两个三环己基锡芳香羧酸酯的合成、结构、热稳定性及体外抗癌活性研究

甲醇中三环己基氢氧化锡分别与呋喃-2-甲酸、2,4,6-三甲基苯甲酸反应,合成了2个三环己基锡芳香羧酸酯Cy3SnO2CC4H3O(1)和Cy3SnO2CC6H2Me3(2)(Cy为环己基)。通过IR、1H和13C NMR、元素分析及X-射线单晶衍射表征结构。1和2均属单斜晶系,配合物1空间群P21,晶体学参数:a=0.823 04(2)nm,b=1.111 19(3)nm,c=1.283 90(3)nm,β=101.090(2)°,Z=2,V=1.152 27(5)nm3,Dc=1.381 g·cm-3,μ(Mo Kα)=1.127 mm-1,F(000)=496,R1=0.052 9,wR2=0.138 7。配合物2空间群P21/c,晶体学参数:a=0.999 62(2)nm,b=1.415 97(2)nm,c=1.973 59(3)nm,β=94.042 0(10)°,Z=4,V=2.786 53(8)nm3,Dc=1.266 g·cm-3,μ(Mo Kα)=0.937 mm-1,F(000)=1 112,R1=0.0540,wR2=0.161 9。配合物(1)和(2)的中心锡原子均为畸变四面体构型。通过分子间氢键作用,配合物(1)形成二维网状结构。试验表明,配合物1和2具有良好的热稳定性,对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460增殖均有较强的抑制作用。     

三有机锡(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯的合成、结构和体外抗癌活性

利用三有机锡氢氧化物和手性配体(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸(HL)反应合成了3个三有机锡(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯R3SnL[1,R=c-C6H11(a),C6H5(b),C6H5C(CH3)2CH2(c)],通过元素分析、IR、1H NMR和X-射线单晶衍射表征了其结构。化合物1a属正交晶系,P212121空间群;化合物1b属单斜晶系,P21空间群。二者均为由羧基氧和内酰胺羰基氧桥联配位形成的右螺旋链状有机锡配位聚合物,锡原子具有五配位[SnC3O2]畸变三角双锥构型。化合物1a和1b对体外2种人癌细胞Colo205和Bcap37增殖均有强的抑制作用,其活性为1b1a。     

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。     

含2,6-二(甲基苯并咪唑)吡啶钴、镨配合物的合成、结构、电化学性质和理论计算研究

以2,6-二(甲基苯并咪唑)吡啶和2,2′-联吡啶为配体,合成了一个钴的配合物[Co(mbzimpy)(bipy)Cl]Cl O4·1.3H2O(1)和一个镨的配合物[Pr(mbzimpy)2(NO3)2]Cl O4·2CH3COCH3(2),(mbzimpy=2,6-bis(methylbenzimidazol-2-yl)pyridine,bipy=2,2′-bipyridine)并利用单晶衍射对其结构进行了表征。还对配合物1和2的荧光和电化学性质进行了研究。晶体结构中C-H…O氢键和π-π芳环堆积作用将每个单核分子连接成一个三维的空间结构。配合物1的TD-DFT理论计算的结果表明:实验得到的紫外谱图和理论计算的紫外谱图较好地吻合。通过循环伏安图可以了解金属中心的氧化和还原电子对。在不同偶极矩的溶剂中研究其荧光性能。     

Synthesis of Furo[2,3‐d]pyridazin‐4(5H)‐one and Its N(5)‐Substituted Derivatives

We report the efficient preparation of furo[2,3‐d]pyridazin‐4(5H)‐one and its N‐substituted derivatives starting from methyl 2‐methylfuran‐3‐carboxylate. The Me group was converted to the aldehyde group, which was then condensed with hydrazine derivatives. Then, the ester functionalities were hydrolyzed to the corresponding acids, followed by treatment with SOCl₂ to give N‐substituted furopyridazinone derivatives.     

