8-氨基喹啉取代苯甲酰胺衍生物对汞离子和铜离子的识别

设计合成了可识别金属离子的荧光传感分子8-氨基喹啉取代苯甲酰胺衍生物,通过核磁共振谱和质谱表征其结构;利用其光谱性质研究了该系列物质对过渡金属离子Cu2+,Hg2+,Pb2+,Zn2+,Ni2+和Cd2+的识别性质,初步探讨了其识别机理。实验表明:在乙腈中,8-氨基喹啉苯甲酰胺的吸收光谱在509nm处对Cu2+有响应,溶液由无色变成红色;而其荧光光谱对Hg2+和Cu2+有良好的选择性,荧光增强倍率分别高达368和192,与金属离子形成结合比为1:1配合物。     

香豆素/Betti碱主体合成及其对铷、钡离子的选择性响应(英文)

合成了一个新型香豆素/Betti碱主体化合物1,并对其进行了结构表征。在乙腈/水溶液中进行主体1和碱金属、碱土金属相关离子(Li+,Na+,K+,Rb+,Cs+,Be2+,Mg2+,Ca2+,Sr2+,Ba2+)的相互作用研究时,发现仅Rb+,Ba2+离子对主体1有敏感的紫外光谱及荧光光谱响应,而其它的碱金属、碱土金属离子无敏感性光响应。紫外光谱显示,Rb+,Ba2+离子使主体1产生明显的红移(ε=4.66×102L·(mol·cm)-1,Δ=91nm),肉眼可观察到明显的由浅黄向橙红色的颜色变化,并使主体1的荧光光谱发生一定程度的猝灭。     

主链含苯并噻唑结构单元聚合物的合成

通过钯催化三键聚合反应,合成了主链含2,1,3-苯并噻唑的聚合物.目标化合物在普通有机溶剂,如二氯甲烷﹑氯仿﹑四氢呋喃中有较好的溶解性,目标化合物的最大吸收波长分别在424 nm和510 nm左右,光敏响应630 nm左右,其估算能隙E_g为1.96 eV,具有作为有机太阳电池材料的应用前景.     

Enhanced aggregation of alginate-coated iron oxide (hematite) nanoparticles in the presence of calcium, strontium, and barium cations

Early-stage aggregation kinetics studies of alginate-coated hematite nanoparticles in solutions containing alkaline-earth metal cations revealed enhanced aggregation rates in the presence of Ca2+, Sr2+, and Ba2+, but not with Mg2+. Transmission electron microscopy (TEM) imaging of the aggregates provided evidence that alginate gel formation was essential for enhanced aggregation to occur. Dynamic light scattering (DLS) aggregation results clearly indicated that a much lower concentration of Ba2+ compared to Ca2+ and Sr2+ was required to achieve a similar degree of enhanced aggregation in each system. To elucidate the relationship between the alginate's affinities for divalent cations and the enhanced aggregation of the alginate-coated hematite nanoparticles, atomic force microscopy (AFM) was employed to probe the interaction forces between alginate-coated hematite surfaces under the solution chemistries used for the aggregation study. Maximum adhesion forces, maximum pull-off distances, and the work of adhesion were used as indicators to gauge the alginate's affinity for the divalent cations and the resulting attractive interactions between alginate-coated hematite nanoparticles. The results showed that alginate had higher affinity for Ba2+ than either Sr2+ or Ca2+. This same trend was consistent with the cation concentrations required for comparable enhanced aggregation kinetics, suggesting that the rate of alginate gel formation controls the enhanced aggregation kinetics. An aggregation mechanism incorporating the gelation of alginate is proposed to explain the accelerated aggregate growth in the presence of Ca2+, Sr2+, and Ba2+.     

两种卟啉化合物在Ag溶胶表面的紫外-可见吸收光谱和表面增强拉曼散射光谱研究

表面增强拉曼散射(SERS)自1974年被Fleischmann等^[1]发现以来,日益受到人们的重视.通过SERS谱图分析,可以获得物质结构及其与基体作用的信息.由于SERS可使拉曼信号增强10⁵~10⁶倍^[2],并且在某些情况下银胶还能使表面吸附质的荧光猝灭^[3,4], SERS常用来检测一些普通拉曼光谱难以检测的样品和考察界面络合物的形成.     

