2-羰基-3-苯基丙酸芳甲酰腙二(2,4-二氯苄基)锡配合物的合成、晶体结构及生物活性

二(2,4-二氯苄基)二氯化锡分别与2-羰基-3-苯基丙酸苯甲酰腙及2-羰基-3-苯基丙酸水杨酰腙反应,合成了2个取代苄基锡配合物(C1、C2),通过元素分析、IR、1H NMR、13C NMR、119Sn NMR、X射线单晶衍射以及热重分析等表征了配合物结构。测试了配合物对癌细胞Hela、MCF7、Hep G2、Colo205、NCI-H460以及正常人体胚肾细胞HEK293、正常人体肝细胞HL7702的体外抑制活性;在Tris-HCl缓冲溶液中,以EB做为荧光探针,用荧光光谱法初步研究了配合物与小牛胸腺DNA的相互作用。结果表明:配合物C1、C2对5种癌细胞都有明显的抑制作用,配合物C2对HEK293、HL7702的细胞毒性远小于C1;配合物C1与小牛胸腺DNA作用是插入结合与静电结合共同作用所致,配合物C2与小牛胸腺DNA作用是插入结合作用所致。     

N-(2-丙酸)-芳甲酰腙二对甲基苄基锡配合物的合成、晶体结构及生物活性

二对甲基苄基二氯化锡分别与N-(2-丙酸)-对硝基苯甲酰腙及N-(2-丙酸)-对叔丁基苯甲酰腙反应,合成了2个取代二苄基锡配合物(C1、C2),通过元素分析、IR、UV-Vis、1H NMR、13C NMR、119Sn NMR、X射线单晶衍射以及热重分析等表征了配合物结构。测试了配合物对癌细胞H460、HepG2、MCF7以及正常人体肝细胞HL7702的体外抑制活性;在Tris-HCl缓冲溶液中,以EB作为荧光探针,用荧光光谱法初步研究了配合物与小牛胸腺DNA的相互作用。结果表明:配合物C1、C2对3种癌细胞都有较好的抑制作用,配合物C2对HL7702的细胞毒性远小于C1;配合物C1、C2与小牛胸腺DNA作用均是插入结合作用所致。     

基于取代苯甲酰肼缩丙酮酸配体的二苄基锡配合物的合成、晶体结构及生物活性

二苄基二氯化锡分别与对甲氧基苯甲酰肼缩丙酮酸及对硝基苯甲酰肼缩丙酮酸反应,合成了2个二苄基锡配合物(C1、C2),通过元素分析、IR、~1H NMR、~(13)C NMR、~(119)Sn NMR、HRMS以及X射线单晶衍射等表征了配合物结构。测试了配合物C1、C2的热稳定性以及配合物对癌细胞H460、HepG2、MCF7的体外抑制活性;在Tris-HCl缓冲溶液中,以EB做为荧光探针,用荧光光谱法初步研究了配合物C1与小牛胸腺DNA的相互作用;并且用凝胶电泳法研究了配合物C1切割质粒DNA pBR322的能力。结果表明:配合物C1、C2对3种癌细胞都有较好的抑制作用,但是C1更优于C2;配合物C1与小牛胸腺DNA作用是插入结合作用所致,能有效的将超螺旋DNA pBR322切割成缺刻型DNA。     

2-羰基丙酸芳甲酰腙二对甲基苄基锡配合物的合成、晶体结构及生物活性

在含水甲苯中,对甲基氯苄与锡粉反应合成了二对甲基苄基二氯化锡,将其分别与2-羰基丙酸苯甲酰腙及2-羰基丙酸水杨酰腙反应,合成了2个取代苄基锡配合物(1、2),通过元素分析、IR、1H NMR、13C NMR、X射线单晶衍射以及热重分析等表征了配合物结构。测试了配合物对癌细胞MCF-7、Hep G2、NCI-H460以及正常人体肝细胞HL-7702的体外抑制活性;在Tris-HCl缓冲溶液中,以EB作为荧光探针,用荧光光谱法初步研究了配合物与小牛胸腺DNA的相互作用。结果表明:配合物1、2对3种癌细胞都有明显的抑制作用,配合物2对HL-7702的细胞毒性小于1;配合物1与小牛胸腺DNA作用是插入结合与静电结合共同作用所致,配合物2与小牛胸腺DNA作用是插入结合作用所致。     

2-羰基-3-苯基丙酸芳甲酰腙二(2,4-二氯苄基)锡配合物的合成、晶体结构及生物活性

二（2,4-二氯苄基）二氯化锡分别与2-羰基-3-苯基丙酸苯甲酰腙及2-羰基-3-苯基丙酸水杨酰腙反应,合成了2个取代苄基锡配合物（C1、C2）,通过元素分析、IR、¹H NMR、¹³C NMR、¹¹⁹Sn NMR、X射线单晶衍射以及热重分析等表征了配合物结构。测试了配合物对癌细胞Hela、MCF7、HepG2、Colo205、NCI-H460以及正常人体胚肾细胞HEK293、正常人体肝细胞HL7702的体外抑制活性;在Tris-HCl缓冲溶液中,以EB做为荧光探针,用荧光光谱法初步研究了配合物与小牛胸腺DNA的相互作用。结果表明：配合物C1、C2对5种癌细胞都有明显的抑制作用,配合物C2对HEK293、HL7702的细胞毒性远小于C1;配合物C1与小牛胸腺DNA作用是插入结合与静电结合共同作用所致,配合物C2与小牛胸腺DNA作用是插入结合作用所致。     

