交联壳聚糖树脂对Ni(II)的吸附行为研究

研究了甲醛、环氧氯丙烷交联壳聚糖树脂(AECTS)对Ni(II)的吸附行为和吸附Ni(II)对树脂结构及性能的影响.用FTIR,WAXD,TGA和DSC对吸附产物进行了结构表征,并深入分析了AECTS与Ni(II)之间的作用机理.结果表明:AECTS主要以配位形式吸附Ni(II);AECTS吸附Ni(II)后,结晶度下降、总体上热稳定性变差;Ni(II)对AECTS的主链分解具有明显的催化功能,而空气气氛中对AECTS在500℃附近的分解表现出火焰缓蚀作用.AECTS对Ni(II)的吸附行为符合Langmuir模型,属于单分子层吸附,所有吸附位对Ni(II)的作用近似相同;与壳聚糖(CTS)比较,造成AECTS对Ni(II)吸附量增大的主要原因是AECTS结晶度下降和孔隙率增加,二者导致在交联处理前Ni(II)难于接近的吸附位点“活性”相对增大,使其更容易与Ni(II)相结合;不同介质对AECTS吸附Ni(II)的影响大小顺序为HCl>CdCl2>MgCl2>NaCl,前两者使吸附量减小,MgCl2使吸附量稍有增加,NaCl对吸附量基本没有影响.     

交联壳聚糖树脂对Ni(II)的吸附行为研究

研究了甲醛、环氧氯丙烷交联壳聚糖树脂(AECTS)对Ni(II)的吸附行为和吸附Ni(II)对树脂结构及性能的影响. 用FTIR, WAXD, TGA和DSC对吸附产物进行了结构表征, 并深入分析了AECTS与Ni(II)之间的作用机理. 结果表明: AECTS主要以配位形式吸附Ni(II); AECTS吸附Ni(II)后, 结晶度下降、总体上热稳定性变差; Ni(II)对AECTS的主链分解具有明显的催化功能, 而空气气氛中对AECTS在500 ℃附近的分解表现出火焰缓蚀作用. AECTS对Ni(II)的吸附行为符合Langmuir模型, 属于单分子层吸附, 所有吸附位对Ni(II)的作用近似相同; 与壳聚糖(CTS)比较, 造成AECTS对Ni(II)吸附量增大的主要原因是AECTS结晶度下降和孔隙率增加, 二者导致在交联处理前Ni(II)难于接近的吸附位点“活性”相对增大, 使其更容易与Ni(II)相结合; 不同介质对AECTS吸附Ni(II)的影响大小顺序为HCl＞CdCl₂＞MgCl₂＞NaCl, 前两者使吸附量减小, MgCl₂使吸附量稍有增加, NaCl对吸附量基本没有影响.     

交联壳聚糖树脂吸附Cu2+的机理研究

研究了甲醛、环氧氯丙烷交联壳聚糖(AECTS)对Cu2+的吸附热力学行为,用FTIR对吸附产物进行了结构表征,并研究了溶液中介质种类的不同对Cu2+吸附量的影响.结果表明AECTS主要以配位形式吸附Cu2+;AECTS对Cu2+的吸附符合Langmuir等温方程,属于单分子层吸附;吸附为自发的、吸热的熵增加过程;同时不同介质对树脂吸附Cu2+的影响大小顺序为HCl＞CdCl2＞MgCl2＞NaCl,并对其作用机理进行了探讨.     

交联壳聚糖对Zn2+的吸附性能

研究了甲醛、环氧氯丙烷交联壳聚糖树脂(AECTS)对Zn 2 的吸附行为,探讨温度、溶液的pH、反应时间、再生次数等因素对吸附性能的影响,并用红外光谱(FTIR)和光电子能谱(XPS)对吸附产物表面的元素结构及其结合能的变化进行表征. 结果表明,AECTS对Zn 2 的吸附导致AECTS结构和性能发生显著变化. FTIR和XPS分析表明,Zn 2 以配位键的形式吸附于AECTS,使AECTS中氨基的伸缩振动、变形振动发生了明显变化,N原子发生化学位移,而AECTS分子链上的羟基没有直接参与配位反应;AECTS对Zn 2 有较强的吸附能力和较快的吸附速率,在30 ℃、Zn 2 初始质量浓度为1 g/L的溶液中,吸附量可达163 mg/g树脂,是壳聚糖饱和吸附量的1.7倍左右;吸附量受pH的影响较大,在pH＝5时吸附量最高;AECTS对Zn 2 的吸附行为符合Freundlich等温吸附方程,温度升高吸附量增大,该过程为一吸热过程;AECTS经再生重复使用5次,吸附量基本不变.     