Methylviologen-mediated electrochemical synthesis of silver nanoparticles via the reduction of AgCl nanospheres stabilized by cetyltrimethylammonium chloride

Efficient synthesis of silver nanoparticles stabilized by cetyltrimethylammonium cations (Ag@CTA⁺) is carried out in aqueous medium by methylviologen-mediated electroreduction of silver chloride nanospheres stabilized by surface-active CTA⁺ cations (AgCl@CTA⁺, diameter ~330 nm), on a glassy carbon electrode at potentials of the MV²⁺/MV^?+ redox couple. The nanospheres AgCl@CTA⁺ can be reduced immediately on the electrode at a low rate and the resulting metal is deposited on the electrode. In the mediated reduction, the metal is not deposited on the cathode but the quantitative reduction of AgCl to Ag@CTA⁺ nanoparticles proceeds completely in solution volume at the theoretical charge. In aqueous solution, the nanoparticles are positively charged (electrokinetic (zeta) potential is +74.6 mV), their characteristic absorption maximum is at 423 nm and the average hydrodynamic diameter is 77 nm. Isolated Ag@CTACl nanoparticles have the size of 39 ± 15 nm. The preferential form of metal nanoparticles is sphere with the diameter of 34 ± 24 nm; nanorods are also obtained in small amounts (4%); the average size of metal grains is 8–16 nm.     

纳米α-Fe~2O~3的XANES研究

选择纳米α-Fe~2O~3体系,运用X射线近边吸收谱(XANES)技术对纳米材料进行分析。结果表明,三种尺寸的纳米α-Fe~2O~3样品(颗粒尺寸分别是3nm,10nm和55nm)与粗颗粒商品的氧K边XANES谱的不同之处在于,纳米样品出现了一个新的吸收B峰。研究揭示,该峰可能是纳米α-Fe~2O~3中晶界部分氧的2p-4sp杂化所产生的一个新电子跃迁末态造成的。进一步的研究表明,随着纳米α-Fe~2O~3的粒子尺寸减小,氧的2p轨道和铁的3d轨道杂化增加,主要体现在2p-e~g杂化程度加剧,使得纳米颗粒中铁周围的氧配位八面体畸变程度加强。最后,通过对3nm样品在研磨和不研磨两种制样方式获得的氧K边XANES谱分析,证实纳米粒子体系中存在特殊的协同作用力。     

Ferrocene-based small molecules for dual-channel sensing of heavy- and transition-metal cations

The synthesis, electrochemical, optical, and cation-sensing properties of ferrocene-pentakis(phenylthio)benzene dyads, linked through a putative cation-binding 2-azadiene bridge, are presented. Dyad 5 behaves as a highly selective dual-redox and chromogenic chemosensor molecule for Pb(2+) cations; the oxidation redox peak is anodically shifted (DeltaE(1/2) = 125 mV), and the low energy band of the absorption spectrum is red-shifted (Delta lambda = 119 nm) upon complexation with this metal cation. Linear sweep voltammetry and spectroelectrochemical studies revealed that Cu(2+) and Hg(2+) metal cations induced oxidation of the ferrocene unit. The isomeric dyad 7, in which the nitrogen atom and the ferrocene unit are in closer proximity, has shown its ability for sensing both Pb(2+) and Hg(2+) ions; the oxidation redox peak is anodically higher shifted (DeltaE(1/2) = 340 mV), and the low energy band of the absorption spectrum is lower red-shifted (Delta lambda = 61 nm) that those found for dyad 5. The changes in the absorption spectra are accompanied by dramatic color changes which allow the potential for "naked eye" detection. A further exciting property of dyad 7 is that it behaves as an electrochemically induced switchable chemosensor for Pb(2+) and Hg(2+) because of the low metal-ion affinity of the oxidized 7(*+) species for these metal cations. The experimental data and conclusions about the ion-sensing properties are supported by DFT calculations.     

Synthesis of anisotropic silver nanoparticles and investigation of their sensory properties

A simple procedure has been proposed for synthesis of planar triangular silver nanoparticles. Optimal conditions have been determined for particles to form, and the particles have been characterized by physicochemical methods. The halide-ion-sensory properties of sols of anisotropic silver nanoparticles prepared in different ways have been studied; sensitivity to halide ions is based on the changes in positions and intensities of longitudinal surface plasmon resonance (SPR) peaks in the range 500–800 nm in the optical absorption spectra of solutions.     

