碳点在鲁米诺和草酸酯化学发光体系中的研究进展

作为一种无需光、热、声、电、磁激发的自发光现象,化学发光已经在化学分析检测、冷光源、生物成像等领域得到了广泛应用。对于多数化学发光体系而言,其化学发光性质不仅取决于化学反应的底物,更与化学反应中使用的催化剂和发光中间体相关。碳点是一种新型的零维发光碳纳米材料,以其优异的物理化学性质和丰富的结构形貌已在各种化学发光体系中获得了广泛的应用。本文主要从鲁米诺和过氧草酸酯两种常见化学发光体系出发,总结了碳点在鲁米诺和过氧草酸酯化学发光体系中的相关研究进展,探讨了碳点在鲁米诺和过氧草酸酯基化学发光中可能存在的作用机制,以及碳点在鲁米诺和过氧草酸酯化学发光体系中的相关应用。为合成具有特定化学发光性能的纳米材料提供思路,有望推动化学发光纳米材料的进一步发展。     

场致发光ZnS:Er~(3 )薄膜的激发机理

在掺杂稀土离子的ZnS薄膜中,其发光中心为电场所激发的机理,过去认为可能有以下两种:(1)经由热电子直接碰撞激发;(2)基质晶格的碰撞离化产生了电子空穴对,继而发生从电子空穴对到发光中心的能量谐振迁移。 最近,Krupka证实了在ZnS:Tb~(3 )薄膜中的场致发光是由热电子直接碰撞而发生的。他观测了作为加在ZnS:Tb~(3 ),Ta_2O_5多层结构上的外加电压函数的荧光强度比     

高电荷态离子N6+与He原子碰撞激发过程的实验研究

利用电子迴旋共振(ECR)多电荷离子源产生的高电荷态离子束和LHT-30VUV真空紫外单色仪,对N⁶⁺与He碰撞激发过程进行研究,观察到三种碰撞激发过程:(1)单电子俘获;(2)双电子俘获;(3)入射离子直接激发过程。 关键词：     

ZnS中Er3+的正向注入电致发光

已报导的三价稀土离子(RE3+)和二价锰离子发光的电致发光器件,都是激发机理为碰撞激发的高场发光器件[1,2]。我们研究了znS:RE2+的带边激发光谱,由此提出了实现正向注入下三价稀土离子电致发光的发光器件的设想,这种器件的必要条件是在存在三价稀土离子的区域同时注入电子和空穴。在离子注入的ZnS:Er3+发光二极管上观察到了这种发光,实验证明不是碰撞激发,而是正向注入产生的发光。     

Er3+:Yb3+共掺杂氟氧混合物玻璃的上转换发光研究

制备了化学配方为 (5 0 -x)GeO2 ·PbF2 ·WO3·(6 +x)CdF2 ·1 4Yb2 O3·0 6Er2 O3(x =10 ,2 0 ,30 )氟氧混合物玻璃。研究了 930nm发光二极管激发下Er3+ :Yb3+ 共掺杂情形下的Er3+ 离子的上转换发光特性 ,观测到了Er3+ 离子中心波长位于 5 4 3,5 5 0和 6 5 5nm处的三个强荧光发射带。通过对样品的反斯托克斯喇曼光谱的测量 ,确定了基质的最大声子能量 ,在此基础上分析了上转换荧光的产生机制。利用基质的平均电负性差和平均阳离子场强这两个参数 ,讨论了基质材料中GeO2 和CdF2 含量的调整对上转换发光的影响。     

闪烁晶体的发光研究进展

概述了近年来闪烁体发光研究的进展,主要介绍用于未来高能物理实验的新型闪烁体发光机理研究,选取我们在研BaF₂,BaF₂:RE,CeF₃以及PbWO₄中的一些新进展。重点谈及三点:(1)在BaF₂的“价带^→芯带”跃迁发光研究基础上进行稀土(Gd³⁺-Eu³⁺)掺杂时观察到的量子剪裁以及对多光子发光的新思考;(2)CeF₃晶体发光的级联能量传递中,Ce³⁺(290nm发射带)与缺陷发光中心(340nm发射带)间能量传递及其传递效率的温度依赖;(3)PbWO₄晶体的发光中心研究中,提出以“WO₄^-2+O_i”绿光中心替代“WO³+F”中心观点的依据。同时也简介了医用闪烁体的最新进展。     

