CdTe量子点荧光猝灭法测定微量铅

以CdTe量子点作为荧光探针,基于荧光猝灭法对铅进行了定量检测,考察了缓冲溶液体系、量子点浓度、反应时间等多种因素的影响。实验结果表明,在pH 7.5的0.2mol/L Na2HPO4-NaH2PO4缓冲液中,反应时间为10min,铅浓度为2.0×10-6—3.5×10-5mol/L范围时,其线性回归方程为ΔF=26.35+11.47C(×10-6mol/L),相关系数和检出限分别为0.9991和1.8×10-8mol/L。该方法灵敏度高,为铅的测定提供了新的方法。     

单质碘对水溶性CdTe量子点的荧光猝灭研究

合成了不同尺寸的、巯基丙酸和半胱氨酸修饰的水溶性CdTe量子点,并研究了I2与CdTe量子点的相互作用,实验发现I2能够明显猝灭CdTe量子点的荧光,且猝灭程度与量子点的修饰剂有关,没有表现出明显的尺寸依赖效应。     

CdTe量子点荧光猝灭法测定钴

以CdTe量子点作为荧光探针,基于荧光猝灭法对钴(Ⅱ)进行了定量检测,考察了缓冲溶液体系、量子点浓度、反应时间等多种因素的影响。实验结果表明,在pH8.0的0.2mol/LNa2HPO4-NaH2PO4缓冲液中,反应时间为10min,钴(Ⅱ)浓度为1.6×10-5—20×10-5mol/L范围时,其线性回归方程为F0/F=1.45+0.096Q(10-5mol/L),检出限为3×10-7mol/L。该方法检测范围宽,灵敏度高,为钴的测定提供了新的方法。     

Spectrofluorometric Determination of Iron II Based on the Fluorescence Quenching of Cadmium/Tellurium Quantum Dots

Water-soluble and stable CdTe quantum dots were synthesized in aqueous solution with thioglycolic acid as the stabilizer. A spectrofluorometric method for the determination of iron (II) has been developed based on quenching of the fluorescence of CdTe quantum dots by iron (II) in aqueous solutions. It can perform an accurate and simple determination of iron (II) concentration in water samples. Under optimum conditions, the quenched fluorescence intensity increased linearly with the concentration of iron (II) ranging from 5.0 × 10^?8 to 4.0 × 10^?6 mol/L with a correlation coefficient R = 0.9969. The limit of detection for iron (II) was found to be 1.2 × 10^?8 mol/L. As an application, the proposed method was successfully applied to the analysis of iron (II) in water samples, and the results were satisfactory.     

巯基乙胺稳定的CdTe量子点荧光猝灭法测定间苯二酚

以CdTe量子点作为荧光探针,基于荧光猝灭法对间苯二酚进行了定量检测,考察了缓冲溶液体系、量子点浓度、反应时间等多种因素的影响.实验结果表明,在pH 6.5的0.2mol/LNa<,2>HPO<,2>-NaH<,2>PO<,4>缓冲液中,反应时间为15min.间苯二酚浓度为1.6×10<'-6>-2.0×10<'-5>...     

Enhancement of Intracellular Delivery of CdTe Quantum Dots (QDs) to Living Cells by Tat Conjugation

Quantum dots (QDs), as novel fluorescence probes, have shown a great potential for bio-molecular labeling and cellular imaging. To stain cellular targets, the sufficient intracellular delivery of QDs is required. In this work the tat, a typical membrane-permeable carrier peptide, was conjugated with thiol-capped CdTe QDs to form CdTe Tat-QDs, and the intracellular deliveries of CdTe QDs or CdTe Tat-QDs were compared in human hepatocellular carcinoma (QGY) cells and human breast cancer (MCF7) cells in vitro by means of confocal laser scanning microscopy. Added into the cell dishes, both QDs and Tat-QDs adhered to the outer leaflet of the plasma membrane of cells within a few minutes, but the binding amount of Tat-QDs was obviously higher than that of QDs. Then both QDs and Tat-QDs can penetrate into cells, and their cellular contents increased with incubation time but both saturated after 3 hours incubation. However the cellular levels of Tat-QDs were higher than those of QDs, with the ratio of 2.1 (±0.3) times in QGY cells and 1.5 (±0.2) times in MCF7 cells, demonstrating the enhancing effect of Tat conjugation on the intracellular delivery of QDs.     

