基于扩散强化的Pickering界面生物催化系统构建及CO2矿化过程研究

CO₂的有效利用有助于解决环境和生态问题.碳酸酐酶(CA)等酶分子可精准活化CO₂分子以降低反应能垒,为CO₂的高效和高选择性转化提供了一种有前景的途径.然而,酶离开生物体后易失活,且难以重复利用.目前,包埋型固定化酶是常用且有效的提高酶稳定性与回用率的方法之一,但载体的存在会造成反应物CO₂内扩散阻力增加,降低反应活性.此外,CO₂酶促转化是一个气-液-固三相反应过程,反应体系中CO₂的外扩散性能也需要加强.金属有机骨架(MOFs),特别是咪唑酯骨架(ZIFs),常被用作酶固定化的载体.ZIFs的拓扑结构可被设计成不同形貌,进而通过ZIFs的结构工程来加强分子向其中的内扩散.Pickering乳液是指以固体颗粒代替常规表面活性剂而稳定的乳液.当固体颗粒具有催化活性时,催化剂颗粒会扩大液-液-固或气-液-固三相接触面积,从而有效协调反应物在不同相中的扩散时间.如果酶被用作这些颗粒的活性中心,所制备的Pickering乳液也可能具备类似的特性,可加强底物分子向酶的外扩散.本文选择两种具有不同结构的ZIFs(ZIF-L和ZIF-8),原位包埋CA后形成CA@ZIFs颗粒以稳定Pickeirng乳液.ZIF-L和CA@ZIF-L颗粒显示出独特的二维层状堆叠结构.ZIF-8和CA@ZIF-8颗粒呈棱角清晰的十二面体结构.与CA@ZIF-8颗粒相比,CA@ZIF-L颗粒显示出更大的孔径和更宽的孔径分布,这有助于CO₂从CA@ZIF-L颗粒表面扩散至酶活性中心.利用酶活测试来研究内扩散是否通过结构工程得到了加强,发现CA@ZIF-L颗粒的活性比CA@ZIF-8颗粒高22.3%,推测这是由于CA@ZIF-L颗粒特殊的十字花状结构会缩短CO₂从颗粒表面扩散至酶活性中心的距离.同时,十字花状结构可暴露更多的酶活性位点(CA@ZIF-L颗粒的暴露面积是CA@ZIF-8颗粒的~8倍),从而提升了反应物浓度并显示出更高的催化活性.本文还设计了吸附实验来进一步验证上述假设,发现BSA@ZIF-L颗粒对香豆素的吸附率远高于BSA@ZIF-8颗粒,说明与ZIF-8相比,酶包埋于ZIF-L具有更强的捕获小分子的能力,表明CO₂分子向CA@ZIF-L的扩散速度更快,即CA@ZIF-L的十字花状结构可强化系统的内扩散过程.进一步比较了PIBS和游离多酶体系的催化活性,将CO₂通入每个系统,在反应前20 min,PIBS的pH值下降速度比游离体系快得多,说明PIBS通过在气相和液相间构建更大的界面,缩短了CO₂向CA的扩散距离,从而提高了催化效率,促进了CO₂转化.上述假设也通过扩散动力学的计算得到了验证.为进一步研究PIBS的CO₂矿化能力,本文开展了CaCO₃矿化反应,发现PIBS的CaCO₃产量远高于游离多酶体系,表明构建的PIBS在强化内外扩散方面具有显著优势.最后,评估了PIBS在工业应用中的性能,由CA@ZIF-L和CA@ZIF-8颗粒构建的PIBS显示出较好的可回收性,在第8个循环后,PIBS仍可保持8.9 mg/5 min的CaCO₃产量.综上,PIBS可为CO₂的酶促转化和框架提供一个新方法和新平台.     

