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Co2+的机理研究

研究了甲醛、环氧氯丙烷交联壳聚糖 (AECTS) 对Co2 的吸附热力学行为,用FTIR、WXRD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Co2 吸附量的影响.结果表明:AECTS主要以配位吸附和物理吸附形式吸附Co2 ;树脂与Co2 配位后,结晶度下降;AECTS对Co2 的吸附行为同时符合Freundlich模型和Langmuir模型;吸附为自发的、放热的熵减小过程;不同介质对树脂吸附Co2 的影响大小顺序为HCl>CdCl2>MgCl2>NaCl,前两者使吸附量减小,后两者使吸附量增加,作用机理相差较大.     

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.     

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.     

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。     

不同交联剂含量对戊二醛交联壳聚糖膜结构与性 能影响的研究

仔细研究壳聚糖膜的结晶度、溶胀度及其对二价铜离子的吸附量与交联剂戊二醛含量(特别是在戊二醛含量较低时)的关系。结果发现膜的结晶度、溶胀度以及对铜离子的吸附量均在戊二醛摩尔分数为0.25%时达到极大值。结晶度的增大可归结于轻度交联能使壳聚糖分子链在成膜时排列更为有序;而溶胀度和对铜离子吸附量的增加则可认为是交联能使壳聚糖中原先被氢键作用所束缚的氨基获得了自由。     

新型吸附剂的合成、表征及其对Ni(II)的吸附研究

利用滴加法合成了球形含Ni2 交联壳聚糖,并通过胺化引入大量活性氨基,再经除镍制成对重金属镍离子具有较好吸附能力的新型吸附剂[P-C-CTS(Ni)].通过Ni2 吸附容量的测定,IR及XPS分析,验证了合成技术路线的正确性.通过研究pH值对吸附量的影响,初步讨论了无柠檬酸根(Cit)配位体存在时,吸附剂对Ni(II)的吸附为螯合作用.通过Cit存在条件下(cNi=cCit=0.852mmol·L-1),吸附剂对Ni(II)离子和Cit的吸附量随pH值的变化,结合相应pH值下金属镍的形态分布,探讨了其对Ni(II)的吸附机理,研究认为不仅仅是简单的螯合作用,其吸附机理和吸附量与溶液中金属离子的存在形式有关,引入静电吸附原理解释了吸附剂对Ni(II)的吸附现象.     

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.     

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%).     

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.     

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.     

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.     

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.