9,10-二苯基蒽衍生物的制备及对铜离子上、下转换检测研究

Cu2+是人体正常代谢所必需的微量元素之一,但是过量的Cu2+会造成代谢紊乱,进而诱发各种疾病。长期以来,铜材料的过度使用和后处理不当导致生活环境中的Cu2+浓度超标,成为重金属污染物之一,因此生活环境中Cu2+含量的检测成为人们关注的热点。基于荧光探针的荧光光谱法由于选择性好、灵敏度高等优点被广泛应用于离子检测领域。利用荧光探针分子与待检测离子可发生选择性的弱相互作用,研究者们探索并设计了诸多可用于Cu2+检测的荧光探针。然而普通的荧光探针由于灵敏度较差或选择性不理想等问题缺乏实际应用价值。设计并合成了一种新的化学型荧光探针分子9,10-二(3’-羟基-4’-亚甲胺氨基硫脲苯基)蒽（b-HTPA）。该探针分子通过与Cu2+的络合作用,改变自身的电子排布结构,使得其荧光性能发生显著变化,由此对Cu2+产生灵敏的响应。通过上、下转换荧光光谱来研究b-HTPA对Cu2+检测的各项性能,并结合拟合计算得出最终结果。选择性研究结果表明,相比其他13种金属阳离子,Cu2+对b-HTPA荧光猝灭效果最为显著,空白探针分子荧光与加入Cu2+后的荧光强度比可达150∶1。灵敏性研究结果表明,b-HTPA对Cu2+的最低检测限为2.78×10-7 mol·L-1,远低于中国卫生部《生活饮用水卫生标准》（GB5749-2006）,表现出良好的荧光响应灵敏性和理想的最低检测限。响应时间测试结果表明,b-HTPA与Cu2+在0~2 min时间范围内反应速率最大,并在约10 min后反应完全,说明b-HTPA在对Cu2+检测中可以短时间产生响应,降低实际应用中的检测时间和周期。还使用八乙基卟啉钯（PdOEP）作为光敏剂,以b-HTPA为湮灭剂,利用上转换荧光光谱对b-HTPA/PdOEP/Cu2+体系的灵敏性和检测限进行测试研究。结果表明,探针的上转换荧光强度随着Cu2+浓度的增加而降低,具有良好的响应性,通过拟合计算,得出b-HTPA对Cu2+的检测限为3.78×10-6 mol·L-1,低于《生活饮用水卫生标准》规定的检测下限。设计合成的新型荧光探针分子9,10-二(3-羟基-4-亚甲胺氨基硫脲苯基)蒽对Cu2+具有高选择性、高灵敏度和理想的检测限,且响应速度快,展现了上转换发光在检测领域具有应用潜力。     

HHT时频分析土壤光谱的重金属铜离子污染信息提取模型

土壤中不同浓度Cu2+含量映射到土壤光谱上的信息量十分微弱,并且这些高光谱数据中也存在着难以避免的噪声,因而本研究的关键是如何在土壤光谱复杂的噪声环境中提取微弱Cu2+信息。经验模态分解算法(EMD)能够有效去除高光谱数据中的噪声,且EMD是Hilbert变换对“非线性非稳定”信号时频分析的前提,当引入Huang变换后,可利用Hilbert-Huang变换(HHT)模型时频分析高光谱数据以实现降噪处理与信息提取。通过时频的HHT分析不同浓度Cu2+污染下的土壤光谱,完成从原始光谱经EMD分解出各本征模态函数(IMF)分量的包络线、调制信号和频谱等曲线中挖掘土壤光谱的Cu2+污染信息。研究结果表明,相同浓度Cu2+污染时的土壤光谱HHT时频分析结果相同,不同浓度时则不同,所以也可依据IMF分量反演土壤Cu2+含量。因此,高光谱数据的HHT时频分析能为土壤光谱的信息挖掘、光谱诊断和Cu2+含量反演等提供一种新的方法和思路。     

