以交联聚丙烯酸甲酯为载体的二乙烯三胺/铜(Ⅱ)络合物的合成及其对尿素的吸附性能

以大孔交联聚丙烯酸甲酯为原料,通过二乙烯三胺胺化和铜络合反应,合成了以交联聚丙烯酸甲酯为载体的二乙烯三胺/铜(Ⅱ)络合物,研究了这类高分子铜络合物在不同条件下对尿素的吸附性能.结果表明,高分子铜络合物对尿素的吸附主要是通过铜(Ⅱ)与尿素之间的配位作用进行的.在尿素浓度为130mg/dL,于pH为7的NaH₂PO₄-Na₂HPO₄缓冲溶液中,28℃时吸附4h,以交联聚丙烯酸甲酯为载体的二乙烯三胺/铜(Ⅱ)络合物对尿素的最大吸附量可达71.5mg/g.     

以交联聚丙烯酸甲酯为载体的多乙烯多胺／铜（Ⅱ）络合物的合成及其对尿素的吸附性

以大孔交联聚丙烯酸甲酯为原料，引入多乙烯多胺［Ｈ（ＮＨＣＨ２ＣＨ２）ｎＮＨ２，ｎ＝２，３，４］配体，络合二价铜离子，合成出一系列以交联聚内烯酸甲酯为载体的多乙烯多胺／铜（Ⅱ）络合物，研究了这类高分子络合物在不同条件下对尿素的吸附性能。结果说明，在载体树脂相同时．配体不同的络合物树脂对尿素的吸附性能有很大差异，以二乙烯三胺或三乙烯四胺为配体，产物树脂对尿素的吸附量较大，而以四乙烯五胺为配体则吸附量较小。在尿素浓度１３０ｍｇ／ｄｌ、吸附时间８小时、介质为ｐＨ＝７的Ｎａ２ＨＰＯ４－ＮａＨ２ＰＯ４缓冲溶液、温度１８℃时，该类高分子络合物对尿素的最大吸附量达到７５．２ｍｇ／ｇ。     

壳寡糖和磷酸化壳寡糖对Cu(Ⅱ)的络合和缓释性能

以壳寡糖(COS)和磷酸化壳寡糖(PCOS)为原料与铜离子反应,制备了壳寡糖铜(Ⅱ)络合物(COS-Cu)和磷酸化壳寡糖铜(Ⅱ)络合物(PCOS-Cu),讨论了pH、时间、温度和PCOS取代度对络合物吸附量的影响.释放性能表明COS-Cu(Ⅱ)和PCOS-Cu(Ⅱ)均具有缓释性能,且PCOS-Cu(Ⅱ)具有更加均匀的释放速率.     

壳聚糖预分离富集-离子色谱法测定痕量草酸根

本文通过壳聚糖(CTS)对水样中草酸根的预富集,利用离子色谱作为检测手段,建立了测定痕量草酸根的新方法。研究了CTS对C2O42-的吸附行为,考察了吸附时间、CTS用量、共存离子等对吸附率的影响。结果表明:在pH=3.0时,CTS对C2O42-的吸附率最大,可达100%;吸附后的C2O42-用0.1 mol/L的NaOH即可定量解吸,解吸率为96%;C2O42-的检出限为4.3μg/L,相对标准偏差(RSD)为7%(n=6)。CTS对C2O42-的等温吸附特性符合Langmuir方程,其饱和吸附量为194.0 mg/g。本方法用于水样中C2O42-的测定,结果满意。     

槲皮素金属配位分子印迹聚合物的识别性能

以槲皮素与Zn(Ⅱ)的配合物为模板,在甲醇溶液中制备金属配位分子印迹聚合物.通过紫外光谱研究了槲皮素与Zn(Ⅱ)的配位方式及配位比,验证了槲皮素、Zn(Ⅱ)和4-乙烯基吡啶之间的三元配位作用.利用红外光谱对产物的结构进行了表征.用平衡结合实验考察了功能单体及交联剂用量对聚合物吸附性能的影响,优化了聚合物的反应配比.同时对系列印迹聚合物的识别体系进行了考察.结果表明,槲皮素-Zn(Ⅱ)模板印迹聚合物对槲皮素-Zn(Ⅱ)的配合物表现出明显的吸附选择性和特异性,对槲皮素结构类似物芦丁和柚皮素的吸附选择性较差,分离因子分别为3.21和1.91.     