Preparation of silver nanoparticles with controlled particle size

Silver colloids show different colors due to light absorption and scattering in the visible region based on plasmon resonance. The resonance wavelength depends on particle size and shape. Here we report chemical reduction methods for preparation of silver nanoparticles exhibiting multicolor in aqueous solutions. Depending on chemical conditions the obtained nanoparticles are different regarding size and morphology.In order to investigate the relationship between size, stability and color of silver colloids we obtained silver nanoparticles in aqueous solutions using different reducing agents. The effect of polyvinyl pyrrolidone (PVP) and polyvinyl alcohol (PVA) on stabilization of obtained silver colloids was investigated. We have also studied the effect of silver precursor and its concentration on the formation of stable silver colloids.UV-VIS spectrum for silver colloids contains a strong plasmon band near 410 nm, which confirms silver ions reduction to Ag° in the aqueous phase. The formation of metal silver was also confirmed by powder X-ray diffraction (XRD) analysis. The diameter size of silver nanoparticles was in the range from 5 nm to 100 nm     

Synthesis and characterization of stable organosols of silver nanoparticles by electrochemical dissolution of silver in DMSO

Stable organosols of silver nanoparticles (AgNPs) without any capping agents have been synthesized by an electrochemical dissolution of a sacrificing silver electrode in dimethyl sulfoxide (DMSO). The peak at 425 +/- 5 nm observed in the UV-vis spectra was attributed to the surface plasmon resonance for silver. The formation of nanoparticles of silver was confirmed by X-ray diffraction analysis (XRD). In TEM, three ranges of particle size were observed, namely, 3.75 +/- 0.8, 6.25 +/- 0.5, and 9.25 +/- 0.3 nm. The correlation among these sizes was explained by a new model based on a droplet coalition. Based on that, sizes correlation fits very well in the empirical formula 5d(1)(3)n' + (3 - n')d(2)(3) = d(3)(3) where d(1), d(2), and d(3) are three sizes of particles and n' is an integer having values 0, 1, 2, 3, .... The sols prepared in DMSO were stable against flocculation for months. An unusual solution stability without any capping agents was attributed to the formation of Ag(I)DMSO complex on particle surface, which was confirmed by FTIR, fluorescence spectroscopy, and thermal analysis.     

Silver and gold glyconanoparticles for colorimetric bioassays

The color changes associated with the aggregation of metal nanoparticles has led to the development of colorimetric-based assays for a variety of target species. We have examined both silver- and gold-based nanoparticles in order to establish whether either metal exhibits optimal characteristics for bioassay development. These silver and gold nanoparticles have been stabilized with a self-assembled monolayer of a mannose derivative (2-mercaptoethyl alpha-d-mannopyranoside) with the aim of inducing aggregation by exploiting the well-known interaction between mannose and the lectin Concanavalin A (Con A). Both metal glyconanoparticles were determined to be ca. 16 nm in diameter (using TEM measurements). Aggregation was observed on addition of Con A to both silver and gold nanoparticles resulting in a shift in the surface plasmon absorption band and a consequent color change of the solution, which was monitored using UV-visible spectrophotometry. Mannose-stabilized silver nanoparticles at a concentration of 3 nM provide an assay for Con A with the largest linear range (between 0.08 and 0.26 microM). Additionally, the kinetic rate of aggregation of the silver-nanoparticle-based bioassay was significantly greater than that of the gold-nanoparticle system. However, in terms of sensitivity, the mannose-stabilized gold-nanoparticle-based assay was optimum with a limit of detection of 0.04 microM Con A, as compared with a value of 0.1 microM obtained for the mannose-stabilized silver nanoparticles. Additionally, a lactose derivative (11-mercapto-3,6,9-trioxaundecyl beta-D-lactoside) was used to stabilize gold nanoparticles to induce aggregation upon addition of the galactose specific lectin Ricinus communis agglutinin (RCA(120)). To examine the specificity of the bioassay, lactose-stabilized gold nanoparticles were mixed with a solution of mannose-stabilized silver nanoparticles to give an aggregation assay capable of detecting two different lectins. When either Con A or RCA(120) was added to the mixed glyconanoparticles, selective recognition of the respective natural ligand was shown by aggregation of a single metal nanoparticle. Centrifugation and removal of the aggregated species enabled further bioassay measurements using the second glyconanoparticle system.     

