Syntheses,Crystal Structures and Properties of Mn(Ⅱ) and Co(Ⅱ) Coordination Complexes Based on 1,10-Phenanthroline Derivative

Two new coordination complexes[Mn(L)_(2)(DNSA)](1) and[Co(L)(1,4-bdc)]_n (2) have been achieved under hydrothermal conditions (H_(2)DNSA=3,5-dinitro-salicylic acid,1,4-bdc=1,4-benzenedicarboxylic acid and L=2-(2-fluoro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline).1 crystallizes in monoclinic,space group P2_1/c with a=15.871(3),b=17.274(4),c=16.078(3)A,β=113.03(3)^(o),V=4056.6(16)A^(3),Z=4,C_(45)H_(22)Cl_(2)F_(2)Mn N_(10)O_(7),M_(r)=978.57,D_(c)=1.602 g/cm^(3),F(000)=1980,μ(Mo Ka)=0.536 mm^(–1),R=0.0437 and w R=0.1065.2 belongs to the monoclinic system,space group C2/c with a=14.665(2),b=30.856(4),c=11.237(2)A,β=111.166(2)^(o),V=4742.0(12)A^(3),Z=8,C_(27)H_(14)Cl Co FN_(4)O_(4),M_r=517.80,D_(c)=1.602 g/cm^(3),F(000)=2312,μ(Mo Ka)=0.889 mm^(–1),R=0.0364 and w R=0.0862.The central Mn(II) ion in 1 is six-coordinated by four nitrogen atoms from two L ligands and two oxygen atoms from one DNSA anion.In 2,the two kinds of 1,4-bdc ligands link neighboring Co(II) atoms to yield a two-dimensional layer structure.The luminescence of 1 has been studied in detail.Moreover,thermal behaviors of 1 and 2 are also investigated.

SPECTROPHOTOMETRIC STUDY OF DDQ CHARGE-TRANSFER COMPLEXES WITH 1,10-PHENANTHROLINE AND ITS DERIVATIVES

1,10-phenanthroline and its derivatives can form charge-transfer complexes with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone(DDQ).The absorption spectra and conditions of complex formation,such as the reaction time,the quantity of DDQ, and the solvents, have been studied.After the HMO calculation of phenanthrolines,the molar absorptivities were found to depend on the substituents on the phenanthroline rings.

Trinuclear Metal Complexes Based on 1,10-Phenanthroline Derivates as Catalysts for Cleavage of a RNA-Model Substrate

Two multidentate ligands 2,9-di[6＇-（2″-hydroxyl-3″-methoxyphenyl）-n-2＇,5＇-diazahexyl]-1,10-phenanthroline（LA）and 2,9-di（6＇-α-phenol-n-2＇,5＇-diazahexyl）-1,10-phenanthroline（LB）were synthesized and fully characterized.Protonation of the ligands and the stability of the complexes of the ligands with divalent metal ions were investigated.The trinuclear metal complexes [Cu（Ⅱ）and Zn（Ⅱ）] of the ligands were studied,as catalysts,for the transphosphorylation of the RNA-model substrate 2-hydroxypropyl-p-nitrophenyl phosphate（HPNP）.The second-order rate constants of HPNP-hydrolysis catalyzed by M3L and M3LH-1 were obtained,which indicated that Zn3LBH-1 was the most efficient catalyst among them.The proposed mechanisms included the activation of the substrate via binding to the metal ions and intramolecular nucleophilic attack by the deprotonated C2-hydroxyl of HPNP.

Crystal Structures and Luminescent Properties of Three Coordination Polymers Based on 2,5-Furandicarboxylic Acid Ligand and 1,10-Phenanthroline

