Carborane-Containing Matrix Metalloprotease (MMP) Ligands as Candidates for Boron Neutron-Capture Therapy (BNCT)

Based on the previously reported potent and selective sulfone hydroxamate inhibitors SC-76276, SC-78080 (SD-2590), and SC-77964, potent MMP inhibitors have been designed and synthesized to append a boron-rich carborane cluster by employing click chemistry to target tumor cells that are known to upregulate gelatinases. Docking against MMP-2 suggests binding involving the hydroxamate zinc-binding group, key H-bonds by the sulfone moiety with the peptide backbone residues Leu82 and Leu83, and a hydrophobic interaction with the deep P1’ pocket. The more potent of the two triazole regioisomers exhibits an IC₅₀ of 3.7 nM versus MMP-2 and IC₅₀ of 46 nM versus MMP-9.     

高燃速推进剂用硼氢化物的研究进展

对硼氢化物的合成进行了简单介绍,综述了离子型氢硼酸盐、碳硼烷及其衍生物、金属碳硼烷和硼烷类含能离子液体(盐)作为固体推进剂燃速调节剂研究工作的最新进展。离子型氢硼酸盐与碳硼烷均可较大范围调节固体推进剂的燃速,但离子型氢硼酸盐合成工艺相对简便、成本较低;含能离子液体(盐)具有高密度、高能量、钝感及毒性低等特点,将其应用于推进剂及炸药方面具有良好的发展前景。     

Synthesis of carborane acrylate and flame retardant modification on silk fabric via graft copolymerization with phosphate‐containing acrylate

A novel carborane acrylate monomer (1‐acryloyloxyethyl carborane) was synthesized by addition reaction, hydrolysis, and esterification and characterized by proton nuclear magnetic resonance (¹H NMR) spectroscopy and Fourier transform infrared spectroscopy (FT‐IR) analysis. Subsequently, the carborane monomer and a phosphate‐containing methacrylate monomer were applied on the modification of a silk fabric. The heat resistance and flame retardancy of the silk fabric before and after modification were compared. Energy‐dispersive X‐ray spectrometer (EDS) and FT‐IR showed that carborane monomer and phosphate‐containing methacrylate were grafted onto the surface of the fibers. The cross‐sectional morphology of silk fabrics after burning was observed by scanning electron microscope (SEM), and the flame‐retardant mechanism was analyzed. Thermal‐gravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis revealed that the thermal stability of the modified silk increased with the increase of the grafting yield. The MCC‐2 microcalorimeter (MCC) test showed that, when using 1‐acryloyloxyethyl carborane as monomer and blending with phosphate‐containing methacrylate, the maximum heat release rate (PHRR) of the modified silk fabric decreased from 97.6 W/g (before grafting) to 51.3 and 45.8 W/g, respectively, and the total heat release (THR) decreased from 10.2 kJ/g (before grafting) to 5.9 and 5.2 kJ/g, respectively. The limiting oxygen index (LOI) test revealed that using 1‐acryloyloxyethyl carborane and phosphate‐containing methacrylate as mixed monomers to modify the silk fabric obtained good flame retardancy, whose LOI value reached 29.8%.     

新型耐高温PI胶粘剂用单体的合成及表征

为了提高聚酰亚胺(PI)胶粘剂的耐热性能,将碳硼烷引入PI分子链中,首次合成出一种新型含碳硼烷的PI单体,并采用红外光谱(FT-IR)法对其结构进行了表征。结果表明:含碳硼烷的PI单体在400～500℃升温过程中可交联固化;以此作为PI胶粘剂的基体,可赋予PI胶粘剂极佳的热稳定性能(500～1 300℃时热失重变化不大),从而为制备耐高温胶粘剂提供了新的途径和新的方法。     

碳硼烷类燃速催化剂的研究进展

综述了国内外碳硼烷类燃速催化剂的研究情况,介绍了各种碳硼烷类催化剂的性能特点,指出碳硼烷类燃速催化剂是适用于高燃速和超高燃速推进剂配方的燃速催化剂,具有显著提高推进剂燃速的作用,对压强指数的影响依据配方组成的不同而有区别.     

碳硼烷二元酸的合成与耐热性能研究

以A(1,2-碳硼烷)为原料,分别采用琼斯试剂氧化法、CO2法和ClCOOCH3(氯甲酸甲酯)法合成了D(1,2-二羧基碳硼烷);然后D和B(1,2-二羟甲基碳硼烷)进一步酯化缩聚后,成功合成了P6(聚1,2-二羧基碳硼烷-1,2-二羟甲基碳硼烷酯)。研究结果表明:3种合成方法均能成功合成D,其中CO2法是最理想的合成方法;碳硼烷基团的引入,有效提高了P6的耐热性能(N2气氛中P6失重5%时的热解温度为190℃,700℃时的残炭率为59%);P6在耐高温领域中具有良好的应用前景,也是制备耐高温型PU(聚氨酯)胶粘剂的宝贵原材料。     

Acridine/Acridone–Carborane Conjugates as Strong DNA-Binding Agents with Anticancer Potential

Synthesis of acridine derivatives that act as DNA-targeting anticancer agents is an evolving field and has resulted in the introduction of several drugs into clinical trials. Carboranes can be of importance in designing biologically active compounds due to their specific properties. Therefore, a series of novel acridine analogs modified with carborane clusters were synthesized. The DNA-binding ability of these analogs was evaluated on calf thymus DNA (ct-DNA). Results of these analyses showed that 9-[(1,7-dicarba-closo-dodecaborane-1-yl)propylamino]acridine ( 30 ) interacted strongly with ct-DNA, indicating its ability to intercalate into DNA, whereas 9-[(1,7-dicarba-closo-dodecaborane-1-yl)propanamido]acridine ( 29 ) changed the B-form of ct-DNA to the Z form. Compound 30 demonstrated cytotoxicity, was able to inhibit cell proliferation, arrest the cell cycle in the S phase in the HeLa cancer cell line, and induced the production of reactive oxygen species (ROS). In addition, it was specifically localized in lysosomes and was a weak inhibitor of Topo IIα.     

Structural-Chemical Conception of Stabilization of Aromatic Polymers as Exemplified by Arylene Carboranes

Abstract

The paper discusses the specific features of thermal behaviour of carborane-containing polymers and the stabilizing effect of the carborane groups as exemplified by arylene carboranes. The results obtained explain as a whole the stabilizing effect of aromatic polymers by carborane-containing additives.     

Syntheses of novel soluble carborane polyimides with ultrahigh thermal stability

Novel carborane polyimides were synthesized and studied. Aromatic meta‐carborane diamines of different structures were initially prepared. Polymerization of these new diamines with the commercially available 4,4′‐oxydiphthalic dianhydride led to meta‐carborane polyimides with various structures and thermal properties. The amorphous polymers obtained are of moderate molecular weight and show good solubility in organic solvents. Thermal analyses of these polyimides reveal that they have moderate to ultrahigh thermal stability depending on their specific structures, with 5% decomposition temperatures ranging from 382 to 786 °C in nitrogen. Different thermal properties of these polyimides are observed when the analyses are performed in dry air, with 5% decomposition temperatures shifting to temperatures ranging from 388 to 1128 °C. Due to the ever‐present requirement of higher performance polymers in fields like aerospace and defense, the methods developed here could be an impetus for the development of these industries. © 2015 Society of Chemical Industry