含硫磷酸钙纳米颗粒的制备及对铅离子的高效选择性去除

用一种简易共沉淀法制备了非晶含硫磷酸钙（SCP）材料,实现硫原子原位引入磷酸钙纳米颗粒中,并研究了其对Pb（II）的吸附特性和机理。与羟基磷灰石相比,SCP对Pb（II）的去除性能显著增强,在10 min内能快速将20 ppm的Pb（II）溶液降低至饮用水标准下。由Langmuir吸附等温线模型计算可知,SCP对Pb（II）的最大饱和吸附量高达1720.57 mg/g,这个数值远远超过以往所报道的绝大部分吸附剂材料。在竞争离子Ni（II）,Co（II）,Zn（II）和Cd（II）共存的条件下,SCP还表现出对Pb（II）的选择性去除。研究表明,SCP对Pb（II）超高的去除效率和优异的亲和力归因于其可通过溶解沉淀和离子交换反应在其表面形成棒状的羟基磷酸铅晶体,以及形成沉淀物硫化铅。SCP以其对Pb（II）快速、高效和优异选择性成为在实际铅污染治理中的理想材料.     

Kinetics and thermodynamics of Pb(II) adsorption onto modified spent grain from aqueous solutions

Spent grain, a main by-product of the brewing industry, is available in large quantities, but its main application has been limited to animal feeding. Nevertheless, in this study, spent grain modified with 1 M NaCl solution as a novel adsorbent has been used for the adsorption of Pb(II) in aqueous solutions. Isotherms, kinetics and thermodynamics of Pb(II) adsorption onto modified spent grain were studied. The equilibrium data were well fitted with Langmuir, Freundlich and Dubinin-Radushkevick (D-R) isotherm models. The kinetics of Pb(II) adsorption followed pseudo-second-order model, using the rate constants of pseudo-second-order model, the activation energy (E_a) of Pb(II) adsorption was determined as 12.33 kJ mol⁻¹ according to the Arrhenius equation. Various thermodynamic parameters such as ΔG^ads, ΔH^ads and ΔS^ads were also calculated. Thermodynamic results indicate that Pb(II) adsorption onto modified spent grain is a spontaneous and endothermic process. Therefore, it can be concluded that modified spent grain as a new effective adsorbent has potential for Pb(II) removal from aqueous solutions.     

Static and Dynamic Quenching of Tryptophan Fluorescence in Various Proteins by a Chromium (III) Complex

The interaction of a chromium (III) complex, (R,R)-N,N′-Bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diaminochromium (III), with human serum albumin, bovine serum albumin, lysozyme, and free tryptophan was studied using steady-state fluorescence spectroscopy. Dynamic and static quenching constants were calculated using Stern-Volmer kinetics. The complex bound more tightly to the serum albumins than to lysozyme or free tryptophan, but only one binding site was determined in all systems. The interaction was also determined to be thermodynamically favorable, and the binding constants were on the order of 10³–10⁶. The fluorescence quenching was static in nature with Forster distances in the 1.8–2.0 nm range.     

Analysis of the ESR Spectrum of a Rhodium (II) Complex

Abstract

Rh(II) complexes are rather scarce¹ and often form dimeric structures, which are diamagnetic. The ESR spectra of definite Rh(II) species have so far been claimed for Rh in ZnWO₃ ², [Rh S₄C₄(CN)₄]^{2 ?}, ^3′4 [Rh(π-C₅H₅)₂]⁵, [(π-C₅H₅)Rh(π-C₂H₄)₂]⁺⁶, and an irradiation produced [RhCπ₂(CN)₄]^{2 ?} complex.⁷ A detailed analysis has been performed on the first², the second⁴ and the last⁷ complexes. The first system shows an almost axial symmetry and the unpaired electron has been assigned to the d_xy orbital² (the x,y,z axes are defined along the octahedral metal-ligand directions). The sulfur ligand complex and the dichlorotetracyano system have their unpaired electron in the d_Z ² orbital. ^4,7 In the course of studies ^8-10 on oxygenation of a Rh(I) complex, [RhCπ(C₈H₁₄)₂]₂, we observed ¹⁰ that a well defined ESR spectrum develops during the reaction in N,N′-dimethylacetamide (DMA) - lithium chloride media. For experimental detail, reference 10 should be consulted. The data summarized in the table refer to the spectrum B in that reference and are attributed to a Rh(II) species.     