全球大气重力波联测期间电离层扰动的台阵观测

本文利用武汉电离层观象台的加密频高图和三站Doppler图记录及新近提出的短波扰动反演方法,分析了1985年全球大气重力波联测(WAGS)期间10月18日这天白天的重力波扰动,发现在该日扰动中有两列不同形态的波列分别属于中尺度的内重力波和大尺度的导制重力波。本文还进一步估算了这两列重力波的水平传播参量,深入分析了它们的频谱结构的高度变化特征,发现了重力波功率谱谱峰的分裂和偏移等重要现象。本文结果表明,新的反演方法使电离层无线电汉诊断的简易短波实验系统,也能成为探测和研究重力波一类大尺度电离层动力过程的有效手段。     

基于扩散强化的Pickering界面生物催化系统构建及CO2矿化过程研究

CO₂的有效利用有助于解决环境和生态问题.碳酸酐酶(CA)等酶分子可精准活化CO₂分子以降低反应能垒,为CO₂的高效和高选择性转化提供了一种有前景的途径.然而,酶离开生物体后易失活,且难以重复利用.目前,包埋型固定化酶是常用且有效的提高酶稳定性与回用率的方法之一,但载体的存在会造成反应物CO₂内扩散阻力增加,降低反应活性.此外,CO₂酶促转化是一个气-液-固三相反应过程,反应体系中CO₂的外扩散性能也需要加强.金属有机骨架(MOFs),特别是咪唑酯骨架(ZIFs),常被用作酶固定化的载体.ZIFs的拓扑结构可被设计成不同形貌,进而通过ZIFs的结构工程来加强分子向其中的内扩散.Pickering乳液是指以固体颗粒代替常规表面活性剂而稳定的乳液.当固体颗粒具有催化活性时,催化剂颗粒会扩大液-液-固或气-液-固三相接触面积,从而有效协调反应物在不同相中的扩散时间.如果酶被用作这些颗粒的活性中心,所制备的Pickering乳液也可能具备类似的特性,可加强底物分子向酶的外扩散.本文选择两种具有不同结构的ZIFs(ZIF-L和ZIF-8),原位包埋CA后形成CA@ZIFs颗粒以稳定Pickeirng乳液.ZIF-L和CA@ZIF-L颗粒显示出独特的二维层状堆叠结构.ZIF-8和CA@ZIF-8颗粒呈棱角清晰的十二面体结构.与CA@ZIF-8颗粒相比,CA@ZIF-L颗粒显示出更大的孔径和更宽的孔径分布,这有助于CO₂从CA@ZIF-L颗粒表面扩散至酶活性中心.利用酶活测试来研究内扩散是否通过结构工程得到了加强,发现CA@ZIF-L颗粒的活性比CA@ZIF-8颗粒高22.3%,推测这是由于CA@ZIF-L颗粒特殊的十字花状结构会缩短CO₂从颗粒表面扩散至酶活性中心的距离.同时,十字花状结构可暴露更多的酶活性位点(CA@ZIF-L颗粒的暴露面积是CA@ZIF-8颗粒的~8倍),从而提升了反应物浓度并显示出更高的催化活性.本文还设计了吸附实验来进一步验证上述假设,发现BSA@ZIF-L颗粒对香豆素的吸附率远高于BSA@ZIF-8颗粒,说明与ZIF-8相比,酶包埋于ZIF-L具有更强的捕获小分子的能力,表明CO₂分子向CA@ZIF-L的扩散速度更快,即CA@ZIF-L的十字花状结构可强化系统的内扩散过程.进一步比较了PIBS和游离多酶体系的催化活性,将CO₂通入每个系统,在反应前20 min,PIBS的pH值下降速度比游离体系快得多,说明PIBS通过在气相和液相间构建更大的界面,缩短了CO₂向CA的扩散距离,从而提高了催化效率,促进了CO₂转化.上述假设也通过扩散动力学的计算得到了验证.为进一步研究PIBS的CO₂矿化能力,本文开展了CaCO₃矿化反应,发现PIBS的CaCO₃产量远高于游离多酶体系,表明构建的PIBS在强化内外扩散方面具有显著优势.最后,评估了PIBS在工业应用中的性能,由CA@ZIF-L和CA@ZIF-8颗粒构建的PIBS显示出较好的可回收性,在第8个循环后,PIBS仍可保持8.9 mg/5 min的CaCO₃产量.综上,PIBS可为CO₂的酶促转化和框架提供一个新方法和新平台.     

