羧甲基壳聚糖/明胶共混膜的结构表征与吸湿保湿性

壳聚糖通过羧甲基化得到水溶性N，O-羧甲基壳聚糖，并将其配制成4Wt％水溶液，与4Wt％明胶水溶液共混，成功制得了羧甲基壳聚糖／明胶共混膜。采用红外光谱、x射线衍射、扫描电镜对共混膜进行结构表征，结果表明，共混膜中羧甲基壳聚糖和明胶分子间存在着较强的相互作用及良好的相容性。通过共混膜的力学性能测试，发现当羧甲基壳聚糖含量为20％时，共混膜的抗张强度达到最大值(75MPa)，分别比单独的羧甲基壳聚糖(45MPa)和明胶(43MPa)提高了66．7％和74％。经过吸湿和保湿性能测试，发现当羧甲基壳聚糖含量为80％时，吸湿率和保湿率分别为33．4％和69．2％，比单独的明胶膜分别提高了1．8倍和2．1倍。     

聚偏氟乙烯/左旋聚乳酸的相容性及其共混膜的结构和性能研究

动态力学分析(DMA)、溶度参数法、聚合物混合焓法对聚偏氟乙烯(PVDF)和左旋聚乳酸(PLLA)的相容性分析结果显示,随着共混体系中PLLA的增加,PVDF和PLLA之间的相容性变差。扫描电镜(SEM)、广角X-射线衍射(WAXD)和拉伸实验对共混膜中PVDF/PLLA配比对其微观结构和力学性能影响的分析结果显示,随PLLA含量从10%增加到50%,共混膜由均匀致密结构变为存在缝隙的多孔结构,共混膜结晶度增加,断裂伸长率下降,断裂强度先增加后下降,在PLLA含量为40%时,强度达到最大。     

接枝改性多面体齐聚倍半硅氧烷对左旋聚乳酸结晶行为的影响

以二氯甲烷为溶剂,利用溶液共混法将三种多面体齐聚倍半硅氧烷(POSS)分别与左旋聚乳酸(PLLA)进行共混,制备了不同POSS含量的单氨基POSS[(POSS-NH2)/PLLA]、POSS接枝聚乙二醇[(POSSPEG)/PLLA]和POSS接枝聚乳酸[(POSS-g-PLLA)/PLLA]复合材料。利用差示扫描量热仪和偏光显微镜(POM)分别对复合材料的本体结晶行为、结晶形貌和生长速率进行了观察。结果表明,当加入不同质量分数的POSS-PEG时,PLLA的结晶能力均得到改善,而POSS-NH2和POSS-g-PLLA仅在质量分数较低(1(wt)%)时提高了PLLA的结晶能力,具有较高质量分数时会阻碍PLLA分子链段的运动,从而限制其结晶。利用POM观察球晶生长过程发现,POSS-PEG的加入提高了PLLA的球晶生长速率。     

聚乳酸共混物立构复合物的形成及其结构性能研究进展

聚乳酸立构复合物(SC-PLA)由左旋聚乳酸(PLLA)和右旋聚乳酸(PDLA)以31螺旋构象并排堆砌而成,由于分子链间的紧密堆积,SC-PLA具有更高的晶体稳定性、熔点(约比PLLA高50℃)以及良好的热、力学、降解等性能。PLLA和PDLA共混是目前制备SC-PLA的一类常用方法,包括溶液共混、熔融共混、微波辐射共混等,SC-PLA在形成过程中会受到PLLA和PDLA的分子量、光学纯度、混合比例等因素影响。本文综述了PLLA和PDLA通过共混形成SC-PLA的条件和机理,以及SC-PLA的微观结构、性能和应用现状。     

壳聚糖水杨酸盐-明胶共混膜结构表征及其抗菌性

以溶液共混法成功制备出壳聚糖水杨酸盐－明胶共浊膜，用FT－IR、XRD、SEM表征了其结构，并测试了其吸水率，力学性能及抑菌性能。结果表明，壳聚糖水杨酸盐－胶胶共混膜中存在强烈的氢键相互作用及良好相容性，共混膜的力学性能随明胶含量增大而明显提高，当明胶含量为30％时，共混膜的抗张强度最大，其干、湿态抗张强度分别达99．9MPa和34．9MPa，比纯壳聚糖膜干，湿态抗张强度分别提高了99．8％有83．75，共浊膜抑菌性随明胶含量增加而下降，但其抑菌性仍明显高于壳聚糖膜。水杨酸的引入有利于改善其力学性能及抗菌性能，该共漫漫经膜作为一种潜在的伤口包扎材料，将具有广阔应用前景。     

聚左旋乳酸/聚氧化乙烯共混物的拉伸行为及结构转变

采用熔融共混方法制备了聚左旋乳酸(PLLA)和超高分子量聚氧化乙烯(PEO)共混物, 通过差示扫描量热(DSC)、 扫描电子显微镜(SEM)和二维广角X射线散射(2D-WAXS)等方法系统研究了PEO的加入对不同温度下PLLA拉伸行为及拉伸过程中微观结构变化的影响. 结果表明, PLLA/PEO共混物为非均相体系, PEO粒子均匀分布在PLLA中形成两相结构. PEO的加入能够显著降低PLLA的玻璃化转变温度(T_g), 在25～60 ℃范围内显著提高PLLA的拉伸性能. 在60 ℃拉伸时, PEO的加入提高了PLLA在拉伸过程中的结晶和形变能力. 在80 ℃拉伸时, 共混物的拉伸断裂伸长率下降, 但共混物的结晶速度仍高于纯PLLA样品.     

