Excited-State Dynamics of Thienoguanosine,an Isomorphic Highly Fluorescent Analogue of Guanosine

Thienoguanosine (^thG) is an isomorphic analogue of guanosine with promising potentialities as fluorescent DNA label. As a free probe in protic solvents, ^thG exists in two tautomeric forms, identified as the H1, being the only one observed in nonprotic solvents, and H3 keto–amino tautomers. We herein investigate the photophysics of ^thG in solvents of different polarity, from water to dioxane, by combining time-resolved fluorescence with PCM/TD-DFT and CASSCF calculations. Fluorescence lifetimes of 14.5–20.5 and 7–13 ns were observed for the H1 and H3 tautomers, respectively, in the tested solvents. In methanol and ethanol, an additional fluorescent decay lifetime (≈3 ns) at the blue emission side (λ≈430 nm) as well as a 0.5 ns component with negative amplitude at the red edge of the spectrum, typical of an excited-state reaction, were observed. Our computational analysis explains the solvent effects observed on the tautomeric equilibrium. The main radiative and nonradiative deactivation routes have been mapped by PCM/TD-DFT calculations in solution and CASSCF in the gas phase. The most easily accessible conical intersection, involving an out-of plane motion of the sulfur atom in the five-membered ring of ^thG, is separated by a sizeable energy barrier (≥0.4 eV) from the minimum of the spectroscopic state, which explains the large experimental fluorescence quantum yield.     

表面增强拉曼光谱在食源性致病微生物检测中的应用研究

食源性致病微生物导致的食源性疾病已成为全球化的公共卫生问题。快速、有效地检测食源性致病微生物是实现食源性疾病预防与控制的关键环节，也是保障食品安全的技术关键。表面增强拉曼光谱(SERS)具有简单、快速、灵敏度高等优点，在食品安全、生物医学、环境监控等领域展现出良好的应用前景。介绍了近年来SERS在食源性致病微生物检测中的应用研究进展。对SERS技术概况、SERS增强理论及SERS增强基底进行了简要介绍，重点回顾了SERS在食源性致病微生物检测中的应用和发展现状。在食品安全分析方面，利用SERS与模式识别方法相结合对食品中常见食源性致病微生物能实现快速、有效鉴别，部分研究已应用于不同食品样品的分析，体现了SERS作为“指纹图谱”的分析优势；在医学诊断方面，SERS可对病理样品(如血液、尿液等)中食源性致病微生物进行快速检测，缩短了样本分析时间，使食源性疾病的快速诊断成为可能；随着微流控技术的发展，微流控平台结合SERS技术被称为“芯片实验室”应用于食源性致病微生物的检测，可提高分析的可控性，稳定性，特异性和灵敏度。通过对比分析，发现不同研究可采用不同分离方法、不同基底、不同目标捕获方式等实现了食源性致病微生物的检测，展示了不同方法间的差异性。已有研究表明了SERS在食源性致病微生物检测中应用可克服传统方法耗时等缺点，实现灵敏快速分析，为食品安全实时监控，食源性疾病即时诊断提供了有效的分析工具。同时，指出了SERS技术应用于食源性致病微生物分析依然面临很大挑战，(1)大多数研究并没有聚焦于实际样品，而标准培养液和实际样品的SERS检测存在较大差异，实际样品组分会对SERS响应产生干扰；(2)不同方法结果有较大差异，主要是由于纳米增强基底差异，吸附方式原理的差异，稳定性的差异等，因此需要更多深入研究进一步优化条件；(3)期望建立标准化的SERS方法替代传统技术，充分展示SERS作为新兴分析工具快速、灵敏、简捷的优势应用于食品安全，医学诊断等领域。将来，随着研究的深入及相关学科的发展，SERS作为极具潜力的快速分析工具，将在食品安全，生物医学等领域具有更广阔的应用前景。     

Preparation and Characterization of Activated Carbon from Microwave and Conventional Heated Almond Shells Using Phosphoric Acid Activation

Activated carbon production from almond shells using phosphoric acid activation agent was achieved by applying both conventional heating and microwave heating in succession. The morphology and surface properties of activated carbon were studied using thermogravimetric and differential gravimetric analysis, Fourier-transform infrared spectroscopy, scanning electron microscopy, and Brunauer–Emmett–Teller analysis. A surface area of 1128 m²/g was achieved by optimizing the microwave power (500?W), microwave application time (15?minutes), conventional heating time (45?minutes), conventional heating temperature (500?°C), and the phosphoric acid:sample ratio (0.7:1). An adsorption capacity of methylene blue of 148?mg/g and an iodine value of 791?mg/g was obtained for the prepared activated carbon.     

