壳聚糖及其改性衍生物对锆(Ⅳ)离子的吸附研究

壳聚糖经双氧水降解得到低分子量壳聚糖,用水杨醛对低分子量壳聚糖进行化学改性得到其相应的衍生物.分别研究了壳聚糖和水杨醛改性的低分子量壳聚糖对锆(Ⅳ)离子的吸附,考察了锆(Ⅳ)离子起始浓度、溶液pH值、吸附时间以及温度对这两种吸附剂吸附锆(Ⅳ)离子性能的影响,得出了最佳吸附条件.用红外对最佳条件下的吸附产物进行了表征.结果表明,壳聚糖吸附锆离子的最佳条件为:锆(Ⅳ)离子的起始浓度为6.5×10-4g/mL,振摇时间为6.5h,pH值为5～6;水杨醛改性的低分子量壳聚糖吸附锆离子的最佳条件为:锆离子的起始浓度为4.7×10-4g/mL,振摇时间为5h,pH值为5～6.这两种吸附剂对锆(Ⅳ)离子的吸附受温度影响均不大,吸附行为均满足Langmuir等温式.红外光谱分析表明,锆(Ⅳ)离子与这两种吸附剂均发生了配位作用.     

交联羧甲基壳聚糖对铅离子的吸附研究

以壳聚糖为原料,先在氨基上引入羧甲基制备出N-羧甲基壳聚糖,再和环氧氯丙烷发生交联反应,合成出新型交联羧甲基壳聚糖,FTIR表征其结构。研究了交联羧甲基壳聚糖对Pb2+的吸附性能,探讨了交联剂用量、铅离子溶液的pH值、温度、吸附时间等因素对其吸附性能的影响,并考察了交联羧甲基壳聚糖对铅离子吸附动力学和热力学实验。实验结果表明,交联羧甲基壳聚糖对铅离子的吸附量优于壳聚糖,平衡吸附量可达297.6 mg/g。交联羧甲基壳聚糖对铅离子的吸附符合准二级动力学模型和Langmuier等温吸附,吸附主要依靠结构中的羧基和氨基基团。     

新型黄原酸壳聚糖对铅离子的吸附及机理研究

以壳聚糖为原料,先合成O-羧甲基壳聚糖,再和二硫化碳反应制备出新型黄原酸壳聚糖,使用元素分析、FT-IR、UV和TG对其结构进行表征。比较了壳聚糖、O-羧甲基壳聚糖和黄原酸壳聚糖对铅离子的吸附能力,并研究黄原酸壳聚糖对水溶液中铅离子的吸附性能,探讨了铅离子溶液的pH值对吸附的影响和黄原酸壳聚糖对铅离子的吸附热力学。结果表明,黄原酸壳聚糖对铅离子吸附量是壳聚糖的8.37倍,平衡吸附量可达600.6mg/g。XPS表明,吸附过程主要通过吸附剂中的氨基、羧基和黄原酸基团与铅离子发生作用完成。     

磁性壳聚糖微球的制备及对Cr(Ⅵ)的吸附性能研究

用壳聚糖包埋磁流体,用戊二醛交联制成磁性壳聚糖微球,并用红外光谱表征其结构。用制备的磁性壳聚糖微球吸附Cr(Ⅵ)离子,考察了其对Cr(Ⅵ)离子的吸附性能;探讨了吸附时间、溶液pH值、吸附剂用量、温度、Cr(Ⅵ)起始浓度以及其他离子存在对Cr(Ⅵ)离子去除率的影响。实验结果表明,磁性壳聚糖微球吸附Cr(Ⅵ)离子的最佳条件为:吸附平衡时间40 min,最佳吸附pH值6左右,磁性壳聚糖微球用量10 mg,温度升高有利于提高磁性壳聚糖微球的吸附效率,Cr(Ⅵ)离子起始质量浓度为12μg/mL,无机盐的存在引起磁性壳聚糖微球的吸附性能降低。并且考察了吸附剂的再生性能,实验结果表明磁性壳聚糖微球具有良好的重复使用性。     

