双功能配体修饰的Ir催化剂在“氢甲酰化-缩醛化”串联反应中的共催化作用

通过对双齿膦配体的单P原子定向甲基化,合成了两种离子型"叔膦-季鏻鎓Lewis酸"双功能配体L2和L3,该类双功能配体分子结构中既含有与过渡金属配位的叔膦基团,又含有具Lewis酸的季鏻鎓基团.研究结果表明,在合成气的体积比(CO/H₂)为4∶1时,双功能配体L2修饰的[Ir(COD)Cl]₂催化剂高效催化烯烃的"氢甲酰化-缩醛化"串联反应,1-辛烯的转化率为98%,缩醛的选择性高达86%,其催化活性好于同等条件下的Rh催化剂.双功能配体L2与[Ir(COD)Cl]₂原位构建的共催化体系的催化效果远优于Ir(I)配合物和季鏻鎓Lewis酸的物理混合;同时还表现出较好的底物普适性.此外,由于双功能配体L2的高极性,其修饰的Ir催化剂可以顺利实现与正己烷溶液的分离,从而实现催化剂的回收循环使用.     

一种利用岩块特征长度估算二维渗吸量的新方法

对于存在大量亲水疏油岩块的天然裂缝性油藏,自发渗吸是基质岩块和裂缝系统油水交换的重要驱动机制.对于一维渗吸问题,前期存在自相似解析解,后期可以用近似解析解描述,从而可以很方便地估算出岩块剩余油饱和度和岩块出油速率.本文研究了二维矩形岩块在不同边界条件下渗吸过程的近似解析解,通过引入特征长度,将二维岩块渗吸问题等效为一维,从而可以有效利用一维近似解析解来估算出二维岩块渗吸过程中剩余油饱和度和岩块出油速率随时间的变化.本文提出了一个新的混合特征长度,在渗吸前期取岩块面积与岩块开放边界长度之比;在渗吸后期,特征长度根据前期特征长度和Ma等提出的特征长度按饱和度插值确定.通过数值检验比较了几种常见的特征长度取法和本文提出的混合特征长度取法,结果表明新的混合特征长度总体性能优于其他已有的特征长度取法,并且适用于本文列举的所有边界条件.     

Design of an activatable NIR-II nanoprobe for the in vivo elucidation of Alzheimer's disease-related variations in methylglyoxal concentrations

Clear elucidation of the changes in Alzheimer''s disease (AD)-related methylglyoxal (MGO) levels in vivo is significant yet highly challenging. Fluorescence imaging in the second near-infrared region (NIR-II, 1000–1700 nm) has gained increasing attention as an observation method in living organisms, but an MGO-activatable fluorescent probe that emits in this region for in vivo brain imaging is lacking because of the existence of the blood–brain barrier (BBB). Herein, a biocompatible Fe₃O₄ nanoparticle (IONP)-conjugated MGO-activatable NIR-II fluorescent probe (MAM) modified with the peptide T7 (HAIYPRH) (named TM-IONP) is reported for the in situ detection of MGO in a transgenic AD mouse model. In this system, the T7 peptide enhances BBB crossing and brain accumulation by specifically targeting transferrin receptors on the BBB. Due to the MAM probe, TM-IONPs emit fluorescence in the NIR-II region and display high selectivity with an MGO detection limit of 72 nM and a 10-fold increase in the fluorescence signal. After intravenous administration, the TM-IONPs are easily delivered to the brain and pass through the BBB without intervention, and as a result, the brains of AD mice can be noninvasively imaged for the first time by the in situ detection of MGO with a 24.2-fold enhancement in NIR-II fluorescence intensity compared with wild-type mice. Thus, this MGO-activated NIR-II-emitting nanoprobe is potentially useful for early AD diagnosis in clinic.

A biocompatible Fe₃O₄ nanoparticle integrating methylglyoxal-activatable NIR-II fluorescent probe and brain-targeting peptide was developed for visualizing Alzheimer''s disease (AD)-related methylglyoxal variation in vivo.     

Intact living-cell electrolaunching ionization mass spectrometry for single-cell metabolomics

While single-cell mass spectrometry can reveal cellular heterogeneity and the molecular mechanisms of intracellular biochemical reactions, its application is limited by the insufficient detection sensitivity resulting from matrix interference and sample dilution. Herein, we propose an intact living-cell electrolaunching ionization mass spectrometry (ILCEI-MS) method. A capillary emitter with a narrow-bore, constant-inner-diameter ensures that the entire living cell enters the MS ion-transfer tube. Inlet ionization improves sample utilization, and no solvent is required, preventing sample dilution and matrix interference. Based on these features, the detection sensitivity is greatly improved, and the average signal-to-noise (S/N) ratio is about 20 : 1 of single-cell peaks in the TIC of ILCEI-MS. A high detection throughput of 51 cells per min was achieved by ILCEI-MS for the single-cell metabolic profiling of multiple cell lines, and 368 cellular metabolites were identified. Further, more than 4000 primary single cells digested from the fresh multi-organ tissues of mice were detected by ILCEI-MS, demonstrating its applicability and reliability.

A novel living-cell mass spectrometry method allows a whole cell to enter entirely into the MS inlet and ionize with almost no sample dilution and matrix interference, which greatly improves the sensitivity of single-cell metabolite detection.     