Hg2+-交联壳聚糖配合物的合成与表征

研究了甲醛、环氧氯丙烷交联壳聚糖树脂(AECTS)对Hg2 的吸附行为和吸附Hg2 对树脂结构及性能的影响。用FT-IR、XRD、TG、DSC和SEM对吸附产物进行了结构表征,并深入分析了AECTS与Hg2 之间的作用机理。结果表明,Hg2 与AECTS中的氨基发生配位、与AECTS中的羟基形成离子键而被吸附;AECTS吸附Hg2 后,结晶度下降,总体上热稳定性变差;Hg2 对AECTS的主链分解具有明显的催化功能;Hg2 的成键使得AECTS的表面形态发生了改变。     

交联壳聚糖树脂与Zn2+的配位作用

研究了甲醛、环氧氯丙烷交联壳聚糖树脂(Chitosan crosslinked by aldehyde and epichlorohydrin,AECTS)吸附Zn2 后对树脂结构及性能所产生的影响.用FTIR、XRD、TG、DSC和SEM对吸附产物进行了结构表征,并分析了AECTS与Zn2 之间的作用机理.结果表明,Zn2 与AECTS中的氨基发生配位而被吸附;AECTS吸附Zn2 后,结晶度下降、总体上热稳定性变差;Zn2 对AECTS的主链分解具有明显的催化功能;Zn2 的配位使得AECTS的表面形态发生了改变.     

交联壳聚糖树脂与Zn2+的配位作用

研究了甲醛、环氧氯丙烷交联壳聚糖树脂(Chitosan crosslinked by aldehyde and epichlorohydrin,AECTS)吸附Zn2 后对树脂结构及性能所产生的影响.用FTIR、XRD、TG、DsC和SEM对吸附产物进行了结构表征,并深入分析了AECTS与Zn2 之间的作用机理.结果表明,Zn2 与AECTS中的氨基发生配位而被吸附;AECTS吸附Zn2 后,结晶度下降、总体上热稳定性变差:Zn2 对AECTS的主链分解具有明显的催化功能;Zn2 的配位使得AECTS的表面形态发生了改变.     

交联壳聚糖-Co配聚物结构与性能初步研究

制备了微球状交联壳聚糖并合成了交联壳聚糖(AECTS)-Co配聚物。用FTIR、WXRD、TGA和DSC等对配聚物进行了结构表征。结果表明：Co^2 与AECTS中的氨基、羟基发生配位而被吸附;树脂与Co^2 配位后,结晶度下降、热稳定性降低。     

非水体系中配位吸附树脂对羟基羧酸吸附性能的研究

采用负载金属离子的配位吸附树脂在不同介质中对羟基羧酸的吸附规律进行研究.考察了吸附介质、树脂基质及所负载的金属离子不同对配位吸附的影响.结果表明,负载Fe3 的大孔磺酸型树脂在正己烷体系中对羟基羧酸类成分的吸附效果最佳,且随着羟基取代数目和位置的不同表现出一定的吸附选择性.     

丙烯酸Fe3+型树脂在非水介质中对鞣酸的配位吸附及洗脱性能

将Fe3 载于丙烯酸树脂上,制备了在非水介质中对鞣酸具有良好吸附性能的配位吸附树脂.在甲醇中,树脂对鞣酸的吸附符合Langmuir单分子层吸附模型,静态饱和吸附量为34mg/g,吸附为粒扩散控制过程.动态吸附中,树脂对鞣酸的泄漏吸附量为25mg/g,饱和吸附量32mg/g.采用5%的甲胺乙醇溶液作洗脱剂,洗脱率95%.树脂在吸附及洗脱过程中未见Fe3 脱落.     

