Li4SiO4对CO2捕集性能的实验研究

以Li₂CO₃和SiO₂为原料,通过高温固相合成法合成了CO₂捕集剂Li₄SiO₄,并用X射线粉末衍射仪(XRD)、扫描电子显微镜(SEM)对所合成的材料在CO₂捕集前后的晶相变化以及微观结构进行了表征。通过热重分析仪(TGA)研究了Li₄SiO₄材料吸附CO₂的性能,并在小型热态实验台架上进行了CO₂热态捕集实验。实验结果表明,Li₄SiO₄对CO₂的捕集性能受Li₄SiO₄合成温度、CO₂的吸附温度以及气体中CO₂含量的影响,在700 ℃下制得的Li₄SiO₄具有最佳的CO₂吸附特性,最大吸附增量可达34%。Li₄SiO₄的吸附能力随着CO₂含量和吸附时间的增加而增加,当CO₂浓度分别为75%、67%、60%时,700 ℃ Li₄SiO₄对CO₂最大吸附量分别可达6.68 mmol/g、3.37 mmol/g、2.02 mmol/g (理论量8.33 mmol/g)。     

聚[吡咯-2,5-二(3-羟基-4-甲氧基苯甲烷)]的吸附性能研究

合成了具有类似开环卟啉结构的高分子——聚[吡咯-2，5-二(3-羟基-4-甲氧基苯甲烷)]。研究了该聚合物对Cu^2 和Mg^2 的吸附性能，讨论了吸附时间、吸附温度和体系pH对吸附量的影响。通过红外光谱分析对聚合物-金属络合物的结构进行了表征。     

N,N-双(二硫代羧基)二乙烯三胺乙基聚合物的合成及其吸附性能

以二乙烯三胺与二硫化碳反应生成中间体[N,N-双(二硫代羧基)二乙烯三胺],进而与1,2-二氯乙烷聚合生成N,N-双(二硫代羧基)二乙烯三胺乙基聚合物,用红外光谱确认了中间体和聚合物的结构.测定了聚合物对一部分重金属离子的吸附性能.结果表明,聚合物能定量地吸附某些重金属离子,对Ag+、Cu2+等离子有较高的吸附容量.     

二(β-氨基乙基)胺型聚苯乙烯树脂的合成和性能研究

以二乙烯三胺和氯甲基化聚苯乙烯树脂微球为起始原料,通过伯胺保护、树脂胺化、脱保护等3个步骤,合成了以二(β-氨基乙基)胺为功能基的聚苯乙烯树脂,分析了该树脂的结构,研究了其对Cu2+的螯合性能。与二乙烯三胺型树脂相比,本文合成的树脂具有吸附速度快、吸附容量大,脱附完全,易于重复使用等优点,对Cu2+吸附量达2.42mmol/g,脱附率为99.8%,吸附-脱附3次后,活性仍达95.0%。     

聚丙烯腈树脂基固态胺吸附剂的制备及其对CO_2吸附性能研究

以丙烯腈(AN)为单体,二乙烯苯(DVB)为交联剂,采用悬浮聚合法制备了多孔聚丙烯腈聚合物(PAN),进一步通过胺化反应制备了含有较高密度胺基的固态胺吸附材料.利用N2吸附-脱附等温线、扫描电子显微镜(SEM)、热重分析(TG)等方法表征了吸附材料的结构和形貌.研究了有机胺化试剂类型对所制备的材料结构的影响,以及吸附温度、湿度等对其CO_2吸附性能的影响.研究结果表明,当吸附温度为25°C、流速为30 m L/min、CO_2浓度为10%、有机胺为四乙烯五胺(TEPA)时,固态胺吸附材料PAN-TEPA对CO_2的吸附量可达1.87 mmol/g.水的存在能显著提高PAN-TEPA的吸附量,饱和水蒸气下,其对CO_2的平衡吸附量为2.97 mmol/g.动力学研究发现,Avrami模型能很好地拟合PAN-TEPA在不同温度下的吸附过程,揭示PAN-TEPA对CO_2的吸附过程是物理吸附和化学吸附共同作用的效果.经过10次循环再生吸附后,PAN-TEPA的吸附量仍可以达到初始吸附量的98%.上述研究结果表明,PANTEPA对CO_2具有良好的吸附性能和稳定的再生性能,其在CO_2的捕集方面具有重要的应用前景.     