Two 3-D Neutral Zn(Ⅱ)-MOFs Generated from the Asymmetric Schiff-base Ligand

Two new Zn(Ⅱ)-MOFs were synthesized based on an asymmetric Schiff-base ligand LH, which is obtained by the condensation of 5-formyl-8-hydroxyquinoline and 3-pyridinecarboxylic acid hydrazide. In different mixed solvents, we get two new isomorphism compounds, [Zn(L)2]·C4H8O2·2MeOH(1) and [Zn(L)2]·CH2Cl2·2MeOH(2). Compounds 1 and 2 have been characterized by single-crystal X-ray diffraction, elemental analysis and IR. Compound 1 crystallizes in monoclinic, space group P21/c, with a = 13.856(4), b = 14.156(4), c = 9.620(3) , β = 110.167(5)°, V = 1771.3(9) 3, Dc = 1.500 g/cm3, C38H38N8O8 Zn, Mr = 800.13, F(000) = 832, μ(MoKα) = 0.761 mm-1, Z = 2, the final R = 0.0596 and wR = 0.1221 for 2112 observed reflections(I 2σ(I)). Compound 2 belongs to monoclinic, space group P21/c, with a = 13.575(3), b = 14.130(3), c = 9.485(2) , β = 107.908(3)°, V = 1731.2(6) 3, Dc = 1.529 g/cm3, C35H32Cl2N8O6 Zn, Mr = 796.96, F(000) = 820, μ(MoKα) = 0.926 mm-1, Z = 2, the final R = 0.0527 and wR = 0.1395 for 2501 observed reflections(I 2σ(I)). The Zn(Ⅱ) centers in both 1 and 2 display a distorted octahedral coordination geometry. The octahedral Zn(Ⅱ) nodes and L linkages build up 2-D nets consisting of parallelogram-like grids in the ab plane. The neighboring nets stack through hydrogen bonds to generate 3-D rhombic channels. In 1, the 1,4-dioxane and MeOH guests alternatively arrange in the channels and effectively take up the free space; while in 2, the CH2Cl2 guests are arranged in the channels. In addition, the encapsulated MeOH molecules are bonded to the framework by hydrogen bonds.     

一种控制矩形光刻胶光栅槽深和占宽比的方法

利用光刻胶的非线性效应可以制作出了矩形的全息光栅。制作矩形光栅时,对槽形的控制被简化为对槽深和占宽比这两个参量的控制。首先借助实时潜像监测技术获得最佳曝光量,然后根据显影监测曲线的特征找出光栅槽底的残胶厚度为零的显影时刻,就能得到槽底干净的矩形光栅,同时保证槽深近似等于光刻胶的初始厚度;如果此后继续显影,就能适度减小占宽比。实验结果和理论分析都证实了这种控制方法的可靠性。对1200lp／mm的光栅,目前工艺能精确调控的最大槽深为1μm,占宽比在0．2～0．6范围内。实验还揭示,为了提高对光栅槽形的调控能力,必须首先提高干涉条纹的稳定性。     

Study of a rectangular coupled cavity extendedinteraction oscillator in sub-terahertz waves

An extended interaction oscillator （EIO） generating 120 GHz wave in sub-terahertz waves is studied by using the three-dimensional electromagnetic simulation software CST and PIC codes. A rectangular reentrant coupled-cavity is proposed as the slow-wave structure of EIO. By CST, the circuit parameters including frequency-phase dispersion, interaction impedance and characteristic impedance are simulated and calculated. The operation mode of EIO is chosen very close to the point where βL = 2π with corresponding frequency 120 GHz, the beam voltage 12 kV and the dimensions of the cavity with the period 0.5mm, the height 3mm and the width 1.4mm. Simulation results of beam-wave interaction by PIC show that the exciting frequency is 120.85 GHz and output peak power 465 W with 12-period coupled-cavity with the perveance 0.17 μP. Simulation results indicate that the EIO has very wide range of the operation voltage.     