磁性壳聚糖复合微球的制备及其Cu~(2+)吸附性能

以球磨后的粉煤灰磁珠(MS)颗粒为磁核,通过溶胶凝胶法和反相微乳液法依次包覆SiO_2和壳聚糖(CS),制备了MS@SiO_2@CS磁性微球。利用扫描电镜及能量色散谱仪、热重分析仪、红外光谱仪、X射线衍射仪、振动样品磁强计对所得样品的结构和磁性进行了系统表征。结果表明,磁珠颗粒表面实现了逐层包覆,较均匀的分散于壳聚糖基体中,MS@SiO_2@CS微球的比饱和磁化强度可达7.04 emu·g~(-1)。Cu~(2+)离子吸附实验表明,所得磁性壳聚糖微球对Cu~(2+)具有良好的吸附能力,最大吸附量可达11.08 mg·g~(-1);而且可通过磁选法高效固液分离。吸附动力学研究表明,MS@SiO_2@CS微球对Cu~(2+)离子的吸附符合准二级动力学模型,以化学吸附为主。     

交联黄原酸壳聚糖对铅离子的吸附研究

以壳聚糖为原料,通过交联和黄原酸化反应制备出交联黄原酸壳聚糖,采用FT-IR和XRD表征了其结构,并探讨壳聚糖及交联黄原酸壳聚糖对Pb2+的吸附性能。研究了初始溶液pH值、温度以及吸附时间等因素对Pb2+吸附量的影响。结果表明,在Pb2+起始浓度0.01 M,起始溶液pH=5,室温25℃吸附2h条件下,壳聚糖和交联黄原酸壳聚糖对铅离子的吸附量分别为126.8 mg/g和238.9 mg/g,交联黄原酸壳聚糖吸附能力为壳聚糖的1.89倍。     

基于SPR技术研究壳聚糖对Pb2+的吸附动力学

采用自主构建的表面等离子共振(SPR)生物传感系统研究了壳聚糖对Pb2+的吸附动力学。通过双官能团偶联剂将壳聚糖固定在传感器芯片表面,利用壳聚糖分子中含有的大量活性基团与Pb2+配位形成金属螯合物,研究了壳聚糖对不同浓度Pb2+的吸附过程,并进行动力学分析。结果表明,壳聚糖对铅离子的吸附符合Langmuir单分子吸附理论所提出的动力学方程,为壳聚糖在处理含铅环境污染物方面提供了一种理论依据。     

羧甲基壳聚糖对铅离子的吸附性能研究

本文研究羧甲基壳聚糖对Pb^2 的吸附作用,探讨反应时间,离子强度,溶液的PH值、羧甲基取代度,温度等因素对吸附性能的影响,结果表明羧基是吸附Pb^2 的主要活性基团,羧甲基壳聚糖对Pb^2 的饱和吸附量为3．1083mmol/g,吸附Pb^2 的能力比壳聚糖,水溶性低聚壳聚糖强。     

X射线光电子光谱法研究壳聚糖吸附镉(Ⅱ)的机理

用X射线光电子光谱法测定了壳聚糖和壳聚糖-Cd^2 络合物表面C、O及N原子的结合能及组成、研究了壳聚糖与镉离子的作用机理,氮原子的化学位移表明氨基是吸附活性基团,由化学分析和XPS得到参与吸附的N/Cd值为1.6,存在物理吸附和化学吸附,在化学吸附中两个N与一个Cd络合。     

铜模板交联壳聚糖对金属离子的吸附性能研究

研究了壳聚糖对CuSO4、Cu(Ac)2、Cu（NO3)2和CuCl2溶液中铜离子的吸附性能，并以各种铜盐为模板合成了戊二醛交联树脂，考察该树脂了对金属离子的选择吸附性能．结果表明，交联树脂对铜离子有较强的“记忆”功能，且以硫酸铜为模板的壳聚糖较其它盐的模板有更高的吸附量和选择性．     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.