Aqueous solutions of colloidal nickel: Radiation-chemical preparation, absorption spectra, and properties

Radiation-chemical reduction of Ni²⁺ ions in aqueous solutions of Ni(ClO₄)₂ containing sodium formate or isopropyl alcohol was studied, γ-Irradiation of deaerated solutions in the presence of polyethyleneimine, polyacrylate, or polyvinyl sulfate gives stable metal sols containing spherical particles 2–4 nm in diameter. The optical absorption spectra of nickel nanoparticles exhibit a band with a maximum at 215±5 nm (ε₂₁₅=4.7·10³ L mol⁻¹ cm⁻¹) and a shoulder at 350 nm. A mechanism for the radiation-chemical reduction of Ni²⁺ ions by hydrated electrons and organic radicals (CO₂- radical anions in the case of HCOONa and Me₂C·OH radicals in the case of PrⁱOH). The redox potentials of the Ni²⁺/Ni⁰ and Ni⁺/Ni⁰ pairs (Ni⁰ is a nickel atom) are approximately −2.2 and −1.7 V, respectively. The nanoparticles are readily oxidized by O₂, H₂O₂, and other oxidants. The reactions of these species with silver ions yield relatively stable nanoaggregates containing both nickel and silver in addition to silver nanoparticles. Published inIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 1733–1739, October, 2000.     

双吲哚啉螺吡喃化合物的合成及其酸和金属离子致变色性能

设计、合成了一种新型双吲哚啉螺吡喃化合物1,用核磁、红外及质谱等技术手段表征了其结构。 利用紫外可见吸收光谱研究了化合物1的酸致变色和金属离子变色性能。 结果表明,化合物1能够在氢离子或金属离子的作用下发生可逆的开环与闭环反应。 当氢离子或金属离子加入到化合物1的异丙醇溶液中,溶液颜色从无色变为红色,同时产生460 nm新吸收峰。 进一步加入氢氧根离子或EDTA溶液后,溶液颜色变回无色,460 nm处的吸收峰又消失。 该化合物的酸和金属离子致变色性质在分子传感和离子识别等领域有潜在的应用价值。     

Multifunctional ferrocene-ruthenocene dyads linked by single or double aza-containing bridges displaying metal-metal interactions and cation recognition properties

The synthesis, electrochemical, electronic, and cation sensing properties of the ruthenocene-terminated 2-aza-1,3-butadiene 2, linear ferrocene-ruthenocene dyads 3 and 5, and the new structural motifs diaza[4.4]ruthenocenophane 7 and mixed ferrocene and ruthenocene metallocenophanes 8 and 10 are presented. The properties of these compounds have been systematically varied by introducing the ferrocene and ruthenocene moieties at the 1- or 4-position of the unsymmetrical 2-aza-1,3-butadiene bridge. Spectroelectrochemical studies of compounds 3 and 8, in which the ruthenocene unit appended at the 1-position of the bridge exhibits a rather unusual electrochemical behavior, revealed the presence of low-energy bands in the near-infrared (NIR) region in the partially oxidized forms, at 1070 and 1163 nm, respectively, which indicate the existence of intramolecular charge transfer between the iron and the ruthenium centers. The electrochemical and intermetallic charge-transfer (MMCT) studies (HAB, lambda and alpha parameters) indicate that the 3*+ and 8*+ systems belong to the Class II classification for a mixed-valence compound. In addition, the low-energy (LE) band of the absorption spectra of all compounds prepared, except compound 10, are red-shifted by complexation with divalent Mg2+, Zn2+, Cd2+, Hg2+, and Ni2+ metal ions. For open dyads, biruthenocene compound 2 exhibited the higher red-shift by 92 nm, whereas for closed compounds the [4.4]ruthenocenoferrocenophane 8 displayed a remarkable red-shift by about 180 nm for Zn2+, Cd2+, Hg2+, and Ni2+ metal ions and by about 146 nm for Mg2+ cation. The changes in the absorption spectra are accompanied by dramatic color changes which allow the potential for "naked eye" detection. The experimental data and conclusions are supported by DFT computations.     

