Photoluminescence of Seven-Coordinate Zirconium and Hafnium Complexes with 2,2′-Pyridylpyrrolide Ligands

Luminescent seven-coordinated zirconium and hafnium complexes bearing three mono-anionic 2,2′-pyridylpyrrolide ligands and one chloride were synthesized. Solid-state structures and the dynamic behaviors in solution were probed by X-ray crystallography and variable temperature ¹H NMR experiments, respectively. Absorption spectroscopy and time-dependent density functional theory (TD-DFT) calculations supported a hybrid of ligand-to-metal charge transfer (LMCT)/ligand-to-ligand charge transfer (LLCT) for the visible light absorption band. The complexes (^MePMP^Me)₃MCl (M=Zr, Hf, ^MePMP^Me=3,5-dimethyl-2-(2-pyridyl)pyrrolide) are emissive in solution at room temperature upon irradiation with visible light due to a combination of phosphorescence and fluorescence characterized by excited state lifetimes in the μs and low to sub-ns timescale, respectively. Electrochemical experiments revealed that the zirconium complex possesses a reversible redox event under highly reducing condition (−2.29 V vs. Fc^+/0).     

Direct calculation of time varying Aharonov-Bohm effect

The Aharonov-Bohm effect (ABE) for steady magnetic fields is a well known phenomenon. However, if the current in the infinite solenoid that creates the magnetic field is time-dependent, that is in the presence of both magnetic and electric fields, there is no agreement whether the effect would be present. In this note, we try to investigate time varying ABE by a direct calculation in a set-up with a weak time dependent magnetic field. We find that the electric field arising out of the time-varying magnetic field in the path of the electrons does not enter the action integral but only changes the path of the electron from the source to the slits and then on to the detector. We find a frequency dependent AB phase shift. At low frequencies the result smoothly approaches the one for a constant field as the frequency tends towards zero. On the other hand, for high frequencies such that the AB-phase induced in the path of the wave packet oscillates rapidly, the net effect will be very small which is borne out by our results.     

水胁迫下典型盐生植被梭梭光谱特征分析

荒漠地区由于气候干燥，降水稀少，水分常成为制约植被生长的因素之一，水分胁迫对植物长势和产量的影响比任何其他胁迫都要大。随着高光谱技术的发展，国内外已有众多学者利用高光谱数据研究植被遭受胁迫作用，然而这些研究对象多集中于甜菜、棉花、玉米、水稻等作物，针对干旱区盐生植被遭受胁迫作用的研究较少。梭梭作为荒漠、半荒漠地区的典型盐生植被之一，具有极高的经济和生态效益。选择梭梭作为研究对象，培育一年生梭梭，并设置三个水分梯度，形成受不同水分量胁迫的梭梭。使用原始光谱、红边位置参数，结合植被指数及二维相关光谱研究其叶片光谱特征，为干旱区利用高光谱遥感监测盐生植被提供借鉴。结果表明：(1)分析梭梭叶片反射光谱曲线发现，在可见光至中红外各波段范围内，受不同水分量胁迫作用的梭梭叶片光谱反射率有显著差异。在可见光(350～610 nm)波段，各水分处理的梭梭叶片反射率依次为100 mL>500 mL>200 mL，这是由于100和200 mL水分促进梭梭内部叶绿素合成，使该波段反射率降低，而过多的水分(500 mL)对梭梭内部的叶绿素合成没有更大的促进作用。在红光区(611～738 nm)，随着水分量的增多，受不同水分量胁迫的梭梭叶片光谱反射率依次减小。在738～1 181和1 228～1 296 nm波段，受不同水分量胁迫作用的梭梭叶片光谱反射率为：200 mL>100 mL>500 mL；在1 182～1 227 nm波段，受不同水分量胁迫作用的梭梭叶片光谱反射率为：100 mL>200 mL>500 mL。这是由于植被细胞结构对近红外区域的反射率影响较大，因而受不同水分胁迫作用的梭梭叶片光谱反射率有显著差异。在1 300～1 365和1 392～1 800 nm波段，受各水分胁迫作用的梭梭叶片反射率为：100 mL>200 mL>500 mL。这表明在500 mL水分胁迫量范围内，水分越多，叶子的细胞液、细胞膜对水分的吸收能力越强，使得反射率下降。通过对原始光谱求取一阶导数并提取红边位置参数发现，各水分处理下的梭梭叶片一阶微分光谱曲线中红边位置未发生移动。这是由于梭梭在长期的干旱环境影响下，形成了特殊的适应机制，水分对其红边位置影响不敏感。(2)选取若干植被指数分析各水分处理下的梭梭光谱指数变化。当水分胁迫量由100 mL增至200 mL时，WI/NDWI，MSI和NDII指数值变化显著，可用于研究水分胁迫下梭梭的光谱特征。(3)使用二维相关光谱技术分析受各水分胁迫作用的梭梭光谱特征，得出在100 mL水分胁迫下，在536，643，1 219和1 653 nm波段处，吸收峰对水分的微扰敏感；在200 mL水分胁迫下，在846和1 083 nm波段处，吸收峰对水分的微扰敏感；在500 mL水分胁迫下，在835和1 067 nm波段处，吸收峰对水分的微扰敏感。总之，在近红外波段，与100 mL水分量相比，梭梭受200和500 mL水分量胁迫时，吸收峰对水分的微扰敏感度上升。由100 mL水分胁迫下梭梭的二维同步相关谱图可知，1 044和1 665 nm，1 072和903 nm，903和1 264 nm，1 230和1 061 nm波段处形成正交叉峰，表明这些波段处光谱强度随水分的干扰同时变化。     

