Conformational Changes and Redox Properties of Bimetallic Single Helicates of Hexapyrrole-α,ω-dicarbaldehydes

The hexapyrrole-α,ω-dicarbaldehydes 1 a and 1 b were metallated with Cu^II, Ni^II, and Pd^II to give bimetallic complexes where a pair of 3 N+O four-coordinate metal planes are helically distorted and the central 2,2′-bipyrrole subunit adopts a cis or trans conformation. X-ray crystallographic analysis of the bisCu complex revealed a closed form with a cis-2,2′-bipyrrole subunit and an open form with a trans-2,2′-bipyrrole subunit. The bisPd complexes took a closed form both in the solid state and in solution. They are regarded as single helicates of two turns and the energy barrier for the interchange between an M helix and a P helix was remarkably influenced by the bulky 3,3′-substituent of the central 2,2′-bipyrrole subunit. Although the bisNi complexes adopt a closed form in the solid state, they exist as a homohelical open C₂-symmetric form or a heterohelical open C_i-symmetric form in solution. A theoretical study suggested that the closed form of 1 a Pd was stabilized by the Pd–Pd interaction. Compound 1 a Pd was reversibly oxidized by one electron at 0.14 V versus ferrocene/ferrocenium (Fc/Fc⁺) and this oxidized species showed Vis/NIR absorption bands at λ=767 and 1408 nm.     

可见/近红外光谱图像在作物病害检测中的应用

农作物病害严重影响了我国正常的农业生产，现代农业迫切需要快速、准确、高效的作物病害诊断方法。首先简单介绍了常用病害检测技术，如：聚合酶链式反应技术、人工感官判定技术、统计学方法等，这些方法或是比较费时、或是只能用于产生明显病斑后的病害诊断，而光谱技术在植物病害的快速检测方面有一定的潜力，目前已有大量的研究成果。主要围绕可见/近红外光谱图像在病害检测的应用展开分析和讨论，讨论了该技术所涉及的仪器，并从细胞、植物组织、冠层及更大尺度层面分析了该技术在病害检测中的现况。目前大部分与植物病害有关的可见/近红外光谱研究都以植物叶片为对象，而在更小尺度（细胞至显微尺度）和更大尺度（冠层至航空/航天遥感方面）上的研究较少，特别是单细胞级别的病害研究，只在动物细胞领域展开，而且以荧光、拉曼、红外光谱为主。可见/近红外在以植物叶片为主要研究对象的器官尺度上有大量的成功应用，目前的研究已涉及了大部分的常见作物及其主要病害，包括真菌性、细菌性等各种病原引起的病害的检测。植物叶片尺度的研究主要从以下三个方面展开：(1）基于计算机图像处理和模式识别的病害信息自动快速判断；(2）基于化学计量学方法的高光谱或高光谱图像病害程度模型；(3）建立与作物病害有关的叶片某些理化参数的光谱模型，从而量化病害的程度。在植物叶片这一尺度相关研究的主要问题是：研究过于碎片化，往往只研究了某一种或少数几种病害，所建的模型只能用于特定实验条件，无法直接自动判断任意田间样本的染病种类与程度。在近地冠层尺度，植株的三维形态对光谱模型有较大的干扰，有文献表明以植株近地冠层2D图像作为病害检测数据，偏差较大，所建模型不稳定，基于卫星影像的病害模型较少。还讨论了常用光谱及光谱图像建模与分类方法。目前可见/近红外光谱在农作物病害方面有一定的应用潜力，但存在研究内容的不平衡、研究系统性不够、各学科合作研究不够深入等几大问题。最后提出可见/近红外光谱在病害检测领域中应更注重多学科的深入合作，并急需相关的仪器设备、方法模型方面的突破。     

涤棉混纺织物近红外定量分析模型的建立及相关问题探讨

在废旧纺织品回收再利用中，纤维类型和含量的快速、准确测定是回收方案的关键部分。以598个废旧涤棉混纺织物为研究对象，采用便携式近红外（NIR）光谱仪测试了样品的原始近红外光谱。在1 400～1 700和1 900～2 200 nm光谱区域，100％棉和100％聚酯样品的光谱存在明显差异，并且这些光谱差异存在于各种颜色纤维上。同时探讨了斜线光谱产生的原因可能是由于织物表面效果、着色方法及粘附在纤维表面的细小颗粒造成的。深色样品易造成其光谱基线在短波区发生漂移，经导数预处理后，基线漂移基本消除，斜线光谱呈现出正常光谱的特征。利用偏最小二乘（PLS）法结合一阶导数、S-G平滑、均值中心化和正交信号校正法，建立了废旧棉-涤混纺织物定量分析模型。为了验证模型的可靠性，选取346个样本采用内部交叉验证均方根误差（RMSECV）和预测样品集外部检验法对模型进行检验，模型的RMSECV值0.002、校正集相关系数R_C＝0.998、预测相关系数R_P=0.997、预测标准差SEP＝1.121，模型预测正确率可达97％。对模型进行匹配样本t检验结果显示，NIR方法与国家标准方法无显着性差异。NIR预测值与重量法测定值误差在±3％以内时，二者的一致性在90％以上，当误差在±5％以内，二者的一致性在95％以上，分析时间小于10 s。因此，利用近红外技术结合所建模型可以快速、准确地预测废旧棉/涤混纺织物纤维成分的含量。     

