Diffusion exchange NMR spectroscopic study of dextran exchange through polyelectrolyte multilayer capsules

Diffusion exchange of dextran with molecular weights 4.4 and 77 kDa through polyelectrolyte multilayer (PEM) hollow capsules consisting of four bilayers of polystyrene sulfonate/polydiallyldimethylammonium chloride has been investigated using two-dimensional nuclear-magnetic-resonance methods: diffusion-diffusion exchange spectroscopy (DEXSY) and diffusion-relaxation correlation spectroscopy (DRCOSY). Results obtained in DRCOSY experiments show that the diffusion process of dextran 77 kDa exhibits an observation time dependence suggesting a diffusion behavior restricted by confinement. We find evidence for both single capsule and capsule aggregate states, with a partitioning of the 77-kDa dextran between the free and capsule states much larger than that suggested by volume fraction alone. Results from DEXSY experiments show that dextran 77 kDa is in diffusive exchange through the capsules with an exchange time of around 1 s. In contrast, the capsules have no detectable influence on the diffusion process of the dextran 4.4 kDa. This quantitative information may be used in designing PEM capsules as drug carriers.     

The growth of perylene on Ru(0001)

The structure of perylene adsorbed on Ru(0001) surface has been studied by ultraviolet photoemission spectroscopy (UPS) and low-energy electron diffraction. An ordered p(4x4) structure is observed from a monolayer (about 4 A thickness) of the perylene on Ru(0001) surface. UPS measurements show the molecular features, from the perylene multiplayer, between 2 and 10 eV below the Fermi level. Angle-resolved ultraviolet photoemission spectroscopy measurements suggest that the perylene molecular plane is parallel to the substrate. Temperature dependent UPS measurements show that the perylene multilayer is stable on Ru(0001) surface up to 125 degrees C. The desorption of the multilayer and the decomposition of the monolayer are observed above 125 degrees C.     

纳米阵列电极研究

纳米阵列电极作为一种人工组装的纳米结构体系,具有高传质速率、低双电层充电电流、小时间常数、小IR降及高信噪比、可操作性强和测量灵敏度高等优势,因而在电化学理论研究、生物传感器、电催化材料和高能化学电源电极材料等方面等具有广阔的应用前景。迄今为止,人们采用多种材料设计制备出包括圆盘状、圆柱形、球形、圆锥形、叉指状和井状等各种形状的纳米阵列电极。其制作方法主要包括模板法、刻蚀法和自组装法等,电极的表征主要采用电子显微镜技术和电化学方法。本文结合我们的工作和国内外文献,就纳米阵列电极制作方法、表征和应用等方面进行了评述,并对目前纳米阵列电极研究中存在的问题及发展前景进行了探讨和展望。     

Integrating a Luminescent Porous Aromatic Framework into Indicator Papers for Facile,Rapid, and Selective Detection of Nitro Compounds

Porous aromatic framework materials with high stability, sensitivity, and selectivity have great potential to provide new sensors for optoelectronic/fluorescent probe devices. In this work, a luminescent porous aromatic framework material (LNU-23) was synthesized via the palladium-catalyzed Suzuki cross-coupling reaction of tetrabromopyrene and 1,2-bisphenyldiborate pinacol ester. The resulting PAF solid exhibited strong fluorescence emission with a quantum yield of 18.31%, showing excellent light and heat stability. Because the lowest unoccupied molecular orbital (LUMO) of LNU-23 was higher than that of the nitro compounds, there was an energy transfer from the excited LNU-23 to the analyte, leading to the selective fluorescence quenching with a limit of detection (LOD) ≈ 1.47 × 10⁻⁵ M. After integrating the luminescent PAF powder on the paper by a simple dipping method, the indicator papers revealed a fast fluorescence response to gaseous nitrobenzene within 10 s, which shows great potential in outdoor fluorescence detection of nitro compounds.     

