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、^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DNApBR322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DNApBR322切割成缺刻型DNA。

两个取代苄基锡配合物的合成、抗癌活性及其与DNA相互作用

利用二(2,4-二氯苄基)二氯化锡分别与对甲基苯甲酰肼或对叔丁基苯甲酰肼、丙酮酸钠在甲醇中发生反应,合成了2个二(2,4-二氯苄基)锡配合物(C1、C2),通过元素分析、IR、^(1)H NMR、^(13)C NMR、^(119)Sn NMR、HRMS以及X射线单晶衍射表征了配合物结构。测试了配合物C1、C2的热稳定性以及配合物对NCI-H460(人肺癌细胞)、HepG2(人肝癌细胞)和MCF7(人乳腺癌细胞)的体外抑制活性,发现配合物C1对癌细胞均表现较好的抑制作用。利用UV-Vis光谱、荧光光谱以及黏度法研究了2个配合物与ct-DNA之间的相互作用,结果表明配合物是以经典的嵌入模式与DNA结合。

四个基于酰腙配体的双核苄基锡配合物的合成、晶体结构及体外抗癌活性

通过微波“一锅法”合成了4个双核苄基锡配合物:{[C4H3S(O)C=N-N=C(Me)COO](PhCH2)2Sn(MeOH)}2(C1)、{[C4H3S(O)C=N-N=C(Me)COO](p-Cl-C6H4CH2)2Sn(MeOH)}2(C2)、{[C4H3S(O)C=N-N=C(PhCH2)COO](PhCH2)2Sn(MeOH)}2(C3)、{[C4H3S(O)C=N-N=C(PhCH2)COO](p-Cl-C6H4CH2)2Sn(MeOH)}2(C4),利用元素分析、IR、1H NMR、13C NMR、119Sn NMR、HRMS以及X射线单晶衍射等表征了配合物结构。4个配合物分子均为双锡核分子,以Sn2O2四元环为中心对称,且中心锡原子与配位原子形成七配位畸变五角双锥构型。测试了配合物C1~C4的热稳定性以及配合物对癌细胞H460、HepG2、MCF7的体外抑制活性,结果表明:配合物C2是4个新合成的配合物中抑制癌细胞效果最好的化合物。

Syntheses, Crystal Structures and Biological Activities of the 2-Oxo-3-phenylpropionic Acid Arylformylhydrazone Dibenzyltin Complexes

Two 2-oxo-3-phenylpropionic acid arylformylhydrazone dibenzyltin(IV)complexes{[C4H3O(O)C=N-N=C(PhCH2)COO](C6H5CH2)2Sn(CH3OH)}2(Ⅰ)and{[t-Bu-C6H4(O)C=N-N=C(PhCH2)COO](C6H5CH2)2Sn(CH3OH)}2(Ⅱ)have been synthesized and characterized by IR,1H,13C and 119Sn NMR spectra,HRMS,and elemental,thermal stability and single-crystal X-ray diffraction analyses.Complex I crystallizes in the triclinic system,space group P1 with a=9.0392(9),b=10.249(1),c=15.5762(15)?,α=98.605(1)°,β=103.765(1)°,γ=104.056(1)°,Z=2,V=1326.3(2)?3,Dc=1.511 Mg·m^–3,m(MoKa)=1.005 mm–1,F(000)=612,R=0.0206 and wR=0.0524.Complex Ⅱ belongs to triclinic system,space group P1,a=11.4643(3),b=11.8885(3),c=13.0362(4)?,α=73.800(1)°,β=71.679(1)°,γ=79.006(1)°,Z=2,V=1609.34(8)?3,Dc=1.381 Mg·m^–3,m(MoKa)=0.833 mm–1,F(000)=688,R=0.0244 and wR=0.0244.In vitro antitumor activities of both complexes were evaluated by MTT against three human cancer cell lines(NCI-H460,HepG2 and MCF7)and human cell lines(HL7702).Both complexes exhibit better antitumor activity.Furthermore,the interaction between both complexes and calf thymus DNA was studied with EB fluorescent probe.

“从茶叶中提取咖啡因”实验教学的思政元素设计

有机化学实验是有机化学教学的重要内容。在“三全育人”的教育背景下,将思政元素融入有机化学实验教学是非常必要的,既能有效地激发学生的学习兴趣,又有利于学生树立正确的世界观、人生观和价值观。“茶叶中咖啡因的提取”实验是有机化学实验的重要内容之一,蕴含着丰富的思政元素,对该实验教学进行思政研究是践行习近平总书记在高校思想政治工作会议上讲话精神的重要步骤。

Syntheses, Crystal Structures and in vitro Anticancer Activities of Dibenzyltin Compounds Based on the N-(2-Phenylacetic acid)-aroyl Hydrazone