Stabilization of copper nanoparticles prepared by reduction from solutions of poly(acrylic acid) complexes with Cu2+ ions and poly(ethylene glycols)

Copper sols are prepared via the reduction of copper ions with hydrazine borane in dilute aqueous solutions of mixtures of the PAA-Cu²⁺ complex and poly(ethylene glycols) of various molecular masses at PEG: PAA = 0.25 base-mol/base-mol and PAA: Cu²⁺ = 10 base-mol/mol in the pH range 4.0–7.0. The stability of sols against oxidation (dissolution) or aggregation (enlargement) of metal nanoparticles is much higher than that of sols prepared in the absence of PEG. With an increase in the initial pH or a decrease in the molecular mass of PEG, the formed copper nanoparticles are much larger (no less than 20 nm in diameter) than copper nanoparticles occurring in the sol prepared in a solution of the PAA double complex with Cu²⁺ ions and high-molecular-mass PEG at a low initial pH (3–10 nm in diameter). Copper nanoparticles in sols prepared in solutions of complexes based on the high-molecular-mass PEG do not aggregate during exposure, thereby indicating the high stability of polymer screens on their surfaces.     

Colorimetric detection of lead (II) based on silver nanoparticles capped with iminodiacetic acid

We report on a colorimetric probe for the determination of Pb(II). It is based on the use of silver nanoparticles that have been functionalizd with iminodiacetic acid (IDA-Ag NPs). The absorption spectrum and solution color of IDA-Ag NPs undergo dramatic changes on exposure to Pb(II) with a new absorption peak appearing at 650 nm and a concomitant color change from yellow to green. This is assumed to result from the aggregation of IDA-Ag NPs induced by Pb(II). Under optimum conditions, there is a linear relationship between the ratio of the absorbances at 650 and 396 nm, respectively, and the concentration of Pb(II) in the 0.4 to 8.0 μM concentration range, with a detection limit of 13 nM. The method was applied to the determination of Pb(II) in tap water and urea samples, and recoveries ranged from 93.7 % to 98.6 %.

Aqueous synthesis of alkanethiolate-protected Ag nanoparticles using Bunte salts

The one-pot synthesis of monolayer-protected metal nanoparticles derived from sodium S-dodecylthiosulfate (Bunte salt) in aqueous solution is described. Silver nanoparticles, which were produced by the borohydride reduction of silver nitrate in H2O, were stabilized by the adsorption of S-dodecylthiosulfate followed by the removal of the SO3- moiety. Temporary stabilization of silver sols by the adsorption of borohydride and borate prevented aggregation of silver nanoparticles in H2O. The syntheses of other metal nanoparticles, including gold, copper, and palladium particles in H2O, were less successful. Gold and copper particles were completely aggregated and precipitated out immediately after the addition of NaBH4, yielding only insoluble clusters. Stable and soluble palladium nanoparticle could be prepared, but the presence of Pd-thiolate complex was also observed. These nanoparticles were characterized using 1H NMR, UV-vis spectroscopy, FT-IR spectroscopy, and transmission electron microscopy.     

Optical properties of sol-gel synthesized calcium doped ZnO nanostructures

Optical properties of Ca doped ZnO nanoparticles prepared at room temperature through wet chemical method have been investigated. X-ray diffraction studies show that particles are crystalline in nature and doping did not induce impurity phases. Optical absorption measurements show an absorption peak at ∼372 nm which is due to excitonic absorption of the ZnO. Photoluminescence studies reveal a broad emission at an excitation wavelength of 335 nm and the bands are attributed to near band edge emission, oxygen vacancies, surface dangling bonds and zinc interstitials. Incorporating Ca²⁺ induces reduction in near band edge emission and there is an enhancement in the oxygen vacancy peaks which are attributed to the shape changes in the nanoparticles.     

Vibrational study of the salicylate interaction with metallic ions and surfaces

Infrared and Raman spectroscopy are used in this work to study the metallic complexes of salicylic acid with silver and copper, comparing the interaction between salicylate and the cations (Ag+ and Cu2+) in the metal complexes with the SERS spectra when adsorbed on colloidal metal surfaces of the same metals. The salicylate complexes with the above metals were compared to those of Na+, Fe3+ and Al3+ cations. A different interaction mechanism is deduced for salicylate in the metal complex and when adsorbed on the metal surface.