A fluorescence enhanced probe for sulfur dioxide detection and fluorescence imaging in living cellsEI北大核心CSCD

基于香豆素和苯并吡啶基团,构建了用于二氧化硫(SO_(2))高效检测的荧光探针P1,其化学结构通过核磁氢谱(^(1)H NMR)、碳谱(^(13)C NMR)和高分辨质谱(HR-MS)确证。在缓冲溶液体系中,单独的探针P1具有微弱的荧光,识别SO_(2)后荧光发射强度明显增强,能够实现对SO_(2)的专一性裸眼识别,检出限为126 nmol/L。生物应用实验结果表明,该探针具有较低的细胞毒性,可用于生物活细胞中外源性SO_(2)的荧光成像。     

Chalcogen Effect of Atom Substitution on the Properties of Tris(2,4,6-trichlorophenyl)methyl(TTM) Radical

Luminescent open-shell organic radicals have recently been regarded as one of the most potential materials in organic light-emitting diodes(OLEDs). Herein, we have synthesized two new organic radicals, namely tris{4-[4-(tert-butyl)phenoxy]-2,6- dichlorophenyl}methane radical(TTM-O) and tris(4-{[4-(tert-butyl)- phenyl]thio}-2,6-dichlorophenyl)methane radical(TTM-S), by the substitution of chalcogen atom elements at the para position of conventional tris(2,4,6-trichlorophenyl)methyl(TTM) radical moiety. Interestingly, both TTM-O and TTM-S exhibited significantly enhanced photostability compared with the unsubstituted TTM radical parent. Moreover, the chalcogen atom also had a crucial impact on the photoluminescence quantum yield(PLQY) of the radicals, i.e., the PLQY of TTM-S was greatly enhanced compared to TTM radical while TTM-O was nearly non-emissive. Particularly, TTM-S showed intense PLQY of 37.54% and 185-fold longer photostability than that in cyclohexane solution of TTM.     

Composite Mesoporous Silica Nanoparticles with Dual-color Afterglow for Cross-correlation-based Living Cell Imaging

Room temperature phosphorescence (RTP) materials are characterized with emission after removing the excitation source. Such long-lived emission feature possesses great potential in biological fluorescence imaging because it enables a way regarding temporal dimension for separating the interference of autofluorescence and common noises typically encountered in conventional fluorescence imaging. Herein, we constructed a new type of mesoporous silica nanoparticles (MSNs)-based composite nanoparticles (NPs) with dual-color long-lived emission, namely millisecond-level green phosphorescence and sub-millisecond-level delayed red fluorescence by encapsulating a typical RTP dye and Rhodamine dye in the cavities of the MSNs with the former acting as energy donor (D) while the latter as acceptor (A). Benefiting from the close D-A proximity, energy match between the donor and the acceptor and the optimized D/A ratio in the composite NPs, efficient triplet-to-singlet Förster resonance energy transfer (TS-FRET) in the NPs occurred upon exciting the donor, which enabled dual-color long-lived emission. The preliminary results of dual-color correlation imaging of live cells based on such emission feature unequivocally verified the unique ability of such NPs for distinguishing the false positive generated by common emitters with single-color emission feature.     

Separating Vibrational Coherences in Ground/Excited Electronic States of Solvent/Solute Following Non-Resonant/Resonant Impulsive Excitation

In a quest to track down the origin of coherent vibrational motions observed in femtosecond pump-probe transients, whether they arise from ground/excited electronic state of solute or are contributed by the solvent, we demonstrate a method for extricating vibrations under resonant and non-resonant impulsive excitations using a diatomic solute in condensed phase (iodine in carbon tetrachloride) with aid of spectral dispersion of the chirped broadband probe. Most importantly, we show how a sum over intensities for a select region of detection wavelengths and Fourier transform of data over select temporal window untwine contributions from vibrational modes of different origins. Thus, in a single pump-probe experiment, vibrational features specific to solute as well as solvent are disentangled that are otherwise spectrally overlapping and are non-separable in conventional (spontaneous/stimulated) Raman spectroscopy employing narrowband excitation. We envision wide-ranging applications of this method to unveil vibrational features in complex molecular systems.     

