O-（4-双胍基苯甲酰基）壳聚糖盐酸盐的制备及其抗菌活性

通过壳聚糖与含双胍基结构的芳酰氯反应,得到具有抗菌活性的双胍基化壳聚糖衍生物。利用对双胍基苯甲酸盐酸盐与氯化亚砜的反应,得到盐酸对双胍基苯甲酰氯后,再在甲烷磺酸-二甲基亚砜（MeSO3H-DMSO）介质中与壳聚糖进行缩合反应,得到了O-（4-双胍基苯甲酰基）壳聚糖盐酸盐（p-BGBC）。用FT-IR、1H-NMR、GP...     

肝靶向性磁共振成像造影剂——含D—半乳糖基的DTPA双酰胺钆…

通过二乙三胺五乙酸的双Ｎ－羟基琥珀酰亚胺活性酯与含氨基的乳糖或Ｄ－半乳糖衍生物反应，合成了８种含有Ｄ－半乳糖基的二乙三胺五乙酸非离子型配体，并进一步合成了其钆（Ⅲ）配合物，配体及配合物的结构经ＩＲ，＾１ＨＮＭＲ与元素分析表征，对配合物的体外驰豫性能和小鼠急性毒性作了初步研究，家兔在磁共振成像实验表明这种上类造影剂具有肝靶向的特性。     

低硒对大鼠血管一氧化氮合酶和微循环的影响

采用低硒饲料饲养大鼠造成体内贫硒。１４周时测定血浆中脂质过氧化物（ＬＰＯ）、前列环素（ＰＧＩ２）和血栓素（ＴＸＡ２）的水平以及部分血液流变学指标。实验第３９周,测定血管组织一氧化氮合酶（ＮＯＳ）活性及一氧化氮（ＮＯ）水平。结果显示,低硒饲料组的血管ＮＯＳ活性、ＮＯ水平显著低于常规饲料的对照组;而在实验第１４周时,当低硒饲料组的血硒、血谷胱甘肽过氧化物酶（ＧＳＨ－Ｐｘ）活性显著下降、血浆ＬＰＯ水平明显上升的同时,其对应的血浆６－酮－ＰＧＦ１α水平也显著降低,但其ＴＸＢ２与对照组无显著差异。此外,随着大鼠体内的贫硒,其红细胞变形能力下降,但红细胞聚集指数和血沉方程Ｋ值提高。因此,硒不足可能会通过影响ＮＯＳ活性和ＰＧＩ２的合成以及红细胞特性而损害微循环功能。     

“推—拉”型偶氮苯分子的光谱性质和二阶非线性光学性质

研究了具有“推－拉”电子结构的４‘－（Ｎ，Ｎ－二羟乙基）氨基４－硝基偶氮苯（Ｒ－ＨＡＮＢ）衍生物的光谱性质和二阶非线性光学性质，Ｒ－ＨＡＮＢ是一类假芪型偶氮苯分子其激发态具有相似的能级结构，且在不同状态下均具有较高的二阶非线性光学活性，其粉末二次谐波信号多数强于分散红１，一阶超极化率与基太偶极矩动量 合量用溶为色法测得为〉３．４×１０＾８２Ｃ＾２ｍ＾４／Ｖ＾２，其５％掺杂聚甲基丙烯酸甲酯薄膜以电晕     

Schiff碱型壳聚糖高分子冠醚的合成和表征

将４‘－甲酰基苯并１５－冠和－５和４‘－甲酰基苯并１８－冠－６与矣糖分子中的氨基反应,使冠醚单元接枝到高分子壳聚糖上,合成了Ｓｃｈｉｆｆ碱型壳聚糖冠醚,经元素分析,ＩＲ,Ｘ－粉末衍射分析和固体＾１３Ｃ ＮＭＲ分析表征了其结构。实验结果表明壳聚糖冠醚与预期结构相符。并初步考究他其对某些金属离子的吸附选择性。     