L-argininato copper(II) complexes in solution exert significant selective anticancer and antimicrobial activities

A search for new drugs that overcome the multidrug resistance of microorganisms or are effective against cancer cells prompted us to investigate the binary and ternary Cu(II) complexes containing L-arginine, [CuCl(L-Arg)(phen)]Cl·2H₂O (phen = 1,10-phenanthroline) ( 1 ) and [Cu(L-Arg)₂(H₂O)]C₂O₄·6H₂O ( 2 ), for which crystal and molecular structures were characterized previously. In order to discuss the biological function, the complexes have been screened for their antitumor activity against A549 (human lung cancer cells), HepG2 (human liver hepatocellular carcinoma cells) and antimicrobial activity. To identify the complexes forms existing in the solutions of 1 and 2 crystals, the results obtained from EPR, NIR–Vis–UV and MS (mass spectrometry) measurements were correlated with those from analysis of potentiometric titration of Cu(II)―L-Arg and Cu(II)―L-Arg―phen systems. This comprehensive study indicated that the [Cu(L-Arg)(phen)]²⁺ and [Cu(L-Arg)₂]²⁺ species are dominant in the solution. Complexes 1 and 2 were found to present specific ligand-dependent cytotoxic and antiproliferative potential against cancer cells. They also show antibacterial activity against Gram-positive and Gram-negative bacteria as well as display antifungal properties.     

Janus Gold Nanostars–Mesoporous Silica Nanoparticles for NIR-Light-Triggered Drug Delivery

Janus gold nanostar–mesoporous silica nanoparticle ( AuNSt–MSNP ) nanodevices able to release an entrapped payload upon irradiation with near infrared (NIR) light were prepared and characterized. The AuNSt surface was functionalized with a thiolated photolabile molecule ( 5 ), whereas the mesoporous silica face was loaded with a model drug (doxorubicin) and capped with proton-responsive benzimidazole-β-cyclodextrin supramolecular gatekeepers ( N 1 ). Upon irradiation with NIR-light, the photolabile compound 5 photodissociated, resulting in the formation of succinic acid, which induced the opening of the gatekeeper and cargo delivery. In the overall mechanism, the gold surface acts as a photochemical transducer capable of transforming the NIR-light input into a chemical messenger (succinic acid) that opens the supramolecular nanovalve. The prepared hybrid nanoparticles were non-cytotoxic to HeLa cells, until they were irradiated with a NIR laser, which led to intracellular doxorubicin release and hyperthermia. This induced a remarkable reduction in HeLa cells viability.     

SPA-PLS的高含水原油近红外光谱含水率分析

准确及时的检测原油含水率对注水策略调整、原油开采能力评估、油井开发寿命预测等均具有重要意义。然而，当前我国大多数油田均已进入高含水的开发中晚期，含水率测量难度大且准确率不高。在此背景下，开展了高含水情况下利用近红外光谱进行原油含水率测量的研究。 首先介绍了目前原油含水率检测的常用方法，分析了它们的优劣。理论上，由于水的近红外光吸收带与原油中C-H键的吸收带有明显区别，根据Lambert-Beer吸收定律和吸光度线性叠加定律可知，不同含水率高含水原油近红外光谱会存在较强响应差异。为此，对高含水原油进行近红外光谱检测，建立原油含水率与近红外光谱响应间的非线性映射模型，可实现高含水原油含水率的精确测量。为了验证该方法的有效性，搭建了近红外光谱数据采集实验装置：采用白炽灯作为光源，经过光路调节成平行光后垂直射入样品池，用近红外光谱仪（海洋光学NIR512）采集光谱用于分析。其中，接收光谱仪带宽为900～1 700 nm，平均分成512个波段。光谱数据利用光谱仪配套软件储存在电脑中。样本采用相同厚度不同比例的油水混合物，样本含水率范围为70%～99%，共采集数据60组，每组重复3次取平均值。得到原始数据后，先进行原始数据预处理，以减少数据采集时来自高频随机噪音及温度不稳定、样本不均匀、基线漂移、光散射等不利因素的影响。分别选用了S-G滤波、一阶导数和S-G滤波+一阶导数作为数据预处理的方法，利用连续投影算法(SPA)对光谱数据进行降维，并利用偏最小二乘法（PLS）和多元线性回归（MLR）进行建模，模型精度通过计算均方根误差值（RMSE）和相关系数（r）来验证。对比发现，使用S-G滤波+一阶导数建立的模型RMSE值最小（RMSE=0.007 0，r=0.998 3）。使用SPA降维后的模型要优于全波段PLS模型（RMSE=0.083 3，r=0.920 6）与MLR模型（RMSE=0.099 9，r=0.967 1）。利用SPA提取出的31个特征波长建立的模型仅占全波段的6.05%，并获得了较好的精度。证明了利用光谱检测高含水原油含水率可行性，并且得到了满意的精度，为高含水原油的含水率检测提供了新的方法, 为进一步利用近红外光进行高含水原油的快速检测与在线监测提供参考。     

