C60与叠氮化合物的单加成反应

本文从实验以及理论研究两方面介绍了C60与叠氧化合物的单加成反应。依照叠氮化合物的不同,C60与叠氮合物的单加成反应可分为烷基叠氮化物与C60的反应,酰基叠氧化物与C60的反应以及苯基叠氮化与C60的反应三类,而反应产物则为C60亚氨基[6,6]闭环衍生物和C60亚氨基[5,6]开环衍生物两类,不同类型的反应具有不同的反应机理,某些C60亚氨基[5,6]开环衍生物可以转化为C60亚氨基[6,6]闭环衍生物。本文还介绍了碳纳米管与叠氮化合物的加成反应。     

61-甲基-61-[12-(18-N-四氯邻苯二甲酰亚氨基)脱氢枞胺]-1,2-亚甲基富勒烯[60]的合成

以脱氢枞胺为原料,经氨基酰化、12位乙酰化、与对甲苯磺酰肼形成对甲苯磺酰腙衍生物,再通过卡宾中间体与C60进行[2+1]环加成反应合成了C60-脱氢枞胺衍生物。目标化合物经IR,UV-Vis,1H NMR,13C NMR,MALDI-TOF MS表征,所得化合物为[6,6]闭环结构C60加成产物。     

61-甲基-61-[12-(N,N-四氯邻苯二甲酰基)脱氢枞胺]-1,2-亚甲基富勒烯[60]的合成

以脱氢枞胺为原料,经氨基酰化、12位乙酰化、与对甲苯磺酰肼形成对甲苯磺酰腙衍生物,再通过卡宾中间体与C60进行[2+1]环加成反应合成了C60-脱氢枞胺衍生物。目标化合物经IR,UV-Vis,1H NMR,13C NMR,MALDI-TOF MS表征,所得化合物为[6,6]闭环结构C60加成产物。     

1,6-亚甲基桥[10]轮烯并[3,4-g]-蒽醌衍生物的合成

采用无溶剂合成法,以1,6-亚甲基桥[10]轮烯-3,4-二甲酸酐为原料,Zr OCl2·8H2O/Na Cl为催化剂,于165℃下分别与取代苯经Friedel-Crafts缩合反应合成了4个新型的1,6-亚甲基桥[10]轮烯并[3,4-g]-蒽醌衍生物,其结构经1H NMR,13C NMR,IR,MS和HR-MS表征。     

三组分反应合成1,4-[6,6’-(3-三氟甲基吡唑并[3,4-d]嘧啶)]哌嗪衍生物

在乙醇钠的催化下,1-苯基-3-三氟甲基-5-(三苯基氨基膦叶立德)-4-羧酸乙酯(膦亚胺2)、芳基异氰酸酯与无水哌嗪或其取代物的三组分反应制得1,4-[6,6’-(3-三氟甲基吡唑并[3,4-d]嘧啶)]哌嗪衍生物,产率为55%～87%.产物结构经1H NMR,IR,MS表征和元素分析确证.     

新型硫杂杯[4]芳烃衍生物的合成

在对叔丁基硫杂杯[4]芳烃(1)的下缘1,3-位引入芳醛基制得硫杂杯[4]二醛基衍生物(3);3在水合肼中肼解制得硫杂杯[4]二醛腙基衍生物(4);4与5,5'-亚甲基二水杨酰基二水杨酰氯经缩合反应合成了具有桥连结构的硫杂杯[4]芳烃桥联氮杂衍生物(6),3,4和6为新化合物。其结构经1H NMR,IR,ESI-MS和元素分析表征。     

富勒烯[60]膦酸酯衍生物纳米颗粒水悬液的制备与自由基清除活性

自由基清除是富勒烯及其衍生物的一种重要特性. 首次制备了1种二加成亚甲基富勒烯[60]膦酸酯衍生物(bis-methanophosphonate [60]fullerene, BMPF)的纳米颗粒水悬液(n-BMPF), 并采用邻苯三酚自氧化法结合分光光度法, 测定了n-BMPF对超氧阴离子自由基的清除作用. 结果显示, 制备的n-BMPF溶液较稳定, 适合生物学实验. 同时, 它表现出很强的清除超氧阴离子自由基的能力, 并具有浓度依赖性. 当n-BMPF的终浓度为12 μmol/L时, 其对超氧阴离子自由基的清除率达到91.96%. n-BMPF的活性远大于已报道具有自由基清除作用的水溶性富勒烯衍生物富勒醇. 这些数据表明n-BMPF可能作为一种新型高效的自由基清除剂, 在生物医学领域具有潜在的应用价值.     