稀土硫氧化物固溶体在X射线激发下的发光与应用

本文用稀土氧化物高温硫化法合成了(Y1-xLax)2O2S:Tb(0.002)、(Y1-xGdx)2O2S:Tb(0.002)和(Gd1-xLax)2O2S:Tb(0.002)三个二元稀土硫氧化物固溶体体系.研究了在X射线下激发它们的发光亮度、发射光谱.研究了激活剂Tb3+离子浓度对体系发光的影响.在上述实验的基础上,选择了其中的几种发光材料,研制出X射线增感屏,测定了屏的技术参数。     

甲磺酸帕珠沙星的铽增敏化学发光法测定

甲磺酸帕珠沙星(PM)与Tb3+容易结合形成配合物Tb3+-PM,该配合物通过能量转移反应对KMnO₄-Na₂SO₃这一弱化学发光体系有很强的增敏作用。据此,结合流动注射技术建立了稀土敏化化学发光测定PM的新方法。在最佳试验条件下,PM的浓度与增强的化学发光强度在0.10 ～12 mg·L-1范围内呈良好的线性关系,方法的检出限是0.04 mg·L-1,对1.0 mg·L-1的PM进行11次平行测定,相对标准偏差RSD为1.9%。用于测定注射液和体液中PM的含量,方法简单、快速、灵敏、重现性好,分析结果令人满意。实验对该化学发光体系(KMnO₄-NaSO₃-Tb3+-PM)的发光机理进行了探讨。     

TFEL器件亮度波形的快速过程

研究了TFEL亮度波形的上升与衰减过程,发现除一般的直接碰撞激发外,在发光中心的离导带较近的能级跃迁的发光中还存在另一种非常快的发光过程.通过分析ZnS:Er³⁺、Tin³⁺、Ce³⁺+Nd³⁺等不同样品,我们认为这种快过程属于导带中的慢电子与离化了的发光中心的复合.     

稀土掺杂碱土金属硫化物晶体中的载流子俘获中心

研究了典型红外激励发光材料XS:Ra,Sm(X=Sr,Ca;Ra=Ce,Eu)的激励发光过程中电子与空穴的俘获中心及其转移过程,通过激发前后的红外吸收光谱的差异及吸收差与光激励谱的细微结构说明,电子俘获中心并不是Sm³⁺离子,但与Sm³⁺离子处于相邻的空间位置关系,Sm³⁺离子在载流子俘获与复合的过程中也没有发生价态或数量的变化,进一步的EPR谱研究表明Eu²⁺离子的价态在激发前后也没有发生变化。与共价性强的Ⅲ-Ⅴ族半导体晶体不同的是,在这类离子性较强的晶体中,载流子被杂质所引起的晶格缺陷而非杂质本身俘获。在多种发光中心的情况下,不同的激发波长可以使空穴束缚在不同的发光中心附近,随后产生不同的光激励发光。     

Microwave-Triggered Metal-Enhanced Chemiluminescence (MT-MEC): Application to Ultra-fast and Ultra-sensitive Clinical Assays

In this rapid communication we describe a new approach to protein detection with chemiluminescence. By combining common practices in protein detection with chemiluminescence, microwave technology, and metal-enhanced chemiluminescence, we show that we can use low power microwaves to substantially increase enzymatic chemiluminescent reaction rates on metal substrates. As a result, we have found that we can in essence trigger chemiluminescence with low power microwave (Mw) pulses and ultimately, perform on-demand protein detection assays. Using microwave triggered metal-enhanced chemiluminescence (MT-MEC), we not only improve the sensitivity of immunoassays with enhanced signal-to-noise ratios, but we also show that we can accurately quantify protein concentrations by integrating the photon flux for discrete time intervals.     

