Preparation of Sulfonamide Containing Cellulose Based Sorbent for Removal of Mercury Ions

A new sulfonamide containing cellulose based sorbent was prepared in three steps; poly (acrylonitrile) (PAN) grafting onto cellulose by redox polymerization method, amination of PAN grafted cellulose with ethylenediamine, and sulfamidation with benzene sulfonyl chloride. The resulting polymeric sorbent, which had a sulfonamide content of 3.4 mmol/g, was effective for the removal of mercury ions from aqueous solutions. The mercury sorption capacity of the sorbent is around 1.95 mmol/g under non-buffered conditions. The experiments performed under identical conditions with some metal ions reveal that Cd(II), Mg (II), Zn(II), and Fe(III) ions are also extractable in low quantity (0.02–0.46 mmol/g). The sorbed mercury can be eluted by repeated treatment with hot acetic acid.     

Preparation of Dicarboxylic Acid Containing Sulfonamide Based Resin and Removal of Basic Dyes

Polymer and dye interaction leading to polymer-dye complex formation exhibits many interesting and important practical features. For this purpose, dicarboxylic acid containing resin was prepared in two steps starting from poly (styrene-divinyl benzene) (PS-DVB) (10% crosslinking) based beads with a particle size of 400-590 µm, according to the synthetic protocol; chlorosulfonation, sulfamidation with iminodiacetic acid. Dye extraction experiments were carried out by contacting wetted resin samples with aqueous dye solutions at room temperature. Capacities were determined by colorimetric analysis of the residual dye content. Dye sorption capacity of the resin was found to be (0.67-0.63 g g^?1 resin). This material is also able to remove the cationic dyes completely even from highly diluted aqueous dye solutions.     

嵌段共聚物PLL-PEG-PLL/DNA复合物胶束

对复合物胶束PLL-PEG-PLL/DNA的形态、大小、对核酶抗性和转染效果等进行了测试,结果表明：复合物胶束直径在10～35nm之间,有较强核酶抗性,对昆虫细胞的转染实验获得成功。这些结果对于基因治疗具有重要意义。     

含聚二甲基硅氧烷的嵌段共聚物的制备技术

按聚合机理划分方法综述了含聚二甲基硅氧烷的嵌段共聚物的相关制备技术.包括阴离子聚合法、缩聚法、氧氮自由基聚合法、原子转移自由基聚合法、可逆加成-断裂链转移聚合法.     

Removal of Lead and Cadmium Ions from Aqueous Solutions Using Sulphur and Oxygen Donor Ligand Bearing Hydrogels

A new thiourea and urea functional monomers were synthesized. A series of hydrogels were prepared by photopolymerization. The hydrogels were used for the removal of Pb(II) and Cd(II) ions from aqueous solutions. The influence of the uptake conditions such as the pH, the time, and the initial feed concentration on the metal ion binding capacity of hydrogel was tested. The selectivity of the hydrogels towards the different metal ions was also tested. The adsorption isotherm models were applied. The limits of detection and quantification were calculated. The usability of the hydrogels for preconcentration studies were also investigated.     

Experimental Investigation on the Removal of p-Toluic Acid from Aqueous Solution using Functionalized Polymeric Sorbent

Polystyrene-divinylbenzene copolymer (PsDVB) was covalently functionalized with monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA) by a simple method. The functionalized sorbents were characterized in terms of functionality and morphology, and used for the removal of p-toluic acid (p-TA) from aqueous solution. It was found that DEA-PsDVB has higher adsorption capacity than MEA- and TEA-PsDVB due to more accessible nitro and hydroxyl groups on its surface. Further investigation on the adsorptive properties of DEA-PsDVB indicated that the maximum uptake of p-TA occurred at the optimum pH of 5.3. The kinetics data was successfully represented by the pseudo-first-order model, and the behavior of the adsorption isotherms followed the Freundlich model well. Thermodynamic studies showed that the adsorption of p-TA onto DEA-PsDVB was an endothermic and spontaneous process along with the positive change in entropy. The regeneration of DEA-PsDVB was performed with 0.1 M NaOH solution, and results showed that 99% of the initial capacity was conserved after eight successive adsorption/regeneration cycles.     