Two dibenzyltin compounds,{[C6H5O(O)C=N-N=C(Ph)COO](m-Cl-C6H4CH2)2-Sn(CH3OH)}2(1)and{[p-Me-C6H4O(O)C=N-N=C(Ph)COO](m-Cl-C6H4CH2)2Sn(CH3OH)}2(2),have been synthesized by microwave“one pot”reaction with benzoylhydrazine(or p-methyl benzhydrazine),phenylglyoxylic acid and di-m-chlorobenzyltin dichloride.Compound 2 contains two crystals 2a and 2b.The compounds have been characterized with IR,elemental analysis,1H,13C and 119Sn NMR spectra,H RMS.Three crystals are all binuclear molecules with a Sn2O2 four-membered ring plane,and each Sn atom center is seven-coordinated with[SnO4C2N]to form a distorted pentagonal bipyramidal configuration.In vitro antitumor activities of all compounds and carboplatin were evaluated by MTT against three human cancer cells such as NCI-H460(lung cancer cells),HepG2(liver cancer cells)and MCF7(breast cancer cells),and compound 2 exhibited better antitumor activity.

Syntheses, Crystal Structures and Biological Activity of the Diorganotin 2-(2-(4-Methoxybenzoyl)hydrazono)-3-phenylpropanoic Carboxylate Complexes

Diorganotin 2-(2-(4-methoxybenzoyl)hydrazono)-3-phenylpropanoic carboxylate complexes Ⅰ{[p-CH3 O-C6 H4 O(O)C=N-N=C(Ph CH2)COO](n-Bu)2 Sn(CH3 OH)}2 and Ⅱ {[p-CH3 O-C6 H4 O(O)C=NN=C(Ph CH2)COO](Ph CH2)2 Sn(CH3 OH)}2 have been synthesized. The complexes have been characterized by IR, 1 H, 13 C and 119 Sn NMR spectra, HRMS, elemental analysis, thermal stability analysis and the crystal structures have been determined by X-ray diffraction. The crystal of complex I belongs to triclinic system, space group P1 with a = 10.437(2), b = 11.576(3), c = 13.085(3) ?, α = 66.272(2)°, β = 86.920(3)°, γ = 73.367(3)°, Z = 2, V = 1383.3(5) ?3, Dc = 1.381 Mg·m-3, m(Mo Kα) = 0.959 mm-1, F(000) = 592, R = 0.0233 and w R = 0.0644. The crystal of complex Ⅱ is of triclinic system, space group P1 with a = 10.446(1), b = 11.720(1), c = 13.063(2) ?, α = 84.190(1)°, β = 71.610(1)°, γ = 72.624(1)°, Z = 1, V = 1448.3(3) ?3, Dc = 1.475 Mg·m-3, m(Mo Kα) = 0.925 mm-1, F(000) = 656, R = 0.0169 and w R = 0.0432. In vitro antitumor activities of both complexes were evaluated by MTT against three human cancer cell lines(NCI-H460, Hep G2 and MCF7), and two complexes exhibited good antitumor activity. The interaction between complex Ⅰ and calf thymus DNA were studied by UV-vis and fluorescence spectroscopy, the interaction of complex Ⅰ with calf thymus DNA were intercalation.

Syntheses,Crystal Structures and Property of Pyridine Zinc(Ⅱ)Complexes Based on Halogenated Salicylaldehyde Schiff Base

Schiff base pyridine zinc(II)complexes 1~4 were synthesized by the reaction of the 2-((2-hydroxybenzylidene)amino)phenol Schiff base with appended donor functionality,zinc acetate,and pyridine.The results of the structural characterization of the complex show that they have the same coordination mode and similar steric structure.Complexes 1 and 3 form a one-dimensional chain structure and two-dimensional grid struc-ture by lots of hydrogen bonds,respectively.Thermogravimetric analysis shows complexes 1~4 can exist stably be-low 150℃.The results of the fluorescence quenching experiments between the complexes and DNA-EB show that the interaction between them is intercalation,and the effect of complex 1 is the most obvious.It is speculated that the steric hindrance of complex 1 is relatively small,and the aromatic ring on the ligand is more likely to inserted into the base pair of DNA.

Syntheses,Crystal Structures,Anticancer Activities and DNA-Binding Properties of the Dibutyltin Complexes Based on Benzoin Aroyl Hydrazone

