HO2 ELIMINATION FROM α-HYDROXYALKYLPEROXYL RADICALS IN AQUEOUS SOLUTION

Abstract— In aqueous solutions α-hydroxyalkylperoxyl radicals undergo a spontaneous and a base catalysed HO₂ elimination. From kinetic deuterium isotope effects, temperature dependence, and the influence of solvent polarity it was concluded that the spontaneous reaction occurs via an HO₂ elimination followed by the dissociation of the latter into H⁺ and O₂^-. The rate constant of the spontaneous HO₂ elimination increases with increasing methyl substitution in α-position ( k (CH₂(OH)O₂) < 10s^-1 k (CH₃CH(OH)O₂) = 52s^-1 k ((CH₃)₂C(OH)O₂) = 665 s^-1). The OH^- catalysed reaction is somewhat below diffusion controlled. The mixture of peroxyl radicals derived from polyhydric alcohols eliminate HO₂ at two different rates. Possible reasons for this behaviour are discussed. The mixture of the six peroxyl radicals derived from d -glucose are observed to eliminate HO₂ with at least three different rates. The fastest rate is attributed to the HO₂ elimination from the peroxyl radical at C-l ( k > 7000s^-1). Because of the HO₂ eliminations the peroxyl radicals derived from d -glucose do not undergo a chain reaction in contrast to peroxyl radicals not containing an α-OH group. In competition with the first order elimination reactions the α-hydroxylalkylperoxyl radicals undergo a bimolecular decay. These reactions are briefly discussed.     

Monochalcoplatin: An Actively Transported,Quickly Reducible,and Highly Potent PtIV Anticancer Prodrug

Recently, Pt^IV prodrugs have attracted much attention as the next generation of platinum‐based antineoplastic drug candidates. Here we report the discovery and evaluation of monochalcoplatin, a monocarboxylated Pt^IV prodrug that is among the most cytotoxic Pt^IV prodrugs to date. Compared with its dicarboxylated counterpart chalcoplatin, monochalcoplatin accumulates astonishingly effectively and rapidly in cancer cells, which is not ascribed to its lipophilicity. The prodrug is quickly reduced, causes DNA damage, and induces apoptosis, resulting in superior cytotoxicity with IC₅₀ values in the nanomolar range in both cisplatin‐sensitive and ‐resistant cells; these IC₅₀ values are up to 422‐fold higher than that of cisplatin. A detailed mechanistic study reveals that monochalcoplatin actively enters cells through a transporter‐mediated process. Moreover, monochalcoplatin shows significant antitumor activity in an in vivo colorectal tumor model. Our study implies a practical strategy for the design of more effective Pt^IV prodrugs to conquer drug resistance by tuning both cellular uptake pathways and activation processes.     

High Crystalline Prussian White Nanocubes as a Promising Cathode for Sodium‐ion Batteries

Prussian blue and its analogues (PBAs) have been recognized as one of the most promising cathode materials for room‐temperature sodium‐ion batteries (SIBs). Herein, we report high crystalline and Na‐rich Prussian white Na₂CoFe(CN)₆ nanocubes synthesized by an optimized and facile co‐precipitation method. The influence of crystallinity and sodium content on the electrochemical properties was systematically investigated. The optimized Na₂CoFe(CN)₆ nanocubes exhibited an initial capacity of 151 mA h g^?1, which is close to its theoretical capacity (170 mA h g^?1). Meanwhile, the Na₂CoFe(CN)₆ cathode demonstrated an outstanding long‐term cycle performance, retaining 78 % of its initial capacity after 500 cycles. Furthermore, the Na₂CoFe(CN)₆ Prussian white nanocubes also achieved a superior rate capability (115 mA h g^?1 at 400 mA g^?1, 92 mA h g^?1 at 800 mA g^?1). The enhanced performances could be attributed to the robust crystal structure and rapid transport of Na ions through large channels in the open‐framework. Most noteworthy, the as‐prepared Na₂CoFe(CN)₆ nanocubes are not only low‐cost in raw materials but also contain a rich sodium content (1.87 Na ions per lattice unit cell), which will be favorable for full cell fabrication and large‐scale electric storage applications.     

