微波/电热板组合消解-电感耦合等离子体质谱(ICP-MS)法测定土壤中重金属元素

为提高土壤检测的重金属得率,采用了微波消解/电热板组合预处理-电感耦合等离子体质谱法(ICP-MS)测定土壤重金属含量。分析了硝酸(HNO3)、氢氟酸(HF)、高氯酸(HClO4)和盐酸(HCl)组合消解液及赶酸温度对土壤预处理影响。结果显示：在硝酸和盐酸混合消解液中,硝酸占比越高,铬(Cr)、钴(Co)、铜(Cu)、镉(Cd)得率更高;消解液体系中加入氢氟酸可使消解更加彻底,提高铬与铜的得率。最优预处理消解条件为硝酸 6ml+ 氢氟酸 2ml消解液组合进行微波消解,1ml 高氯酸于155℃电热板上赶酸。经土壤标准样品GBW07401(GSS-1)和GBW07452(GSS-23)实际应用,预处理条件优化后测试准确度和稳定性均显著提高。此外使用元素铑(Rh)作为内标物时,其方法稳定性和准确性高于内标物钪(Sc)和锗(Ge)。可为相关国家土壤重金属测定标准的修制订提供方法学参考。     

KIT-6负载CeO2催化CO2和甲醇合成碳酸二甲酯

采用不同老化温度(80、100、120和150℃)合成了一系列KIT-6载体,并通过浸渍法制备了相应的CeO_2/KIT-6催化剂。结合X射线衍射、N_2物理吸附、NH_3程序升温脱附、CO_2程序升温脱附、透射电子显微镜、傅里叶变换红外光谱和X射线光电子能谱等表征结果,详细考察了老化温度对KIT-6结构以及CeO_2/KIT-6催化剂直接催化CO_2和甲醇合成碳酸二甲酯(DMC)反应活性的影响。结果表明,不同老化温度下制备的KIT-6均保持其独特的三维孔道结构。随着老化温度升高,KIT-6比表面积先增大后减小,当老化温度为100℃时,KIT-6比表面积达到最大(683 m~2·g~(-1))。KIT-6较高的比表面积有利于提高CeO_2分散度,进而提高暴露的活性位点数量,催化活性随催化剂表面中等碱/酸性吸附位数量和Ce~(3+)含量的增加而逐渐提高。其中,CeO_2/100-KIT-6催化剂中CeO_2颗粒尺寸最小(5.9 nm),暴露的活性位数量最高,催化活性最佳。随后,考察了反应温度和压力对CeO_2/100-KIT-6催化活性的影响。随着反应温度提高,催化活性先升高后降低,当反应温度为140℃时,催化活性最高;且催化活性随反应压力的提高而逐渐增加。在反应温度为140℃、压力为6.8 MPa条件下,催化剂经6次循环后,DMC收率由15 mmol·g_(CeO_2)~(-1)逐渐降低至2.8 mmol·g_(CeO_2)~(-1),原因归结为反应过程中CeO_2纳米颗粒发生团聚,使暴露出的活性位数量减少。     

Accessing the spatiotemporal heterogeneities of single nanocatalysts by optically imaging gas nanobubbles

Catalysts that catalyze the generation of products in the gas phase, especially those involved in the hydrogen evolution reaction (HER), hold great promise for ecofriendly and sustainable energy development. In general, gas chromatography is widely used to measure catalytic activity. Unfortunately, it gives an averaged output that washes out the heterogeneities among individuals. To assess the unique catalytic properties at the single nanoparticle level, various methods based on single particle catalysis have been proposed. Over the past fifteen years, tremendous breakthroughs have been achieved, which uncovered hidden spatial and temporal heterogeneities. Although powerful, effectively quantifying the activities of single HER nanocatalysts remains challenging because of the fast diffusion of hydrogen (H₂). In 2017, a novel approach based on a nanobubble indicator was proposed to correlate the kinetics of gas bubble evolution with the catalytic activities of individual nanoentities during the HER process. Since then, a plethora of optical microscopy techniques have been utilized to monitor dynamically evolved nanobubbles and to measure the catalytic activities of single HER catalysts. In this minireview, we summarized state-of-the-art optical microscopy for in operando imaging of dynamic nanobubbles involved in gas-generating reactions while highlighting some important discoveries, including the blinking photocatalytic activity and heterogeneous distribution of active sites. Finally, challenges and future perspectives in this promising field were identified.     

