热塑性淀粉/聚乙烯醇/蒙脱土三元纳米复合材料

用熔融挤出的方法制备了甘油塑化热塑性淀粉（TPS）/聚乙烯醇（PVA）/蒙脱土（MMT）纳米复合材料,添加蒙脱土和聚乙烯醇用以提高热塑性淀粉材料的力学性能。 在相对湿度50%的条件下,复合材料的XRD衍射谱图和透射电子显微镜测试表明,MMT以剥离状态均匀分布在TPS/PVA基体中;力学测试表明,当MMT的质量分数从0％增至5％时,复合材料的力学性能明显提高。 当蒙脱土的质量分数为3%时,复合材料最大抗张强度达到13.24 MPa,杨氏模量达到61.46 MPa。 这说明蒙脱土在复合材料中可以起到物理交联点的作用,提高了复合材料的力学性能。     

热塑性淀粉/PBS共混物的微生物降解性研究

以甘油作为增塑剂,采用玉米淀粉与改性后的聚丁二酸丁二醇酯(PBS)熔融共混制备出淀粉/PBS共混材料.对这种改善了两相相容性的共混材料在特定微生物条件下的降解行为进行了研究.结果显示,共混物降解28天后,含有30%PBS的共混物质量损失达到35%左右,其力学性能只有降解前的20%,甘油含量减小和PBS含量增加均能减缓材料的降解.且随着降解时间的延长,PBS的结晶度和熔点有所提高.     

MgAlZnFe-CO3 LDHs对PBS膨胀阻燃体系性能的影响

采用恒定pH值共沉淀法在自制反应器中合成了不同原料配比的碳酸根型镁铝锌铁层状双羟基金属氧化物（MgAlZnFe-CO₃ LDHs）,并通过熔融共混MgAlZnFe-CO₃ LDHs、聚磷酸铵（APP）、三聚氰胺（MA）和全降解材料聚丁二酸丁二醇酯（PBS）制备出PBS膨胀阻燃材料. 采用傅里叶红外光谱（FTIR）、热失重（TG）、X射线衍射（XRD）、扫描电子显微镜（SEM）及元素分析（ICP）对MgAlZnFe-CO₃ LDHs进行了表征,并对PBS膨胀体系进行了力学性能和阻燃性能等测试. 结果表明,当Mg²⁺,Zn²⁺,Al³⁺和Fe³⁺的摩尔比为9：3：3：1时,合成的MgAlZnFe-CO₃ LDHs热稳定性最好,晶态结构规整,呈形貌规则的六边形片状;当MgAlZnFe-CO₃ LDHs的添加质量分数为1%时（阻燃剂的总添加质量分数为20%）时,PBS膨胀阻燃体系的极限氧指数（LOI）达到35%,垂直燃烧测试达到UL-94 V-0级别,力学性能得到较大改善. 实验结果表明,低添加量的MgAlZnFe-CO₃ LDHs与膨胀阻燃剂（IFR）协效阻燃PBS,一方面能够改善膨胀阻燃剂恶化PBS力学性能的现象,另一方面协同效应能够明显提高PBS的阻燃性能.     

甲醇乳化柴油分散特性的研究

利用显微摄像技术及算术统计的方法表征了甲醇乳化柴油分散相-甲醇的平均粒径。研究了甲醇乳化柴油分散相（甲醇）的粒径分布随高速分散器转子转速、乳化时间、乳化剂用量和甲醇的质量分数等参数的变化。结果表明,甲醇乳化柴油分散相的平均粒径随转速、乳化剂用量的增加而减小,但随甲醇含量的增加而增大;当乳化时间为2min和转子转速为5×2800r/min,乳化剂的质量分数为5%和甲醇的质量分数为10%时,甲醇乳化柴油中分散相存在最佳的分散度,其值为16μm。
     

聚丙烯酸酯/偏二氯乙烯/蒙脱土复合乳液的制备

以偏二氯乙烯和蒙脱土作改性剂,采用种子乳液聚合方法制备了聚丙烯酸酯 偏二氯乙烯/蒙脱土（PEA VDC/MMT）共聚物复合乳液,研究了蒙脱土质量分数对共聚物乳胶粒径、乳胶膜抗拉强度与断裂伸长率及热稳定性的影响。 结果表明,当蒙脱土质量分数从1%增加至5%时,PEA-VDC/MMT共聚物乳胶的平均粒径从141 nm增至243 nm;在蒙脱土质量分数为2%时, 乳胶膜的拉伸强度和断裂伸长率达到最大值,分别为3.23 MPa和1.330%。 PEA VDC共聚物的成碳率和热分解温度均随蒙脱土质量分数的增加而略有增加。     

Mg-5Sm-xGd合金及其抗拉强度反常温度效应

采用光学显微镜、扫描电镜、 X射线衍射和电子拉伸试验等研究了时效态Mg-5Sm-xGd (x=1, 2, 3, 4)合金的显微组织和力学性能。结果表明：时效态合金主要由α-Mg基体以及位于晶内弥散分布的稀土相Mg₅Gd和Mg₄₁Sm₅组成,随Gd含量的增加,稀土相的种类没有发生明显变化;Gd含量可改变晶粒大小,随Gd含量的增多晶粒大小先减小后增大,在Gd含量为3%时合金晶粒最小;合金抗拉强度总体变化趋势为随温度升高先升高后降低,出现了抗拉强度反常温度效应;在同一温度下,3%Gd含量的合金抗拉强度最高,并随温度升高而升高,在300℃达到峰值229.9 MPa;合金的屈服强度随温度升高而升高,随Gd含量的增加先升高后降低然后再升高,在Gd含量为3%,拉伸温度为300℃时屈服强度最大;合金拉伸断裂方式主要为脆性断裂,随温度升高逐渐向韧性断裂转变;合金的抗拉强度反常温度效应可能与晶格常数,晶粒大小及第二相的变化有关。     