溶剂诱导的聚乳酸/聚乳酸衍生物共结晶行为

通过溶液浇铸法制备不同组分的左旋聚乳酸(PLLA)和聚(L-2-羟基-3-甲基丁酸)(PL-2H3MB)共混物。运用差示扫描量热仪(DSC)、偏光显微镜(POM)、广角X射线衍射(WAXD)和热重分析仪(TGA)分析共混物的结晶、熔融行为和热稳定性。通过观察到DSC加热曲线中新的熔融峰判断PLLA和PL-2H3MB共晶的形成,共晶显著提高PLLA起始结晶温度和WAXD曲线中特征衍射峰的变化,证实了溶液浇铸共混物中的共结晶现象。同时,共混物中PL-2H3MB和PLLA还表现出优于单组分PLLA和PL-2H3MB的热稳定性。PLLA和PL-2H3MB的共结晶行为可能为调控PLLA的热稳定性、力学性能以及降解性能提供了一种新的潜在方法。     

接枝改性POSS对PLLA结晶行为的影响*

以二氯甲烷为溶剂,利用溶液共混法将三种聚笼形多面体倍半硅氧烷(POSS)分别与聚左旋乳酸(PLLA)进行共混,制备了不同POSS含量的单氨基POSS(POSS-NH₂)/PLLA、POSS接枝聚乙二醇(POSS-PEG)/PLLA和POSS接枝聚乳酸(POSS-g-PLLA)/PLLA复合材料。利用差示扫描量热仪(DSC)、热重分析仪(TGA)、偏光显微镜(POM) 分别对复合材料的本体结晶行为、热稳定性及结晶形貌和生长速率进行了观察。结果表明当加入不同质量分数(1 wt%, 5 wt%, 10 wt%)的POSS-PEG时,PLLA的结晶能力均得到改善,而POSS-NH2和POSS-g-PLLA仅在质量分数较低(1wt%)时对PLLA起成核剂的作用,具有较高质量分数时会阻碍PLLA分子链段的运动,从而限制其结晶。三种复合材料中仅POSS-PEG在一定程度上提高了PLLA的热稳定性,利用POM观察球晶生长过程发现POSS-PEG的加入提高了PLLA的球晶生长速率。     

壳聚糖/明胶/TiO2三元复合膜的制备与功能特性

纳米TiO2用阴离子表面改性剂SDS改性后,以溶液共混法制备了壳聚糖／明胶/TiO2复合膜,用FTIR、XRD、SEM、TEM表征了其结构与形态,并测试了其吸水率、透光率、力学性能和抑菌性能。进而探讨了复合膜中明胶和纳米TiO2含量对壳聚糖膜性能的影响。结果表明：复合膜中,壳聚糖、明胶和TiO2微粒间存在强烈的氢键相互作用,从而使明胶与壳聚糖具有良好的相容性,TiO2与壳聚糖、明胶分子间有很好的界面作用。适量TiO2的加入,可使壳聚糖／明胶共混膜的力学性能得到改善,明胶质量分数为0．30时,掺杂wTiO2为0．01、0．02的复合膜较壳聚糖／明胶共混膜的湿强及干态韧性分别提高了55．9％,40．8％和49．7％,47．9％。此外,复合膜的抑菌性能随明胶的增加而降低,但随TiO2的掺杂比的增加而增强,纳米TiO2的引入拓宽了壳聚糖和明胶两种天然高分子材料的应用范围。     

羟乙基壳聚糖的合成及其与聚乳酸的相容性

本文以异丙醇为溶剂,碱化壳聚糖与2-氯乙醇反应制备了羟乙基壳聚糖,对产物的结构与性能进行了分析表征;然后以二甲基亚砜为溶剂,采用溶液共混法制备了一系列不同组成的壳聚糖/聚乳酸和羟乙基壳聚糖/聚乳酸复合膜,对两组分间的相容性进行了研究。结果表明,羟乙基化反应在-OH和-NH2上均有发生,壳聚糖单元糖环上的羟乙基取代度为2.46;改性后,壳聚糖结晶性能和起始热分解温度下降,溶解性能得到改善。复合膜的电镜结果显示,在壳聚糖/聚乳酸复合膜中,相分离现象显著存在,壳聚糖在聚乳酸基体中的分散不均匀,有团聚现象,随着壳聚糖含量增加,两组分间的相分离程度增大,团聚现象更为严重,当壳聚糖含量达到50%时,已难以制备完整的复合膜;与之相反,羟乙基壳聚糖/聚乳酸复合膜中两种组分之间的相容性有所改善,相分离现象不明显,并且,当羟乙基壳聚糖含量从10%增加到50%,复合膜中两种组分之间的相容性变化不大。     

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%.     

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.     

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.     

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.     

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.     

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.     

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.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.