二元Pluronic嵌段共聚物相互作用 II.PPO嵌段长度不等的P94/L64二元混合水溶液

用I2 探针增溶分光光度方法 ,考察了Pluronic两亲嵌段共聚物P94/L6 4二元混合水溶液的胶束化行为 ,发现在溶液体相中L6 4的质量摩尔分数XL64 <0 4时 ,由于P94/L6 4混合预胶束的形成 ,导致P94分子在较高浓度时才生成单组分胶束 ;当XL64 >0 4后 ,溶液中生成了P94/L6 4混合胶束。P94和L6 4二种分子PPO嵌段长度不同 ,造成这种不同浓度比例区间内胶束组成的差异。温度升高促进了胶束化行为     

Exploitation of Beach Sand as a Low Cost Sorbent for the Removal of Pb(II) Ions from Aqueous Solutions

Abstract

Beach sand is used to remove traces of Pb(II) ions from aqueous solutions. Effect of shaking speed, amount of sorbent, shaking time, nature and concentration of different electrolytes and deionized water along with buffer of pH 2–10 Apak, R., Guclu, K. and Turgut, M. H. 1998. Modeling of copper(II), cadmium(II), and lead(II) adsorption on red mud. J. Colloid Interface Sci., 203: 122 Ma, Y. Q., Traina, S. J., Logen, T. J. and Rayan, J. A. 1994. Effect of aqueous Al, Cd, Cu, Fe, Ni, and Zn on Pb immobilization by hydroxyapatite. Environ. Sci. Technol., 28: 1219 Zhang, P. and Ryan, J. A. 1998. Formation of pyronorphite in analgesite‐hydroxiapatite suspension under varying pH conditions. Environ. Sci. Technol., 32: 3318 Marcantonio, F., Flower, G., Thien, L. and Ellgaard, E. 1998. Pb isotopes in tree rings chronology of pollution in BayouTrepagnier; Louesiana. Environ. Sci. Technol., 32: 2371 Klaassen, C. D. 2001. Casarett and Doull's Toxicology: the basic science of poisons, 6th Ed. Edited by: Klaassen, C. D. New York: McGraw Hill. Plunkett, E. R. 1987. Handbook of Industrial Toxicology USA: Edward Arnold Publication Co; Inc. Hasany, S. M. 2000. Inorganic ion‐exchangers for the treatment and disposal of industrial effluents. The Nucleus, 37: 187 (and references therein) Hasany, S. M., Ahmed, R. and Chaudhary, M. H. 2003. Investigation of sorption of Hg(II) ions onto coconut husk from aqueous solution using radiotracer technique. Radiochim. Acta., 91: 533 (and reference therein) Hasany, S. M., Saeed, M. M. and Ahmed, M. 2003. Sorption of traces of silver ions onto polyurethane foam from acidic solution. Talanta, 54: 89 (and reference therein)  have been studied. Maximum sorption of Pb(II) ions (>94%) is achieved from 10^?4M HNO₃. Sorption data have been tested using Langmuir, Freundlich, and Dubinin‐Radushkevich (D‐R) sorption isotherms. Thermodynamic parameters such as ΔH, ΔS, and ΔG have been evaluated. Kinetics of sorption is followed by Morris‐ Weber, Reichenberg and Lagergren equations. Influence of diverse ions on the sorption of Pb(II) ions is also investigated.     

Preparation and Characterization of Copolymer Micelles Formed by Poly(ethylene glycol)-Polylactide Block Copolymers as Novel Drug Carriers

Diblock copolymer poly(ethylene glycol) methyl ether-polylactide (MePEG-PLA) micelles were prepared by dialysis against water. Indomethacin (IMC) as a model drug was entrapped into the micelles by dialysis method. The critical micelle concentration (CMC) of the prepared micelles in distilled water investigated by fluorescence spectroscopy was 0.0051 mg/mL which is lower than that of common low molecular weight surfactants. The diameters of MePEG-PLA micelles and IMC loaded MePEG-PLA micelles in number-averaged scale measured by dynamic light scattering were 52.4 and 53.7 nm respectively. Transmission electron microscope and scanning electron microscope observation showed that the appearance of MePEG-PLA micelles was in a spherical shape. The content of IMC incorporated in the core portion of the micelles was 18 wt.%. The effects of the synthesis method of the copolymer on the polydispersity of the micelles and the yield of the micelles formation were discussed.     

New Preparation and Purification Methods for Metallo-Supramolecular Block Copolymers

The bis-complex formation of two terpyridine-modified polymers using microwave assisted reaction conditions was investigated in detail. In order to construct a heteroleptic block copolymer polystyrene, which was prepared by nitroxide-mediated radical polymerization (NMRP), and a commercial available poly(ethylene oxide) were used. These studies include the influence of temperature, reaction time, concentration and the use of different solvent mixtures on complexation. The conversion was determined by GPC measurements. The amphiphilic metallo-supramolecular block copolymers were investigated towards their formation of micellar aggregates in water. Other characterization techniques include ¹H-NMR, UV/vis spectroscopy, dynamic light scattering (DLS), atomic force spectroscopy (AFM) and transmission electron microscopy (TEM) techniques. This paper is dedicated to Professor Ian Manners for his scientific contributions to inorganic and organometallic polymers.     