硫杂杯芳烃基胶束自组装荧光化学传感器制备及其性能研究

以对叔丁基硫杂杯[4]芳烃（TCA）为受体、苝和十二烷基苯磺酸钠（SDBS）分别为荧光体和自组装模板剂,通过在水中的胶束自组装作用制备得到一种新型的“ON–OFF”型Cu2+荧光化学传感器。论文选用荧光猝灭率为考察指标,详细考察了受体TCA用量、自组装模板剂SDBS浓度、Cu2+浓度和共存金属离子等影响因素对胶束自组装荧光化学传感器Cu2+检测性能的影响情况。实验结果表明,当受体TCA与荧光体苝的摩尔浓度比值达到1 000,自组装模板剂SDBS浓度为50 mmol·L-1,该荧光化学传感器对水中铜离子具有较好的检测能力,待测Cu2+浓度在一定浓度范围内与荧光猝灭率呈线性相关。此外,荧光化学传感器的Cu2+检测性能基本不受Pb2+, Cd2+, Mn2+, Na+, K+, Ca2+, Mg2+, Al3+,Ni2+,Zn2+等共存金属离子干扰。该胶束自组装荧光化学传感器对Cu2+的选择性检测性能主要归因于胶束表面活性剂分子层中TCA受体对Cu2+的识别作用,而传感器荧光猝灭主要基于胶束内部的电荷转移或能量转移机制。     

Effect of π-Extended Substituents on Photophysical Properties of BODIPY Dyes in Solutions

Four boron-dipyrrine (BODIPY) based dyes with π-extended substituents in 8-position of dipyrrin ligand have been synthesized and characterized. Photophysical properties of the obtained compounds have been investigated in different individual solvents. Deposits of solvent polarity and viscosity were evaluated. BODIPY with 8-biphenyl substituent was found to be the fluorescent molecular rotor in contrast to more extended substituents. The complex nature of solvent-solute interactions leads to the poor applicability of standard multiparameter approaches to BODIPY solvatochromic properties. Fluorescence intensity was found to increase in case of solvent polarity growth, it is not typical for BODIPY. Taking that into account the BODIPY with π-extended substituents could be used for fluorescence viscosity measurements, and as the fluorescent media polarity indicators in analytical chemistry and biochemistry.     

设计合成亚胺类化合物用于金属阳离子逻辑门识别及双控荧光分子开关构建

报道了首次设计合成希夫碱还原产物N,N-双(4-甲氧基苯)乙基-1,2-二胺受体分子L.通过考察L与12种金属阳离子作用时的荧光性质变化,发现Cu2+和Fe3+对L有显著的荧光猝灭作用,Zn2+和Cd2+对L有明显的荧光增强作用;因此可构建受体分子L对两对金属阳离子的"OR"逻辑门作用关系,形成逻辑识别体系.测定了Zn...     

污泥生物淋滤过程中黄铁矾对重金属离子的吸附与共沉淀作用的模拟研究

生物淋滤处理可加速污泥中重金属(Zn,Cu和Cr)的溶出。但在淋滤后期,约有31%的已溶出的Cu2+被重新固持。并且,Cu2+浓度的再次下降与Fe3+沉淀形成黄铁矾的反应在时间上具有同步性。为阐明Cu2+固持机理,文章利用氧化亚铁硫杆菌的生物催化氧化作用,模拟生物淋滤环境在纯体系合成了黄铁矾。吸附试验表明,在pH 2.0～2.5的范围内(污泥生物淋滤过程中重金属溶出范围),黄铁矾对10 mg·L-1 Cu2+(该浓度与供试污泥生物淋滤中的Cu2+浓度相近)的吸附率低于9%,不能完全解释Cu2+的重新固持现象。共沉淀试验表明,Cu容易与黄铁矾形成共沉淀而掺入矿物的晶格。当Cu2+为10 mg·L-1时,约有44.6%的Cu2+与黄铁矾产生共沉淀而进入固相。可以认为,Cu与黄铁矾的共沉淀效应,是导致污泥生物淋滤后期Cu2+浓度再次下降的主要原因,黄铁矾对Cu2+的吸附只起极小的作用。     