The Plasticity of the Carbohydrate Recognition Domain Dictates the Exquisite Mechanism of Binding of Human Macrophage Galactose-Type Lectin

The human macrophage galactose-type lectin (MGL), expressed on macrophages and dendritic cells (DCs), modulates distinct immune cell responses by recognizing N-acetylgalactosamine (GalNAc) containing structures present on pathogens, self-glycoproteins, and tumor cells. Herein, NMR spectroscopy and molecular dynamics (MD) simulations were used to investigate the structural preferences of MGL against different GalNAc-containing structures derived from the blood group A antigen, the Forssman antigen, and the GM2 glycolipid. NMR spectroscopic analysis of the MGL carbohydrate recognition domain (MGL-CRD, C181-H316) in the absence and presence of methyl α-GalNAc (α-MeGalNAc), a simple monosaccharide, shows that the MGL-CRD is highly dynamic and its structure is strongly altered upon ligand binding. This plasticity of the MGL-CRD structure explains the ability of MGL to accommodate different GalNAc-containing molecules. However, key differences are observed in the recognition process depending on whether the GalNAc is part of the blood group A antigen, the Forssman antigen, or GM2-derived structures. These results are in accordance with molecular dynamics simulations that suggest the existence of a distinct MGL binding mechanism depending on the context of GalNAc moiety presentation. These results afford new perspectives for the rational design of GalNAc modifications that fine tune MGL immune responses in distinct biological contexts, especially in malignancy.     

QEPAS系统中石英音叉模态仿真计算与研究

对石英音叉增强型光声光谱(QEPAS)系统中常用的石英音叉进行了有限元模态计算，获得石英音叉前6阶振型与模态频率，认知了第4阶对称摆动振型为有效振动，利用单因素法分析了石英音叉的音臂长度l₁、音臂宽度w₁、音臂厚度t、音臂切角θ、音臂圆孔直径d及音臂圆孔高度h对低阶有效共振频率(Fre)的影响，敏感度依次为： l₁> w₁>d>θ>t>h，考虑实际设计情形，筛选出了l₁，w₁，d与h四个石英音叉设计变量，采用Box-Behnken实验设计方案与RSM(response surface methodology)方法，以Fre为函数目标，建立l₁，w₁，d与h的二次回归响应面模型，得到了参数之间的交互作用，利用Design-Expert软件对响应面模型进行设计参数反求，结果表明，在15 000 Hz≤Fre≤25 000 Hz计算区域内误差较小，基本满足QEPAS系统的计算需求，所提出的研究与设计方法具有一定通用性，可为QEPAS系统中石英音叉结构参数设计提供参考。     

Dynamic Interactions in Synthetic Receptors: A Guest Exchange Saturation Transfer Study

The accumulated knowledge regarding molecular architectures is based on established, reliable, and accessible analytical tools that provide robust structural and functional information on assemblies. However, both the dynamicity and low population of noncovalently interacting moieties within studied molecular systems limit the efficiency and accuracy of traditional methods. Herein, the use of a saturation transfer-based NMR approach to study the dynamic binding characteristics of an anion to a series of synthetic receptors derived from bambusuril macrocycles is demonstrated. The exchange rates of BF₄⁻ are mediated by the side chains on the receptor (100 s⁻¹<k_ex<5000 s⁻¹), which play a critical role in receptor-anion binding dynamics. The signal amplification obtained with this approach allows for the identification of different types of intermolecular interactions between the receptor and the anion, something that could not have been detected by techniques hitherto used to study molecular assemblies. These findings, which are supported by a computational molecular dynamic study, demonstrate the uniqueness and added value of this NMR method.     

焦炉上升管内壁结焦炭层的光谱学分析及结焦机理研究

以焦炉上升管内壁结焦炭层块为研究对象，采用X射线荧光光谱仪（XRF）、X射线衍射仪（XRD）、傅里叶红外光谱仪（FTIR）和激光共聚焦拉曼光谱仪（Raman）对结焦炭层的元素组成，以及各结焦炭层的矿物组成、组成结构和分子结构进行测试。分析从结焦炭层块外表面向内表面过渡的各结焦炭层的差异性，揭示焦炉上升管内壁结焦机理。结果表明焦炉上升管内粉尘中Fe，S和Cr极易催化荒煤气中蒽、萘等稠环芳烃化合物成炭，在焦炉上升管内壁形成炭颗粒沉积，为焦油凝结挂壁提供载体，在荒煤气温度降至结焦温度时易结焦积碳。结焦炭层均含有芳香层结构，随着结焦炭层从外表面向内表面过渡，各结焦炭层的面层间距(d₀₀₂)逐渐降低、层片直径(L_a)先降低后增加、层片堆砌高度(Lc)和芳香层数(N)先稳定后增加。结焦炭层石墨化过程是由结焦炭层内表面向外表面进行，主要包括其片层外缘的羧基和部分C-O结构的降解剥离，从而形成高度规整的共轭结构。结焦炭层块中C元素是以结晶碳与无定型碳的混合物形式存在。以上研究为解决焦炉上升管内壁结焦及腐蚀问题，提高换热器换热效率，有效回收焦炉荒煤气显热，降低焦化企业能耗提供实验基础和理论依据。     