Forty years of the Staebler–Wronski effect

This article describes highlights of investigations of the Staebler–Wronski effect (SWE), observed in hydrogenated amorphous silicon since its discovery. Some of the basic characteristics of SWE are discussed along with some solved and unsolved puzzles. Particular emphasis is given to a recent model based on long-range potential fluctuations caused by heterogeneities present in the films. Evidence is reviewed for the presence of several kinds of dangling-bond defects produced by light exposure (hv?>?1.3?eV) at different temperatures between 4.2 and 360?K. With exposure at lower temperature the defects become less stable, but they possess larger recombination cross-sections. Voids in the material have been identified as the location for light-induced defects most harmful to the efficiency of solar cells. Ways to eliminate them are discussed. We suggest that progress in this field was delayed by lack of sample sharing among laboratories.     

A solid-state electrochemiluminescence biosensing switch for detection of DNA hybridization based on ferrocene-labeled molecular beacon

A solid-state electrochemiluminescence (ECL) biosensing switch incorporating quenching of ECL of ruthenium(II) tris-(bipyridine) (Ru(bpy)₃²⁺) by ferrocene (Fc) has been successfully developed for DNA hybridization detection. The important issue for this biosensing system is based on the ferrocene-labeled molecular beacon (Fc-MB), i.e. using the special Fc-MB to react with the target DNA and then change its structure, resulting in an ECL intensity change. Under the optimal conditions, the difference of ECL intensity before and after the hybridization reaction (ΔI_ECL) was linearly related to the concentration of the complementary sequence in the range of 10 fM-10 pM and the detection limit was down to 1.0 fM.     

Photoconductivity in polyacetylene

The results of steady state photoconductivity experiments on cis- and trans-(CH)_x are interpreted in terms of charged solitons, photogenerated either directly (threshold hv = 4Δ/π) or indirectly through coupling of the lattice to electron-hole pair excitations (hv ? 2Δ). The transient photocurrent, after laser pulse excitation, decays as a power law, I(t) ? t^?0.6, suggesting dispersive transport of the photogenerated carriers.     

Electrogenerated chemiluminescence of benzo 15‐crown‐5 derivatives

Novel electrogenerated chemiluminescence (ECL) reagents C1 , C2 , and C3 with high fluorescence quantum yields bearing 15‐crown‐5 moiety have been synthesized and characterized. The photophysical, electrochemical, and ECL characters of these compounds have been studied in a 1:1 (v/v) PhH/MeCN mixed solvent. The ECL intensity is enhanced distinctly with the increase in the fluorescence quantum yield. Their ECL behaviors have been studied using annihilation and co‐reactant methods (tri‐n‐propylamine (TPrA) was used as a co‐reactant), respectively. The stable ECL emissions of compounds C1 – C3 can be ascribed to the typical and simple monomer ECL emission via S‐route. Copyright © 2008 John Wiley & Sons, Ltd.     

Electrogenerated chemiluminescence of luminol at a carbon nanotube-perfluorosulfonate polymer (Nafion) modified gold electrode

A multi-wall carbon nanotube/Nafion modified gold electrode (CNT/Nafion/GE) was fabricated by casting the composite film on the electrode surface. Electrogenerated chemiluminescence (ECL) of luminol at the modified gold electrode was studied under conventional cyclic voltammetry in alkaline Na₂CO₃-NaHCO₃ buffer solution. Three ECL peaks were obtained. The most strong ECL peak (ECL-1) was enhanced about 20-fold at the CNT/Nafion modified gold electrode compared with that at the bare gold electrode. The emitter of all the ECL peaks was indentified as 3-aminophthalate. The intensities of ECL peaks were found to depend on the ratio of CNT/Nafion, the electrolytes, the pH, and the presence of O₂ and N₂. The mechanisms of all ECL peaks have been proposed. The results indicate that carbon nanotubes have a significantly catalytic effect on luminol ECL, which might further expand the analytical application of nanomaterial-modified electrode in the field of electrogenerated chemiluminescence.     