铜铅胁迫下玉米叶片弱光谱信息的LD-CR-SIDSCAtan探测模型

农作物在受到重金属污染以后,会破坏本身的组织细胞结构和叶绿素含量,从而影响农作物的新陈代谢和健康状况。人和动物如果食用了污染的农作物以后,会有致命的伤害。高光谱遥感目前被广泛应用于监测农作物受重金属污染的程度。重金属污染下的农作物叶片的光谱变化很微小,传统的监测方法和常规的光谱特征参数很难将光谱之间的微弱差异区别开,目前高光谱遥感应用是研究的重点和难点。通过设置不同浓度的Cu2+和Pb2+胁迫下玉米盆栽实验,采集玉米叶片的光谱数据、叶绿素的相对含量以及重金属Cu2+和Pb2+的相对含量。提出了包络线去除(CR)、光谱相关角(SCA)、光谱信息散度(SID)以及正切函数(Tan)和兰氏距离(LD)相结合的LD-CR-SIDSCA_tan模型,将其与传统的光谱测度方法,如光谱相关系数(SCC)、光谱角(SA)、光谱角正切(DSA)、光谱信息散度-光谱相关角正切(SIDSAM_tan)、光谱信息散度-光谱梯度角正切(SIDSGA_tan)和常规的光谱特征参数,如红边最大值(MR)、绿峰高度(GH)、红边一阶微分包围面积(FAR)、红边一阶微分曲线陡峭度(FCDR)、蓝边(DB)、红谷吸收深度(RD)相比较,验证了该模型的优越性和可行性。并且将LD-CR-SIDSCA_tan模型应用于不同浓度下Cu2+和Pb2+胁迫的玉米叶片的整体波形和子波段的光谱差异信息的测度上。结果表明,LD-CR-SIDSCA_tan模型实现了重金属Cu2+和Pb2+污染的定性分析,能够测度光谱相关系数达到0.99以上的相似光谱之间的差异信息,波形差异信息与叶片测得的叶绿素相对含量和重金属Cu2+和Pb2+相对含量显著相关,也分别找到了重金属Cu2+和Pb2+胁迫下的光谱响应波段。在测度光谱数据的整个波段区间范围,模型值为负值时的光谱差异要比模型值为正值更加明显;在模型值为正值时,如果数值越大,光谱的差异性也越大。因此,随着重金属Cu2+和Pb2+浓度的增加,光谱的差异增大,意味着重金属Cu2+和Pb2+污染程度更为严重;玉米植株受到重金属Cu2+胁迫污染,在测度光谱数据的局部子波段区间范围时,“蓝边”、“红边”、“近谷”、“近峰B”处对重金属Cu2+胁迫污染响应特别的敏感,可以作为监测重金属Cu2+污染程度的有效波段;当玉米植株受到重金属Pb2+胁迫污染时,在“紫谷”、“蓝边”、“黄边”、“红谷”、“红边”、“近峰A” 处对重金属Pb2+胁迫污染响应特别的敏感,可以作为监测重金属Pb2+污染程度的有效波段。最后通过LD-CR-SIDSCA_tan模型的应用结果与玉米叶片中Cu2+和Pb2+含量进行线性拟合分析,从而反演和预测了重金属Cu2+和Pb2+对玉米植株的污染程度。     

基于功能化的金纳米的共振瑞利散射方法手性识别肉碱对映体

一种不经分离而同时测定手性对映体的简便方案是非常有趣和有用的.提出一种基于共振瑞利散射(RRS)光谱技术手性识别新方法,利用功能化的金纳米粒子(Au NPs)同时检测肉碱对映体.Au NPs的RRS强度很弱,但当Cu2+存在时,RRS强度显著增加.更有趣的是,肉碱对映体均可以降低Cu2+-Au NPs体系的RRS强度,但D-肉碱使RRS降低更多.在最优实验条件下,均有良好的线性关系并有很好的相关系数以及较低的检出限.由此,这种方法可以计算出肉碱对映体的对映体比率和对映体分数.并应用于胶囊样品中肉碱对映体混合物手性识别的研究.该方法不需要复杂的手性修饰处理,并具有简捷低消耗、灵敏度高、选择性好等优点.     

