罗格列酮氧钒配合物的合成及表征

目的:合成罗格列酮氧钒配合物并进行表征。方法:取罗格列酮与五水硫酸氧钒(VOSO4·5H2O)在适当的条件下(溶剂为乙醇,反应pH值为6)合成罗格列酮氧钒配合物,运用核磁共振氢谱和红外光谱等分析方法对配合物的结构进行了初步确证。结果与结论:确证形成了新的化合物即罗格列酮氧钒配合物,配合物中罗格列酮的化学结构未发生变化,其中2个氧钒均与1个罗格列酮和3个水分子结合。     

不同剂量吡唑啉酮希夫碱衍生物铜配合物对小鼠的急性毒性实验

目的: 研究吡唑啉酮希夫碱衍生物铜配合物[Cu(PMPP-SAL)(EtOH)]对小鼠腹腔注射后急性毒性反应,评估其安全性。方法: 采取腹腔注射法给小鼠一次性给药,观察15 d内12.5,25,50,200,400,800 mg·kg^-1共6个剂量组小鼠的生长发育、行为变化、血液学变化。计算[Cu(PMPP-SAL)(EtOH)]腹腔注射半数致死率(LD₅₀)及95%的可信区间。结果: 高剂量组中毒小鼠均出现不同程度的呼吸心跳加快、抽搐等症状。经腹腔注射[Cu(PMPP-SAL)(EtOH)] LD₅₀为:33 mg·kg^-1,95%的可信限为:25.5~43 mg·kg^-1。25 mg·kg^-1剂量组与阳性药物(顺铂,DDP,12.5 mg·kg^-1)组相比具有相似的毒性作用。结论: 低浓度的[Cu(PMPP-SAL)(EtOH)]毒性较小,具有较好的安全性。     

木犀草素缩苯胺席夫碱配合物的合成及抑菌活性

目的：基于木犀草素的生物活性和席夫碱的特有性质基础上,设计与金属形成一系列新型席夫碱金属配合物。方法：利用缩合反应,在无水乙醇中合成未见报道的黄酮类席夫碱过渡金属配合物。并通过元素分析、紫外光谱、红外光谱、摩尔电导等手段对其进行了结构表征和抗菌活性实验。结果：通过分析,初步确定了其分子式、结构和其．生物活性。结论：结构式为：配合物MLx．nC2H5OH。形成配合物后抑菌活性大大增强。     

木犀草素Cu(II)配合物的合成与结构表征

目的：木犀草素配合物的研究。方法：在无水乙醇溶剂中，通过溶解、回流合成了木犀草素和醋酸铜金属配合物，并通过元素分析、红外光谱、电子光谱和摩尔电导等表征手段，初步确定了配合物的结构。结果：通过分析可以基本得到金属配合物的分子式和结构：M2L2(Ac)4。结论：得到所合成配合物。     