Three new coordination polymers,namely [Zn（FDA）（phen）（H2O）·H2O]n（1）,[Cd（HFDA）（phen）2（NO3）]（2） and [Cd（FDA）（phen）]n（3）（H2FDA = 2,5-furandicarboxylic acid,phen = 1,10-phenanthroline） have been synthesized by the solvothermal method and characterized by elemental analysis,IR,powder X-ray diffraction,thermogravimetric analysis and X-ray single-crystal diffraction analysis.For 1,the neighboring Zn^2＋ ions are bridged by FDA2-as linkers to form one-dimensional（1D） chains,and phen ligands are as the terminal ligands.Furthermore,the 1D chains are packed into a three-dimensional（3D） supramolecular structure through hydrogen bonds and π-π interactions.For 2,the H2FDA ligand is partial deprotonation,which is a rare phenomenon among other coordination polymers based on H2FDA.Under the synergetic effect of phen ligands and the partial deprotonation of H2FDA,the structure of 2 is discrete.For 3,the Cd^2＋ ions are linked by two carboxylates of FDA^2-ligand to give rise to 1 D zig-zag chains,and phen ligands chelate the Cd^2＋ ions like 1.In addition,solid-state luminescent spectra of three coordination polymers were also studied at room temperature.

Synthesis of 2-Phenyl-10-substituted Hymenialdisine Derivatives

A series of novel 2-phenyl-10-substituted hymenialdisine derivatives was synthesized via the micro-wave-assisted Suzuki-Miyaura cross-coupling reactions of the 2-phenyl derivative of hymenialdisine and boronic acid, which enabled the successful introduction of electron-donating and electron-withdrawing groups to the 2-phenyl- hymenialdisine derivatives in good yields.

Stability of Rare Earth Ion-N,N′-bis(2′-Pyridine)methyl-1,10-Phenanthroline-2,9-Dimethanmine Binary Complexes

The stability constants of binary complexes Ln-L (Ln = La3+, Ce3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+ Tb3+, Dy3+, Ho3+, L = N, N'-bis (2'-pyridine) methyl-1, 10-phenanthroline-2, 9-dimethanamine) were determined by pH potentiometric titration method at 25 +/- 0.1degreesC in 0.1 mol . L-1 NaClO4. The probable structures of the corresponding complexes were proposed. The influence of the metal ions to the stability of binary complexes and the stability difference between the complexes of rare earth ion and the corresponding complexes of Co2+, Ni2+, Cu2+ ions were discussed. The stability constants of the corresponding binary complex of radioactive Pm3+ ion were estimated by linear regression.

Preparation and Structural Analysis of Lanthanide Complexes with α-Hydroxyl-phenyl-acetic Acid and 1,10-Phenanthroline as Ligands

A series of ternary lanthanide complexes Ln （C6H5CHOHCOO）3（phen） （H2O） （Ln= La, Ce, Pr, Nd, Sm, Eu） were synthesized with α-hydroxyl-phenyl-acetic acid and 1, 10-phenanthroline （phen） as ligands. The sturcture and property of complexes were characterized by elemental analysis, IR, 1^H-NMR, UV and TGA, and the coordinate mede of both ligands was discussed. It was shown that the co-ordinate mode of 1, 10-phenanthroline was chelated, while α-hydraxyl-phenyl-acetate ion was monedentate or bridging. The mechanism of thermal determinde by thermogravimetry was indicated that the degree of co-ordinate ability of ligand was： α-hydroxyl-phenyl-acetate ion 〉 1, 10- phenanthroline（phen）.

Shift in pKa of 1,10-Phenanthroline in TBAB and PEG-400 Micellar Media: A Potentiometric Study

The acid-base equilibrium of 1,10-phenanthroline (1,10-phen) in the presence of polyethylene glycol 400 (PEG-400, non-ionic) and tetrabutylammonium bromide (TBAB, ionic) micellar media has been studied by Calvin-Wilson titration technique at different mole fractions (0.5% - 2.5%) of PEG-400 and TBAB micellar solutions at an ionic strength of 0.16 mol dm-3 NaCl and at a temperature of 298 K. The pH metric data were subjected to SCPHD program to obtain correction factor and Kw which were given as initial inputs for MINIQUAD75 program to refine protonation constants. HySS program was then used to generate the species distribution diagrams versus pH using the results obtained from the MINIQUAD75 program and SIM run data. The difference in values of protonation constants in aqueous medium (logβ1 = 4.93 & logβ2 = 6.22) and in the micellar media (PEG-400, logβ1 = 4.89 & logβ2 = 5.91 and TBAB, logβ1 = 4.84 & logβ2 = 5.73) is attributed to different intrinsic solvent characteristics of micelles. In case of ionic surfactants, the electrostatic micellar surface is an additional contributing factor.

