A Comparison of Two Isoreticular Metal–Organic Frameworks with Cationic and Neutral Skeletons: Stability,Mechanism, and Catalytic Activity

Although many ionic metal–organic frameworks (MOFs) have been reported, little is known about how the charge of the skeleton affects the properties of the MOF materials. Herein we report how the chemical stability of MOFs can be substantially improved through embedding electrostatic interactions in structure. A MOF with a cationic skeleton is impervious to extremely acidic, oxidative, reductive, and high ionic strength conditions, such as 12 m HCl (301 days), aqua regia (86 days), H₂O₂ (30 days), and seawater (30 days), which is unprecedented for MOFs. DFT calculations suggested that steric hinderance and the repulsive interaction of the cationic framework toward positively charged species in microenvironments protects the vulnerable bonds in the structure. Diverse functionalities can be bestowed by substituting the counterions of the charged framework with identically charged functional species, which broadens the horizon in the design of MOFs adaptable to a demanding environment with specific functionalities.     

Direct Intermediate Regulation Enabled by Sulfur Containers in Working Lithium–Sulfur Batteries

Polysulfide intermediates (PSs), the liquid-phase species of active materials in lithium–sulfur (Li-S) batteries, connect the electrochemical reactions between insulative solid sulfur and lithium sulfide and are key to full exertion of the high-energy-density Li-S system. Herein, the concept of sulfur container additives is proposed for the direct modification on the PSs species. By reversible storage and release of the sulfur species, the container molecule converts small PSs into large organosulfur species. The prototype di(tri)sulfide-polyethylene glycol sulfur container is highly efficient in the reversible PS transformation to multiply affect electrochemical behaviors of sulfur cathodes in terms of liquid-species clustering, reaction kinetics, and solid deposition. The stability and capacity of Li-S cells was thereby enhanced. The sulfur container is a strategy to directly modify PSs, enlightening the precise regulation on Li-S batteries and multi-phase electrochemical systems.     

微波瑞利散射法测定空气电火花激波等离子体射流的时变电子密度

大气压空气电火花激波等离子体射流的电子密度在亚微秒时间尺度上瞬变,其电子密度的测定很难.基于微波瑞利散射原理,本文测量了空气电火花冲击波流注放电等离子体射流的时变电子密度.实验结果表明:测量系统的标定参数A为1.04 × 105 V·Ω·m–2;空气流注放电等离子体射流的电子密度与等离子体射流的半径和长度有关,结合高速放电影像展示的等离子体射流的等效半径和等效长度,测定的电子密度在1020 m–3的量级,且随时间先快速增长至峰值再成指数衰减.此外,本文还探讨了等离子体射流的不同等效尺度对测定结果的影响;分析结果表明,采用时变等效半径和时变等效长度的计算结果最有效,且第1个快速波峰是由光电离的电离波导致的.     

Investigation of β-Ga_2O_3 films and β-Ga_2O_3/GaN heterostructures grown by metal organic chemical vapor deposition

In this work,(-201) β-Ga_2O_3 films are grown on GaN substrate by metal organic chemical vapor deposition(MOCVD). It is revealed that the β-Ga_2O_3 film grown on GaN possesses superior crystal quality, material homogeneity and surface morphology than the results of common heteroepitaxial β-Ga_2O_3 film based on sapphire substrate. Further, the relevance between the crystal quality of epitaxial β-Ga_2O_3 film and the β-Ga_2O_3/GaN interface behavior is investigated. Transmission electron microscopy result indicates that the interface atom refactoring phenomenon is beneficial to relieve the mismatch strain and improve the crystal quality of subsequent β-Ga_2O_3 film. Moreover, the energy band structure of β-Ga_2O_3/GaN heterostructure grown by MOCVD is investigated by X-ray photoelectron spectroscopy and a large conduction band offset of 0.89 eV is obtained. The results in this work not only convincingly demonstrate the advantages of β-Ga_2O_3 films grown on GaN substrate, but also show the great application potential of MOCVD β-Ga_2O_3/GaN heterostructures in microelectronic applications.     