Dibutyltin benzoin benzoyl hydrazone complex Ⅰ[C_(6)H_(5)(O)C=N-N=C(Ph)CH(Ph)O]_(2)[(n-Bu)_(2)Sn]_(2)and dibutyltin benzoin salicyl hydrazone complex Ⅱ[2-(OH)-C_(6)H_(4)(O)C=N-N=C(Ph)CH(Ph)O]_(2)[(n-Bu)_(2)Sn]_(2)were synthesized and characterized by IR,^(1)H,^(13)C and^(119)Sn NMR spectra,HRMS,elemental analysis and thermal stability analysis,and the crystal structures were determined by X-ray diffraction.The crystal of complex I belongs to monoclinic system,space group P2_(1)/n with a=11.1942(8),b=10.4754(7),c=23.6700(17)?,?=101.529(2)?,Z=2,V=2719.6(3)?^(3),D_(c)=1.371 Mg·m^(–3),?(Mo Kα)=0.966 mm^(–1),F(000)=1152,R=0.0458and w R=0.1312.The crystal of complex II is of triclinic system,space group P1 with a=9.9960(4),b=11.2466(4),c=14.0509(5)?,α=69.4190(10)?,?=70.0600(10)?,γ=81.8090(10)?,Z=1,V=1389.69(9)?^(3),D_(c)=1.380 Mg·m^(–3),?(Mo Kα)=0.950 mm^(–1),F(000)=592,R=0.0284 and w R=0.0690.In vitro antitumor activities of both complexes were evaluated by CCK8 method against three human cancer cell lines(MCF7,NCI-H460 and Hep G2),and complex II exhibited better antitumor activity than I.The interaction between complexes and calf thymus DNA was studied by UV-vis,fluorescence spectroscopy and viscosity measurements.

Syntheses,Crystal Structures and Inhibitory Activity against MCF-7,NCI-H460 and HepG2 Cancer Cells of the Di-2,4-dichlorobenzyltin Thiophene-2-carbohydrazone Complexes

Di-2,4-dichlorobenzyltin-2-(2-(thiophen-2-formyl)hydrazono)-propanoic carboxylate complex I{[C_(4)H_(3)S(O)C=N-N=C(CH_(3))COO]_(2)[(2,4-Cl_(2)-C_(6)H_(3)CH_(2))_(2)Sn]_(2)(CH_(3)OH)_(2)}and di-2,4-dichlorobenzyltin-2-(2-(thio-phen-2-formyl)hydrazono)-3-phenylpropanoic carboxylate complexⅡ{[C_(4)H_(3)S(O)C=N-N=C(PhCH_(2))COO](2,4-Cl_(2)-C_(6)H_(3)CH_(2))_(2)Sn}n were synthesized and characterized by IR,^(1)H,^(13)C and^(119)Sn NMR spectra,HRMS,elemental analysis and thermal stability analysis,and the crystal structures were determined by X-ray diffraction.The crystal of complex I belongs to monoclinic system,space group P2_(1/n)with a=11.987(3),b=35.359(9),c=12.982(3)Å,β=103.028(5)°,Z=4,V=5361(2)Å3,Dc=1.688 Mg·m^(–3),μ(MoKα)=1.463 mm^(–1),F(000)=2704,R=0.0572 and wR=0.1423.The crystal of complexⅡis of monoclinic system,space group P2_(1/n)with a=15.5758(17),b=9.6020(10),c=19.599(2)Å,β=98.886(2)°,Z=4,V=2896.0(5)Å3,Dc=1.663 Mg·m^(–3),μ(MoKα)=1.357 mm^(–1),F(000)=1440,R=0.0341 and wR=0.0936.In vitro antitumor activities of both complexes were evaluated by MTT against three human cancer cell lines(MCF7,NCI-H460 and HepG2),and they all exhibited good antitumor activity.The interaction between complexes and calf thymus DNA was studied by UV-vis and fluorescence spectroscopy,it indicated intercalation as probable mode of interaction.

Self-assembly Syntheses,Crystal Structures and Quantum Chemistry of Two UO^(2+)_(2)Complexes

Two U0^(2+)_(2) complexes{[C_(5)H_(4)N(0)C=N-N=C(PhHPh)C=N-N=C(0)-C_(5)H_(4)N]2U02(CH30H)}(I)and{[C_(5)H_(4)N(0)ON-N=C(Ph)-(Ph)C=N-N=C(0)-C_(5)H_(4)N]2U02(C_(5)H_(4)N(0)C=N-NH_(2))}(II)were synthesized and characterized by IR,elemental analysis and thermal stability analysis,and the crystal structures were determined by X-ray diffraction.The crystal of complex I belongs to monoclinic system,space group P2_(1/n) with α=11.7678(4),6=16.9667(6),c=14.3051(5)A,β=98.918(3)°,Z=4,F=2821.64(17)A^(3),D_(c)=1.837 Mg·m^(-3),μ(MoKα)=5.805 mm^(-1),F(000)=1504,R=0.0346 and wR=0.0688.The crystal of complex II is of triclinic system,space group Pi with a=11.6417(5),b=11.7297(5),c=14.2197(5)A,α=71.697(4)°,β=86.020(3)°,γ=71.572(4)°,Z=2,K=1748.02(12)A^(3),D_(c)=1.742 Mg·m^(-3),μ(MoKa)=4.704 mm^(-1),F(000)=894,R=0.0283 and wR=0.0537.The U1 is a seven-coordinate pentagonal bipyramidal configuration in I and an eight-coordinate hexagonal dipyramidal configuration in II.The thermal stability and quantum chemical calculations of I and II were also investigated.