溴化5-［4-(2-吡啶-乙氧基)苯基］-10，15，20-三苯基卟啉对铜离子的显色反应研究

本文研究了溴化 5- [4 - ( 2 -吡啶 -乙氧基 )苯基 ]- 10 ,15,2 0 -三苯基卟啉与 Cu2 +的显色反应条件 ,在 p H=4 .0时 ,其络合物最大吸收波长为 4 13nm,试剂最大吸收波长为 4 4 3.5nm。对比度大约为 30 nm。试剂与铜络合比为 1∶ 1,其络合物表观摩尔吸光系数为 3.4× 10 5L·mol-1· cm-1,铜含量在 0— 0 .5μg/ 10 m L范围内符合比耳定律 ,本研究可用于痕量铜的测定     

Scaling properties of azimuthal anisotropy in Au+Au and Cu+Cu Collisions at sqrt[s NN]=200 GeV

Differential measurements of elliptic flow (v2) for Au+Au and Cu+Cu collisions at sqrt[sNN]=200 GeV are used to test and validate predictions from perfect fluid hydrodynamics for scaling of v2 with eccentricity, system size, and transverse kinetic energy (KE T). For KE T identical with mT-m up to approximately 1 GeV the scaling is compatible with hydrodynamic expansion of a thermalized fluid. For large values of KE T mesons and baryons scale separately. Quark number scaling reveals a universal scaling of v2 for both mesons and baryons over the full KE T range for Au+Au. For Au+Au and Cu+Cu the scaling is more pronounced in terms of KE T, rather than transverse momentum.     

悬浮液进样-原子吸收法测定中药材中铜、锌、铁

本文提出了一种悬浮液进样－火焰原子吸收法测定中药材－－怀药（怀山药、怀牛膝、怀菊花）的新方法。并成功地进行了Cu,Zn,Fe的测定。将粉碎后的怀药悬浮于琼脂胶体中制成悬浮液，对悬浮剂的选择及化不干扰的消除进行了考察。将试液喷入空气－乙炔火焰中，用标准加入法测定，结果与HNO3＋H2SO4＋HClO4处理法一致。t检验结果表明：两种样品处理方法之间无显著性差异，可以采用悬浮液进样法取代HNO3＋H2SO4＋HClO4处理法，该方法快速简便、安全，有效，结果令人满意。     

Φ Meson Production in Heavy Ion Collisions at RHIC

We present Φ meson production in Cu+Cu and Au+Au collisions measured by the STAR experiment at RHIC.The hadronic decay mode Φ→K~+K~- is used in the analysis.The yields for Φ meson in Cu+Cu and Au+Au collisions at a given beam energy are scaled by the number of participant.The N_(part) normalized Φ meson yields in heavy ion collisions over those from p+p collisions are larger than 1 and increase with collision energy.These results suggest that the source of enhancement of strange hadrons is related to the formation of a dense medium in high energy heavy ion collisions and can not be only due to canonical suppression of their production in smaller systems.We also present STAR results on the Φ meson elliptic flow υ_2 from 2~(1/SNN)=200 GeV Cu+Cu at RHIC.The elliptic flow in Cu+Cu system that has the similar relative magnitude and qualitative features as that in Au+Au system.The observations imply the hot and dense matter with partonic collectivity has been formed in heavy ion collisions at RHIC.However,eccentrality normalized υ_2,υ_2/(n_qε_(part)) is lower for Cu+Cu than for Au+Au collisions at 200 GeV.So this might indicate thermalization has not been reached in 200 GeV Cu+Cu collisions.     

Cu/CeO2(110)界面特性的第一性原理研究

Cu-CeO₂体系因其特殊的催化能力而在固体氧化物燃料电池和水煤气转化反应等多个催化领域有重要应用. 采用基于密度泛函理论的第一性原理方法, 在原子和电子层面上系统地研究了单个Cu原子及Cu小团簇在CeO₂(110)面上的吸附构型, 价键特性和电子结构, 结果表明: 1) 单个Cu原子的最稳定吸附位是两个表面O的桥位; 2) Cu团簇的稳定吸附构型为扭曲的四面体结构; 3) Cu原子及Cu团簇的吸附在CeO₂(110)面的gap区域引入了间隙态, 这些间隙态主要来自于Cu及其近邻的O和表层还原形成的Ce³⁺, 间隙态的出现表明Cu的吸附增强了CeO₂(110)表面的活性; 4) 吸附的单个Cu原子及Cu团簇分别被CeO₂(110)面表层的Ce⁴⁺离子氧化形成了Cu^δ+和Cu₄^δ+, 并伴随着Ce³⁺离子的形成, 这个反应可归结为Cu_x/Ce⁴⁺→Cu_x^δ+/Ce³⁺; 5) Cu团簇的吸附比Cu单原子的吸附引入了更多的Ce³⁺离子, 进而形成了更多的Cu^δ+-Ce³⁺催化活性中心. 结合已报道的Cu/CeO₂(111)界面特性, 更加全面地探明了Cu与CeO₂(111)和(110)两个较稳定低指数表面的协同作用特性, 较为系统地揭示了Cu增强CeO₂催化特性的原因及Cu与CeO₂协同作用的内在机理. 关键词： 2')" href="#">Cu/CeO₂ U')" href="#">DFT+U 吸附 电子结构     

