Solid state reactions of nitrogenous heterocyclic compounds (I) —Solid state reactions of 3-methyl-1-phenyl-5-pyrazolone with carbonyl compounds

The solid state reaction of 3-methyl-1-phenyl-5-pyrazolon(eM PP) with aromatic aldehydes and ketones, benzil derivatives and imides, and the solid state Michael addition reaction of MPP with 4-arylidene-3-methyl-lphenyl-5-pyrazolone2 were investigated. Some new solid state reactions between the reactants were found, from which a series of new compounds were obtained. The structures of the products were identified by IR,¹H NMR, MS, elemental analyses and also by X-ray crystal analysis, and the reaction mechanism of MPP with aromatic aldehydes and ketones was proposed. Project supported by the National Natural Science Foundation of China.     

Solid state reactions of nitrogenous heterocyclic compounds (II)

Solid state Michael addition reaction of indole with α, β-unsaturated carbonyl compounds was carried out, by which a series of compounds containing three different heterocyclic groups binding to one carbon atom were ob-tained. In the presence of Lewis acid, indole could undergo the solid state condensation reaction with aromatic ketones and aldehydes or quinones. The solid state reaction showed higher selectivity and yield than solution reaction. The structures of products were identified by IR,¹H NMR, MS. elemental analysis and X-ray crystal analysis. The reac-tion mechanism was also proposed. Project supported by the National Natural Science Foundation of China     

可控碳改性Pd/TiO2用于直接合成双氧水:非均相界面对催化性能的影响（英文）

双氧水(H2O2)是一种重要的绿色氧化剂,广泛应用于纺织、医疗、废水处理、军事等重要领域.目前, H2O2的工业生产以蒽醌法为主,该法设备投资大、运行成本高,同时工艺涉及大量的有机溶液,活性中间体蒽醌也会发生缓慢降解,产生有毒副产物.与蒽醌法相比,通过负载型贵金属催化剂催化H2与O2反应直接合成H2O2,过程绿色环保且生产工艺简单,引起了各界广泛关注.然而,从热力学上分析, H2和O2更容易反应生成H2O, H2O2只是该反应的中间产物,会继续发生加氢和直接分解反应生成H2O,导致H2和O2的低效利用,开发高H2O2选择性且高反应效率的催化剂已成为氢氧直接合成H2O2研究的重点与难点.目前大部分研究策略旨在通过调控或影响反应中心结构、价态来抑制H2O2的副反应,进而提升H2O2的选择性和反应效率;尽管已取得了良好的进展,但仍需发展新的调控策略来满足工业应用的要求.本课题组前期研究表明,促使H2O2从催化剂上脱附可以有效地提升H2O2的选择性和产率.相比于针对反应中心的调控,不稳定的H2O2从催化剂上快速脱附同样起到抑制H2O2参与副反应的作用.为此,本文提出一种炭量可控的非均一界面改性方法,以常规的Pd/TiO2作为研究对象,借助各种结构表征,发现炭物种在TiO2表面呈非均一分散状态,而且改性对于催化剂的几何结构影响较小;另外,催化剂表面的疏水性会随着碳含量的增加而增加,导致其与H2O2间的吸附能相应变小.反应结果显示,表面非均一的炭化改性技术可以显著提升Pd/TiO2催化剂的H2O2选择性和产率.通过构效关系分析,可知这种改性技术可以保持Pd颗粒与TiO2间相互作用的同时,还可以促进H2O2的快速脱附,进而提升改性Pd/TiO2催化剂的H2O2直接合成效率.该改性方法简单、易控,可拓展应用到其他类型催化剂的H2O2直接合成性能调控与改进.     

A novel small-molecule near-infrared II fluorescence probe for orthotopic osteosarcoma imaging

Osteosarcoma is the most common primary malignant tumor of bone, particularly among children and adolescents. Advances in imaging, surgical techniques, and implants have dramatically reduced the need for amputation in the past three decades.Recently, in vivo fluorescence imaging in the second near-infrared window(NIR-II, 1,000–1,700 nm) shows impressive advantages of deeper tissue penetration and higher spatial resolution, which makes it a promising tool for the early diagnosis and post-operative observation of Osteosarcoma. To the best of our knowledge, this paper is the first time to develop a novel NIR-II fluorescence probe conjugated with an osteosarcoma targeted oligopeptide for molecular tumor imaging in a xenograft orthotopic osteosarcoma mouse model.     