基于单颗粒气溶胶质谱的人体呼出颗粒物粒径分布与化学成分的分析方法研究

人体呼出气中内源性颗粒物和外源性颗粒物的粒径和化学成分信息可为肺部疾病诊断、环境暴露评价等研究提供参考。该文初步考察了单颗粒气溶胶质谱(Single particle aerosol mass spectrometry,SPAMS)同时获取人体呼出气中颗粒物(Exhaled breath particles,EBPs)粒径分布和化学成分的可行性。结果表明,健康成人的EBPs数浓度为227~1 043个/L,获取具有统计意义的粒径分布所需的EBPs检出限为2 500个颗粒物,粒径范围为200~1 000 nm,峰值出现在460 nm。与环境空气颗粒物的粒径分布相比,EBPs更多分布在200~300 nm和440~660 nm,从化学成分来看,这两段粒径范围内的EBPs含有更多的碳元素,不易在体内发生吸湿增长,提高了被呼出的概率。EBPs的化学成分可能反映内源性颗粒物和外源性颗粒物组成,如HSO_4~-、PO_3~-、CN~-、CNO~-和C_xH_yO_z~+(x=1~3,y=1~7,z=1~3)可能与内源性颗粒物中的蛋白含量、磷酸酯酰甘油等成分有关,碳簇峰C_3~-、C_4~-、C~+、C_3~+、C_3H~+和C_4~+推测与外源性颗粒物中的碳元素有关。     

Highly efficient mesoporous WO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/KIT-6 catalysts for oxidative desulfurization of dibenzothiophene with hydrogen peroxide

Oxidative desulfurization (ODS) of organic compounds containing sulfur element from a model oil was performed using tungsten oxide catalysts supported on mesoporous silica with cubic Ia3d mesostructure, well-defined mesopores (7.2 nm), high surface area (719 m²/g), and three-dimensional pore network (WO _x /KIT-6). The prepared WO _x /KIT-6 catalysts (5–20 wt% WO _x ) were characterized by X-ray diffraction analysis, N₂ sorption measurements, electron microscopy, H₂-temperature programmed reduction, Raman spectroscopy, and thermogravimetric analysis. Among the mesoporous catalysts, 10 wt% WO _x /KIT-6 exhibited the best catalytic performance. Sulfur-containing organic compounds, such as dibenzothiophene, 4,6-dimethyldibenzothiophene, and benzothiophene, were completely (100 %) removed from the model oil over 10 wt% WO _x /KIT-6 catalyst in 2 h. In addition, the catalyst could be reused several times with only slight decrease in catalytic activity.     

A tridentate CNO‐donor palladium(II) complex as efficient catalyst for direct C―H arylation: Application in preparation of imidazole‐based push–pull chromophores

A series of imidazolium chlorides for the formation of tridentate CNO‐donor palladium(II) complexes featuring N‐heterocyclic carbene moieties have been developed from cheap and readily available starting materials with high yields. Their palladium complexes were prepared by reactions between the ligand precursors and PdCl₂ using K₂CO₃ as base in pyridine with reasonable yields. These air‐stable metal complexes were characterized using ¹H NMR and ¹³C{¹H} NMR spectroscopy and elemental analyses. Heteronuclear multiple bond correlation experiments were performed to identify key NMR signals of these compounds. The structures of two of the complexes were also established by single‐crystal X‐ray diffraction analysis. One of these complexes was successfully applied in the direct C―H functionalization reactions between heterocyclic compounds and aryl bromides, producing excellent yields of coupled products. The coupling reactions were scalable, allowing grams of coupled products to be obtained with a mere 2 mol% of Pd loading. The catalyst system developed allowed the large‐scale preparation of several push–pull chromophores straightforwardly. Photophysical properties based on UV–visible and fluorescence spectroscopy for these chromophores were investigated. Deep blue photoluminescence with moderate quantum efficiency and twisted intramolecular charge transfer excited state were observed for these chromophores. Density functional theory (DFT) and time‐dependent DFT calculations were performed to support the experimental results.     