Synthesis and characterization of nano-peanuts of lead(II) coordination polymer [Pb(qcnh)(NO3)2]n with ultrasonic assistance: A new precursor for the preparation of pure-phase nano-sized PbO

A sonochemical method was used to synthesize nano-peanuts of a new lead(II) coordination 1D polymer, [Pb(qcnh)(NO₃)₂]_n (1), where qcnh = 2-quinolincarbaldehyde nicotinohydrazide. The compound was characterized by scanning electron microscopy (SEM), elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray powder diffraction (XRD), and single crystal X-ray analysis. The X-ray structure revealed that the Pb(II) atom is coordinated by one oxygen and three nitrogen atoms from two qcnh ligands and five oxygen atoms from three nitrate ligands in an 8 + 1 fashion with a PbN₃O₆ donor set. One of the PdN distances in the vicinity of the central atom is a bit longer (Pb1N1 = 2.939(4) Å), which shows the effect of the 6s² lone electron pair localized within the valence shell of the lead(II) atom. PbO nanoparticles were obtained by thermolysis of 1 at 180 °C with oleic acid as a surfactant. The average diameter of the nanoparticles was estimated by XRD to be 28 nm. The morphology and size of the prepared PbO nanoparticles were further studied using SEM.     

Competition Between Energy Transfer Quenching and Chelation Enhanced Fluorescence in a Cu (II) Coordinated Conjugated Polymer System

An investigation of the mechanism of the fluorescence quenching by Cu²⁺ for a conjugated polymer system initially designed as a fluorescence “turn-on” chemosensor based on chelation enhanced fluorescence (CHEF) is described in this paper. Unlike all other metal cations tested, the polymer/Cu²⁺ hybrid system with a 1:1 ratio between the receptor and Cu²⁺ has only weak fluorescence with λ_max = 490 nm and a quantum yield of 0.004 in THF at room temperature. In solvent glasses at 77 K the fluorescence remained quenched suggesting that the quenching mechanism was due to energy transfer between the Cu²⁺ and the conjugated polymer backbone. The energy transfer quenching competes effectively with the electron transfer involved in the CHEF resulting in a more selective chemosensory system. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

CdS_xSe_(1-x)/ZnS(核/壳)量子点的光谱截面及其掺杂光纤的传光特性

测量了不同组份比例x的CdS_xSe_(1-x)/ZnS(核/壳)量子点的吸收谱和发射谱,确定了量子点的吸收系数、吸收截面和发射截面.量子点吸收截面随粒径的增大而增大、随x的增大而减小.采用紫外固化胶,制备了掺杂浓度为0.1~5mg/mL的CdS_(0.4)Se_(0.6)/ZnS量子点光纤,测量了不同掺杂浓度量子点光纤中473nm泵浦功率的吸收衰减速率.吸收衰减速率和吸收截面弱关联于掺杂浓度.测量了光致荧光光谱强度随光纤长度和量子点浓度的变化.量子点光纤的光致荧光峰值强度随掺杂浓度和光纤长度变化而变化,且存在一个与最大峰值强度对应的饱和掺杂浓度和光纤长度.本文的实验结果有助于进一步构建新型的CdS_xSe_(1-x)/ZnS量子点增益型光电子器件.     

Quenching of perylene fluorescence by Co2+ ions in dipalmitoylphosphatidylcholine (DPPC) vesicles

We report the fluorescence quenching of perylene by CoCl₂·6H₂O in small unilamellar DPPC vesicles via energy transfer. At the probe-to-lipid ratio of 1200 and quencher to lipid ratios of 12.51, donor-donor energy transfer between clustered perylene molecules was observed as well as energy transfer from the perylene molecules to cobalt ions bothabove andbelow the main phase transition temperature of the lipid. The fluorescence quenching of perylene by CoCl₂·6H₂O in the lipid gel state is shown to be well described by Förster long-range energy transfer when both donor-donor and donor-acceptor energy transfer are considered. In the liquid crystalline phase diffusion of the molecules is described as well as energy transfer. The interaction radiusR ₀ for energy transfer from perylene to Co²⁺ is found to be 13.4±1.1 Å in the gel phase at 303 K, in good agreement with the theoretical value forR ₀ of 13.9 Å. In the liquid crystalline phase at 323 K the lower value obtained forR ₀, 11.3±1.6 Å, is attributed to saturation of the Co²⁺ ions at the interfacial region of the bilayer. A diffusion coefficient of (1.06±0.15)×10^–6 cm² s^–1 is obtained for perylene-cobalt diffusion in the liquid crystalline phase at 323K.     

