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。     

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。     

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.     

Synthesis of α-fluoro-α,β-unsaturated esters monitored by 1D and 2D benchtop NMR spectroscopy

For optimization and control of pharmaceutically and industrially important reactions, chemical information is required in real time. Instrument size, handling, and operation costs are important criteria to be considered when choosing a suitable analytical method apart from sensitivity and resolution. This present study explores the use of a robust and compact nuclear magnetic resonance (NMR) spectrometer to monitor the stereo-selective formation of α-fluoro-α,β-unsaturated esters from α-fluoro-β-keto esters via deprotonation and deacylation in real time. These compounds are precursors of various pharmaceutically active substances. The real-time study revealed the deprotonation and deacylation steps of the reaction. The reaction was studied at temperatures ranging from 293 to 333 K by interleaved one-dimensional ¹H and ¹⁹F and two-dimensional ¹H–¹H COSY experiments. The kinetic rate constants were evaluated using a pseudo first-order kinetic model. The activation energies for the deprotonation and deacylation steps were determined to 28 ± 2 and 63.5 ± 8 kJ/mol, respectively. This showed that the deprotonation step is fast compared with the deacylation step and that the deacylation step determines the rate of the overall reaction. The reaction was repeated three times at 293 K to monitor the repeatability and stability of the system. The compact NMR spectrometer provided detailed information on the mechanism and kinetics of the reaction, which is essential for optimizing the synthetic routes for stepwise syntheses of pharmaceutically active substances.     

火星车载激光诱导击穿光谱仪(MarsCoDe)在轨定标样品选取研究

我国首次火星全球遥感与区域巡视探测任务已获批立项，首个火星探测器也即将前往火星。为满足火星物质成分分析的需求，我国研制了不同类型的火星物质成分分析仪器，其中包括火星表面成分探测仪（MarsCoDe），应用了激光诱导击穿光谱技术（laser-induced breakdown spectroscopy，LIBS）。火星表面覆盖尘埃，探测仪器想要准确获取火星尘埃之下的物质成分，必须剥去尘埃或者进行破坏从而深入岩层取样。LIBS可以用激光烧蚀待测物体表面，获得深部物质光谱信息，在火星表面探测中具有其他仪器无法取代的优势。LIBS在火星探测中几乎适用于探测每一个元素，包括轻元素H，Li，Be，B，C，N，O等，帮助寻找有机物和含水地质过程的证据。由于LIBS在火星环境工作，等离子体的物理性质与地球上完全不同。为了确保火星车载LIBS返回数据的光谱质量，需要对LIBS在着陆后开展在轨定标。借助火星车的携带在轨定标样品，对探测数据进行在轨定标，确保返回数据的可靠性。定标样品的选择是一项十分重要的工作，存在仪器工程条件限制、定标样品类型的代表性、元素成分分布范围、样品稳定性等多种考虑因素，需满足科学任务的同时达到加工工艺要求。总结了国外已有的火星车载LIBS在轨定标的研究进展，重点分析了LIBS在轨定标样品选择依据、国外选择样品的优缺点，并总结经验提出了几点建议，为我国在轨定标工作提供参考。对火星探测数据的正确解译，对未来研究火星的起源、火星的长期地质演变过程等具有重要的科学意义。     

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.     

Study of γ‐Fast Neutron Attenuation and Mechanical Characteristics of Modified Concretes for Shielding and Sheltering Purposes

The study of γ‐neutrons attenuation and mechanical characteristics of modified concrete are vital and crucial parameters for the construction of civilian radiological, nuclear shielding, and/or shelters. In this work, fifteen samples of ordinary concretes with five different additives; steel fibers, polypropylene, silica fume, and fly ash, with variation of cement percentages, were prepared and used for performing the mechanical and radiation attenuation investigations. The compressive strength, tensile strength, slump test, bulk density, and water permeability were also carried out for the prepared concrete mixes. Collimated coherent beams from ⁶⁰Co and Pu‐Be fast neutron sources were used to check the radiation penetrability through the syntheized mixed concrete‐additives. Very sensitive and well calibrated gamma‐neutron pulse shape discriminating spectrometer with its electronic componenets and stilbene organic detector and 3′′ × 3′′ NaI scintillation crystal was used to measure the radiation before and after attenuation and transmission. The integrated fast neutron removal macroscopic cross section (Σ_r) and linear attenuation coefficient of total gamma rays (μ) were calculated for all the analysed concrete mixes. The results of measurements, tests, analyses and calculations are given and explained. The investigated modified concrete mixes show good workability and properties from the view point of mechanical loads and γ‐fast neutrons penetrability and resistance. These results can be used for shielding and sheltering design.