Correlating Charge-Carrier Dynamics with Efficiency in Quantum-Dot Solar Cells: Can Excitonics Lead to Highly Efficient Devices?

The photovoltaic performance of quantum-dot solar cells strongly depends on the charge-carrier relaxation and recombination processes, which need to be modulated in a favorable way to obtain maximum efficiency. Recently, significant efforts have been devoted to investigate the carrier dynamics of nanocrystal sensitizers, both in solution and deposited on TiO₂ photoanodes, with the aim to correlate the excitonics with solar-energy conversion efficiency. This Minireview summarizes some proof of the concepts that efficiency can be directly correlated to the exciton dynamics of quantum-dot solar cells. The presented findings are based on CdSeS alloy, CdSe/CdS core/shell, Au/CdSe nanohybrids, and Mn-doped CdZnSSe nanocrystals, where the favourable excitonic processes are optimized to enhance the efficiency. Future prospects and limitations are addressed as well.     

The Hydrogen Bond and Beyond: Perspectives for Rotational Investigations of Non-Covalent Interactions

In the last decade, experiment and theory have expanded our vision of non-covalent interactions (NCIs), shifting the focus from the conventional hydrogen bond to new bridging interactions involving a variety of weak donor/acceptor partners. Whereas most experimental data originate from condensed phases, the introduction of broadband (chirped-pulse) microwave fast-passage techniques has revolutionized the field of rotational spectroscopy, offering unexplored avenues for high-resolution studies in the gas phase. We present an outlook of hot topics for rotational investigations on isolated intermolecular clusters generated in supersonic jet expansions. Rotational spectra offer very detailed structural data, easily discriminating the isomeric or isotopic composition and effectively cancelling any solvent, crystal, or matrix bias. The direct comparison with quantum mechanical predictions provides insight into the origin of the inter- and intramolecular interactions with much greater precision than any other spectroscopic technique, simultaneously serving as test-bed for fine-tuning of theoretical methods. We present recent examples of rotational investigations around three topics: oligomer formation, chiral recognition, and identification of halogen, chalcogen, pnicogen, or tetrel bonds. The selected examples illustrate the benefits of rotational spectroscopy for the structural and energetic assessment of inter-/intramolecular interactions, which may help to move from fundamental research to applications in supramolecular chemistry and crystal engineering.     

Formation of intermediate coupling optical polarons and bipolarons in two-dimensional systems

The formation of the optical polaron and bipolaron in two-dimensional (2D) systems is studied in the intermediate electron–phonon coupling regime. The total energies of the 2D polaron and bipolaron are calculated by using the Buimistrov–Pekar method of canonical transformations. The obtained results are compared with other existing results obtained by using the Feynman path integral method and the modified Lee–Low–Pines unitary transformation method. It is shown that the electron–phonon correlation significantly reduces the total energy of the 2D polaron in comparison with the energy of the strong coupling (adiabatic) polaron. It is found that the polaron formation in 2D systems is possible when the electron–phonon coupling constant α is greater than the critical value ${\alpha }_c?2.94$, which is much lower than a critical value of the electron–phonon coupling constant α in three-dimensional (3D) systems. The critical values of the Fröhlich coupling constant α and the ratio $\eta ={\epsilon }_{\infty }/{\epsilon }_0$ (where ${\epsilon }_{\infty }$ and ${\epsilon }_0$ are the high frequency and static dielectric constants, respectively), which determine the bipolaron stability region in 2D systems, are calculated numerically. It is interesting for application to the layered cuprate superconductors that the (bi)polarons are formed more easily in quasi-2D regions than in the bulk. It is argued that the high-$T_c$ cuprate superconductivity can exist above the bulk superconducting transition temperature $T_c$ as the persisting superfluidity of polaronic (bosonic) Cooper pairs and large bipolarons at quasi-2D grain boundaries or in the CuO₂ layers above $T_c$.