Hg(II) Coordination Studies in Penicillamine Enantiomers by 199mHg-TDPAC

In order to study the binding of the toxic heavy metal ion Hg²⁺ to penicillamine, complexes with the D- and L-enantiomers of penicillamine were investigated by the nuclear quadrupole interaction of ¹⁹⁹Hg monitored by time differential perturbed angular correlation spectroscopy. It was found that bound Hg(II) occurs in two-fold, three-fold and four-fold coordinations. This revised version was published online in September 2006 with corrections to the Cover Date.     

Meso-5,10,15,20-四(4-甲氧基苯基)卟啉荧光熄灭法测定铅

基于铅对荧光试剂 Meso- 5 ,10 ,15 ,2 0 -四 (4 -甲氧基苯基 )卟啉 (TMOPP)的荧光熄灭 ,建立了测定微量铅的荧光分析方法。在 p H9.5的 Tris- HCl缓冲体系中 ,最大激发波长和发射波长分别为 4 2 4 nm和6 5 7nm,测定铅浓度的线性范围为 5 .5 0× 10 -7— 7.5 0× 10 -5mol/ L,检出限为 8.5 0× 10 -8mol/ L。用于环境水样中铅含量的分析 ,结果满意。     

Chemical optimisation of a sol-gel procedure for the development of fluorescence Cu(II) nanosensors

A template-assisted sol-gel procedure was developed and optimised for the preparation of silica thin films embedding the fluorescent dye 3-(dansylamido)-propyl-triethoxysilane (DNS-APTES) for Cu(II) sensing purposes. The different parameters involved (solution composition, nature of the template, deposition and annealing conditions, post-synthesis deposition of additional coatings, etc.) were independently changed in order to evaluate their effect on the final microstructure, composition and sensor performances of the films. The optimisation procedure encompassed also the choice of the suitable parameters to ensure stability of the sensing films and to avoid the leaching of the fluorescent dye.Films prepared by using the non-ionic surfactant F127, without an additional coating and with a post-deposition annealing at 100 °C for 2 h, were proven to be the best performing ones, characterised by the largest and fastest fluorescence quenching. In particular, the presence of a template was demonstrated to play a major role in determining the efficiency of the sensing device. The surface and in-depth composition of thin films was analysed by X-Ray Photoelectron Spectroscopy (XPS) and Secondary Ion Mass Spectrometry (SIMS). The sensing performances of the films were tested by titration experiments with Cu²⁺.     

槲皮素-Sn(II)配合物荧光、紫外及红外光谱的测量与分析

以NH4Cl-NH3.H2O为缓冲液,十六烷基三甲基溴化铵(CTAB)为荧光增强剂,用荧光分光光度计分别采集槲皮素、槲皮素-Sn(II)配合物溶液、槲皮素-Sn(II)-NH4Cl-NH3.H2O、槲皮素-Sn(II)-NH4Cl-NH3.H2O-CTAB溶液以及将其溶液分别静置7h和21h后的荧光光谱,并对光谱进行分析。在不加CTAB的条件下,用紫外分光光度计分别测量加入缓冲液前后的紫外光谱。用漫反射方法测定配合物的红外光谱,并对其结构进行初步分析。在缓冲液的作用下,槲皮素-Sn(II)配合物的结构发生了变化;通过分析,发现与缓冲液发生反应的主要基团为酚羟基,红外光谱中酚羟基的消失和NH4+基团的出现,说明了配合物中的酚羟基与NH4+发生了取代反应。     

二阶导数同步荧光光谱测定卷烟主流烟气中的苯并(a)芘

研究了卷烟主流烟气粒相物中苯并(a)芘(BaP)的同步荧光及其一阶和二阶导数光谱, 发现二阶导数同步光谱可明显减少背景及BaP同系物对BaP测定的干扰。据此建立了一种固相萃取-二阶导数同步荧光光谱法测定卷烟主流烟气粒相物中BaP的新方法。方法检测限为0.2 ng·mL-1,平均回收率为80.2%～86.2%,相对标准偏差为2.64%～3.02%。