Separation,identification, and structural characterization of sucrose ester isomers from tobacco

Sucrose esters (SEs) are crucial tobacco smoke flavor precursors and play a significant role in tobacco's functionality. Due to their structural complexity, the separation and analysis of SEs in tobacco remain a major challenge, and massive structures of SEs have not yet been fully identified. In this study, the fractions enriched in SEs were obtained from oriental and flue-cured tobacco through a series of pretreatments, and two types of SEs (Types I and II) were distinguished by liquid chromatography-tandem mass spectrometry (LC-MSⁿ) analysis, with Type II SEs newly characterized in tobacco. Five groups of main SEs were further purified using preparative high-performance LC (HPLC) coupled to an evaporative light scattering detector, and their structures were characterized by nuclear magnetic resonance spectrometry techniques including ¹H, ¹³C, correlation spectroscopy, heteronuclear single quantum correlation, and heteronuclear multiple bond correlation. By combining LC-MSⁿ and nuclear magnetic resonance spectrometry, the structures of eight SE isomers were finally proposed, of which four were newly identified. These findings further enhance the understanding of the structural diversity of SEs in tobacco, serving as a valuable reference for future research on the elucidation, synthesis, and metabolism of SEs.     

Local inverse inelastic mean free path at interface

We calculated a local inverse inelastic mean free path (local-IIMFP) for electrons crossing a medium–medium interface, considering various incident electron energies, crossing angles and combinations of materials. We used an extension of a classical dielectric model developed by Li and co-workers for an electron crossing a surface (interface vacuum-medium). Moreover, the integration over the distance of the local-IIMFP allows to obtain the interface excitation parameter (or IEP) characterizing the change in excitation probability for an electron crossing an interface once caused by the presence of the interface in comparison with an electron for which only volume excitations are considered. We perform these calculations for angles between 0° and 80°, for electron energies between 500 and 2500 eV and for various pairs of materials, as Al/In for its academic interest or Au/Si and SiO₂/Si for their technological importance. Small but not negligible variations of the local-IIMFP and the IEP were observed for metal–metal or metal–semiconductor interfaces, while quite significant variations are obtained when one of the materials is a insulator.     

扩展基于AD9874数字接收机谱宽的二次抽取算法

针对基于AD9874芯片的数字接收机的最小谱宽和谱宽允许设置的数目均不能满足常规临床用磁共振成像技术的要求,本文从软件角度提出了一种扩展数字接收机谱宽的二次抽取算法. 该算法具体实现过程主要包括两个步骤：(1) 自适应过采样倍率和自动谱宽调整;(2) 数字滤波和抽取. 为了验证这个二次抽取算法的有效性,本文分别用单脉冲实验和磁共振成像实验加以了验证.     

普适的基于能量的分块局域激发态聚类算法

在普适的基于能量的分块(GEBF)方法的框架下, 大体系的局域激发(LE)能可通过一系列活性子体系激发能的线性组合近似得到, 从而有效降低了计算的时间标度. 然而, 在体系的局域激发具有多个激发态的情形下, 如何有效识别所有活性子体系的激发特征并将其组合是一个挑战. 提出了一种基于局域激发态聚类的算法. 该方案基于空穴-电子分析和基于密度的聚类(DBSCAN)机器学习算法, 可以自动地聚合不同子体系中最相似的激发态并组合得到相应的局域激发态能量或激发能. 结合该算法改进的LE-GEBF方法在荧光分子衍生物、 荧光染料-水团簇及绿色荧光蛋白模型体系的计算中均获得了令人满意的结果. 该算法有望大大提升LE-GEBF方法在计算局域激发时的稳定性和准确性, 并可以有效处理吸收光谱具有多重峰的大体系.     