武昌电离层F_2区峰值上、下部电子含量观测结果的分析研究

本文介绍了武昌台自1980年4月至1982年2月对ETS-Ⅱ卫星的136兆赫信号法拉第旋转的连续测量所得到的电离层总电子含量N_F的观测结果。并利用该台同时记录的2500余张电离层频高图,分析了F₂峰以下电子含量N_b对N_F的贡献。总含量N_F、下部含量N_b和最大电子浓度N_max的日变化曲线表明,电离层中经常存在大气声重波扰动,这种波状扰动在不同高度上有时很不相同。N_F,N_b和N_max的季节变化呈现明显的Appleton异常和腊月异常。电离层峰以上和峰以下电子含量的比率N_a/N_b,白天受电离最大净生成率所在高度随太阳天顶角变化的影响;在1200—2200LT时段内受外层大气温度变化的影响;午夜至黎明前接近一个常数。     

Cherenkov terahertz radiation from Dirac semimetals surface plasmon polaritons excited by an electron beam

We demonstrate a physical mechanism for terahertz(THz) generation from surface plasmon polaritons(SPPs). In a structure with a bulk Dirac semimetals(BDSs) film deposited on a dielectric substrate, the energy of the asymmetric SPP mode can be significantly enhanced to cross the light line of the substrate due to the SPP-coupling between the interfaces of the film. Therefore, the SPPs can be immediately transformed into Cherenkov radiation without removing the wavevector mismatch. Additionally, the symmetric SPP mode can also be dramatically lifted to cross the substrate light line when a buffer layer with low permittivity relative to the substrate is introduced. In this case, dual-frequency THz radiation from the two SPP modes can be generated simultaneously. The radiation intensity is significantly enhanced by over two orders due to the field enhancement of the SPPs. The radiation frequency can be tuned in the THz frequency regime by adjusting the beam energy and the chemical potential of the BDSs. Our results could find potential applications in developing room temperature, tunable, coherent, and intense THz radiation sources to cover the entire THz band.     

Improved performance of MoS2 FET by in situ NH3 doping in ALD Al2O3 dielectric

Since defects such as traps and oxygen vacancies exist in dielectrics, it is difficult to fabricate a high-performance MoS$_{2}$ field-effect transistor (FET) using atomic layer deposition (ALD) Al$_{2}$O$_{3}$ as the gate dielectric layer. In this paper, NH$_{3}$ in situ doping, a process treatment approach during ALD growth of Al$_{2}$O$_{3}$, is used to decrease these defects for better device characteristics. MoS$_{2}$ FET has been well fabricated with this technique and the effect of different NH$_{3}$ in situ doping sequences in the growth cycle has been investigated in detail. Compared with counterparts, those devices with NH$_{3}$ in situ doping demonstrate obvious performance enhancements: $I_{\rm on}/I_{\rm off}$ is improved by one order of magnitude, from $1.33\times 10^{5}$ to $3.56\times 10^{6}$, the threshold voltage shifts from $-0.74 $ V to $-0.12$ V and a small subthreshold swing of 105 mV/dec is achieved. The improved MoS$_{2}$ FET performance is attributed to nitrogen doping by the introduction of NH$_{3}$ during the Al$_{2}$O$_{3}$ ALD growth process, which leads to a reduction in the surface roughness of the dielectric layer and the repair of oxygen vacancies in the Al$_{2}$O$_{3}$ layer. Furthermore, the MoS$_{2}$ FET processed by in situ NH$_{3}$ doping after the Al and O precursor filling cycles demonstrates the best performance; this may be because the final NH$_{3}$ doping after film growth restores more oxygen vacancies to screen more charge scattering in the MoS$_{2}$ channel. The reported method provides a promising way to reduce charge scattering in carrier transport for high-performance MoS$_{2 }$ devices.     

二维空间电荷限制流实验研究

对基于圆柱平板结构电子枪的二维空间电荷限制流进行了研究.采用粒子模拟软件详细探讨了二维空间电荷限制流随间距、电压、逸出功、温度、阴极结构等物理量的变化关系.设计了一种实用圆柱平板结构电子枪,对其空间电荷限制流和发射性能进行了实验探索.通过测试,发射电流与二维模型的比较吻合,远大于一维模型的结果.