Adsorption of Co, Ni, Cu, and Zn on hydrous manganese dioxide from complex electrolyte solutions resembling sea water in major ion content

Adsorption of Co, Ni, Cu, and Zn onto a poorly crystalline hydrous manganese dioxide (delta-MnO2) has been studied in complex electrolyte solutions such as (a) 0.5 M NaCl+0.054 M MgCl2, (b) 0.5 M NaCl+0.028 M Na2SO4, and (c) artificial sea water prepared according to the standard literature method. These three solutions allow us to identify the specific effect of major cations, major anions, and the mixture of major cations and anions (including carbonate and bicarbonate) that is present in real sea water. The adsorption isotherm in major ion sea water at pH 7.25 indicates that while Co and Zn exhibit increases in adsorption with increase in concentration, Ni shows relatively poor adsorption, reaching a plateau at 0.075 mM concentration. The three trace metals (Co, Ni, and Zn) show Langmuirian behavior for adsorption at low concentration. It is generally observed that the fractional adsorption vs pH curve shifts to higher pH either in the presence of 0.054 M MgCl2 or in sea water. In the presence of 0.028 M Na2SO4 the fractional adsorption vs pH curve remains almost unchanged with respect to a 0.5 M NaCl solution. The competitive adsorption of one trace metal in the presence of other three in major ion sea water indicates that this phenomenon is more predominant with Ni and Zn than with Co and Cu.     

Interface tension of silica hydroxylated nanoparticle with brine: a combined experimental and molecular dynamics study

We have used molecular dynamics simulations to calculate the interfacial tension of hydroxylated SiO(2) nanoparticles under different temperatures and solutions (helium and brine with monovalent and divalent salts). In order to benchmark the atomistic model, quartz SiO(2) interfacial tension was measured based on inverse gas chromatography under He atmosphere. The experimental interfacial tension values for quartz were found between 0.512 and 0.617 N/m. Our calculated results for the interfacial tension of silica nanoparticles within helium atmosphere was 0.676 N/m, which is higher than the value found for the system containing He∕α-quartz (0.478 N/m), but it is similar to the one found for amorphous silica surface. We have also studied the interfacial tension of the nanoparticles in electrolyte aqueous solution for different types and salts concentrations (NaCl, CaCl(2), and MgCl(2)). Our calculations indicate that adsorption properties and salt solutions greatly influence the interfacial tension in an order of CaCl(2) > MgCl(2) > NaCl. This effect is due to the difference in distribution of ions in solution, which modifies the hydration and electrostatic potential of those ions near the nanoparticle.     

Adsorption of guar gum onto quartz from dilute mixed electrolyte solutions

The effect of potassium, sodium, calcium, magnesium, and hydrogen cations on adsorption of guar gum onto quartz was investigated at natural pH. The role of the background ions was analyzed in terms of their water-structure making or breaking capabilities. In dilute solutions (0.01 mol/L) of structure-makers (NaCl, HCl, CaCl2, and MgCl2), the guar gum adsorption density did not change compared to the adsorption densities obtained in distilled water. Potassium, the only structure-breaking ion (chaotrope) among the tested cations, significantly enhanced guar gum adsorption. The results obtained in mixed electrolytes demonstrate that the strong structure-breaking properties of K+ overcome any contributions from weak structure making ions (kosmotropes), and guar gum adsorption remains at the levels observed in KCl alone. Only when strongly hydrated Mg2+ ions are mixed with KCl, the overall effect becomes additive and the influence of potassium is proportionally reduced by increasing concentrations of magnesium cations. In this approach, guar gum adsorption on quartz is viewed as a competition between polysaccharide and water molecules for silanol surface sites. The hydration of the quartz surface inhibits the adsorption process but the competition equilibrium, and hence polysaccharide adsorption, can be affected by the presence of chaotropes or kosmotropes.     

Controlled binding of a L-cysteinato cobalt(III) octahedron to a cadmium(II) center