N-(2-丙酸)-芳甲酰腙二对甲基苄基锡配合物的合成、晶体结构及生物活性

二对甲基苄基二氯化锡分别与N-（2-丙酸）-对硝基苯甲酰腙及N-（2-丙酸）-对叔丁基苯甲酰腙反应,合成了2个取代二苄基锡配合物（C1、C2）,通过元素分析、IR、UV-Vis、¹H NMR、¹³C NMR、¹¹⁹Sn NMR、X射线单晶衍射以及热重分析等表征了配合物结构。测试了配合物对癌细胞H460、HepG2、MCF7以及正常人体肝细胞HL7702的体外抑制活性;在Tris-HCl缓冲溶液中,以EB作为荧光探针,用荧光光谱法初步研究了配合物与小牛胸腺DNA的相互作用。结果表明：配合物C1、C2对3种癌细胞都有较好的抑制作用,配合物C2对HL7702的细胞毒性远小于C1;配合物C1、C2与小牛胸腺DNA作用均是插入结合作用所致。     

2-羰基丙酸芳甲酰腙二对甲基苄基锡配合物的合成、晶体结构及生物活性

在含水甲苯中,对甲基氯苄与锡粉反应合成了二对甲基苄基二氯化锡,将其分别与2-羰基丙酸苯甲酰腙及2-羰基丙酸水杨酰腙反应,合成了2个取代苄基锡配合物（1、2）,通过元素分析、IR、¹H NMR、¹³C NMR、X射线单晶衍射以及热重分析等表征了配合物结构。测试了配合物对癌细胞MCF-7、HepG2、NCI-H460以及正常人体肝细胞HL-7702的体外抑制活性;在Tris-HCl缓冲溶液中,以EB作为荧光探针,用荧光光谱法初步研究了配合物与小牛胸腺DNA的相互作用。结果表明：配合物1、2对3种癌细胞都有明显的抑制作用,配合物2对HL-7702的细胞毒性小于1;配合物1与小牛胸腺DNA作用是插入结合与静电结合共同作用所致,配合物2与小牛胸腺DNA作用是插入结合作用所致。     

基于酰腙配体的双锡核二(2,4-二氯苄基)锡配合物的合成、结构及生物活性

二(2,4-二氯苄基)二氯化锡分别与对甲氧基苯甲酰肼缩2-丁酮酸或2-噻吩酰肼缩2-丁酮酸酸反应,合成了两个二(2,4-二氯苄基)锡配合物(C1、C2),通过傅里叶变换红外光谱仪(FTIR)、核磁共振波谱仪(NMR)、高分辨质谱仪(HRMS)以及X射线单晶衍射(SCXRD)等表征了配合物结构。 两个配合物分子均为双锡核分子,以Sn₂O₂四元环为中心对称,且锡原子与配位原子形成七配位畸变五角双锥构型。 配合物C1、C2在空气氛围,120 ℃以下可稳定存在。 配合物C1、C2对人肺癌细胞(NCI-H460)、人肝癌细胞(HepG2)和人乳腺癌细胞(MCF7)均有较好的抑制作用,配合物C1略优于C2。 配合物C1、C2通过插入结合方式与小牛胸腺DNA相互作用,并且配合物C1与DNA的作用略强于C2。     

对氯苄基锡酰腙配合物的合成、抗肿瘤活性及其与DNA相互作用

用二对氯苄基二氯化锡分别与对甲基苯甲酰肼缩苯甲酰甲酸及苯甲酰肼缩苯甲酰甲酸反应,合成了2个对氯苄基锡配合物(C1、C2),通过元素分析、IR、1 H NMR、13C NMR、119Sn NMR、HRMS以及X射线单晶衍射等表征了配合物结构。测试了配合物C1、C2的热稳定性以及配合物对癌细胞NCI?H460、HepG2、MCF7的体外抑制活性,发现配合物C2对癌细胞NCI?H460、HepG2、MCF7等均表现出良好的抑制作用。利用紫外吸收光谱、荧光猝灭光谱以及粘度法研究了配合物C2与ct?DNA之间的相互作用,结果表明配合物C2以插入模式与DNA结合。     

2-羰基丙酸(芳甲酰基)腙二(2,4-二氯苄基)锡配合物的合成、晶体结构、热稳定性及与DNA相互作用研究

在含水甲苯中,2,4-二氯苄与锡粉反应合成了二(2,4-二氯苄基)二氯化锡,将其分别与2-羰基丙酸(苯甲酰基)腙及2-羰基丙酸(水杨酰基)腙反应,合成了2个取代苄基锡配合物(C2、C3),配合物C2和C3通过元素分析、1H NMR、13C NMR、IR、UV-Vis等表征,运用X-射线单晶衍射测试了2个有机锡配合物的分子结构,结构分析表明,锡与配位原子形成变形五角双锥构型的双核有机锡配合物,分子以Sn2O2四元环为中心对称。热分析结果表明,在空气氛下,配合物C2在121℃、C3在128℃以下可稳定存在;在Tris-HCl缓冲溶液中,以EB做为荧光探针,用荧光光谱法初步研究了配合物与鲱鱼精DNA的相互作用,结果表明配合物与鲱鱼精DNA作用是插入结合与静电结合共同作用所致。     

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.     

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.     

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.     

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.