Investigation of Molecular Diffusion at Block Copolymer Thin Films Using Maximum Entropy Method-Based Fluorescence Correlation Spectroscopy and Single Molecule Tracking

Fluorescence correlation spectroscopy (FCS) has been widely used to investigate molecular diffusion behavior in various samples. The use of the maximum entropy method (MEM) for FCS data analysis provides a unique means to determine multiple distinct diffusion coefficients without a priori assumption of their number. Comparison of the MEM-based FCS method (MEM-FCS) with another method will reveal its utility and advantage as an analytical tool to investigate diffusion dynamics. Herein, we measured diffusion of fluorescent probes doped into nanostructured thin films using MEM-FCS, and validated the results with single molecule tracking (SMT) data. The efficacy of the MEM code employed was first demonstrated by analyzing simulated FCS data for systems incorporating one and two diffusion modes with broadly distributed diffusion coefficients. The MEM analysis accurately afforded the number of distinct diffusion modes and their mean diffusion coefficients. These results contrasted with those obtained by fitting the simulated data to conventional two-component and anomalous diffusion models, which yielded inaccurate estimates of the diffusion coefficients. Subsequently, the MEM analysis was applied to FCS data acquired from hydrophilic dye molecules incorporated into microphase-separated polystyrene-block-poly(ethylene oxide) (PS-b-PEO) thin films characterized under a water-saturated N₂ atmosphere. The MEM analysis revealed distinct fast and slow diffusion components attributable to molecules diffusing on the film surface and inside the film, respectively. SMT studies of the same materials yielded trajectories for mobile molecules that appear to follow the curved PEO microdomains. Diffusion coefficients obtained from the SMT data were consistent with those obtained for the slow diffusion component detected by MEM-FCS. These results highlight the utility of MEM-FCS and SMT for gaining complementary information on molecular diffusion processes in heterogeneous material systems.

Graphical Abstract

     

High‐Level Incorporation of Silver in Gold Nanoclusters: Fluorescence Redshift upon Interaction with Hydrogen Peroxide and Fluorescence Enhancement with Herbicide

High‐level incorporation of Ag in Au nanoclusters (NCs) is conveniently achieved by controlling the concentration of Ag⁺ in the synthesis of bovine serum albumin (BSA)‐protected Au NCs, and the resulting structure is determined to be bimetallic Ag₂₈Au₁₀‐BSA NCs through a series of characterizations including energy‐dispersive X‐ray spectroscopy, mass spectroscopy, and X‐ray photoelectron spectroscopy, together with density functional theory simulations. Interestingly, the Ag₂₈Au₁₀ NCs exhibit a significant fluorescence redshift rather than quenching upon interaction with hydrogen peroxide, providing a new approach to the detection of hydrogen peroxide through direct comparison of their fluorescence peaks. Furthermore, the Ag₂₈Au₁₀ NCs are also used for the sensitive and selective detection of herbicide through fluorescence enhancement. The detection limit for herbicide (0.1 nm ) is far below the health value established by the U.S. Environmental Protection Agency; such sensitive detection was not achieved by using AuAg NCs with low‐level incorporation of Ag or by using the individual metal NCs.     

3D打印贝壳仿生复合材料的拉伸力学行为

采用硬质和软质双组分材料,通过调控两种基体材料的装配夹角,采用光固化3D打印技术制备了不同装配方式的仿贝壳珍珠层复合材料,开展了准静态拉伸实验,结合扫描电镜观察,分析了其拉伸力学性能、断裂及能量耗散机理。研究结果表明,保持胞元边长不变,随着面内装配角度增加,仿贝壳珍珠层复合材料的强度呈线性增加趋势,断裂应变呈线性减小的趋势;随着面外装配角度增大,断裂应变呈线性减小趋势,而强度在面外装配角小于45°时呈增强趋势,超过45°时趋于稳定;面外装配角度为45°时,材料的强度达到最大值。试样在断裂前主要通过硬质材料的拔出、软/硬相界面处微裂纹的生成及微裂纹在扩展过程中的合并和偏转等方式耗散能量。     

Fast Modulation of d-Band Holes Quantity in the Early Reaction Stages for Boosting Acidic Oxygen Evolution

Synthesis of highly active and durable oxygen evolution reaction (OER) catalysts applied in acidic water electrolysis remains a grand challenge. Here, we construct a type of high-loading iridium single atom catalysts with tunable d-band holes character (h-HL−Ir SACs, ∼17.2 wt % Ir) realized in the early OER operation stages. The in situ X-ray absorption spectroscopy reveals that the quantity of the d-band holes of Ir active sites can be fast increased by 0.56 unit from the open circuit to a low working potential of 1.35 V. More remarkably, in situ synchrotron infrared and Raman spectroscopies demonstrate the quick accumulation of *OOH and *OH intermediates over holes-modulated Ir sites in the early reaction voltages, achieving a rapid OER kinetics. As a result, this well-designed h-HL−Ir SACs exhibits superior performance for acidic OER with overpotentials of 216 mV @10 mA cm⁻² and 259 mV @100 mA cm⁻², corresponding to a small Tafel slope of 43 mV dec⁻¹. The activity of catalyst shows no evident attenuation after 60 h operation in acidic environment. This work provides some useful hints for the design of superior acidic OER catalysts.     

新型Poisson括号意义下的无穷维Lie代数

本文首先针对ＫｄＶ方程的Ｈａｍｉｌｔｏｎ形式，建立一种比较容易验证的新型Ｐｏｉｓｓｏｎ括号和无穷维Ｌｉｅ代数．其次，研究ＫｄＶ方程的Ｈａｍｉｌｔｏｎ形式的第一积分与新型Ｐｏｉｓｏｎ括号的关系，得到判定第一积分的充分必要条件．最后，构造ＫｄＶ方程的第一积分．     

非线性水波Hamilton系统理论与应用研究进展

概述了辛几何理论与辛算法在Hamilton力学中的应用，综述非线性水波的Hamilton理论研究进展．阐述非线性水波Hamilton变分原理与方法的优越性与局限性，探讨KdV方程和BBM方程的Hamilton描述、对称性与守恒律，提出非线性水波Hamilton描述研究中有待进一步研究的问题和解法设想．     

层状两相流动的基本方程式

本文将两相流动的雷诺方程沿深度方向进行平均,出求了平均后的运动方程、连续方程和能量方程式,在适当的物理假定下,简化得到可适用于考虑固-液流动及气-液流动两种情况下的两相层状流动基本方程.     

Removal of oxygen from silicon by electron beam melting

Small amounts of multicrystalline silicon were melted in an electron beam furnace in different experimental conditions in order to investigate the oxygen evaporation behavior during the electron beam melting (EBM) process. The oxygen content level before and after EBM was determined by secondary ion mass spectroscopy. The oxygen content was reduced from 6.177 to 1.629 ppmw when silicon was melted completely at 15 kW with removal efficiency up to 73.6 %. After that, it decreased continually to <0.0517 ppmw when the refining time exceeded 600 s with a removal efficiency of more than 99.08 %. During the melting process, the evaporation rate of silicon is 1.10 × 10^?5 kg/s. The loss of silicon could be reduced up to 1.7 % during oxygen removal process to a desirable figure, indicating EBM is an effective method to remove oxygen from silicon and decrease the loss of silicon.