新型尿素吸附剂研究—褐藻酸Cu（Ⅱ）络合物吸附脲分子研究

首次利用褐藻酸Cu(Ⅱ)络合物配位吸附尿素分子,系统研究了影响尿素吸附的各种因素,并用红外光谱,紫外可见光谱分析手段对尿素吸附机制作了初步探讨,结果表明,褐藻酸Cu(Ⅱ)络合物在模拟人体生理介质下可络合吸附近60mg/g的吸附容量,其中尿素吸附液浓度为130.0mg/dl,介质为磷酸氢二钠和磷酸二氢钠的缓冲液(pH=7.0),温度为37℃。     

过氧化氢在乙酸均相体系中对壳聚糖的降解

为制备分子量较低的可溶于水的壳低聚糖,研究了在乙酸均相体系中过氧化氢氧化降解壳聚糖的过程,采用凝胶渗透色谱法跟踪测定了壳聚糖氧化降解过程中分子量及其分布的变化,探索制备不同分子量壳低聚糖的适宜条件。     

交联聚氨基壳聚糖螯合树脂的制备及吸附性能研究

以壳聚糖为原料合成了交联聚氨基球状螯合树脂,并考察了其对Hg(Ⅱ)、Pb(Ⅱ)、Zn(Ⅱ)的吸附性能及影响因素。结果表明,对高浓度金属离子(约0.01mol/L)吸附量的大小为Hg(Ⅱ)>Pb(Ⅱ)>Zn(Ⅱ),对Zn(Ⅱ)几乎不吸附;而在低浓度时(约20ug/ml)树脂对三种离子均具有较高的吸附率(>55%)。     

Cu(Ⅱ)对壳聚糖的配位控制降解

对壳聚糖进行液态均相络合反应制得壳聚糖铜配合物,IR、UV、元素分析及热重分析等检测证实了壳聚糖铜配合物中配位键的存在,且显示壳聚糖在形成配位结构后存在有利于降解的优势构象。以H₂O₂对壳聚糖-Cu(Ⅱ)络合物及壳聚糖进行氧化降解,考察降解过程中粘度的变化及降解产物分子量分布,在相同的降解条件下,壳聚糖铜配合物的降解速度明显高于壳聚糖,降解产物分子量分布较壳聚糖直接降解窄,结果进一步证明壳聚糖铜配合物中存在有利于降解的优势结构,同时证明以金属离子Cu(Ⅱ)对壳聚     

离子交换法纯化重组类人胶原蛋白Ⅱ的研究

用阳离子交换树脂CM-52分离纯化类人胶原蛋白Ⅱ（Human Collagen-like Bioprotein Ⅱ，HCBⅡ）。通过实验，分别确定了静态吸附和柱层析吸附的操作条件，即静态吸附：在pH4．0、NaCl0．15mol／L、进料浓度7g／L，处理量17．26ml／g树脂的条件下进行吸附，吸附时间为60min；柱层析：在pH4．0、NaCl0．15mol／L、进料浓度5g／L、流速5ml／min的条件下进行吸附。然后上柱，在pH4．0、NaCl0．30mol／L下进行脱附。实验表明，采用静态吸附的方式吸附HCBⅡ，然后上柱洗脱，HCBⅡ的吸附量可达到48、6mg／g树脂，回收率83．8％，操作时间短，分辨率高，最终纯化的HCBⅡ达电泳纯，分子量为97kD。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.