核交联的含磺酸甜菜碱pH敏感胶束的制备与表征

制备了一种在疏水段带有侧基叠氮官能团的两亲性pH敏感的聚合物——聚己内酯-聚(甲基丙烯酸二乙氨基乙酯-磺酸甜菜碱)((PCL-ACL)-PDEAS);同时合成了两端带有炔基中间带有二硫键的交联剂,用红外、核磁表征了目标分子.通过两亲性高分子自组装形成胶束,并通过点击化学反应获得了核交联的胶束.通过动态光散射测定粒径,胶束酸碱滴定表征胶束的pH敏感性,还原条件下释放药物的速度,对比了非交联胶束和交联胶束的性质.结果表明,交联胶束在正常生理条件下的释放速度比未交联胶束更慢;而在有DTT的存在条件下,交联胶束由于二硫键断裂,释放速率明显加快.因此,核交联载药胶束有可能响应肿瘤的微环境实现靶向释放.     

A versatile synthetic strategy for nanoporous gold–organic hybrid materials for electrochemistry and photocatalysis

Nanoporous gold (npAu) was employed as high surface area substrate for immobilization of redox- and photooxidative-active organic molecules. A two-step synthetic routine is demonstrated as a versatile and robust method for immobilization of various molecules. First, self-assembled monolayers (SAMs) of thiols containing an azide moiety were prepared on npAu substrates. Then, alkyne-modified ferrocene, tetrathiafulvalene, and zinc(II)phthalocyanine derivatives were covalently bound via the click reaction to this linker. Following the provided synthetic procedures high performance composite materials are generated for electrochemistry and photochemistry. The robust bonding between the organic functional group and the gold support provides stability even under strongly oxidizing conditions (applied potential or singlet oxygen).     

Synthesis of porphyrin-quinolone conjugates

meso-Tetrakis(pentafluorophenyl)porphyrin reacts with propargyl alcohol to afford porphyrins substituted with one, two, three or four prop-2-yn-1-yloxy groups in the 4-position of the meso-aryl groups. These new porphyrin derivatives react with a 6-azidoquinolone under ‘click-chemistry’ conditions to give porphyrin-quinolone conjugates linked by 1,2,3-triazole units.     

Study on the green click-chemistry synthesis of 4-trifluoroacetyl-1,2,3-triazoles

A metal-free and solvent free click-chemistry procedure has been revealed for the synthesis of 4-trifluoroacetyl-1,2,3-triazoles from corresponding azides and alkyne with high yield and selectivity. The pure products could be easily obtained via crystallization of the reaction mixture (standing for 1 day). Among the 4-trifluoroacetyl-1,2,3-triazoles, 3ba showed the best anticancer activity against HepG2 cell with IC₅₀ of 0.0267?μmol/ml. This method has the advantages of less pollution, low cost, simple treatment and more efficiency.     

Rapid in situ synthesis of [C]methyl azide and its application in C click-chemistry

We synthesized [¹¹C]methyl azide ([¹¹C]MeA) by reacting [¹¹C]methyl iodide ([¹¹C]MeI) in situ with an azide-donor and used it in the synthesis of ¹¹C-labeled 1,2,3-triazoles. A one-pot click approach comprised the infusion of gaseous [¹¹C]MeI into a mixture of NaN₃, ethynylbenzene, and CuI in water at a temperature of 100 °C yielding the ¹¹C-triazole in radiochemical yields (RCY) of 25%. In a two-step labeling protocol, we synthesized the [¹¹C]MeA in acetonitrile in advance to the click step. Using the more soluble complex as source of , a much higher trapping efficiency of [¹¹C]MeI in this solvent ensured an almost quantitative conversion of [¹¹C]MeI to [¹¹C]MeA within 5-10 min at room temperature. The [¹¹C]MeA was thereafter reacted with ethynylbenzene at 100 °C yielding 1-[¹¹C]methyl-4-phenyl-1H-1,2,3-triazole in preparative RCY of 60%. As a final proof of applicability, we used ¹¹C-click-chemistry for the labeling of N-terminal 4-ethynylbenzene derivatized d-Glu-d-Tyr-[Cys-Tyr-Trp-Lys-Thr-Cys]-Thr, a cyclic water-soluble Tyr³-octreotate derivative.     

Microwave-mediated ‘click-chemistry’ synthesis of glycoporphyrin derivatives and in vitro photocytotoxicity for application in photodynamic therapy

In this paper, we report the synthesis of a series of porphyrins, designed as photodynamic therapy (PDT) agents, substituted by three glycosyl units linked by a triazole group to chromophore in the aim to target tumor cells overexpressing lectin-type membrane receptors, by ‘click-chemistry’ under microwave heating.     

New mono- and bidentate P-ligands using one-pot click-chemistry: synthesis and application in Rh-catalyzed hydroformylation

Three families of new phosphorus ligands have been prepared using the click-chemistry approach proceeding in only two steps and without intermediate P-protection. The methodology allows the high yield production of mono- and bidentate P-ligands, bearing at least one P–O bond. The ligands were tested in the Rh-catalyzed hydroformylation of 1-octene.     

An efficient route to VEGF-like peptide porphyrin conjugates via microwave-assisted ‘click-chemistry’

Synthetic cyclopeptides, and particularly those derived from VEGF sequence, present considerable interest for the development of nanodevices devoted to tumour imaging or targeting. In order to provide selective peptide-targeted tetrapyrrolic structures, we designed two meso-porphyrin derivatives anchored to a 17-residue-long cyclopeptide, potent antagonist of VEGF receptors, via a flexible tetraethylene glycol chain. Anchoring was achieved by two different strategies: a classical secondary amide bond formation and microwave-assisted Cu(I)-catalyzed azide-alkyne 1,3-dipolar cycloaddition (‘click-chemistry’). These compounds appear to be promising candidates for applications in PDT.     

Copper(I)-doped Wyoming’s montmorillonite for the synthesis of disubstituted 1,2,3-triazoles

A new catalytic system based on copper(I)-doped Wyoming’s montmorillonite was elaborated. This system was studied and was found to catalyze the formation of 1,4-disubstituted 1,2,3-triazoles when starting from azides and alkynes. It was used for the synthesis of a few triazole derivatives to show its usefulness.