单颗粒光散射显微成像技术在生化医药分析中的应用

等离子体纳米颗粒(PNPs)具有体积小、易表面修饰、生物相容性好、毒性低等优点,在生物传感、生物成像、疾病诊断、肿瘤治疗、材料科学等领域得到了广泛的应用。PNPs的光散射光学性质可以通过调节其大小、组成、形貌和微环境来控制,可用于生化和药物分析。此外,由于单粒子散射显微技术具有高空间分辨率和高灵敏度,借助PNPs具有的独特局域表面等离子体共振(LSPR)特性,可在单颗粒水平进行实时成像。根据PNPs的大小、组成、形态、微环境或耦合变化引起的信号变化,研究人员发展了多种显微成像分析方法,主要分为4种,包括散射光谱的波长位移、单粒子散射强度的变化、高通量RGB分析和计数方法。基于纳米颗粒LSPR散射光谱位移变化的方法准确、灵敏,但需要昂贵的单颗粒散射光谱仪和复杂的操作。基于纳米颗粒散射强度变化的方法简单可行,但易受纳米颗粒粒径和曝光时间等因素的影响。高通量RGB分析方法灵敏度高、成本低,但不适用于颜色变化不明显的单颗粒分析,且重复性差。单粒子计数法灵敏度高,但有时粒子分布不均匀,背景杂质的干扰限制了方法的准确度。因此,这4种定量方法各有优缺点。此外,近年来逐渐发展了一些新的定量方法。例如,研究人员开发了新的时间分辨分析定量方法,并将暗场显微镜与偏振器、滤光片等光学器件相结合以消除背景干扰,以及与电化学、拉曼等仪器相结合以扩大应用范围。此外,为提高分析方法的准确度和灵敏度,暗场显微镜与深度学习、云计算、人工智能等现代计算机科学技术的结合,越来越受到人们的欢迎。基于以上原因,该文重点介绍了单粒子光散射显微镜在生化和药物分析领域的应用,总结了近年来的最新研究进展,讨论了单粒子光散射显微镜在定量分析中的几种主要定量方法,提出了未来的发展趋势,以期为相关研究领域的新人提供一定的学术参考。     

Field-flow fractionation in microfluidic channels of low aspect ratio

The shape of the steady-state three-dimensional flow velocity profile established in carrier liquid flowing inside the rectangular cross-sectional channel for field-flow fractionation should be taken into account to optimize the separation. The central parts of this profile in the planes parallel to the main channel walls are flat with almost identical flow velocities which drop down to zero at the side walls. The separated species transported by the flow in the close-to-side walls regions move with lower average velocities compared to the species transported in the central part of the channel and are undesirably broadened. The hydrodynamic splitting of the carrier liquid at the entry of the channel where the sample is injected only into the central part of the channel eliminates the excessive zone broadening. The aspect ratio of the breadth to the thickness of the channel ratio can thus be reduced. The effect of various aspect ratios on the shape of the flow velocity profile is calculated and the results are used to optimize the aspect ratio of microfluidic channels. The experiments carried out by microthermal field-flow fractionation confirmed that the aspect ratio cannot be reduced to a value of 1, proposed by other authors.     

Convergence of a non-failable mean-field particle system

The existing literature contains many examples of mean-field particle systems converging to the distribution of a Markov process conditioned to not hit a given set. In many situations, these mean-field particle systems are failable, meaning that they are not well defined after a given random time. Our first aim is to introduce an original mean-field particle system, which is always well defined and whose large number particle limit is, in all generality, the distribution of a process conditioned to not hit a given set. Under natural conditions on the underlying process, we also prove that the convergence holds uniformly in time as the number of particles goes to infinity. As an illustration, we show that our assumptions are satisfied in the case of a piece-wise deterministic Markov process.     

A stochastic portfolio optimization model with complete memory

In this article, we consider a portfolio optimization problem of the Merton’s type with complete memory over a finite time horizon. The problem is formulated as a stochastic control problem on a finite time horizon and the state evolves according to a process governed by a stochastic process with memory. The goal is to choose investment and consumption controls such that the total expected discounted utility is maximized. Under certain conditions, we derive the explicit solutions for the associated Hamilton–Jacobi–Bellman (HJB) equations in a finite-dimensional space for exponential, logarithmic, and power utility functions. For those utility functions, verification results are established to ensure that the solutions are equal to the value functions, and the optimal controls are also derived.     

分布式通信响应优化问题及其内点法求解

为了优化移动互联网的分布式通信系统的响应速度,建立分布式通信系统响应速度最优化问题的数学模型,并设计和改进求解该最优化问题的内点法.针对该最优化问题发展一套高效率预条件方法来帮助求解内点法,不但改善计算方法的数值稳定性,而且提高算法的计算效率.通过数值实验验证该预条件对算法稳定性和效率的提高.     

An adaptive nonmonotone global Barzilai–Borwein gradient method for unconstrained optimization

The Barzilai–Borwein (BB) gradient method has received many studies due to its simplicity and numerical efficiency. By incorporating a nonmonotone line search, Raydan (SIAM J Optim. 1997;7:26–33) has successfully extended the BB gradient method for solving general unconstrained optimization problems so that it is competitive with conjugate gradient methods. However, the numerical results reported by Raydan are poor for very ill-conditioned problems because the effect of the degree of nonmonotonicity may be noticeable. In this paper, we focus more on the nonmonotone line search technique used in the global Barzilai–Borwein (GBB) gradient method. We improve the performance of the GBB gradient method by proposing an adaptive nonmonotone line search based on the morphology of the objective function. We also prove the global convergence and the R-linear convergence rate of the proposed method under reasonable assumptions. Finally, we give some numerical experiments made on a set of unconstrained optimization test problems of the CUTEr collection. The results show the efficiency of the proposed method in the sense of the performance profile introduced (Math Program. 2002;91:201–213) by Dolan and Moré.