Alkali Blues: Blue-Emissive Alkali Metal Pyrrolates

2-Iminopyrroles [H^tBuL, 4-tert-butyl phenyl(pyrrol-2-ylmethylene)amine] are non-fluorescent π systems. However, they display blue fluorescence after deprotonation with alkali metal bases in the solid state and in solution at room temperature. In the solid state, the alkali metal 2-imino pyrrolates, M(^tBuL), aggregate to dimers, [M(^tBuL)(NCR)]₂ (M=Li, R=CH₃, CH(CH₃)CNH₂), or polymers, [M(^tBuL)]_n (M=Na, K). In solution (solv=CH₃CN, DMSO, THF, and toluene), solvated, uncharged monomeric species M(^tBuL)(solv)_m with N,N′-chelated alkali metal ions are present. Due to the electron-rich pyrrolate and the electron-poor arylimino moiety, the M(^tBuL) chromophore possesses a low-energy intraligand charge-transfer (ILCT) excited state. The chelated alkali cations rigidify the chromophore, restricting intramolecular motions (RIM) by the chelation-enhanced fluorescence (CHEF) effect in solution and, consequently, switch-on a blue fluorescence emission.     

基于荧光光谱技术的菜籽油氧化状态智能评价

菜籽油在加工及贮藏过程中，易受氧气、温度、光照等因素的影响，产生氧化酸败现象。为准确判断油脂氧化程度，实现不同氧化模式下菜籽油品质的快速判别，采用三维同步荧光光谱技术结合平行因子分析法及BP神经网络法建立菜籽油氧化状态的智能评价模型。以冷榨菜籽油为原料，将样品分别置于常温、Schaal烘箱、高温模式中氧化处理，期间采集菜籽油的三维同步荧光光谱数据及理化指标，当理化指标超出国标限定范围时，停止采集数据。结果表明，菜籽油中荧光物质在不同氧化模式中的演变规律呈显著差异，氧化温度对菜籽油荧光光谱有明显影响。常温氧化350 d与第1 d相比，菜籽油的特征荧光峰位置无变化，仅在激发波长Ex为620和660 nm附近荧光峰强度发生微弱变化；Schaal烘箱氧化26 d后，在激发波长Ex为620和660 nm附近荧光峰强度显著减弱，且在激发波长Ex为350～450 nm之间有新的荧光峰生成；高温氧化48 h后，Ex为620和660 nm处荧光峰消失，在Ex为400～550 nm处产生显著荧光峰，相对Schaal烘箱氧化，荧光波长发生一定程度红移，这是由于高温氧化过程中油脂氧化生成的物质稳定性较差引起的。利用平行因子分析法对三维同步荧光光谱数据进行分解获取有效的二维荧光光谱数据，当组分数为6，Δλ=60 nm时激发波长的载荷值最大，不同样品间差异最显著。选定Δλ=60 nm波段的二维荧光光谱数据用于智能评价，作为BP神经网络模型的输入值，以极性组分作为模型输出值，分别对菜籽油三种氧化模式数据建模训练。实验结果表明，三种氧化模式对应的训练集、验证集、测试集模型相关系数r均能达到0.9以上，其中常温氧化模式中验证集及测试集模型的相关系数r为1，输出值与目标值较接近，模型的预测效果较好；综合三种氧化模式数据建模，对应训练集、验证集、测试集模型的相关系数分别为0.999，0.913和0.988，均方误差均较小，说明该模型能准确判断菜籽油的不同氧化状态。因此，三维同步荧光光谱技术结合平行因子分析法、BP神经网络法建立快速检测模型能实现菜籽油不同氧化状态的判别，为菜籽油的氧化程度的评价提供新方法，同时为其他食用油的品质评价提供参考。     