深共融溶剂中合成2,4-二取代喹啉衍生物

在氯化胆碱和氯化锌组成的深共融溶剂中,以2-氨基苯乙酮和芳香炔烃为原料,通过环化偶联反应,合成了一系列2,4-二取代喹啉衍生物;当n(氯化胆碱)∶n(氯化锌)=1∶2,反应温度为80℃时,反应3 h即获得高达98%的产率.该方法无需额外添加催化剂,而且反应条件温和、操作简单、底物范围较广泛.     

可用于连续识别Cu^2+和阴离子、中性分子荧光探针的研究进展

铜(Cu)含量的高低直接影响着生命体的正常运转和自然体系的平衡.检测铜离子的方法多种多样,其中具有较高敏感度和选择性的荧光化学传感器应用更加广泛.综述了以Cu^2+为基的荧光化学传感器通过替换法实现了对阴离子S^2-, CN^-, H2PO4^-, PPi和I^-以及中性分子ATP、ADP和生物硫醇等的连续识别的研究进展.     

Synthesis,structure and the e.s.r. spectrum of the mixed-valence molybdovandate Na2(NH4)4[(VIVVV8Mo)O28] · 10H2O

The mixed-valence molybdovanadate compound Na₂(NH₄)₄[V^IVV^V ₈Mo)O₂₈] · 10H₂O [Vanadata(6-)tetradeca--oxotetra-₃-oxodi-₆-oxoheptaoxo(oxomolybdate) nonatetrammonium disodium, decahydrate] has been synthesized from sodium molybdate(VI) dihydrate and sodium metavanadate dihydrate in aqueous solution by adding NH₂OH · HCl. The molecular structure has been determined by X-ray diffraction and is based on the isopolydecavanadate structure. The molybdate atom is crystallographically disordered over 6MO₆ octahedral sites. The e.s.r. spectrum clearly indicates that one vanadium atom has the oxidation number +4.     

二次纳流电喷雾电离耦合超高分辨质谱检测人体呼出气中相对高分子量化合物

二次电喷雾电离源耦合超高分辨质谱(SESI-UHRMS)有望检出人体呼出气中分子量大于300的相对高分子量化合物,这些化合物的发现将有助于更准确地理解呼出气中挥发性有机化合物(VOCs)的来源、产生机制以及SESI源电离机理,更好地实现SESI-UHRMS的转化应用.本研究自组装nanoSESI源(尚无商业产品)耦合四极杆-静电场轨道阱质谱(最高质量分辨率1.2×10~5),考察了该装置对健康人体呼出气中分子量为300~500化合物的检出情况.结果表明,所搭建的nanoSESI-UHRMS装置检测人体呼出气的重现性好、灵敏度高,可检出数十种分子量为300~500的化合物.根据这些化合物在单次呼气过程中信号强度随时间变化的趋势,推断其来源分别为内源性和外源性;各化合物的元素组成主要包括C,H,N和O,环-双键当量(RDB)的均值为(4.5±3.1),表明检出的化合物可能为醛酮或不饱和脂肪酸,容易在SESI源中被电离.本研究初步验证了自组建nanoSESI-UHRMS检测人体呼出气中相对高分子量化合物的可行性,为后续进一步开展方法应用奠定了基础.     

含磷/氮/硫环交联磷腈微纳米管的合成及对环氧树脂的阻燃作用

采用原位模板法,以六氯环三磷腈(HCCP)和二羟基二苯砜(BPS)为原料合成了一种环状交联型不溶不熔的磷腈大分子——聚环三磷腈-二羟基二苯砜(PZS)微纳米管,研究了PZS对环氧树脂(EP)的阻燃作用及阻燃机理.利用红外光谱(FTIR)、扫描电子显微镜(SEM)及透射电子显微镜(TEM)对PZS微纳米管进行了表征;采用热重分析(TG)考察了EP/PZS阻燃材料的热稳定性,并通过极限氧指数(LOI)和微型量热分析(MCC)测试了EP/PZS的阻燃性能.热降解实验结果表明,PZS微纳米管的加入使环氧树脂热降解温度降低,但残炭率显著提高.PZS微纳米管可以显著提高环氧树脂的阻燃性能,当阻燃剂添加量为5%时,环氧树脂的残炭率提高了46%,热释放速率峰值降低了约40%;LOI值从纯环氧树脂的26.0%提高到了30.6%.PZS微纳米管的加入还增强了环氧树脂的力学强度.阻燃性能的显著提高和力学性能的改善归因于PZS微纳米管在环氧树脂基体中的良好分散,以及燃烧炭化过程中生成的石墨化程度较高的类石墨烯结构的残炭,具有较高的抗氧化能力.研究结果表明,PZS微纳米管是一种优良、高效的具有潜在应用价值的阻燃剂.