Organic/Inorganic Species Synergistically Supported Unprecedented Vanadomolybdates

Vanadomolybdates (VMos), comprised of Mo and V in high valences with O bridges, are one of the most important types of polyoxometalates (POMs), which have high activity due to their strong capabilities of gaining/losing electrons. Compared with other POMs, the preparation of VMos is difficult due to their relatively low structural stability, especially those with unclassical architectures. To overcome this shortcoming, in this study, triol ligands were applied to synthesize VMos through a beaker reaction in the presence of V₂O₅, Na₂MoO₄, and organic species in the aqueous solution. The single-crystal X-ray diffraction results indicate that two VMo clusters, Na₄{V₅Mo₂O₁₉[CH₃C(CH₂O)₃]}∙13H₂O and Na₄{V₅Mo₂O₁₉[CH₃CH₂C(CH₂O)₃]}∙13H₂O, with a similar architecture, were synthesized, which were both stabilized by triol ligand and {MoO₆} polyhedron. Both clusters are composed of five V ions and one Mo ion in a classical Lindqvist arrangement with an additional Mo ion, showing an unprecedented hepta-nuclear VMo structure. The counter Na⁺ cations assemble into one-dimensional channels, which facilitates the transport of protons and was further confirmed by proton conductivity experiments. The present results provide a new strategy to prepare and stabilize VMos, which is applicable for developing other compounds, especially those with untraditional architectures.     

Recent Progress in Biosensors for Detection of Tumor Biomarkers

Cancer is a leading cause of death worldwide, with an increasing mortality rate over the past years. The early detection of cancer contributes to early diagnosis and subsequent treatment. How to detect early cancer has become one of the hot research directions of cancer. Tumor biomarkers, biochemical parameters for reflecting cancer occurrence and progression have caused much attention in cancer early detection. Due to high sensitivity, convenience and low cost, biosensors have been largely developed to detect tumor biomarkers. This review describes the application of various biosensors in detecting tumor markers. Firstly, several typical tumor makers, such as neuron-specific enolase (NSE), carcinoembryonic antigen (CEA), prostate-specific antigen (PSA), squamous cell carcinoma antigen (SCCA), carbohydrate, antigen19-9 (CA19-9) and tumor suppressor p53 (TP53), which may be helpful for early cancer detection in the clinic, are briefly described. Then, various biosensors, mainly focusing on electrochemical biosensors, optical biosensors, photoelectrochemical biosensors, piezoelectric biosensors and aptamer sensors, are discussed. Specifically, the operation principles of biosensors, nanomaterials used in biosensors and the application of biosensors in tumor marker detection have been comprehensively reviewed and provided. Lastly, the challenges and prospects for developing effective biosensors for early cancer diagnosis are discussed.     

Electrochemical oxidative rearrangement of tetrahydro-β-carbolines in a zero-gap flow cell

Oxidative rearrangement of tetrahydro-β-carbolines (THβCs) is one of the most efficient methods for the synthesis of biologically active spirooxindoles, including natural products and drug molecules. Here, we report the first electrochemical approach to achieve this important organic transformation in a flow cell. The key to the high efficiency was the use of a multifunctional LiBr electrolyte, where the bromide (Br⁻) ion acts as a mediator and catalyst and lithium ion (Li⁺) acts as a likely hydrophilic spectator, which might considerably reduce diffusion of THβCs into the double layer and thus prevent possible nonselective electrode oxidation of indoles. Additionally, we build a zero-gap flow cell to speed up mass transport and minimize concentration polarization, simultaneously achieving a high faradaic efficiency (FE) of 96% and an outstanding productivity of 0.144 mmol (h⁻¹ cm⁻²). This electrochemical method is demonstrated with twenty substrates, offering a general, green path towards bioactive spirooxindoles without using hazardous oxidants.

A zero-gap flow cell was designed for the first electro-oxidative rearrangement of tetrahydro-β-carbolines to spirooxindoles with high yield, faradaic efficiency and productivity when LiBr was discovered as a bi-functional mediator and catalyst.     

Synthesis and Pesticidal Activity of New Niacinamide Derivatives Containing a Flexible,Chiral Chain

Natural products are a source for pesticide or drug discovery. In order to discover lead compounds with high fungicidal or herbicidal activity, new niacinamide derivatives derived from the natural product niacinamide, containing chiral flexible chains, were designed and synthesized. Their structures were confirmed by ¹H NMR, ¹³C NMR and HRMS analysis. The fungicidal and herbicidal activities of these compounds were tested. The fungicidal activity results demonstrated that the compound (S)-2-(2-chloronicotinamido)propyl-2-methylbenzoate (3i) exhibited good fungicidal activity (92.3% inhibition) against the plant pathogen Botryosphaeria berengriana at 50 μg/mL and with an EC₅₀ of 6.68 ± 0.72 μg/mL, which is the same as the positive control (fluxapyroxad). Compound 3i was not phytotoxic and could therefore be used as a fungicide on crops. Structure-activity relationships (SAR) were studied by molecular docking simulations with the succinate dehydrogenase of the fungal mitochondrial respiratory chain.     