新型含偶氮功能团的双炔类衍生物非线性光学性质的理论研究

在ＡＭ１和ＺＩＮＤＯ方法基础上，按完全态求和公式计算分子二阶非线性光学βｉｋ和三介非线性光学系数γｉｊｋｉ，并对含偶氮功能团的双炔类衍生物的二阶、三阶非线性光学性质进行了系统的理论研究，即在基础上，在分子在左端引入推电子基Ｎ（ＣＨ３），右端分别引入推电子基ＣＨ２ＯＨ、２，５－二氮－４－硫甲苯基，研究取代基变化时β、γ变化的规律，地计算结果所反映的规律性在微观上给予了解释。     

含磺酸酯基液晶的合成

把硫原子引入液晶分子,取代液晶分子中的碳原子和氧原子可得到含硫代苯甲酸酯［１］、砜基［２］、亚砜基［３］和亚磺酸基［４］等结构的液晶化合物,性能独特．但含磺酸酯基的液晶化合物尚未见文献报道．本文应用Ｎ,Ｎ二环己基碳二亚胺（ＤＣＣ）和４Ｎ,Ｎ二甲...     

2,4,6—三氧—1,3,5,2—三氮磷杂环己烷衍生物的合成及其抗肿瘤活性

利用Ｎ，Ｎ－二（２－氯乙基）氨基磷酰二异氰酸酯和胺的加成反应，合成了２，４，６三氧－１，３，５，２三氮磷杂环己烷衍生物，它们的结构经＾１ＨＮＭＲ，ＩＲ和元素分析所证实。初步生物活性测试结果表明，部分化合物具有一定的抗肿瘤活性。     

铜(Ⅱ)与苯基羧酸(HPCA)和2,2''''-联吡啶衍生物(dpx)混配配合物的合成和表征

合成了铜（Ⅱ）与苯基羧酸根［ＰＣＡ－＝苯甲酸根（Ｂｚ－），２－苯乙酸根（ＰＡｃ－），３－苯丙酸根（ＰＰｒ－），４－苯丁酸根［ＰＢｕ－）］和２，２′－联吡啶衍生物（ｄｐｘ：２，２′－联吡啶胺ｄｐａ、２，２′－联吡啶酮ｄｐｋ、２，２′－联吡啶甲烷ｄｐｍ）三大系列１２种新的三元配合物。用元素分析、摩尔电导、红外光谱、１Ｈ核磁共振、差热分析等实验方法表征了它们的组成和性质。确定该系列配合物化学组成为Ｃｕ（ＰＣＡ）２（ｄｐａ）、Ｃｕ（ＰＣＡ）２（ｄｐｍ）、Ｃｕ（ＰＣＡ）２（ｄｐｋ）·ｎＨ２Ｏ（ｎ＝２－４）。它们具有相似的组成和配位方式。它们的可能结构为：二个ＰＣＡ－与Ｃｕ（Ⅱ）单齿配位，一个ｄｐｘ与Ｃｕ（Ⅱ）Ｎ，Ｎ二齿螯合配位。ｄｐｋ的羰基在金属离子Ｃｕ２＋的存在下发生水化作用成ｄｐｋ·Ｈ２Ｏ。用１ＨＮＭＲ法研究了Ｃｕ（Ｂｚ）２（ｄｐｘ）·ｎＨ２Ｏ和Ｃｕ（ＰＡｃ）２（ｄｐｘ）·ｎＨ２Ｏ二个体系其分子内或分子间可能存在的非共价键作用。     

2,4,6—三氧—1,3,5,2—三氮磷杂环己烷衍生物的合成及其生物活性

利用Ｎ，Ｎ－二（２－氯乙基）氨基磷酰二异氰酸酯和胺的加成反应，合成了２，４，６－三氧－１，３，５，２－三氮磷杂环己烷衍生物，它们的结构经１ＨＮＭＲ，ＩＲ，ＭＳ和元素分析所证实．初步生测结果表明，部分化合物具有一定的抗肿瘤活性．     

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%.     

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.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.