Photoswitchable Near‐Infrared‐Emitting Boron‐dipyrromethene (BODIPY) Nanoparticles

The reversible photoswitched near‐infrared‐(NIR)‐emitting Boron‐dipyrromethene (BODIPY) containing nanparticles are reported. Dithienylethene derivatives are used as the photochromic unit in the nanoparticle to control the on and off of fluorescence BODIPY molecules. As a result, it is demonstrated that these nanoparticles conduct robust reversible modulation of the NIR fluorescence in vitro and in the cell culture with negligible toxicity. This study may offer a new approach to the use of these nanomaterials for numerous photonic and biophotonic applications.     

Formation processes of CuCl and regenerated Cu crystals on bronze surfaces in neutral and acidic media

The paper is devoted to investigating the formation of CuCl and regenerated Cu crystals on bronze. Electrochemical behaviour of bronze in simulated anoxic edaphic media and occluded cell (O.C.) solutions was studied with cycle voltammetry (CV) and X-ray diffraction (XRD). Within potential range of −800 to +800 mV, oxidation occurred was largely a process in which Cu is oxidized to CuCl and the reduction process was a reverse of it. An atomic force microscopy (AFM) was used to observe the morphology of CuCl crystals, regenerated Cu crystals and corrosion interface at nm level. The deposition of regenerated Cu on simulated archaeological bronzes was simulated under experimental conditions for the first time. CuCl could be thoroughly reduced to pure Cu if reduction time interval were sufficiently prolonged. This provided a theoretical and experimental basis for getting rid of harmful CuCl patina from archaeological bronzes with electrochemical means.     

Cu/SiO_2及Cu-NaCl/SiO_2催化剂的原位紫外激光诱导发光光谱研究

本文采用原位激光诱导发光光谱对Cu/SiO2催化剂和经过NaCl修饰后的Cu-NaCl/SiO2催化剂中Cu物种的价态和所处环境对其影响展开研究。原位表征结果表明:通过改变催化剂的处理气氛,激光诱导发光光谱灵敏地给出了不同价态的Cu物种的电子态信息。出现在562nm处被归属为Cu+-Cu+二聚体的光致发光带由于NaCl的加入位移到574nm,这可能是Na+和Cl-的静电作用引起。     

黄腐酸络合铜离子光谱学特征及机理构建

二价金属离子C u2+在很多工矿企业周围水源及土壤中存量超标,造成生态环境恶化,传统的药剂及生物处理容易产生二次污染.黄腐酸由性质相似分子团簇构成,具有水溶性好、络合作用强及化学活性高的特点,对环境中C u2+分布、迁移和生物利用度可以实现高效控制与环保处理,是近年科学研究热点.现代多光谱表征分析有助于揭示黄腐酸与金属...     