衬底温度对Ga液滴在Al_(0.4)Ga_(0.6)As表面形成纳米结构的影响

本文研究了不同衬底温度对Ga液滴在Al_(0.4)Ga_(0.6)As表面形成纳米结构的影响,当300℃≤T≤380℃时,Ga液滴演化成纳米孔(Nanohole)和盘状结构(diffusion halo),纳米结构的尺寸随温度升高而增大.当T≥385℃时,盘状结构消失,形成一定平坦的Al_xGa_(1-x)As薄膜,Ga液滴在界面处继续向下刻蚀直至耗尽,形成平均直径为75 nm,平均孔深为5.52 nm的纳米孔.本文还通过盘状结构测出平均扩散长度△R,并拟合出Ga原子在Al_(0.4)Ga_(0.6)As表面的激活能E_A=0.78(±0.01) eV和扩散前因子D_0=0.15(×4.1~(±1))10~(-2 ) cm~2s~(-1).     

Chameleonlike metashells in microfluidics: A passive approach to adaptive responses

Heat energy can transfer via convection, conduction, and radiation. Based on convection and conduction in microfluidics, people have designed and fabricated many novel devices. However, almost none of them has adaptivity, thus restricting practical applications under different conditions. To solve this problem, here we propose a passive approach to adaptive responses. That is,we consider the thermal convection-conduction process in microfluidic structures where Darcy’s law and Fourier’s law are both valid. By carefully designing two key parameters(i.e., tensorial thermal conductivity and tensorial permeability) of a metashell,we theoretically reveal that its effective properties(i.e., effective thermal conductivity and effective permeability) can adaptively change according to the inside object, thus yielding the "chameleonlike metashell". Further, this metashell is passive since it requires no prior knowledge of the inside object. We also report that the chameleonlike behavior can occur for anisotropic inside objects, nonuniform external fields, or even complex shapes. All theoretical analyses agree well with finite-element simulations.The chameleonlike metashell can act as an intelligent metamaterial in microfluidics for its adaptive responses, and it can also benefit other physical fields where convection plays a role, such as mass diffusion.     

Chemical Synthesis and Immunological Evaluation of a Pentasaccharide Bearing Multiple Rare Sugars as a Potential Anti-pertussis Vaccine

With the infection rate of Bordetella pertussis at a 60-year high, there is an urgent need for new anti-pertussis vaccines. The lipopolysaccharide (LPS) of B. pertussis is an attractive antigen for vaccine development. With the presence of multiple rare sugars and unusual glycosyl linkages, the B. pertussis LPS is a highly challenging synthetic target. In this work, aided by molecular dynamics simulation and modeling, a pertussis-LPS-like pentasaccharide was chemically synthesized for the first time. The pentasaccharide was conjugated with a powerful carrier, bacteriophage Qβ, as a vaccine candidate. Immunization of mice with the conjugate induced robust anti-glycan IgG responses with IgG titers reaching several million enzyme-linked immunosorbent assay (ELISA) units. The antibodies generated were long lasting and boostable and could recognize multiple clinical strains of B. pertussis, highlighting the potential of Qβ-glycan as a new anti-pertussis vaccine.     

241Am-Be中子参考辐射的蒙特卡罗模拟研究

研究用于校准场所中子剂量监测仪表的241Am-Be中子参考辐射场计量特性。采用蒙特卡罗方法模拟了空气自由中子参考辐射(FRNR),GB/T 14055规定的最小尺寸中子参考辐射(SRNR)和实际中子参考辐射(ARNR)中不同检验点处中子周围剂量当量率、散射中子占比和能谱分布特征。研究结果表明,空气对FRNR中的剂量率和能谱分布影响小,近似为理想中子参考辐射;采用5%含硼聚乙烯作屏蔽的最小尺寸SRNR可减少热中子,降低散射中子占比,影锥法不适用于小尺寸中子参考辐射中对散射中子的修正;ARNR中的散射中子更少、占比更低,影锥法所得散射中子占比与理论值基本一致。     

缺中子Np新核素的α衰变研究

合成远离稳定线的新核素、探索原子核存在的极限是目前核物理研究的重要课题。在中子壳N=126的最丰质子一侧，极端缺中子的超铀核素处于质子滴线和中子壳的交叉位置，合成和研究该核区核素对研究N=126壳结构的演化性质具有重要意义。基于兰州重离子加速器上的充气反冲核谱仪装置(SHANS)，利用36,40Ar+185,187Re熔合蒸发反应，合成了极缺中子的219,220,223,224Np新核素，在中子壳N=126附近首次建立了Np同位素链的$ \alpha$衰变系统性，获得了N=126壳效应在Np同位素链中依然存在的实验证据。依据单质子分离能的系统性分析，确定了Np同位素链中质子滴线的位置，219Np也成为目前已知的最重的质子滴线外核素。此外，基于实验测量的反应截面，并与理论模型的计算结果相比较，讨论了进一步合成该核区其它新核素218,221,222Np的可行性。