The binding ability of a chiral L-cysteinato cobalt(III) complex, [Co(L-cys-N,S)(en)2]+ (l-H2cys = L-cysteine, en = ethylenediamine), toward a cadmium(II) center, together with the construction of S-bridged CoIIICdII structures that are controlled by anions and pH, is reported. The reaction of Lambda(L)-[Co(L-Hcys-N,S)(en)2](ClO4)2 having a pendent COOH group with CdCl2 in a 1:1 ratio in water, followed by the addition of NaCl, gave an S-bridged CoIIICdII dinuclear complex, Lambda(L)-[CdCl4{Co(L-Hcys-N,S)(en)2}] (1Cl), in which a cadmium(II) ion is weakly coordinated by a thiolato group from a Lambda(L)-[Co(L-Hcys-N,S)(en)2]2+ unit, besides four Cl- anions. The corresponding 1:1 reaction with CdBr2 and NaBr yielded an S-bridged CoIIICdIICoIII trinuclear complex composed of an S-bridged CoIIICdIICoIII trinuclear cation and a [CdBr4]2- anion, (Lambda(L))2-[CdBr3{Co(L-Hcys-N,S)(en)2}{Co(L-cys-N,S)(en)2} ][CdBr4] (2), while a CoIIICdII dinuclear complex analogous to 1Cl, Lambda(L)-[CdBr4{Co(L-Hcys-N,S)(en)2}] (1Br), was obtained by the addition of HBr instead of NaBr. In the CoIIICdIICoIII cation of 2, a CdII center is very weakly coordinated by two thiolato groups from Lambda(L)-[Co(L-Hcys-N,S)(en)2]2+ and Lambda(L)-[Co(L-cys-N,S)(en)2]+ units, besides three Br- anions, with the trinuclear structure being sustained by an intramolecular COOH...OOC hydrogen bond. On the other hand, no S-bridged structure was obtained by the corresponding 1:1 reaction with CdI2 and NaI, giving only a mononuclear CoIII species with a [CdI4]2- counteranion, Lambda(L)-[Co(L-Hcys-N,S)(en)2][CdI4] (3). When Lambda(L)-[Co(L-cys-N,S)(en)2]ClO4 having a deprotonated pendent COO- group was reacted with CdCl2 in a 1:1 ratio in water, followed by the addition of NaCl, a one-dimensional (CoIIICdII)n polymeric complex, (Lambda(L))n-[CdCl3{Co(L-cys-N,S)(en)2}]n (4Cl), in which Lambda(L)-[Co(L-cys-N,S)(en)2]+ units are alternately linked by [CdCl3]- moieties through thiolato and carboxylate groups, was constructed. An analogous (CoIIICdII)n polymeric structure having [Cd(NCS-N)3]- moieties, (Lambda(L))n-[Cd(NCS-N)3{Co(L-cys-N,S)(en)2}]n (4NCS), was also produced by the use of Cd(ClO4)2 and NaSCN.     

壳聚糖缩合呋喃甲醛螯合树脂的合成及性能研究

利用壳聚糖C2 位上活泼氨基与呋喃甲醛缩合反应 ,合成了一种新型树脂。通过L9(34 )正交试验 ,研究了缩合反应的最佳条件 :80℃乙醇中溶胀 1h ,反应 5h ,pH =4.0～ 4.5 ,反应物配比 (氨基摩尔∶醛基摩尔 )为 1∶4,缩合率达到 90 %以上。并测定了上述螯合树脂对过渡金属离子的吸附性能。     

The influence of cobalt incorporation and cobalt precursor selection on the structure and bioactivity of sol–gel-derived bioactive glass

Cobalt (Co) is a potential therapeutic ion used to enhance angiogenesis through a stabilizing effect on hypoxia-inducible factor 1 alpha (HIF-1α), and its incorporation into the structure of bioactive glass is a promising strategy to enable sustained local delivery of Co to a wound site or bone defect. Here Co-releasing bioactive glasses were obtained through the sol–gel method, comparing cobalt nitrate and cobalt chloride as precursors. The effect of using different Co precursors on the sol–gel synthesis and in the obtained bioactive glass structure, chemical composition, morphology, dissolution behaviour, hydroxycarbonate apatite (HCA) layer formation was investigated. When the chloride salt was used as Co precursor, evidence of crystalline cobalt (II, III) oxide (Co₃O₄) phase formation was found, along with the presence of Co³⁺ species as evaluated by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), whereas an amorphous glass containing mainly Co²⁺ species was obtained when the nitrate salt was the Co source. The presence of a crystalline phase decreased the surface area and pore volume of the final glass, consequently reducing the Co-release rate. Evidence of HCA layer formation after immersion in simulated body fluid (SBF) was still found when different precursors were used, although the rate of formation was reduced by the presence of Co. Therefore, this study showed that Co incorporation and the proper selection of the precursor could affect the final material structure, and properties, and should be considered when designing new bioactive glass compositions for tissue engineering applications.

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四元交互体系Cd2+, Na+//Cl-, SO42——H2O 298 K时的相平衡

采用等温溶解平衡法研究了四元交互体系Cd2+, Na+//Cl-, SO2-4-H2O在298 K的相平衡关系. 研究发现, 该平衡体系存在Na2CdCl4·3H2O复盐相区, 平衡相图中有七条单变度曲线, 三个共饱和点和五个结晶相区. 其平衡固相的结晶区分别为Na2SO4、CdSO4、CdCl2·2.5H2O、Na2CdCl4·3H2O和NaCl. 该四元交互体系平衡液相的物化性质随着Cd2+浓度的增加呈现有规律的变化. 研究结果表明, 镉盐在该体系中的溶解度大, 迁移性强, 增加了土壤环境污染风险.