氧化偶氮苯双席夫碱化合物对Cu~(2+)的比色识别

为得到简便地识别Cu~(2+)的传感器,设计合成了氧化偶氮苯双席夫碱化合物。采用紫外吸收光谱法研究了化合物对Cu~(2+)的配合作用及对As~(3+)、Mo~(6+)、Mn~(2+)、Zn~(2+)、Fe~(3+)、Pb~(2+)、Al~(3+)、Hg~(2+)、Ni~(2+)、Pt~(4+)、Mg~(2+)、Be~(2+)、Sr~(2+)、Cs+、Os4+、Cd~(2+)、Se~(4+)、Cr~(6+)、Co~(2+)、Rb+、Ba~(2+)、V6+、Ca~(2+)等23种金属离子的干扰作用。采用等摩尔的连续变化法(Job-plot),研究了化合物与Cu~(2+)形成配合物的配比。用红外光谱法研究了配合机理。同时研究了在EDTA存在时,化合物对Cu~(2+)的"off-on"性质。结果表明,合成的化合物具有大共轭体系,结构新颖且稳定。化合物可以克服23种金属离子的干扰,对Cu~(2+)的选择性很高。化合物与Cu~(2+)形成1∶1型强发光配合物,可以达到比色(裸眼)识别。在1.32~13.0μmol·L~(-1)范围内,化合物紫外光谱吸光度值与Cu~(2+)浓度呈现良好的线性关系,线性范围宽,最低检出限为2.6×10-7mol·L~(-1)。在EDTA存在时,该配合物释放出Cu~(2+),表现出对Cu~(2+)的"off-on"模式,红外光谱法研究明确了化合物与Cu~(2+)的结合位点。研究结果表明,所合成的氧化偶氮苯双席夫碱化合物可以对Cu~(2+)实现简便易行的比色(裸眼)识别。     

Synthesis and Properties of Meso-unsubstituted 3-Pyrrolyl Boron Dipyrromethene

We report the synthesis of meso-free 3-pyrrolyl boron dipyrrin (3-pyrrolyl BODIPY) and fully unsubstituted meso-free boron dipyrrin (parent BODIPY) in one pot under simple reaction conditions by treating meso-free dipyrromethane with pyrrole in CHCl₃ followed by oxidation with DDQ, neutralization with triethylamine and complexation with BF₃.OEt₂. The compounds were separated by column chromatography on silica and isolated in 6–10 % yields. The compounds are characterized by HR-MS mass, NMR, absorption, electrochemical and fluorescence techniques. The meso-free 3-pyrrolyl BODIPY exhibit red shifted absorption and emission bands compared to meso-free BODIPY. The meso-free BODIPY exhibit green fluorescence and meso-free 3-pyrrolyl BODIPY exhibit orange fluorescence in solution. Furthermore, compared to meso-phenyl 3-pyrrolyl BODIPY, the meso-free 3-pyrrolyl BODIPY is more strongly fluorescent with nearly 41 % increase in quantum yield. Electrochemical studies showed that meso-free 3-pyrrolyl BODIPY exhibit one irreversible reduction and one ill-defined oxidation indicating that the compound is not stable under redox conditions. Computational studies revealed that meso-free pyrrolyl BODIPY has reduced HOMO-LUMO gap compared to parent meso-free BODIPY. Furthermore, the meso-free 3-pyrrolyl BODIPY exhibit much higher quantum yield compared to meso-aryl analogue of 3-pyrrolyl BODIPY.      

New insights into the colour origin of archaeological Egyptian blue and green by XAFS at the Cu K‐edge

New results on the local chemical environment of Cu²⁺ in archaeological Egyptian blue and green and also modern Egyptian green were obtained by x‐ray absorption fine structure (XAFS) analysis. The information is essential for the understanding of the colouring mechanisms in both pigments. In a previous study, a clear physico‐chemical characterisation of Egyptian blue and green was achieved using a complementary analytical approach with ancient and modern synthesized pigments. Electron microscopy (SEM–EDX and TEM), x‐ray diffraction and micro‐Raman and UV–visible spectroscopy were used to gain information about the conditions of the ancient Egyptian fabrication processes and permitted the clear distinction of both pigments. However, the exact colouring mechanisms could not be elucidated by these methods. Different Cu‐bearing amorphous and crystalline phases were found in both pigments. These phases should be at the origin of the blue and turquoise colours. Using XAFS data at the Cu K‐edge, new insights into the origin of the colouring mechanisms of both pigments could be obtained from the precision of the Cu speciation. In Egyptian blue, Cu²⁺ is mainly allocated in a square‐planar site in a crystalline cuprorivaite phase, whereas in Egyptian green, Cu²⁺ is basically situated in a distorted octahedral site in an amorphous phase. Copyright © 2006 John Wiley & Sons, Ltd.