十六烷基三甲基溴化铵/山梨醇酐硬脂酸酯微乳液凝胶固定化脂肪酶的催化活性及立体选择性

制备了能在水溶液中长时间稳定存在的十六烷基三甲基溴化铵/山梨醇酐硬脂酸酯（CTAB/Span-60）微乳液凝胶（MBG）,确定了Span-60在乳化剂EM（正丁醇与Span-60的混合物）中的质量分数范围;分别以正己酸与正己醇的酯化反应、α-单硬脂酸甘油酯的水解反应、消旋布洛芬与正辛醇的不对称酯化反应为指示反应,研究了CTAB/Span-60 MBG固定化脂肪酶的催化活性及立体选择性。 结果表明,Span-60在EM中的质量分数小于57%时可形成机械强度较好的CTAB/Span-60 MBG;其固定化脂肪酶在有机溶剂中的酯化活性随EM中Span-60含量的增加先是逐渐增大,35%时最大,后又逐渐小幅度降低,在所考察的Span-60含量范围内均比在CTAB MBG中高;在水溶液中固定化脂肪酶能顺利催化α-单硬脂酸甘油酯的水解反应,24 h后反应转化率不再随反应时间的延长而增加,其水解活性在重复使用9次后仅降低13.68%,表明CTAB/Span-60 MBG固定化脂肪酶能够顺利进行分离并重复使用;此体系的脂肪酶也选择性地催化生成S-构型布洛芬辛酯,产物对映体过量值（eee）随反应的进行缓缓下降,但降幅不大,即其立体选择性要比在CTAB MBG中高。 因此,CTAB/Span-60 MBG作为脂肪酶固定化载体既可用于有机溶剂中又可用于水溶液中的生物合成与生物转化反应,扩大了微乳液凝胶固定化脂肪酶的应用范围。     

蜂窝状Ho改性Fe-Mn/TiO2催化剂的制备及其低温选择催化还原(SCR)脱硝性能

采用模压法制备了蜂窝状Ho改性的Fe-Mn/TiO₂催化剂,研究了结构助剂、黏合剂和造孔剂等对成型催化剂低温选择催化还原（SCR）脱硝性能的影响。优选出一套理想的成型参数：水粉质量比为40%且逐次分批加入;结构助剂玻璃纤维的用量为10%（质量分数）;黏合剂羧甲基纤维素的用量为5%（质量分数）;助挤剂甘油的添加量为10%（质量分数）且分批加入;造孔剂活性炭粉的用量为2%（质量分数）。该蜂窝状催化剂在120 ℃下脱硝率维持在90%以上,并且在SO₂体积分数低于0.02%时具有一定的抗硫抗水性。表征结果表明,成型后蜂窝状催化剂比表面积降低,颗粒分散程度明显减弱,并且表面酸量和表面Mn⁴⁺含量下降,对催化活性有一定的影响。     

钴含量和制备方法对AB5型储氢合金不同温度电化学容量的影响

报道了钴替代镍对储氢合金Ml（NiCoMnAl）5.4的微观结构以及-30-＋80℃的电化学容量的影响，其中钴含量分别为：0，1．31，2．63，3．94，5．25，6．56％（质量分数）。所有合金都先采用真空还原熔炼，然后进行快淬。结果发现，合金在不同温度下的电化学容量取决于合金的成分和制备方法。随钴含量增加，合金在较高温度（40-80℃）下的电化学容量提高，温度较低（-30-0℃）时则容量降低。随温度升高，快淬技术与铸锭技术相比，更能有效地提高舍金的容量。充放电电位曲线分析表明，高钴含量和快淬技术可以提高合金的析氢电位，从而有效地提高合金的高温容量。相反，较低的钴含量和铸态工艺可改善合金低温时的容量，这是由于低钴含量和铸成立工艺可使低温时的析氢电位提高，析氢反应滞后，同时充放电的电位差减小。X射线衍射表明，所有合金样品都是单相的六方晶系CaCu5型结构，并且随钴含量增加，晶格参数增大。由于成分更加均匀同时晶格应力和缺陷减少，快淬带主峰的半高宽值降低。     

掺铁碳化硅陶瓷的制备及其吸波性能

将羰基铁和液态聚碳硅烷(LPCS)反应生成的铁(Fe)溶胶与固态聚碳硅烷(PCS)混合,合成出不同Fe质量分数的PCS先驱体,然后经氧化交联和高温热解制备了不同Fe质量分数的磁性碳化硅陶瓷(Fe/SiC),系统地研究了Fe元素的引入对SiC陶瓷的组成、结构、磁性能和介电性能的影响规律。 研究发现,当Fe质量分数小于8.94%时,在热解过程中,Fe元素可以显著促进SiC_xO_y的分解,生成β-SiC,且随着Fe质量分数的增加,β-SiC的结晶峰越来越强;但随着Fe质量分数继续增加,达11.78%时,则主要生成Fe₃Si;Fe/SiC陶瓷均呈铁磁性,其饱和磁化强度随着Fe质量分数的增加而呈指数形式增加;当Fe质量分数为4.19%时Fe/SiC陶瓷在12.4 GHz具有最小的反射损耗,为-9.4 dB,同时低于-5 dB的带宽为2.4 GHz,Fe质量分数为8.94%时,低于-5 dB的带宽则为3.7 GHz,可用作良好的微波吸收材料。     

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.     

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.     

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.     

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.