Decacyclene Radical Anions Showing Strong Low‐energy Intramolecular Absorption and Magnetic Coupling of Spins in a Hexagonal Network

Two salts of the aromatic hydrocarbon decacyclene, {cryptand[2.2.2](Cs⁺)} (decacyclene^.?) ( 1 ) and {Bu₃MeP⁺}(decacyclene^.?) ( 2 ), were obtained. In both salts, decacyclene^.? radical anions formed channels occupied by cations. However, corrugated hexagonal decacyclene^.? layers could be outlined in the crystal structure of 1 with several side‐by‐side C???C approaches. The decacyclene^.? radical anions showed strong distortion in both salts, deviating from the C₃ symmetry owing to the repulsion of closely arranged hydrogen atoms and the Jahn‐Teller effect. Radical anions showed intense unusually low energy absorption in the IR‐range, with maxima at 4800 and 6000 cm^?1. According to the carculations, these bands can originate from the SOMO‐LUMO+1 and SOMO‐LUMO+2 transitions, respectively. Radical anions exhibited a S=1/2 spin state, with an effective magnetic moment of 1.72 μ_B at 300 K. The decacyclene^.? spin antiferromagnetically coupled with a Weiss temperature of ?11 K. Spin ordering was not observed down to 1.9 K owing to spin frustration in the hexagonal decacyclene^.? layers.     

Direct Near Infrared Light–Activatable Phthalocyanine Catalysts

The high penetration of near-infrared (NIR) light makes it effective for use in selective reactions under light-shielded conditions, such as in sealed reactors and deep tissues. Herein, we report the development of phthalocyanine catalysts directly activated by NIR light to transform small organic molecules. The desired photocatalytic properties were achieved in the phthalocyanines by introducing the appropriate peripheral substituents and central metal. These phthalocyanine photocatalysts promote cross-dehydrogenative-coupling (CDC) under irradiation with 810 nm NIR light. The choice of solvent is important, and a mixture of a reaction-accelerating (pyridine) and -decelerating (methanol) solvents was particularly effective. Moreover, we demonstrate photoreactions under visible-light-shielded conditions through the transmission of NIR light. A combined experimental and computational mechanistic analysis revealed that this NIR reaction does not involve a photoredox-type mechanism with electron transfer, but instead a singlet-oxygen-mediated mechanism with energy transfer.     

Synthesis of N,N‐Dialkylamino‐nor‐Dihydroxanthene‐Hemicyanine Fused Near‐Infrared Fluorophores and Their First Water‐Soluble and/or Bioconjugatable Analogues

The effective synthesis of extended conjugated N ,N ‐dialkylamino‐nor ‐dihydroxanthene‐based fluorophores is described from diversely functionalized salicylic aldehydes. The access to these original fluorescent derivatives proceeded in two steps through a one‐pot construction of the unusual nor ‐dihydroxanthene (nor ‐DHX) scaffold followed by a diversification step providing a wide variety of nor ‐DHX‐hemicyanine fused dyes emitting in the range of 730–790 nm. The versatility of our approach has enabled a further extension to the late‐stage introduction of negatively/positively charged polar groups onto their terminal nitrogen heterocyclic subunit, thereby giving access to the first water‐soluble and/or bioconjugatable members of this emerging class of NIR fluorophores. Our water‐solubilizing method is easily implementable, and the nor ‐DHX‐hemicyanine skeleton maintains satisfying fluorescence quantum yields (5–20 %) under physiological conditions. Finally, the bioconjugation ability of fluorescent derivatives bearing a free carboxylic acid was demonstrated through the covalent labeling of a model protein, namely, bovine serum albumin.     

A Near-Infrared Dye That Undergoes Multiple Interconversions through Acid–Base Equilibrium and Reversible Redox Processes

A near-infrared (NIR) polymethine dye ( 1 ), consisting of a cyclohepta[1,2-b;4,3-b′]dithiophene and two phenol moieties, was synthesized. This dye exhibited pH-responsive changes in its photophysical properties due to a two-step acid–base equilibrium that produced a protonated cation ( 1H⁺ ) and an anion ( 1⁻ ). While 1H⁺ showed an intense fluorescence in the red region of the visible spectrum, 1⁻ exhibited a strong absorption in the NIR region. The tropylium ion character in 1H⁺ induces high pK_a1 and pK_a2 values for 1 . Moreover, a stable radical ( 1^. ) was prepared, which showed a NIR absorption band with a maximum at circa 1600 nm. The cyclic voltammogram of 1^. revealed a two-step reversible redox process that produced 1⁻ and the cation 1⁺ , which is different from 1H⁺ . These redox processes accompany drastic electrochromic changes in the vis–NIR region. Overall, 1 is susceptible to multiple interconversions between five forms, due to the multifaceted character of the cycloheptadithiophene skeleton.