Carbocation-forming reactions in dimethyl sulfoxide

Mesylate derivatives of 3-aryl-3-hydroxy-beta-lactams and thiolactams react in DMSO-d(6) by first-order processes to give alcohol products. Substituent effect studies implicate carbocation intermediates (ion-pairs) that are captured by DMSO-d(6) to give transient oxosulfonium ions. Rapid reaction of the oxosulfonium ions with trace amounts of water leads to the alcohol product and regenerates DMSO-d(6). H(2)(17)O labeling studies show that (17)O is incorporated into the DMSO. The mesylate derivatives of endo- and exo-2-hydroxy-2-phenylbicyclo[2.2.1]heptan-3-one also react in DMSO-d(6) to give the alcohol products. Ion-pair intermediates that capture DMSO giving unstable oxosulfonium ions are again proposed. Exo-2-phenyl-endo-bicyclo[2.2.1]heptyl trifluoroacetate readily eliminates trifluoroacetic acid in DMSO-d(6) via a cationic mechanism involving loss of the endo-trifluoroacetate leaving group as well as an exo-hydrogen. The O-methyl oxime derivative of alpha-chloro-alpha,alpha-diphenylacetophenone reacts in DMSO-d(6) to give 1-methoxy-2,3-diphenylindole, a product derived from cyclization of a cationic intermediate. A common ion rate suppression provides further evidence for a cationic mechanism. The triflate derivative of pivaloin reacts by a cationic mechanism in DMSO-d(6) to give rearranged products. The rate is even faster than in highly ionizing solvents such as trifluoroethanol or trifluoroacetic acid. 1-Adamantyl mesylate reacts in DMSO-d(6) by a first-order process (Y(OMs) = -4.00) to give a long-lived oxosulfonium ion, 1-Ad-OS(CD(3))(2)(+), which can be characterized spectroscopically. This oxosulfonium ion reacts only slowly with water at elevated temperatures to give 1-adamantanol. DMSO is therefore a viable solvent for k(s), k(C), and k(Delta) cationic processes.     

Multilayer assembly and patterning of poly(p-phenylenevinylene)s via covalent coupling reactions

Poly(p-phenylenevinylene)s with amines and pentafluorophenyl esters on side chains were synthesized and assembled on solid substrates by sequential layer-by-layer (LBL) deposition. This approach enables the creation of robust multilayer thin films via in-situ covalent coupling reactions between successive layers. The buildup of the multilayers was followed by UV/vis absorption spectroscopy and ellipsometry. The observed complex assembly behavior suggests that both covalent and hydrogen-bonding interactions are involved in the formation of multilayer films. The organized structure and surface morphology of resultant multilayers were investigated by reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. This covalent LBL method was further applied to generate conjugated polymer micropatterns using microstamped self-assembled monolayers as templates.     

中空石墨碳材料作为电催化剂载体在直接乙醇燃料电池中的应用

以间苯二酚、苯酚与甲醛为前体,合成了一种中空石墨碳材料(hollow graphitic carbon,HGC).透射电镜(TEM)、N2吸附-脱附和Raman光谱测试结果表明,所制备的HGC为中孔结构,平均孔径为36nm.与商品Vulcan XC-72R相比,HGC中孔结构丰富,石墨化程度高.分别以HGC和XC-72R为载体制备了总金属载量为45%的PtSn/C电催化剂,X射线衍射和TEM结果表明这两个样品的平均粒径和晶格常数相近.单池性能测试表明,以45%PtSn/HGC为阳极催化剂的直接乙醇燃料电池的最大功率密度达到了62mW/cm2,与PtSn/XC-72R的54mW/cm2相比提高了近15%.     

Channelled Porous TiO2 Synthesized with a Water‐in‐Oil Microemulsion

Porous titanium dioxide synthesized with a bicontinuous surfactant template is a promising method that leads to a high active surface area electrode. The template used is based on a water/isooctane/dioctyl sodium sulfosuccinate salt together with lecithin. Several parameters were varied during the synthesis to understand and optimize channel formation mechanisms. The material is patterned in stacked conical channels, widening towards the centre of the grains. The active surface area increased by 116 % when the concentration of alkoxide precursors was decreased and increased by 241 % when the template formation temperature was decreased to 10 °C. Increasing the oil phase viscosity tends to widen the pore aperture, thus decreasing the overall active surface area. Changing the phase proportions alters the microemulsion integrity and disrupts channel formation.     