Synthesis of 5-Substituted 2, 9-Dimethyl-1,10-Phenanthroline Dialdehydes and Their Schiff Bases with Sulfur-Containing Amines

Eight new Schiff bases of 5-nitro and 5-bromo-substituted 1,10-phenanthroline-2,9-dicarboxaldehydes with sulfur-containing amines, thiosemicarbazide, S-alkyl/aryl dithiocarbazates and 2-mercaptoaniline have been synthesized and characterized by a variety of spectroscopic methods. The condensation reactions of the dialdehydes with the amines were carried out both in the presence and absence of conc. sulfuric acid. A significant increase in yield of the Schiff bases was observed when the reactions were carried out in the presence of sulfuric acid.

Antibacterial Activities of New Schiff Bases and Intermediate Silyl Compounds Synthesized from 5-Substituted-1,10-phenanthroline- 2,9-dialdehyde

Schiff bases are known to possess anticancer, antibacterial, antifungal, antitubercular, anti-inflammatory, antimicrobial and antimalarial properties. In this paper antibacterial studies against variety of plants and human pathogenic bacteria with eight newly synthesized Schiff bases and several intermediate silyl compounds have been reported. The antibacterial activities of the synthesized compounds were primarily determined by paper disc diffusion method. The minimum inhibitory concentration (MIC) of each compound was also determined by tube dilution process. Seven different human pathogenic bacteria and eighteen different plant pathogenic bacteria were used for the antibacterial activity studies. While all synthesized compounds have shown significant antibacterial activity, one intermediate silyl compound has shown remarkably high antibacterial property. 5-substituted derivatives have shown relatively higher activity than non-substituted compounds. Polar substituent which increases hydrophilicity may have a positive impact on the antibacterial property.

Reactivity of C-10 Function in Sinenxan A and Its Derivatives

The allylic nature of C-10 in sinenxan A (1) leads to facile SN1 and eliminion reactions

A Facile Synthesis of 9,10-Dimethoxybenzo[6,7]- ox-epino[3,4-<i>b</i>]quinolin-13(6<i>H</i>)-one and Its Derivatives

A concise and efficient method for the synthesis of novel 9,10-imethoxybenzo[6,7]oxepino[3,4-b]quinolin13(6H)-one and its derivatives 7a-p has been developed via the intramolecular Friedel-Crafts acylation reactions of 6,7-dimethoxy-2-(phenoxymethyl)quinoline-3-carboxylic acids 6a-p with polyphosphoric acid (PPA) as catalyst and solvent under mild conditions. The key intermediates 6a-p were prepared through the in situ formation of ethyl 6,7-dimethoxy-2-(phenoxymethyl)quinoline-3-carboxylates 5a-p followed by hydrolysis with aqueous ethanolic sodium hydroxide solution. The novel synthetic method has the advantages of good yields, easy work-up, and environmentally friendly character, which may provide a novel highly efficient process for making quinoline and related azaheterocycle libraries.

维生素D缺乏患者血清25羟维生素D水平与M-MDSCs、TNF-α、IL-10的差异性分析

目的探讨维生素D缺乏患者血清25羟维生素D[25(OH)D]水平与单核细胞型髓源抑制性细胞(M-MDSCs)、肿瘤坏死因子-α(TNF-α)和白细胞介素-10(IL-10)的相关性。方法选取2022年6—9月于银川市第一人民医院就诊的维生素D缺乏症患者24例(维生素D缺乏组)和同期健康体检者24例(正常对照组),收集基础临床指标,采集外周抗凝血,分离外周血浆和血细胞后,提取外周血单个核细胞(PBMCs),采用流式细胞术分析CD45+白细胞和CD45^(+)CD15^(-)CD11b^(+)HLA^(-)DR^(-)CD14^(+)M-MDSCs,采用ELISA法检测外周血清TNF-α、IL-10水平,采用Pearson相关分析探讨血清25(OH)D与M-MDSCs、TNF-α及IL-10的相关性。结果与正常对照组相比,维生素D缺乏组患者外周血白细胞增加、M-MDSCs增高(P均<0.05),血浆中TNF-α水平升高、IL-10降低(P均<0.05)。相关性分析结果显示,25(OH)D与CD45^(+)白细胞、M-MDSCs和TNF-α呈负相关,与IL-10呈正相关(P均<0.05)。结论维生素D缺乏患者25(OH)D水平降低后可促进炎症发生,并与M-MDSCs密切相关。