Theoretical study of keto–enol tautomerism by quantum mechanical calculations (the QM/MC/FEP method)

In this study, the tautomeric equilibrium between the keto and enol forms has been studied for five typical ketones and aldehydes: i‐butanal, acetaldehyde, acetone, acetylacetone, and dimedone. The level of theory used in the gas‐phase calculation was Becke, three‐parameter, Lee–Yang–Parr/6‐311G(d,p)//Becke, three‐parameter, Lee–Yang–Parr/6‐31G(d). The free energies of solvation were included in the calculation by using the free‐energy perturbation method based on Monte Carlo simulation, that is, the quantum mechanical/Monte Carlo/free‐energy perturbation method. Three different models, incorporating no‐water, one‐water, and two‐waters, were adopted. The results showed that in the gas phase the addition of water molecules to the reaction mechanism caused the activation barriers (ΔG^?_gas) to decrease by half relative to the water‐free mechanism, but there was no effect on the relative difference in free energy, ΔG_gas. The solvation effects (ΔG_sol), based on quantum mechanical/Monte Carlo/free‐energy perturbation calculations, were added to those of the gas‐phase results of the one‐water and two‐waters models. The two‐waters model produced values that were very consistent with the experimental data for all of the tautomers. The differences in the relative Gibbs free energy (ΔG_rxn) were less than 1.0 kcal mol^–1. In summary, the inclusion of solvent molecules in gas‐phase calculations plays a very important role in producing results consistent with experimental data. Copyright © 2012 John Wiley & Sons, Ltd.     

Concept of a spectrometer for resonant inelastic X‐ray scattering with parallel detection in incoming and outgoing photon energies

A spectrometer for resonant inelastic X‐ray scattering (RIXS) is proposed where imaging and dispersion actions in two orthogonal planes are combined to deliver a full two‐dimensional map of RIXS intensity in one shot with parallel detection at incoming hv_in and outgoing hv_out photon energies. Preliminary ray‐tracing simulations with a typical undulator beamline demonstrate a resolving power well above 11000 with both hv_in and hv_out near 930 eV, with a vast potential for improvement. Combining this instrument – nicknamed hv² spectrometer – with an X‐ray free‐electron laser source simplifies its technical implementation and enables efficient time‐resolved RIXS experiments.     

The temperature dependence of the edge emission of GaSe single crystals at high excitation levels

The temperature dependence of five edge emission lines of GaSe at high excitation levels has been investigated by using the second harmonic of a neodymium-glass laser. The following lines were indentified at 77.3K:hv_B = 2.102 ± 0.002 eV, annihilation of free excitons; hv_C = 2.082 ± 0.003 eV, Auger recombination of free excitons; hv_D = 2.072 ± 0.003 eV and hv_E = 2.055 ± 0.004 eV, annihilation of free excitons with emission of optical phonons (LO₁ = 31 meVandLO₂ = 45 meV, respectively); hv_G = 2.036 ± 0.004 eV, radiative recombination at indirect transition with emission of LO₁ phonons.     

Mechanistic study of the unimolecular decomposition of 1,2‐dioxetanedione

The unimolecular decomposition of 1,2‐dioxetanedione, the high‐energy intermediate of the chemiluminescence peroxyoxalate reaction, was studied by theoretical means for the first time. Our calculations have provided results in line with the experimental data regarding this compound. 1,2‐Dioxetanedione decomposes due to a step‐wise biradical mechanism. In the biradical region of the decomposition path, there is a path for singlet chemiexcitation. Interactions between the singlet ground and excited states with triplet states can explain the weak unimolecular chemiluminescence of 1,2‐dioxetanedione. Copyright © 2013 John Wiley & Sons, Ltd.