Some mathematical aspects of Anderson localization: boundary effect,multimodality, and bifurcation

Anderson localization is a famous wave phenomenon that describes the absence of diffusion of waves in a disordered medium. Here we generalize the landscape theory of Anderson localization to general elliptic operators and complex boundary conditions using a probabilistic approach, and further investigate some mathematical aspects of Anderson localization that are rarely discussed before. First, we observe that under the Neumann boundary condition, the low energy quantum states are localized on the boundary of the domain with high probability. We provide a detailed explanation of this phenomenon using the concept of extended subregions and obtain an analytical expression of this probability in the one-dimensional case. Second, we find that the quantum states may be localized in multiple different subregions with high probability in the one-dimensional case and we derive an explicit expression of this probability for various boundary conditions. Finally, we examine a bifurcation phenomenon of the localization subregion as the strength of disorder varies. The critical threshold of bifurcation is analytically computed based on a toy model and the dependence of the critical threshold on model parameters is analyzed.     

聚多巴胺包覆的金纳米棒用于大鼠下颌下腺造影成像

用生物相容性好且毒性低的聚多巴胺对金纳米棒进行表面包覆, 利用其造影增强的功能, 将聚多巴胺包覆的金纳米棒应用于大鼠下颌下腺导管, 实现了下颌下腺造影成像.     

CO/light dual-activatable Ru(ii)-conjugated oligomer agent for lysosome-targeted multimodal cancer therapeutics

Stimuli-activatable and subcellular organelle-targeted agents with multimodal therapeutics are urgently desired for highly precise and effective cancer treatment. Herein, a CO/light dual-activatable Ru(ii)-oligo-(thiophene ethynylene) (Ru-OTE) for lysosome-targeted cancer therapy is reported. Ru-OTE is prepared via the coordination-driven self-assembly of a cationic conjugated oligomer (OTE-BN) ligand and a Ru(ii) center. Upon the dual-triggering of internal gaseous signaling molecular CO and external light, Ru-OTE undergoes ligand substitution and releases OTE-BN followed by dramatic fluorescence recovery, which could be used for monitoring drug delivery and imaging guided anticancer treatments. The released OTE-BN selectively accumulates in lysosomes, physically breaking their integrity. Then, the generated cytotoxic singlet oxygen (¹O₂) causes severe lysosome damage, thus leading to cancer cell death via photodynamic therapy (PDT). Meanwhile, the release of the Ru(ii) core also suppresses cancer cell growth as an anticancer metal drug. Its significant anticancer effect is realized via the multimodal therapeutics of physical disruption/PDT/chemotherapy. Importantly, Ru-OTE can be directly photo-activated using a two-photon laser (800 nm) for efficient drug release and near-infrared PDT. Furthermore, Ru-OTE with light irradiation inhibits tumor growth in an MDA-MB-231 breast tumor model with negligible side effects. This study demonstrates that the development of an activatable Ru(ii)-conjugated oligomer potential drug provides a new strategy for effective subcellular organelle-targeted multimodal cancer therapeutics.

The anticancer therapeutics of lysosome disruption/PDT/chemotherapy based on Ru-OTE complex was achieved, which provides a new strategy for developing multimodal and effective stimuli-activatable subcellular organelle-targeted cancer therapeutics.     

Rational design of 3D dendritic TiO2 nanostructures with favorable architectures

Controlling the morphology and size of titanium dioxide (TiO(2)) nanostructures is crucial to obtain superior photocatalytic, photovoltaic, and electrochemical properties. However, the synthetic techniques for preparing such structures, especially those with complex configurations, still remain a challenge because of the rapid hydrolysis of Ti-containing polymer precursors in aqueous solution. Herein, we report a completely novel approach-three-dimensional (3D) TiO(2) nanostructures with favorable dendritic architectures-through a simple hydrothermal synthesis. The size of the 3D TiO(2) dendrites and the morphology of the constituent nano-units, in the form of nanorods, nanoribbons, and nanowires, are controlled by adjusting the precursor hydrolysis rate and the surfactant aggregation. These novel configurations of TiO(2) nanostructures possess higher surface area and superior electrochemical properties compared to nanoparticles with smooth surfaces. Our findings provide an effective solution for the synthesis of complex TiO(2) nano-architectures, which can pave the way to further improve the energy storage and energy conversion efficiency of TiO(2)-based devices.     

Facile Generation of Polymer–Alloy Hybrid Layers for Dendrite‐Free Lithium‐Metal Anodes with Improved Moisture Stability

Lithium‐metal anodes are recognized as the most promising next‐generation anodes for high‐energy‐storage batteries. However, lithium dendrites lead to irreversible capacity decay in lithium‐metal batteries (LMBs). Besides, the strict assembly‐environment conditions of LMBs are regarded as a challenge for practical applications. In this study, a workable lithium‐metal anode with an artificial hybrid layer composed of a polymer and an alloy was designed and prepared by a simple chemical‐modification strategy. Treated lithium anodes remained dendrite‐free for over 1000 h in a Li–Li symmetric cell and exhibited outstanding cycle performance in high‐areal‐loading Li–S and Li–LiFePO₄ full cells. Moreover, the treated lithium showed improved moisture stability that benefits from the hydrophobicity of the polymer, thus retaining good electrochemical performance after exposure to humid air.