二元Pluronic嵌段共聚物相互作用 I.PPO嵌段长度相近的P94/L92和F108/L92二元混合水溶液

以I2 作为探针 ,用可见光度方法测定不同浓度比例的P94/L92和F10 8/L92二元Pluronic嵌段共聚物水溶液的临界胶束浓度。实验结果表明 ,这些PPO嵌段长度相近的分子在全部浓度比例范围内都发生相互作用 ,生成了混合胶束。由于这些分子的PEO嵌段长度不等 ,随着具有较短PEO嵌段的L92分子加入 ,P94/L92和F10 8/L92混合胶束外壳的EO基团数减少 ,从而使混合胶束水化度降低     

The Uptake of Gold(I) from Ammonia Leaching Solution by Imidazole Containing Polymeric Resins

Abstract

The polymeric resins containing guanylthiourea, 1-methylimidazole, 2-mercapto-1-methylimidazole ligands have been synthesized from vinylbenzyl chloride-divinylbenzene copolymers and used in the removal of Au(I) from ammonium buffer and ammoniacal thiosulphate solutions. The best gold sorption from ammonium buffer that contains 100 g/dm³ NH₃ · H₂O and 5 g/dm³ (NH₄)₂SO₄, is reached in the case of 1-methylimidazole resin (2) (27.9 mg/g) and all three resins do not have a measurable sorption of copper(II) ammine complexes. The resins display a higher affinity towards gold(I) from ammoniacal thiosulphate solutions than from the ammonium buffer solution. The XPS analysis of gold loaded resins suggests the presence of gold at Au(I) oxidation state, most likely in the form of ionic pair Au(NH₃)₂ ⁺OH^? or neutral complex AuNH₃OH and as highly-dispersed metallic gold. The degree of gold desorption is about 50% using 1% potassium cyanide solution in 0.3% hydrogen peroxide solution. Resins retain their capacity towards gold in five consecutive sorption/desorption cycles.     

Using a Brush Copolymer as Efficient Dispersant for the Preparation of Highly Stabilized Ag Nanoparticles in Aqueous Suspensions

Silver (Ag) nanoparticle has extremely high surface energy and it is difficult to find an efficient dispersant to prevent its agglomeration in suspensions. A new brush copolymer, succinic anhydride modified epoxy-amine poly[(propylene oxide)-co-(ethylene oxide)]-grafted polymer (EPOA), which can efficiently disperse concentrated aqueous suspensions of Ag nanoparticles is revealed. The dispersion efficiency of EPOA for the dispersion of a 60 nm-Ag nanoparticles in aqueous suspension is studied by measuring its sedimentation and rheological behavior, and the results are compared with those of a commercially available dispersant, ammonium poly(acrylic acid) (PAA-NH₄). Interactions between the dispersants and the Ag nanoparticles are characterized by zeta potential and adsorption analyses. Theoretical calculations are conducted to clarify the adsorption and the dominant dispersion stabilization mechanisms of the dispersants. Compared with PAA-NH₄, EPOA obtains a higher stable suspension of Ag nanoparticles with less significant sedimentation over 1 month. The dispersion homogeneity of the suspension remains excellent even at an extremely high solid loading of 30–40 wt%. According to adsorption analysis, it is suggested that both EPOA and PAA-NH₄ adsorb via single-point attachment through the carboxyl group on the Ag surface. Based on theoretical calculations, the Ag nanoparticles are better stabilized by EPOA via an electrosteric dispersion mechanism.     

含共引发剂胺的聚酯型高分子光引发剂的制备及其性能研究

为克服小分子光引发剂的固有缺陷,通过2-(2,3-二羟基)丙氧基硫杂蒽酮(HPTX)、二酰氯及N-甲基二乙醇胺(MDEA)进行逐步聚合反应,将硫杂蒽酮结构及共引发剂胺结构都引入到同一个高分子链上,制备了侧链含有硫杂蒽酮,主链含有共引发剂胺的聚酯型高分子光引发剂。傅里叶变换红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)证实了高分子光引发剂的结构。紫外光谱(UV-Vis)证实了高分子的结构对硫杂蒽酮单元的最大紫外吸收几乎没有影响。用光致差示扫描量热仪(photo-DSC)研究聚酯型高分子光引发剂引发聚酯丙烯酸酯树脂(PEA)的光聚合反应,结果表明:高分子光引发剂的主链结构对其引发效率有着显著的影响。     

The Adsorption of a Polystyrene-b-Polyisoprene Block Copolymer at the n-Hexadecane/Air Interface

Surface-tension measurements were used to investigate the surface adsorption and micellisation of a polystyrene-b-polyisoprene block copolymer in n-hexadecane which is a selectively bad solvent for polystyrene. Measurements were made over a range of concentrations (1.29–2.88)x10^?4 mol dm^?3 and temperatures 25–40°C. The block copolymer was found to be positively adsorbed at the n-hexadecane/air interface. The linearity of plots of γ against In c just below the critical micelle concentration (c.m.c.) indicated an approximately constant surface concentration. The area per block copolymer molecule at the surface had an average value of 4.1 nm². A plot of In (c.m.c.) against T^?1 gave a value for the standard enthalpy of micellisation of -41.9.3.0 kJ per mole of copolymer chains. The standard entropy contribution (-TΔSΔ) to the standard free energy of micellisation was found to be 19.7.3.0 kJ mol^?1. These thermodynamic values are in good agreement with results obtained earlier for this system by light scattering and calorimetry.     