固体核磁共振Multiple-CP定量技术的参数优化与应用研究

固体核磁共振Multiple-CP定量技术可实现对不同体系、 不同定量信息的检测. 然而, Multiple-CP对样品属性的宽容度较低, 其中有关样品属性的核磁共振参数包括氢的自旋晶格弛豫时间(T_1,H)、 交叉弛豫时 间(T_CH)和自旋锁定场下氢的自旋晶格弛豫时间(T_{\mathrm{1}\rho }^{\text{?}\mathrm{H}})等. 因而需要系统地掌握Multiple-CP各种实验参数与样品上述特性参数之间的关系, 从而确定Multiple-CP技术可适用的体系范围以及最优的实验参数范围. 基于此, 首先以L-丙氨酸为模型样品, 探讨在Multiple-CP实验中弛豫恢复时间(t_d)、 交叉极化接触时间(t_p)和交叉极化次数(n) 3种实验参数对分子中基团比例测量结果的影响规律. 并以L-缬氨酸、 L-丙氨酸/L-缬氨酸的混合物为模型样品, 探讨样品特性参数的差异性对Multiple-CP实验参数范围的影响. 实验结果表明, t_p受T_CH和\text{?}{T}_{\mathrm{1}\rho }^{\text{?}\mathrm{H}}的影响较大. 对于纯净物或均相体系, T_CH是影响t_p参数设置的关键. 依据实验数据发现, 当样品中各基团T_CH差异度小于8%时, 实验对t_p的宽容度较高; 对于混合物体系, 需同时考虑混合物中组分\text{?}{T}_{\mathrm{1}\rho }^{\text{?}\mathrm{H}\text{?}}差异度的影响. 当组分\text{?}{T}_{\mathrm{1}\rho }^{\text{?}\mathrm{H}\text{?}}差异度为32%、 各基团T_CH差异度为21%时, Multiple-CP对t_p的宽容度高, 可在较宽的参数范围内实现定量检测. 而当T_CH差异度较大时, 获取定量结果时t_p的参数范围较小, 实验条件较苛刻. Multiple-CP定量方法更适用于T_CH和\text{?}{T}_{\mathrm{1}\rho }^{\text{?}\mathrm{H}\text{?}}差异度较小的样品体系的定量研究. 通过研究样品T_CH和\text{?}{T}_{\mathrm{1}\rho }^{\text{?}\mathrm{H}\text{?}}对实验参数的影响, 总结了Multiple-CP方法所适用的样品体系特征, 为使用Multiple-CP进行定量检测提供可参考的参数设置方案.     

How the Aggregates Determine Bound Rubber Models in Silicone Rubber? A Contrast Matching Neutron Scattering Study

The correlation between aggregates and bound rubber structures in silicone rubbers(S(phr)) with various silica fractions(ΦSi) has been investigated by contrast matching small-angle neutron scattering(SANS), swelling kinetics, and low-field nuclear magnetic resonance(NMR).Mixed solvents with deuterated cyclohexane fractions of 4.9% and 53.7% were chosen to match the scattering length densities of the matrix(SMP(phr)) and the filler(SMS(phr)), respectively. All the data consistently suggest that:(i) There is a critical threshold ΦSic between 10 and 30 phr;below ΦSic, the isolated aggregates are dominant, while beyond ΦSic, some rubber fraction is trapped among the agglomerate;(ii) ΦSiindependent thicknesses around 7.5 nm(NMR) and 8.6 nm(SANS) suggest that the bound rubber formation is determined by inherent properties of the components, and the power-law around 4.2 suggests an exponential changed gradient density of the bound rubber;(iii) SMS(80) presents a bicontinuous bound rubber with three characteristic lengths of 41, 100, and 234 nm. The expanded correlation length, a 20 nm smaller aggregate sizes suggest that such existent bicontinuous network in dry samples with less ΦSi is kind of impacted by swelling. With the obtained bound rubber models, the reinforcing mechanism of filled silicone rubber is elucidated.