高效液相色谱-三重四极杆质谱法测定克氏原鳌虾中多菌灵残留

建立了高效液相色谱-三重四极杆质谱测定克氏原鳌虾中多菌灵的新方法。样品在碱性条件下经乙酸乙酯提取,离心,上清液经旋转蒸发浓缩并复溶后采用混合型阳离子(MCX)萃取小柱富集净化。以乙腈和水为流动相,采用C18色谱柱进行梯度洗脱分离。在电喷雾正离子源下,采用多反应监测模式检测。结果表明:多菌灵在0.5～50.0μg/L范围内线性关系良好,相关系数(r²)为0.998 5。多菌灵的检出限和定量限分别为0.25μg/kg和0.50μg/kg。当加标水平为0.5、 1. 0、 5. 0和50. 0μg/kg时,加标回收率为83.9%～105.5%,相对标准偏差为1.1%～3.2%(n=6)。该方法能简单、有效地检测出克氏原鳌虾中多菌灵的残留量,且稳定性好,结果可靠。     

国产复合功能光纤实现万瓦激光输出

正作为长距离分布式侧面泵浦技术的典型代表,泵浦增益一体化复合功能激光光纤(Pump-gain integrated Functional Laser Fiber,PIFL-fiber)是包含单根增益光纤与多根泵浦光纤的多功能集成器件。基于倏逝波耦合效应巧妙地解决了超大泵浦功率注入的技术难题,已成为高功率光纤激光放大技术的主流技术方案之一。2018年2月,中国工程物理研究院激光聚变研究中心科研人员成功制备(8+1)型PIFL复合功能激光光     

微放电试验中种子电子加载方法比较

为改进微放电试验的有效性,针对微放电试验中种子电子的加载方法进行了研究,介绍了辐射源、紫外光源、电子枪三种加载方法,并说明和比较了上述方法的优缺点和适用范围。接着重点介绍了两种辐射源加载种子电子的方法：β衰变和γ跃迁,并对两种方法加载种子电子的特性进行了定量分析。所得结果表明,基于β衰变的⁹⁰Sr及同时进行β衰变和γ跃迁的¹³⁷Cs均可产生能够穿透毫米量级铝质微波部件壁厚的不同数量的种子电子, 适合用于微放电试验中的种子电子加载。     

Efficient Degradation of Congo Red in Water by UV-Vis Driven CoMoO4/PDS Photo-Fenton System

In order to improve the catalytic activity of cobalt molybdate (CoMoO₄), a PDS-activated and UV-vis assisted system was constructed. CoMoO₄ was prepared by coprecipitation and calcination, and characterized by XRD, FTIR, Raman, SEM, TEM, XPS, TGA Zeta potential, BET, and UV-Vis DRS. The results showed that the morphology of the CoMoO₄ nanolumps consisted of stacked nanosheets. XRD indicated the monoclinic structures with C2/m (C³_2h, #12) space group, which belong to α-CoMoO₄, and both Co²⁺ and Mo⁶⁺ ions occupy distorted octahedral sites. The pH of the isoelectric point (pHIEP) of CMO-8 at pH = 4.88 and the band gap of CoMoO₄ was 1.92 eV. The catalytic activity of CoMoO₄ was evaluated by photo-Fenton degradation of Congo red (CR). The catalytic performance was affected by calcination temperature, catalyst dosage, PDS dosage, and pH. Under the best conditions (0.8 g/L CMO-8, PDS 1 mL), the degradation efficiency of CR was 96.972%. The excellent catalytic activity of CoMoO₄ was attributed to the synergistic effect of photo catalysis and CoMoO₄-activated PDS degradation. The capture experiments and the ESR showed that superoxide radical (·O₂⁻), singlet oxygen (¹O₂), hole (h⁺), sulfate (SO₄⁻·), and hydroxyl (·OH⁻) were the main free radicals leading to the degradation of CR. The results can provide valuable information and support for the design and application of high-efficiency transition metal oxide catalysts.     

万焦耳激光装置上多热力学路径高压加载技术实验研究

针对极端高压条件物质特性研究需求,在我国万焦耳激光装置上利用其高能量、高功率、任意整形长脉冲输出的技术优势先后开展了冲击压缩、准等熵压缩以及“预冲击准等熵压缩”复合热力学路径压缩等多种热力学路径的高压加载技术研究,建立了实用的高压加载设计方法,重点优化了高压加载源的平面性和干净性,发展了高压状态精密表征技术,实现了10¹¹ Pa以上准等熵,10¹² Pa以上冲击以及两种路径之间的宽区高压加载状态能力,为激光装置上的高压状态方程及相变动力学研究提供了重要的技术基础。     

S波段长脉冲相对论速调管重复频率运行稳定性研究

为了进一步提高S波段高功率强流长脉冲相对论速调管放大器(RKA)的重复频率稳频稳相运行的性能,采用实验结合理论和模拟的方法,分析了其主要制约因素,特别分析了造成器件脉冲缩短和重复频率运行不稳定等问题的根源。研究结果表明,RKA中的中间腔和输出腔的电子反射、电子散焦轰击腔体鼻锥是造成脉冲缩短、重复频率运行不稳定的主要根源。通过采用大漂移管半径的器件结构、在漂移管中加载吸波材料以及引导磁场位形、采用电子发射较均匀的碳/碳复合阴极材料等措施,使杂频振荡、脉冲缩短和重复频率工作不稳定性等问题得到了明显减轻,输出微波相位稳定性得到显著提高。采用电压830 kV、束流7.7 kA、脉宽190 ns的环行电子束驱动S波段3腔RKA,重复频率25 Hz运行得到了峰值功率1.55 GW、脉宽163 ns、相位抖动18°（rms）的输出微波。