Prolonged lifespan of initial-anode-free lithium-metal battery by pre-lithiation in Li-rich Li2Ni0.5Mn1.5O4 spinel cathode

Anode-free lithium metal batteries (AF-LMBs) can deliver the maximum energy density. However, achieving AF-LMBs with a long lifespan remains challenging because of the poor reversibility of Li⁺ plating/stripping on the anode. Here, coupled with a fluorine-containing electrolyte, we introduce a cathode pre-lithiation strategy to extend the lifespan of AF-LMBs. The AF-LMB is constructed with Li-rich Li₂Ni_0.5Mn_1.5O₄ cathodes as a Li-ion extender; the Li₂Ni_0.5Mn_1.5O₄ can deliver a large amount of Li⁺ in the initial charging process to offset the continuous Li⁺ consumption, which benefits the cycling performance without sacrificing energy density. Moreover, the cathode pre-lithiation design has been practically and precisely regulated using engineering methods (Li-metal contact and pre-lithiation Li-biphenyl immersion). Benefiting from the highly reversible Li metal on the Cu anode and Li₂Ni_0.5Mn_1.5O₄ cathode, the further fabricated anode-free pouch cells achieve 350 W h kg⁻¹ energy density and 97% capacity retention after 50 cycles.

Benefiting from highly reversible structure evolution of pre-lithiated Li-rich Li₂Ni_0.5Mn_1.5O₄ cathode, the corresponding anode-free pouch cell delivers a considerable energy density of 350 W h kg⁻¹ and 97% capacity retention after 50 cycles.     

神光-Ⅲ主机装置成功实现60 TW/180 kJ三倍频激光输出

2015年9月15日,由中国工程物理研究院激光聚变研究中心承担研制的神光-Ⅲ主机装置成功完成了48束激光三倍频180 kJ/3 ns、峰值功率60 TW的输出测试实验,标志着神光-Ⅲ主机装置已全面建成并达到设计指标,成为现有输出能力世界排名第二、亚洲排名第一的惯性约束聚变激光驱动器。神光-Ⅲ主机装置可输出48束阵列化的大口径高功率脉冲激光（分为6个束组,每个束组为一个42的光束阵列）,主要由前端、预放、主放、测量与光束控制、靶场、计算机集中控制等六大系统组成。神光-Ⅲ主机装置的研制,凝集了我国在光学、激光、脉冲功率、精密机械、快电子学、自动控制、化学清洗、超精密加工等多个学科领域的顶尖技术成就,堪称中国光学工程界的奇迹。神光-Ⅲ主机装置采用腔内四程放大+变口径90翻转U型反转器+助推三程放大的总体构型,在未使用大口径隔离组件的条件下,采用焦斑控制、精密准直、锥管镜面空间滤波及杂散光管理等技术措施,实现了基频光十万倍增益、10 kJ量级输出状态下的自激振荡抑制与反激光规避,在系统具备50%以上透过率的前提下确保了装置的运行安全,大大提高了装置的性价比。神光-Ⅲ主机装置的建设过程中攻克了高精度种子光源、高品质激光束的预放大、精密同步、辐射定标损伤检测、全光路精密波前校正、甚多束光路自动准直、自动化靶瞄准定位、计算机集中控制、高效谐波转换、一搁准精密安装、超精密光学加工、缺陷控制损伤阈值提升等多项光学工程技术难关,确保了装置具备优秀的技术指标性能。神光-Ⅲ主机装置打破了激光系统串行调试的规律,基于基准体系技术,通过不同束组间的错级并行,实现总体集成工作的满负荷运转,确保了装置建设的总体进度和集成效率。装置从第一个光机模块进场到基本完成集成调试,用时仅四年半,创造了又一个中国速度。在工程建设过程中以自主研发的传输放大动力学设计软件、激光泵浦动力学软件、杂散光树叉追迹软件等为基础,融合了部分光学设计商用软件,构建了覆盖光学、结构、电气、控制等多个学科的高功率激光装置数字化设计平台,基本实现了装置设计的全面数字化。工程建设过程中形成的质量、安全、进度控制体系保证了工程顺利进行。神光-Ⅲ主机装置的全面建成,标志着我国在大型激光驱动器方面的总体设计、总体集成、精密装校、加工制造、光学检测、关键技术等核心能力实现了体系化发展与成熟,面向更大规模的激光驱动器研制的光学工程体系已基本形成。