含共引发剂胺的聚氨酯型高分子光引发剂的制备及性能研究

通过异佛尔酮二异氰酸酯（IPDI）、2-（2,3-二羟基）丙氧基硫杂蒽酮（HPTX）及N取代的二乙醇胺进行逐步聚合反应,将硫杂蒽酮结构及共引发剂胺结构都引入到同一高分子链上,得到侧链含有硫杂蒽酮、主链含有共引发剂胺的聚氨酯型高分子光引发剂（PU-IBTX、Pu—IMTX和Pu．IPTX）。傅立叶红外变换光谱和核磁共振氢谱证实了高分子光引发剂的结构。紫外光谱证实了高分子链的结构对硫杂蒽酮单元的最大紫外吸收几乎没有影响。用光致差示量热计研究聚氨酯型高分子光引发剂引发聚氨酯丙烯酸酯（PUA）树脂的光聚合反应,结果表明,Pu—IPTX是引发PUA光聚合最有效的光引发剂。     

Removal of Mercury (II) Ions from Aqueous Solutions by the Polyacrylamidoxime Chelating Fiber

Abstract

A fibrous sorbent containing chelating amidoxime groups –C(NH₂)?NOH prepared from the Romanian commercial polyacrylonitrile ‐based fiber Melana was used for the removal of Hg²⁺ from aqueous solutions. The optimum conditions for the Hg²⁺ uptake were developed with respect to initial pH of solution, nature of anions, equilibration time, concentration of Hg²⁺, and temperature. The sorption was described quantitatively by fitting the equilibrium data to the Langmuir isotherm. The Langmuir parameters and thermodynamic quantities (ΔG, ΔH, ΔS) were calculated. The chelation mechanism of Hg²⁺ uptake on polyacrylamidoxime fiber was confirmed by IR spectroscopy. The experimental results point out the possibility of polyacrylamidoxime fiber to reversibly bind Hg²⁺ from wastewaters.     

嵌段共聚物PAN-b-PZDMA的合成及表征

使用原子转移自由基聚合法(ATRP)设计合成了大分子引发剂PAN-Br,通过引发甲基丙烯酸锌单体聚合制备得到黏均相对分子质量(简称黏均分子量,下同)分别为7 507、8 517、9 905的嵌段共聚物聚丙烯腈-b-聚甲基丙烯酸锌(PAN-b-PZDMA),利用1HNMR和FTIR确认了大分子引发剂和嵌段共聚物的分子结构。TGA和DSC测试结果显示,ZDMA链段抑制了聚丙烯腈的环化反应,提高了聚合物的热性能。     

Preparation and Effectiveness of Slow-release Polymeric Fertilizer Containing Multiple Nutrients Special for Maize

Slow-release polymeric fertilizer containing multiple nutrients was synthesized through condensation polymerization from raw materials of homemade low-molecular urea-formaldehyde and the compounds of potassium dihydrogen phosphate and phosphoric acid. Adjustment of the proportion of raw materials makes the ingredients of the fertilizer are N：P_2O_5：K_2O =1：0.75：0.13, which satisfy the nutritional requirement for maize growth. Field-experiment results prove that the yield of maize increases by 16.56% when using the polymeric fertilizer special for maize alone, by 56.51% when applying the polymeric fertilizer special for maize plus farmyard manure, and by 49.11% when applying the SV fertilizer special for maize plus manure.     

Optimizing Chain Topology of Bottle Brush Copolymer for Promoting the Disorder-to-Order Transition

The order-disorder transitions (ODT) of core-shell bottle brush copolymer and its structural isomers were investigated by dissipative particle dynamics simulations and theoretically by random phase approximation. Introducing a chain topology parameter λ which parametrizes linking points between M diblock chains each with N monomers, the degree of incompatibility at ODT ((χN)ODT; χ being the Flory–Huggins interaction parameter between constituent monomers) was predicted as a function of chain topology parameter (λ) and the number of linked diblock chains per bottle brush copolymer (M). It was found that there exists an optimal chain topology about λ at which (χN)ODT gets a minimum while the domain spacing remains nearly unchanged. The prediction provides a theoretical guideline for designing an optimal copolymer architecture capable of forming sub-10 nm periodic structures even with non-high χ components.