二乙烯三胺桥联聚倍半硅氧烷的合成及其对Au(Ⅲ)的吸附性能研究

以3-氯丙基三甲氧基硅烷(CPTS)和二乙烯三胺(DETA)为原料,合成二乙烯三胺桥联单体;通过二乙烯三胺桥联单体的自凝胶及其在以十六烷基三甲基溴化铵(CTAB)为致孔剂条件下的溶胶-凝胶反应中,分别合成了两种DETA桥联聚倍半硅氧烷吸附材料。比表面及孔径分析结果表明,CTAB的加入使材料的比表面积略有增加,而累积孔体积和平均孔径则显著增大。吸附实验结果表明,两种DETA桥联聚倍半硅氧烷材料对Au(Ⅲ)表现出优异的吸附能力,静态饱和吸附量高达5~6mmol/g,吸附动力学符合拟二级模型;等温吸附符合Langmuir吸附模型。     

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.     

改性蓝藻基活性炭的制备及常压下对CO_2的捕集性能

以蓝藻为前驱体,采用KOH活化法制备了一系列蓝藻基活性炭;探讨了活化时间、活化温度以及碱炭比等活化参数对其孔结构的影响;进一步分别用HNO_3,HPO_4和NH_3·H_2O进行二次改性,制备了N或P原子掺杂的改性蓝藻基活性炭,研究了不同改性活性炭在25℃和1.01×10~5Pa条件下对CO_2的吸附捕集性能.结果表明,KOH活化的最佳活化时间为2 h,活化温度800℃,碱炭比为2.样品ACK-2-8在该条件下对CO_2的吸附量达到3.85 mmol/g.二次改性后的样品ACK-2-8-1,ACK-2-8-2和ACK-2-8-3对CO_2的吸附量分别高达4.41,3.97和4.63 mmol/g.N的掺杂有利于CO_2的吸附捕集.多批次重复再生实验结果表明,本材料对CO_2吸附再生具有较稳定的重复利用性.     

双底物诱导脂肪酶构象的固定及对底物的吸附特性

以聚乙二醇400二丙烯酸酯和三羟甲基丙烷三甲基丙烯酸酯为原料,加入底物月桂酸和正丁醇对脂肪酶进行活性构象诱导,再经紫外光引发聚合、抽提和干燥后,获得了双底物诱导脂肪酶构象的聚合物(DSLP),对DSLP在30~60℃对配体的吸附能力进行研究。结果表明,DSLP对月桂酸和正丁醇的吸附能力大于空白聚合物(BP)和固定化酶聚合物(ILP),显示底物诱导使DSLP对其配体具有较好的吸附能力。升温有利于增加DSLP对配体吸附量,当温度从30℃升高到40℃时,DSLP对月桂酸的平衡吸附量由25.83mg/g提高到36.08mg/g,DSLP对正丁醇的平衡吸附量由16.82mg/g提高到20.46mg/g。但随着温度的进一步上升,吸附量增加不明显。     

尼莫地平分子印迹聚合物的制备及热力学性能研究

采用本体聚合法,以甲基丙烯酸(MAA)为功能单体、三羟甲基丙烷三丙烯酸酯(TMPTA)为交联剂、尼莫地平为模板分子,制备了分子印迹聚合物。运用平衡结合实验,研究了印迹聚合物对尼莫地平、尼群地平、非洛地平药物分子的选择性识别能力。3种药物的静态吸附分配系数KD值分别为0.221 4、0.197 2、0.051 4。结果表明分子印迹聚合物对尼莫地平有较高的选择性。测定了不同温度下印迹聚合物的吸附等温曲线,表明吸附等温线为Ⅰ型吸附等温线,且随着温度的升高吸附量降低,说明吸附过程是放热过程。为了进一步研究印迹聚合物的吸附机理,进行了热力学性质的研究,测定了不同温度下吸附过程的熵变、焓变和吉布斯自由能变化,实验结果表明吸附是焓控制过程。     

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%).     

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 pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.