二环吡唑啉衍生物的合成及其抗炎活性

设计合成了１３个二环吡唑啉及其衍生物，其中９个为未见文献报道的新化合物，初步抗炎实验表明，大部分化合物都有程度不同的抗炎活性，部分化合物的抗炎活性与布洛芬相当。     

吡唑啉酮衍生物镉(Ⅱ)配合物体内外对黑素瘤B16细胞的抗肿瘤作用

目的研究吡唑啉酮镉(Ⅱ)配合物1-苯基-3-甲基-4-丙酰基-5-吡唑啉酮缩水杨酰肼-镉(Ⅱ)(Cd-PMPP-SAL)体内外对小鼠黑素瘤B16细胞的抗肿瘤作用及其作用机制。方法以Cd-PMPP-SAL1.0,1.5,3.0,5.0和10.0 mg·L~(-1)分别作用小鼠黑素瘤B16细胞24,48和72 h,采用MTT法检测B16细胞存活率;Cd-PMPP-SAL 6.25,12.50和25.00 mg·L~(-1)作用B16细胞24 h,用Hoechst33258染色观察B16细胞形态,AnnenxinⅤ/PI双染色法检测B16细胞凋亡率;胱天蛋白酶活性检测试剂盒检测B16细胞内胱天蛋白酶活性。C57BL/6J小鼠皮下接种B16细胞制备荷瘤模型,5 d后分别瘤内注射Cd-PMPP-SAL 6.25,12.50和25.00 mg·kg~(-1),每天1次,连续12 d。每天检测体质量,给药结束后处死小鼠,测量瘤体积并测瘤质量,计算抑瘤率。HE染色法观察瘤体、肝和肺组织病理变化;免疫组织化学法检测肿瘤组织中血管内皮生长因子(VEGF)和成纤维细胞生长因子2(FGF2)蛋白表达;TUNEL法检测移植瘤组织内的细胞凋亡。结果Cd-PMPP-SAL抑制B16细胞存活,IC_(50)为4.946 mg·L~(-1),95%置信限为4.24~5.65 mg·L~(-1);Cd-PMPP-SAL12.50和25.00 mg·L~(-1)作用24 h,B16细胞凋亡率为(12.8±1.4)%和(18.4±0.4)%,显著高于细胞对照组(1.7±0.1)(P<0.01);Cd-PMPP-SAL 25.00 mg·L~(-1)组胱天蛋白酶3和9活性与细胞对照组比较显著增高(P<0.01),胱天蛋白酶3/7活性变化不明显。瘤内注射Cd-PMPP-SAL 12.50和25.00 mg·kg~(-1)治疗组,从治疗第8天起瘤体积与模型组相比明显减小(P<0.01),对小鼠体质量无明显影响;Cd-PMPP-SAL 12.50和25.00 mg·kg~(-1)治疗组小鼠移植瘤组织有不同程度的坏死,肝、肺组织无明显病理变化;与模型组比较,Cd-PMPP-SAL 12.50和25.00 mg·kg~(-1)治疗组移植瘤组织VEGF和FGF2蛋白表达显著下降(P<0.05),凋亡细胞明显增加(P<0.05)。结论 Cd-PMPP-SAL体内外可有效地抑制B16细胞生长,该作用可能与诱导细胞凋亡及抑制肿瘤内血管生成有关。     

新型喹喔啉衍生物的合成与表征

合成新型喹喔啉衍生物,并对其结构进行表征。以邻苯二胺类为起始原料,采用草酸二乙酯/HCl与苯甲酰甲酸/(C2H5OH,HCl)两种不同的原料进行环合,再用三氯氧磷/DMF进行氯代合成目标化合物。合成的目标化合物测定其物理常数,并通过IR、1HNMR的方法进行结构表征。合成得到的一系列新型喹喔啉衍生物,经表征确认结构。     

7,8-二羟基黄酮及其稀土配合物的合成与表征

目的 寻找具有抗炎、镇痛、抗凝血作用的黄酮金属配合物药物，充分利用内蒙古地区丰富的稀土资源。方法 采用Baker-Venkataraman反应，合成了7，8-二羟基黄酮，该化合物再与几种稀土配合。结果 合成5种未见文献报道的稀土配合物。结论 用改进工艺后的方法合成黄酮，使重排反应收率提高，溶剂成本降低；而且利用具邻苯二酚结构的黄酮作配体合成配合物，为今后开发研制此类化合物提供了参考。     

四苯甲氧基酞菁锌配合物的合成与表征

目的 合成四苯甲氧基酞菁锌酞菁锌配合物。方法 模板反应法合成。产物采用红外和紫外可见光谱表征。结果 合成了分子碎片3-苯甲氧基邻苯二甲腈和四苯甲氧基酞菁锌配合物。结论 四苯甲氧基酞菁配合物是一种很有潜力光动力治疗光敏剂。     

新型双核席夫碱化合物的合成及荧光活性研究

以水杨醛与N,N,N',N'-四[2-(2-氨基乙氨基)甲酰基乙基]乙二胺反应合成了一种新型八齿席夫碱配体(H4L)及其锌配合物,通过元素分析1、HNMR、IR、紫外光谱、摩尔电导等手段对配体及其配合物进行结构和组成进行表征。同时在DMSO溶液中测定了该双核席夫碱及其锌配合物的荧光活性。     

Synthesis,characterization and biological activity of some unsymmetrical Schiff base transition metal complexes