Au促进Pt/WO3催化甘油氢解制1,3-丙二醇

近年来, 以生物质为基础的生物柴油得到了迅速发展, 导致了粗甘油过剩. 通过甘油选择性氢解制1,3-丙二醇, 进而被用于合成高价值的聚对苯二甲酸丙二醇酯被认为是最具工业应用潜力的反应之一, 对于提高生物柴油的利用效率有着极其重要的意义. 但由于反应空间位阻和热力学上的限制给甘油氢解制1,3-丙二醇带来了很大的挑战, 因此需要设计高活性的金属-酸双功能催化剂以降低甘油第二个C-O键断裂的活化能和减少其他副反应的发生. 目前Pt-W和Ir-Re双功能催化剂可高选择性制得1,3-丙二醇, 但仍需较严苛的反应条件实现对氢气的活化和解离. 本课题组曾将准单原子/单原子Pt高度分散于具有大量氧空位和酸位点的WOx载体上, 十分有利于甘油选择性氢解制1,3-丙二醇反应; 在Au-Pt/WOx催化剂中添加Au可促进B酸产生, 进而提高了甘油转化率和1,3-丙二醇的选择性.为了进一步研究Au对Pt/WOx催化剂结构和催化性能的影响, 本文利用CTAB辅助吸附法制备了Au/WO3, 再浸渍Pt制得Pt/Au/WO3双金属催化剂. 在甘油选择性氢解制1,3-丙二醇反应中, 所制催化剂表现出比Au-Pt/WOx更好的催化活性, 1,3-丙二醇时空收率为0.078 g1,3-PDO/(gcat·h), 是后者的1.95倍. 值得一提的是, Au-Pt/WOx催化剂在低压时活性较高, 而Pt/Au/WO3催化剂活性则在压力的升高而提高; 另外反应温度的升高导致副产物正丙醇的选择性上升, 1,3-丙二醇的选择性降低. 因此, 适宜的反应条件为155℃和5 MPa. 与Pt/WO3和Pt/WOx相比, Pt/Au/WO3表现出了更优异的催化性能, 其1,3-丙二醇的时空收率是Pt/WO3的2.36倍和Pt/WOx的4倍.为了探究Au的掺入对Pt/WOx催化剂性能的影响, 通过XRD, TEM, H2-TPR和XPS等技术对催化剂进行了深入表征. 结果表明, 与Pt/WO3相比, Pt/Au/WO3-600催化剂的XRD衍射峰向小角度偏移, 其原因是Au3+离子半径(0.85 ?)比W6+的(0.60 ?)大, Au3+以取代晶格W6+形式进入WO3晶格中; 对H2-TPR前300 ℃耗氢量的计算可知:Pt/WO3可被还原至Pt/WO2.96, 而Pt/Au/WO3可被还原至Pt/Au/WO2.91. 因此与Pt/WO3相比, Pt/Au/WO3表面氧空位更加丰富. TEM和XPS表征可知, 添加0.1 wt%Au后, 促进了更低价态的Pt均匀分散在WO3载体上, 其平均粒径为2.36 nm.综上所述, Au的掺杂改变了Pt/Au/WO3双金属催化剂的结构, 不仅降低了Pt和W的还原温度, 削弱了Pt和W之间的相互作用, 也促进了更低价态的Pt均匀分散于WO3载体上, 使得Pt/Au/WO3双金属催化剂在甘油氢解制1,3-丙二醇反应中具有更为优异的活性和产物选择性. 该催化剂有望被广泛运用于其他生物质平台化合物加氢脱氧的反应中.     

Highly Emissive Fused Heterocyclic Alkynylgold(III) Complexes for Multiple Color Emission Spanning from Green to Red for Solution‐Processable Organic Light‐Emitting Devices

A new class of fused heterocyclic tridentate ligand‐containing alkynylgold(III) complexes with tunable emission color has been successfully designed and synthesized. Structural modification of the σ‐donating fused heterocyclic alkynyl ligands, including substituted fluorene, carbazole, and triphenylamine, enables a large spectral shift of about 110 nm (ca. 3310 cm^?1) that covers the green to red region to be realized with the same tridentate ligand‐containing alkynylgold(III) complexes in solid‐state thin films. Interestingly, the energy of the excimeric emission can be controlled by the rational design of the fused heterocyclic alkynyl ligands. Superior solution‐processable organic light‐emitting devices (OLEDs) with high external quantum efficiencies (EQEs) of 12.2, 13.5, 9.3, and 5.2 % were obtained with green, yellow, orange, and red emission. These high EQE values are comparable to those of the vacuum‐deposited OLEDs based on structurally related alkynylgold(III) complexes.     

基于硅杂蒽类染料的荧光探针及其应用

近年来,荧光成像技术为人们研究活体细胞及组织内的化学生物学过程提供了有效的研究工具,可以无损、实时、原位地以高时空分辨率实现对目标物进行生物荧光成像与分析。荧光成像技术在生物学、环境监测、临床诊断和药物发现等诸多研究领域发挥着越来越重要的作用。生物荧光成像技术的最新进展对发展新型小分子荧光染料及探针提出了更高的要求。激发和发射波长位于近红外光区（600~900 nm）的荧光染料及探针由于具有光毒性低、生物分子自发荧光干扰小、光散射低、组织穿透能力强等优点,非常适合用于生物荧光成像领域。通过将罗丹明分子中O桥原子用Si代替,得到了一类新型的探针分子--硅杂蒽类荧光探针。这类染料分子在保留了氧杂蒽荧光染料优越的光学性质的同时,光谱发生明显红移,满足了近红外荧光检测的要求,具有良好的生物相容性。本文综述了近年来基于硅杂蒽及其衍生物荧光探针的合成及在金属离子、pH值、小分子、生物酶等检测方面的研究进展,并且简要阐述了基于硅杂蒽类探针分子的识别检测机理以及其在生物成像等方面的应用。