两种10-羟基喜树碱碳酸酯的合成及其抗结肠癌活性研究

目的 寻找高效低毒的10-羟基喜树碱新型衍生物。方法 以4-氨基丁醇为起始原料,羟基端通过酯化反应与N-苄氧羰基甘氨酰-L-脯氨酸保护,N端进一步与对硝基苯基氯甲酸酯反应后,再分别与10-羟基喜树碱、7-乙基-10-羟基喜树碱反应得到两种碳酸酯类衍生物,其结构经HR-MS、^(1)H-NMR、^(13)C-NMR表征确认。以伊立替康为阳性对照,采用CCK8法测试它们对人结肠癌细胞(HCT-116、Caco2)、人结肠癌耐药细胞(HCT-15/Taxol、HCT-8/V、HCT-116/5-FU)、人正常结肠上皮细胞(NCM-460)的抑制活性。HPLC初步分析衍生物在不同pH下的稳定性。结果 两种碳酸酯类衍生物对五种结肠癌细胞具有显著的抑制作用,且来源于7-乙基-10-羟基喜树碱的衍生物对HCT-15/Taxol、HCT-8/V、HCT-116/5-FU等结肠癌耐药细胞的抑制活性优于非耐药结肠癌细胞HCT-116、Caco2,IC_(50)分别为2.56、2.70、1.42 μmol·L^(-1)。其对HCT-8/V、HCT-116/5-FU的选择指数(SI)也优于阳性对照伊立替康。在pH 1.0下,该衍生物3 h内可稳定在70%左右,4 h后急剧下降到10%以下;在pH 7.4下,12 h内可稳定在80%~90%。结论 来源于7-乙基-10-羟基喜树碱的碳酸酯衍生物可作为抗结肠癌药物做进一步研究。

哮喘、毛细支气管炎患儿外周血MDSCs、IL-10和IL-12水平及意义

目的探讨哮喘、毛细支气管炎(简称毛支)患儿髓系抑制细胞(MDSCs)占外周单个核细胞比例、血清白介素-10(IL-10)及白介素-12(IL-12)的水平及意义。方法以正常健康儿童及肺炎组为对照,应用流式细胞仪检测哮喘急性发作组、缓解组及毛支Ⅰ组(特应质组)、毛支Ⅱ组(非特应质组)外周血MDSCs占外周单个核细胞的比例(MDSCs%);用ELISA法检测各组儿童血清IL-10、IL-12水平。结果①哮喘发作组较哮喘缓解组、肺炎组及正常对照组外周血MDSCs%、血清IL-10升高,IL-12降低(P<0.05);②毛支Ⅰ组较毛支Ⅱ组、肺炎组及正常对照组外周血MDSCs%、IL-10升高,IL-12降低(P<0.05);③哮喘发作组与毛支Ⅰ组相比,外周血MDSCs%、IL-10、IL-12无明显差异(P>0.05);④相关性分析:哮喘发作组及毛支Ⅰ组MDSCs占外周血单核细胞的比例和血清IL-10水平存在正相关,与血清IL-12水平呈负相关。结论 MDSCs可能通过上调IL-10、下调IL-12水平在毛细支气管炎发展为哮喘的过程中起重要作用,有望成为毛支筛选为哮喘的指标。

以1,10-邻菲罗啉为基体的新型配体研究进展

1,10-邻菲罗啉类配体包括2,9、5,6、3,8位及4,7位等修饰物,具有优异的配位能力,其与过渡金属形成的配合物表现出良好的光化学、电化学以及生物学性能,并且在很多领域得到应用。就近年来对1,10-邻菲罗啉的修饰及作为新型配体的应用进行了综述。