Exploring Potential Energy Surfaces for Aggregation‐Induced Emission—From Solution to Crystal

Aggregation‐induced emission (AIE) is a phenomenon where non‐luminescent compounds in solution become strongly luminescent in aggregate and solid phase. It provides a fertile ground for luminescent applications that has rapidly developed in the last 15 years. In this review, we focus on the contributions of theory and computations to understanding the molecular mechanism behind it. Starting from initial models, such as restriction of intramolecular rotations (RIR), and the calculation of non‐radiative rates with Fermi's golden rule (FGR), we center on studies of the global excited‐state potential energy surfaces that have provided the basis for the restricted access to a conical intersection (RACI) model. In this model, which has been shown to apply for a diverse group of AIEgens, the lack of fluorescence in solution comes from radiationless decay at a CI in solution that is hindered in the aggregate state. We also highlight how intermolecular interactions modulate the photophysics in the aggregate phase, in terms of fluorescence quantum yield and emission color.     

Stimuli-Responsive Fluorescent Nanoswitches: Solvent-Induced Emission Enhancement of Copper Nanoclusters

Copper nanoclusters (CuNCs) as a new class of fluorescent materials have attracted a great deal of interest due to their outstanding fluorescence properties. In this work, a variety of organic solvents were used to induce self-assembly of glutathione-capped CuNCs (GSH-CuNCs) to form ordered assemblies with enhanced fluorescence properties. Assemblies with multicolor fluorescence emission were constructed on the basis of the aggregation-induced emission (AIE) of GSH-CuNCs and the solvent effect. The fluorescence emission from these GSH-CuNCs assemblies can also be tuned from yellow to purple by changing the organic solvent. A possible mechanism based on the size of the assemblies and electron transfer was explored to explain the solvent effects on GSH-CuNCs. Stimuli-responsive nanoswitches with excellent reversibility can be controlled by changing the type of organic solvent and the ratio of the organic solvent to the aqueous solution of GSH-CuNCs. As the CuNCs assemblies exhibit strong, stable, and color-tunable fluorescence, they were employed as color-conversion materials for recognizing different organic solvents.     

Fluorene‐based Lanthanide Coordination Polymer: Structure,Luminescence and Sensing of Picric Acid

Luminescent coordination polymers can be potential chemosensors and extensive efforts are being devoted to improve their selectivity and sensitivity. In this work, we report a new kind of fluorene‐based Tb‐CP, Tb₄L₆·7DMF·5H₂O ( Tb ₄ L ₆ , H₂L = 4,4′‐(9,9‐dimethyl‐9H‐fluorene‐2,7‐diyl)dibenzoic acid), showing 2D network and strong blue emission. Meanwhile, Tb ₄ L ₆ exhibits excellent selectivity and sensitivity for picric acid (PA). The quenching constant (K_sv) of Tb ₄ L ₆ is equal to 4.5 × 10⁴ L/mol during the concentration range of 0–30 μmol/L, which approaches the best reported CPs‐based on PA sensor up to now. Moreover, we went into depth on the possible mechanisms of luminescence quenching.     

Thermoresponsive polymersome from a double hydrophilic block copolymer

The article describes synthesis and thermally triggered self‐assembly of a Poly (ethylene oxide)‐block‐poly (N‐insopropylacrylamide) (PEO‐b‐PNIPAm) in aqueous medium. At rt, the polymer remains as unimer, however, at lower critical solution temperature (LCST) of PNIPAm (32 °C), it forms a rather large undefined aggregate which at slightly elevated temperature (～40 °C) converges to well defined polymersome structure (Critical aggregation concentration = 0.45 mg/mL) with hydrodynamic diameter of 40–50 nm. By lowering the temperature, initial swelling of the compact vesicle followed by reversible disassembly to unimer was noticed. The polymersome exhibits encapsulation ability to a hydrophilic dye Calcein which can be spontaneously released by lowering the temperature below cloud point. Likewise a hydrophobic dye namely 8‐Anilino‐1‐naphthalenesulfonic acid (ANS) can also be encapsulated and released by thermal trigger. Detail photoluminescence studies reveal ANS dye can be used as a generalized probe molecule for detecting LCST of a thermoresponsive polymer by “fluorescence on” above LCST even by cursory observation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2444–2451