In this study, several unsymmetrical Schiff bases and their cobalt and manganese complexes have been synthesized and characterized. The unsymmetrical Schiff bases were prepared from reaction of o-phenylendiamine derivatives with 1-hydroxy-2-acetonaphthone and then the product was reacted with the following aldehydes: salicyaldehyde, 2-hydroxynaphthaldehyde, 2-pyridinecarboxaldehyde and 2-qinolinecarboxaldehyde to produce the desired tetradentate unsymmetrical Schiff base ligands H2SL, H2NL, HPYL and HQN, respectively. Reaction of these ligands with cobalt and manganese salts produced complexes of the general formula [M(SL)], [(NL)], [M(PYL)] and [M(QL)]. All the complexes were characterized by elemental analysis, infrared spectroscopy, UV-visible spectroscopy, electrical conductivity and magnetic susceptibility measurements. The prepared complexes were examined for their anti-bacterial activity using gram-positive and gram-negative pathogens. The following complexes showed strong antibacterial activity against Staphylococcus aureus: MnSL1, MnSL2 and MnSL3. The genotoxic activity of four complexes, which are MnNL1, MnSL1, CoNL1 and CoSL1, were examined using 8-hydroxy-2-deoxy guanosine (8-OHdG) assay in cultured human blood lymphocytes. All examined complexes were found to be genotoxic at examined concentrations (0.1–100?µg/mL), but with variable magnitudes (p?<?0.05). The levels of 8-OHdG induced by MnNL1 and MnSL1 were significantly higher than that induced by CoNL1 and CoSL1 ones. In general, the order of mutagenicity of the compounds is MnSL1?>?MnNL1?>?CoSL1?>?CoNL1. In conclusion, some of the prepared complexes showed some biological activities that might be of interest for future research.     

Schiff base-nickel,palladium, and platinum complexes derived from N-cyclohexyl hydrazine carbothioamide and 3-hydroxy-4-methoxybenzaldehyde: Selective antiproliferative and proapoptotic effects against colorectal carcinoma

The bidentate N-cyclohexyl-2-(3-hydroxy-4-methoxybenzylidene)hydrazine-1-carbothioamide Schiff base ligand (HL) was coordinated to divalent nickel, palladium and platinum ions to form square planar complexes. The nickel and palladium complexes, [NiL₂], [PdL₂] form square planar complexes with 2:1 ligand to metal ratio. The platinum complex, [PtL(dmso)Cl] formed a square planar complex with 1:1 ligand to metal ratio. Platinum undergoes in situ reaction with DMSO before complexing with the ligand in solution. The cytotoxicity of HL, [NiL₂], [PdL₂], and [PtL(dmso)Cl] were evaluated against human colon cancer cell line (HCT-116), human cervical cancer (Hela) cell line, melanoma (B16F10) cells, and human normal endothelial cell lines (Eahy926) by MTT assay. The [NiL₂] complex displayed selective cytotoxic effect against the HCT 116 cancer cell line with IC₅₀ of 7.9 ± 0.2 μM. However, HL, [PdL₂], and [PtL(dmso)Cl] only exhibited moderate cytotoxic activity with IC₅₀ = 75.9 ± 2.4, 100.0 ± 1.8, and 101.0 ± 3.6 μM, respectively. The potent cytotoxicity of [NiL₂] was characterized using Hoechst and Rhodamine assays. The nickel complex, [NiL₂], caused remarkable nuclear condensation and reduction in mitochondrial membrane potential. In addition, molecular docking studies confirms that [NiL₂] possesses significant binding efficiency with Tyrosine kinase. Altogether, the results revealed that [NiL₂] exhibits cytotoxicity against the cancer cells via Tyrosine kinase-induced proapoptosis pathway. This study demonstrates that the [NiL₂] complex could be a promising therapeutic agent against colorectal carcinoma.     

稀土盐及其配合物对芽孢菌的抑菌活性的影响

目的 以稀土氧化物为原料，合成系列稀土盐及其配合物，并研究它们对芽孢菌的抑菌作用规律。方法 采用了滤纸片法、稀释法考察了多种稀土盐及其配合物对多种芽孢菌、普通革兰氏阳性细菌及普通革兰氏阴性细菌的抑菌活性；并用透射电镜观察了芽孢的形态及超微结构变化。结果 稀土盐类及其配合物抑菌性强、抑菌谱广，对生命力强的芽孢菌显示了比对普通革兰氏阳性及阴性细菌更好的强抑菌效果；稀土配合物的抑菌效果较稀土盐更好；各种稀土盐类及其配合物对多种芽孢菌的抑菌活性差别不大；重稀土（Gd）抑菌效果略优于轻稀土(La,Nd,Eu）；不同配体合成的配合物对同一菌株的抑菌效果存在显著差异，这是由于抑菌活性与配合物的稳定性有关；采用透射电镜的负染色及超薄切片术，观测到稀土配合物对芽孢休眠体有直接的溶菌作用。结论 稀土配合物是一类对芽孢菌有特效的抑菌剂。     

稀土元素铕对大黄愈伤组织生长及蒽醌类成分的影响

研究了稀土元素Eu3＋对药用植物大黄愈伤组织生长的影响，结果显示：在MS培养基中附加稀土元素可明显影响愈伤组织的生长；低浓度稀土促进生长，高浓度抑制生长；并对稀土的作用机理做了探讨以及对愈伤组织中的蒽醌类化合物进行了定性、定量分析。     