哮喘患儿外周血髓系抑制细胞、IL-10和IL-12水平检测

目的:检测哮喘患儿外周血髓系抑制细胞(MDSCs)、白细胞介素-10(IL-10)和白细胞介素-12(IL-12)的水平。方法:应用两色荧光标记技术流式细胞仪检测哮喘发作组(n=52)、哮喘缓解组(n=50)、肺炎对照组(n=45)及正常对照组(n=48)儿童外周血MDSCs,用双抗体夹心ELISA法检测血清IL-10、IL-12水平。结果:哮喘发作组较其他3组外周血MDSCs、血清IL-10水平升高,血清IL-12水平降低,差异有统计学意义(F=1043.820、1284.470和1139.380,P均<0.05);肺炎对照组与正常对照组各指标差异无统计学意义(P>0.05)。哮喘发作组患儿外周血MDSCs水平与IL-10呈正相关(r=0.741,P=0.007),与IL-12呈负相关(r=-0.879,P=0.014)。结论:MDSCs可能通过上调IL-10、下调IL-12在儿童哮喘发病中起作用。

黄芪多糖对B16-F10荷瘤鼠髓样抑制细胞免疫活性的影响

目的:观察黄芪多糖对B16-F10荷瘤鼠髓样抑制细胞免疫活性的影响,探讨黄芪多糖在抗肿瘤免疫机制方面所发挥的作用。方法:建立B16-F10荷瘤鼠模型,通过计算抑瘤率观察黄芪多糖的体内抗肿瘤活性;通过流式细胞术检测脾脏中Gr-1+CD11b+髓样抑制细胞比例;采用酶联免疫吸附试验检测血清中IL-10、VEGF水平。结果:与模型组相比,黄芪多糖治疗可以明显抑制荷瘤鼠黑色素瘤的生长,且可以降低荷瘤鼠脾脏Gr-1+CD11b+髓样抑制细胞比例,抑制外周血VEGF、IL-10的分泌,有显著性差异。结论:适当浓度的黄芪多糖可能通过降低髓样抑制细胞的比例,抑制VEGF、IL-10的分泌和肿瘤的生长。

脂肪来源的干细胞移植对脑缺血大鼠脑组织IL-10及TNF-α表达的影响

目的:观察脂肪来源的干细胞(ADSC)移植对脑缺血大鼠脑组织IL-10及TNF含量变化,探讨ADSC对脑缺血损伤的保护机制。方法:将72只清洁级成年雄性Sprague-Darley大鼠随机分为假手术组(Sham组)、脑缺血组(MCAO组)、溶剂对照组(Vehicle组)和ADSC治疗组(ADSC组)四组,每组18只,采用线栓法制作大脑中动脉栓塞(MCAO)模型,ADSC移植前用DAPI标记,ADSC组于造模成功1 d后经侧脑室注射入30μL的经DAPI标记的ADSC细胞悬液,内含1×106细胞,Vehicle组则注射同等剂量的PBS,各组分别于术后4 d、7 d和14 d分批处死后取出脑脑织,采用ELISA法、免疫组织化学法和半定量RT-PCR法,检测大鼠脑组织中IL-10和TNF-α表达的变化。结果:与假手术组相比较,MCAO组大鼠4 d和7 d时脑组织中TNF-α和IL-10的表达明显上调(P<0.05)。MCAO组与vehicle组各相应时间点IL-10和TNF-α表达均无统计学差异(P>0.05)。与vehicle组相比,ADSC组4 d、7 d和14 d时脑组织中IL-10的表达显著上调,TNF-α的表达明显下调(P<0.05)。结论:ADSC移植可上调脑缺血大鼠IL-10的表达,并下调TNF-α的表达,这可能是ADSC具有脑缺血保护作用的机制之一。

海洋生物抗肿瘤多肽海兔毒素10及其衍生物的研究进展

海兔毒素10(dolastatin 10,D10)是从海洋无壳软体动物截尾海兔(Dolabella auricularia)中分离提取的由4个氨基酸组成的线性缩肽类天然毒性蛋白。dolastatin 10及其衍生物可以抑制细胞有丝分裂,具有很强的抗肿瘤活性,已进入临床研究阶段。文中综述对dolastatin 10的发现、结构特点与作用机制,其衍生物及衍生物与相应单克隆抗体偶联物的临床疗效。