1-(3-芳亚甲基氨基)丙基-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷金属络合物的合成及其抗肿瘤活性研究

我们曾对1-亚甲基氨基烷基-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷的合成及其抗肿瘤活性作过研究,发现1-[3-(2-羟基苯亚甲基氨基)丙基]-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷和1-[3-(2,4-二羟基苯亚甲基氨基)丙基]-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷具有较好的抗肿瘤活性。已知亚甲胺类(Schiff碱)化合物与某些金属离子形成络合物后,能提高它们的抗肿瘤活性。为此,我们进一步研究了这两种亚甲胺衍生物的合成及其抗肿瘤活性。     

基于1,6-亚甲基桥[10]轮烯的多环化合物的合成

1,6-亚甲基桥[10]轮烯-4-溴-3-羧酸乙酯经LiAlH4还原后再在冰水浴下与PBr3反应制得3-溴甲基-4-溴-1,6-亚甲基桥[10]轮烯(3);3与PPh3在苯中回流,然后与对甲氧基苯甲醛进行Wittig反应,再经分子内异构化制得3-(p-甲氧基苯乙烯基)-4-溴-1,6-亚甲基桥[10]轮烯(trans-5);trans-5在钯盐催化下完成分子间耦合合成了基于1,6-亚甲基桥[10]轮烯的多环化合物,其结构经NMR,IR和MS表征.     

规整链球型含C_(60)聚(丙烯酸β-羟乙酯)的合成及其在水中的自组装

Ｃ60 由于其独特的物理化学性质 ,在生命科学中引起了人们的广泛兴趣 .例如 :水溶性Ｃ60 的羧酸衍生物 ,羟基取代Ｃ60 ,Ｃ60 的氨基酸水溶性衍生的合成已有报道[1～ 3] ,并被用来研究Ｃ60 的生物化学及医学活性 .Ｔｏｋｕｙａｍａ[4 ] 等合成了酶功能化Ｃ60及与核酸连接的Ｃ60 ,研究并证明了它的细胞毒性及Ｇ 选择ＤＮＡ切割能力等生化活性 .Ｆｒｉｅｄｍａｎ[5]等合成了水溶性Ｃ60 的羧酸衍生物 ,研究了它对ＨＩＶ 1艾滋病毒的抑制作用 ,此外 ,关于不同Ｃ60含量的Ｃ60 蛋白质衍生物的合成及性质的研究也有报道[6] .Ｃ60 是一个直径为 0 71…     

Quantitative trace analysis of fullerenes in river sediment from Spain and soils from Saudi Arabia

A quantitative method based on ultrasound-assisted toluene extraction followed by liquid chromatography–electrospray ionization–tandem mass spectrometry for the analysis of C₆₀ and C₇₀ fullerenes, N-methylfulleropyrrolidine, [6, 6]-phenyl C₆₁ butyric acid methyl ester and [6, 6]-thienyl C₆₁ butyric acid methyl ester has been developed. The method was validated using fortified blank river sediments according to the criteria of Commission Decision 2002/657/EC. The method limits of detection ranged from 14 to 290 pg/g, making it suitable for its application in environmental analysis. The method has been applied to investigate fullerene content in 58 soil samples collected from different urban and industrial areas in Saudi Arabia and in river sediment from six different sites in the Llobregat River Basin. In addition, in the case of the Llobregat River, superficial water samples from the same sites of the sediments were collected and analysed using a previous method. In soils from Saudi Arabia, C₆₀-fullerene was the only compound that was detected and quantified in 19 % of samples. In the sediments of the Llobregat River, C₆₀-fullerene was also the only one detected (33 % of the samples), while in river water, C₇₀-fullerene was the most frequent compound, and it was quantified in 67 % of the samples. However, C₆₀-fullerene was present in two of the six samples, but at higher concentrations than C₇₀-fullerene, ranging from 0.9 to 7.8 ng/L.     

Porphyrin-LEGO®: synthesis of a hexafullereno-diporphyrin using porphyrins programmed for [4+2]-cycloaddition

A hexafullereno-diporphyrinoid was obtained in a sequence of cycloaddition steps using porphyrins programmed for [4+2]-cycloaddition reactions and C(60)-fullerene.     

7-氯-[1，2，3，4]-四氢吩嗪-[2，3]-并富勒烯[60]的合成

60富勒烯及其衍生物因其结构的特殊性,在有机超导、分子磁性、有机发光材料、分子器件、非线性光学活性、能量代谢和生物活性等[1]方面表现出独特的性能和潜在的应用前景,是非常活跃的研究领域之一.     