Tissue deposition and toxicological effects of commercially significant rare earth oxide nanomaterials: Material and physical properties

Rare earth oxide (REO) materials are found naturally in earth's crust and at the nanoscale these REO nanoparticles exhibit unique thermal, electrical, and physicochemical properties. REO nanoparticles are widely used in different industrial sectors for ceramics, glass polishing, metallurgy, lasers, and magnets. Recently, some of these REO nanoparticles have been identified for their potential application in medicine, including therapy, imaging, and diagnostics. Concurrent research into the REO nanomaterials' toxicities has also raised concern for their environmental impacts. The correlation of REO nanoparticles mediated toxicity with their physiochemical properties can help to design nanoparticles with minimal effect on the environment and living organisms. In vitro assay revealed toxicity toward Human squamous epithelial cell line (CCL30) and Human umbilical vascular endothelial cells (HUVEC) at a concentration of 100 µM and higher. In vivo results showed, with the exception of CeO₂ and Gd₂O₃, most of the naoparticles did not clear or had minimum clearance (10–20%) from the system. Elevated levels of alanine transferase were seen for animals given each different nanoparticle, however the increases were not significant for CeO₂ and Dy₂O₃. Nephrotoxicity was only seen in case of Dy₂O₃ and Gd₂O₃. Lastly, histological examination revealed presence of swollen hepatocytes which further confirms toxicity of the commercial REO nanomaterials. The in vivo toxicity is mainly due to excessive tissue deposition (70–90%) due to the commercial REO nanoparticles' poor physical properties (shape, stability, and extent of agglomeration). Therefore, optimization of nanoparticles physical properties is very important. © 2016 Wiley Periodicals, Inc. Environ Toxicol 32: 904–917, 2017.     

Extraction of rare earth elements via electric field assisted mining applying deep eutectic solvents

Rare earth elements play an important role in our society, as they are used in green energy technologies. However, they are considered critical raw materials. For this reason, there is a concern for obtaining alternative and complementary sources for conventional mining. In light of this view, electric field assisted mining arises as a technique to extract species from soils using green electrolytes to help in the extraction of metals. The aim of this paper was to evaluate the effect of different types of biodegradable electrolytes, including the use of deep eutectic solvents, in the electromining process. Six experiments were conducted applying an electric field of 1.0 V cm^?1, and all electrolytes were used at a concentration of 0.1 mol L^?1. The results showed that different electrolytes achieved different selectivities. The maximum efficiency using acetic acid resulted in 69.1% of Ce⁴⁺, citric acid removed 62.3% of La³⁺, and oxalic acid extracted 21.5% of La³⁺. The electromining efficiencies using deep eutectic solvents presented minor results. Therefore, considering the biodegradability and selectivity of the organic acids used, electromining showed to be a promising eco-friendly alternative for preferential extraction of metal species from soils.     

Synthesis, Characterization and Biocidal Activities of Some Schiff Base Metal Complexes

Some new mixed ligand complexes (1-5) of type ML''B (M(II)=Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); HL''= o-vanillidene-2-aminobenzothiazole; B= 1,10-phenanthroline) and Schiff base metal complexes of types (ML₂") (6-10) and (M₂L") (11-15) (HL"= o-vanillidene-2-amino-N-(2-pyridyl)-benzene sulfonamide) were synthesized and characterized by elemental analysis and spectral (IR, ¹H NMR and ¹³C NMR) studies. The free ligands and their metal complexes have been screened for their in vitro biological activities against bacteria, fungi and yeast. The metal complexes show more potent activities compared with Schiff base ligands.     

Synthesis, characterization, and anti-inflammatory activities of rare earth metal complexes of luteolin

Twelve as yet, unreported complexes of luteolin were synthesized with various rare earth ions through refluxing in ethanol. The characterization of these complexes by elemental analysis, infrared spectra, and differential scanning calorimeter demonstrated that luteolin coordinated the various rare earth ions in a similar manner. Experiments designed to study the anti-inflammatory activities of these rare earth-luteolin complexes indicated that they had a significant inhibitory effect on xylene-induced ear edema in mice. Five complexes containing La³⁺, Ho³⁺, Yb³⁺, Lu³⁺, and Y³⁺ were equally effective as luteolin and dexamethasone (DXM). However, their inhibitory effects on carrageenan-induced paw edema in mice, although significant, were weaker than that of either luteolin alone or DXM.