalladium(II) hydroxide and arylpalladium(II) chloride. These compounds are present in two interconnected catalytic cycles and react with hydrazine and base or hydrazine alone to give the product. The selectivity of the hydroxide complex with hydrazine to form aryl over diaryl hydrazine was lower than that of the chloride complex, as well as the catalytic reaction. In contrast, the selectivity of the chloride complex closely matched that of the catalytic reaction, indicating that the aryl hydrazine is derived from this complex. Kinetic studies showed that the coupling process occurs by rate‐limiting deprotonation of a hydrazine‐bound arylpalladium(II) chloride complex to give an arylpalladium(II) hydrazido complex.     

The isolation of olitoriside from jute seeds

Summary 1. The possibility of using ion-exchange resins for the purification of extracts in the isolation of cardiac glycosides has been shown.2. A method is proposed for obtaining olitoriside by using a mixture of anion-exchange and cation-exchange resins to purify the extract, this method giving an increased yield of the preparation.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 81–83, January–February, 1972.     

Phase-transfer reactions catalyzed by phosphonium salts bound to macroporous polystyrene supports

The rate of reaction of alkyl halides with aqueous sodium acetate or cyanide catalyzed by phosphonium salts supported on insoluble polystyrene resins, and rates of ion-exchange of the chloride ion in the catalysts against the acetate ion, were studied as a function of catalyst particle size, the percentage of ring substitution, the morphology of polymer support, and distance between active site and polymer backbone. Rates of 1-bromooctane or benzyl chloride with macroporous, 7–25% ring-substituted catalysts increased with increasing ring substitution. Rates with macroporous catalysts increased as a heptamethylene spacer was introduced between the active site and the polymer backbone. Rates of ion-exchange with macroporous catalysts were facilitated with increasing ring substitution or by the introduction of the spacer chain. A relation between the catalytic activity of macroporous or microporous catalysts and ion-exchange rates under triphase conditions was discussed.     

Accumulation of polysaccharides under the influence of chlorocholine chloride inAronia melanocarpa

Summary As the result of a purification process consisting of precipitation and successive stages of chromatography on ion-exchange resins, electrophoretically homogeneous rat transferrin has been obtained with a molecular weight of 76,500 daltons, a maximum in the absorption spectrum at 465 nm, and isoelectric points of the two isoforms of 6.0 and 6.3.Institute of Bioorganic Chemistry, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 609–612, September–October, 1978.