Preparation of [5,6]- and [6,6]-oxahomofullerene derivatives and their interconversion by Lewis acid assisted reactions of fullerene mixed peroxides

[60]Fullerene mixed peroxides C60(O)(OOtBu)4 exhibit chemo- and regioselective reactions under mild conditions. The epoxy moiety is opened by ferric chloride to form vicinal hydroxy chloride C60Cl(OH)(OOtBu)4. BF3 is also effective in opening the epoxy moiety. The O-O bond of the fullerene mixed peroxide is cleaved by aluminum chloride to form both [5,6]- and [6,6]-fullerene hemiketals (oxohomo[60]fullerenes). A Hock-type rearrangement is proposed for the formation of the hemiketals, in which a fullerene C-C bond is cleaved. Lewis acids and/or visible light can initiate isomerization of the hemiketal isomers. Single-crystal X-ray analysis and theoretical calculations confirmed the results.     

Hydrophilic [60]fullerene carboxylic acid derivatives retaining the original 60π electronic system

Water-soluble carboxylic acid derivatives of [60]fullerene retaining the original 60π electronic configuration are prepared from a tetra-tert-butyl ester of bis(fulleroid).     

Electrophilic substitution of C60F18 into phenols: HF elimination between OH and a 1,3-shifted fluorine giving benzofurano[2',3':10,26]hexadecafluro[60]fullerene and derivatives

The reaction of C60F18 with phenol, 2-naphthol and quinol in the presence of ferric chloride leads to initial electrophilic substitution (aryldefluorination). This occurs at both ortho and para positions for phenol, at the ortho position for quinol, and at the relatively hindered but most reactive 1-position for 2-naphthol. It is followed, where sterically favourable, by HF loss either between the OH group and F (rendered adjacent as a result of a 1,3-shift) or to attack of the OH group at an adjacent double bond with loss of a beta-fluorine, giving benzofurano[2',3':10,26]hexadecafluoro[60]fullerene derivatives. The reaction is accompanied by some complete defluorination leading, in reaction with phenol and with 2-naphthol, to the formation of benzofurano[2',3':1,2][60]fullerene and naphtho[2,1:b]furano[d:1,2][60]-fullerene, respectively. The mechanism of base-catalysed reaction of phenols with C60Cl6 is re-evaluated.     

Intracellular uptake and phototoxicity of 3(1),3(2)-didehydrophytochlorin-fullerene hexaadducts

C(60)-fullerene derivatives are potential building blocks in modular carrier systems for selective tumor targeting. In [5:1] fullerene hexakis adducts, one position can be occupied by an addressing unit (e.g. monoclonal antibody) while the other five positions are suitable for dendrimers or spacers loaded with several drug moieties. This article reports intracellular uptake and phototoxicity of three fullerene hexakis adducts coupled with a different number of photosensitizers: a bis(3(1),3(2)-didehydrophytochlorin)-fullerene [5:1]-hexaadduct (FHP1), a fullerene [5:1]-hexaadduct with six 3(1),3(2)-didehydrophytochlorin groups (FHP6) and a fullerene [6:0]-hexaadduct that carries 12 3(1),3(2)-didehydrophytochlorin units (FHP12). The most promising complex, the hexa-3(1),3(2)-didehydrophytochlorin fullerene hexaadduct FHP6, was also compared with its fullerene-free analogous derivative P6. It was found that the extent of intracellular uptake is influenced by both nanomolecular size and asymmetry (amphiphilicity) of the fullerene complexes. The degree and mechanism of phototoxicity was found to depend on intracellular concentrations and singlet oxygen quantum yields.     

60]Fullerene-fused lactones: manganese(III) acetate-mediated synthesis and novel reductive ring opening

[reaction: see text] [60]Fullerene-fused lactones were prepared by the manganese(III) acetate-mediated reactions of [60]fullerene with carboxylic acids, carboxylic anhydrides, or malonic acids. Novel reductive ring opening of the lactones with Grignard reagents was observed.     

C60富勒烯-哌啶硫代荒酸酯稠合体的合成与三线态特征

C₆₀富勒烯与2-(哌啶-硫代荒酸酯)-1,3-丁二烯通过Diels-Alder环加成反应得到C₆₀富勒烯-哌啶硫代荒酸酯稠合体,运用现代波谱技术等确定了产物结构;用半经验方法PM3和AM1计算预测环加成反应性和C₆₀富勒烯-哌啶硫代荒酸酯稠合体的性能.激光光解时间分辨技术初步探究了单加成的C₆₀富勒烯-哌啶硫代荒酸酯稠合体(C₆₀-PX)三线态特征以及与四-(2-噻吩基)-四硫富瓦烯(TT-TTF)分子间的光诱导电子转移反应.     

Interfacial behavior and film-forming properties of an amphiphilic hexasubstituted [60]fullerene

A new amphiphilic hexasubstituted [60]fullerene bearing 10 cholesterol units and a polar head made of two carboxylic acid functions has been prepared and its aptitude to film forming (Langmuir and Langmuir-Blodgett) evaluated. The results show that this amphiphile has the prerequisite qualities for its incorporation into the cellular membranes of living organisms.