Direct X‐ray Observation of Trapped CO2 in a Predesigned Porphyrinic Metal–Organic Framework

Metal–organic frameworks (MOFs) are emerging microporous materials that are promising for capture and sequestration of CO₂ due to their tailorable binding properties. However, it remains a grand challenge to pre‐design a MOF with a precise, multivalent binding environment at the molecular level to enhance CO₂ capture. Here, we report the design, synthesis, and direct X‐ray crystallographic observation of a porphyrinic MOF, UNLPF‐2, that contains CO₂‐specific single molecular traps. Assembled from an octatopic porphyrin ligand with [Co₂(COO)₄] paddlewheel clusters, UNLPF‐2 provides an appropriate distance between the coordinatively unsaturated metal centers, which serve as the ideal binding sites for in situ generated CO₂. The coordination of Co^II in the porphyrin macrocycle is crucial and responsible for the formation of the required topology to trap CO₂. By repeatedly releasing and recapturing CO₂, UNLPL‐2 also exhibits recyclability.     

Organotin–Oxido Cluster‐Based Multiferrocenyl Complexes Obtained by Hydrolysis of Ferrocenyl‐Functionalized Organotin Chlorides

Three organotin–oxido clusters were formed by hydrolysis of ferrocenyl‐functionalized organotin chloride precursors in the presence of NaEPh (E=S, Se). [R^FcSnCl₃?HCl] ( C ; R^Fc = CMe₂CH₂C(Me)?N?N?C(Me)Fc) and [SnCl₆]^2? formed {(R^FcSnCl₂)₃[Sn(OH)₆]}[SnCl₃] ( 3 a ) and {(R^FcSnCl₂)₃[Sn(OH)₆]}[PhSeO₃] ( 3 b ), bearing an unprecedented [Sn₄O₆] unit, in a one‐pot synthesis or stepwise through [(R^FcSnCl₂)₂Se] ( 1 ) plus [(R^FcSnCl₂)SePh] ( 2 ). A one‐pot reaction starting out from FcSnCl₃ gave [(FcSn)₉(OH)₆O₈Cl₅] ( 4 ), which represents the largest Fc‐decorated Sn/O cluster reported to date.     

Engineering Short Peptide Sequences for Uranyl Binding

Peptides are interesting tools to rationalize uranyl–protein interactions, which are relevant to uranium toxicity in vivo. Structured cyclic peptide scaffolds were chosen as promising candidates to coordinate uranyl thanks to four amino acid side chains pre‐oriented towards the dioxo cation equatorial plane. The binding of uranyl by a series of decapeptides has been investigated with complementary analytical and spectroscopic methods to determine the key parameters for the formation of stable uranyl–peptide complexes. The molar ellipticity of the uranyl complex at 195 nm is directly correlated to its stability, which demonstrates that the β‐sheet structure is optimal for high stability in the peptide series. Cyclodecapeptides with four glutamate residues exhibit the highest affinities for uranyl with log K_C=8.0–8.4 and, therefore, appear as good starting points for the design of high‐affinity uranyl‐chelating peptides.     

基于串联反应的吡虫啉新合成工艺研究

以2-氯-5-氯甲基吡啶(CCMP)、无水乙二胺和硝基胍为原料,运用串联反应方法合成了吡虫啉[化学名:1-(6-氯-3-吡啶甲基)-N-硝基-2-咪唑啉亚胺]。该方法反应中间体无需纯化处理,操作简单,同时解决了活性中间体进一步进行副反应的难题。通过单因素实验,探讨了pH、反应溶剂、温度以及时间等因素对产物收率的影响,得到的优化工艺条件为:以乙腈为溶剂,nCCMP∶n无水乙二胺∶n硝基胍=1∶5∶1,于30℃反应120min,产率可达96.35%。其结构经1H NMR、13C NMR、IR表征。     

Application of ortho-chloro-β-aroylthioamides in synthesis(II): an efficient one-pot, three-component synthesis of tricyclic thiochromeno[2,3-b]pyridine derivatives

Tricyclic thiochromeno[2,3-b]pyridine derivatives have been successfully synthesized in an unusual one-pot multicomponent cascade reaction from ortho-halo-β-aroylthioamides, Meldrum's acid, and aromatic aldehydes. The reaction presumably proceeds via Knoevenagel condensation-Michael addition-cyclocondensation-decarboxylation-rearrangement-intramolecular S_NAr reaction sequence. High bond forming efficiency of this reaction makes it attractive for the synthesis of thiochromeno[2,3-b]pyridine derivatives in a single step operation.