Thermodynamic and conformational investigation of the influence of CdTe QDs size on the toxic interaction with BSA

Water-soluble fluorescent colloidal quantum dots (QDs) have been widely used in some biological and biomedical fields, so the interaction of QDs with biomolecules recently attracts increasing attention. In this study, the fluorescence (FL) quenching method, circular dichroism (CD) technique, attenuated total reflection-Fourier transform infrared (ATR-FTIR) and UV-vis absorption spectra were used to investigate systematically the influence of CdTe QDs size on the toxic interaction with bovine serum albumin (BSA). Three size CdTe QDs with maximum emission of 543 nm (green-emitting QDs, GQDs), 579 nm (yellow-emitting QDs, YQDs) and 647 nm (red-emitting QDs, RQDs) were tested. The Stern-Volmer quenching constant (K_sv) at different temperatures, corresponding thermodynamic parameters (ΔH, ΔG and ΔS), and information of the structural features of BSA were gained. The FL results indicated that QDs can effectively quench the FL of BSA in a size-dependent manner, electrostatic interactions play a major role in the binding reaction, and the nature of quenching is static, resulting in forming QDs-BSA complexes. The CD and ATR-FTIR spectra showed that the secondary structure of BSA was changed by QDs, indicating the toxic on protein.     

Ascorbic Acid Sensor Based on CdS QDs@PDA Fluorescence Resonance Energy Transfer

An ascorbic acid (AA) sensor was constructed based on the fluorescence resonance energy transfer (FRET) between CdS quantum dots (CdS QDs) and polydopamine (PDA) to detect trace AA sensitively. FRET occurred due to the broad absorption spectrum of PDA completely overlapped with the narrow emission spectrum of CdS QDs. The fluorescence of CdS QDs was quenched and in the “off” state. When AA was present, the conversion of DA to PDA was hindered and the FRET disappeared, resulting in the fluorescence of CdS QDs in an “on” state. Importantly, the degree of fluorescence recovery of CdS QDs displayed a desirable linear correlation with the concentration of AA in the range of 5.0–100.0 μmol/L, the linear equation is y=0.0119cAA+0.3113, and the detection limit is 1.16 μmol/L (S/N = 3, n = 9). There was almost no interference with common amino acid, glucose and biological sulfhydryl small molecules to AA. Trace amount of AA in vitamin C tablets were determined and satisfactory results were obtained; the recoveries were observed to be 98.01–100.7%.     

Recognition of DNA based on changes in the fluorescence intensity of CdSe/CD QDs–phenanthroline systems

The CdSe quantum dots (QDs) modified by mercapto-β-cyclodextrin (CD) were synthesized and characterized by transmission electron microscopy, powder X-ray diffraction, excitation and emission spectra, and fluorescence lifetime. When λ_ex = 370 nm, the fluorescence peak of CdSe/CD QDs is at 525 nm. Phenanthroline (Phen) is able to quench their fluorescence, which can be recovered by the addition of DNA. The quenching and restoration of fluorescence intensity were found to be linearly proportional to the amount of Phen and DNA, respectively. The variation of the fluorescence intensity of the CdSe/CD QDs–Phen system was studied, and it was demonstrated to result from a static mechanism due to the formation of a Phen inclusion complex with the CdSe QDs modified by mercapto-β-cyclodextrin. The fluorescence recovery was due to the binding of DNA with Phen in the inclusion complex, leading to the freeing of the CdSe/CD QDs. The binding constants and sizes of the binding sites of the Phen–DNA interaction were calculated to be 1.33 × 10⁷ mol^?1 L and 10.79 bp.     

Interaction between Glyoxal-bis-(2-hydroxyanil) and Bovine Serum Albumin in Solution

The interaction between glyoxal-bis-(2-hydroxyanil) (GBH) and bovine serum albumin (BSA) was studied by spectroscopic methods including fluorescence spectroscopy, circular dichroism (CD) and UV–visible absorption spectra. The mechanism for quenching the fluorescence of BSA by GBH is discussed. The number of binding sites n and observed binding constant K _b were measured by the fluorescence quenching method. The thermodynamic parameters ΔH ^θ , ΔG ^θ , and ΔS ^θ were calculated at different temperatures and the results indicate that hydrogen bonding and van der Waals forces played major roles in the reaction. The distance r between the donor (BSA) and acceptor (GBH) molecules was obtained according to Förster’s theory of non-radiation energy transfer. Synchronous fluorescence and three-dimensional fluorescence spectra were used to investigate the structural change of BSA molecules that occur upon addition of GBH, and these results indicate that the secondary structure of BSA molecules is changed by the presence of GBH.     

Lysine modification of human serum albumin and its effect on protein conformation and nalidixic acid binding

In order to investigate the involvement of lysine residues of human serum albumin (HSA) in nalidixic acid (NA) binding, various modified preparations of HSA such as 44% carbamylated (C₄₄), 83% carbamylated (C₈₃) and 85% acetylated (A₈₅) were made by treating the HSA solution with a different molar excess of potassium cyanate and acetic anhydride. The extent of modification, charge homogeneity and conformational changes of these derivatives were checked by TNBSA reaction method, polyacrylamide gel electrophoresis (PAGE) and gel filtration using Sephacryl S-200 HR column, respectively. Binding of NA to HSA and its derivatives was examined using fluorescence quenching titration method to determine the binding constant. The emergence of a single band in PAGE and single symmetrical peak in gel filtration results confirmed the charge and size homogeneity of these derivatives. Hydrodynamic properties such as Stokes radius and frictional ratio, as obtained from the analytical gel filtration results suggested molecular expansion in C₈₃ and A₈₅ HSAs while C₄₄ HSA retained the native conformation. Addition of NA to both native and modified HSA derivatives quenched the fluorescence intensity of the protein at 344 ​nm to a different extent. Whereas the values of the Stern-Volmer constant (K_SV) and bimolecular quenching rate constant (k_q) suggested, NA-HSA complex formation, binding constant (K_a) value suggested an intermediate binding affinity between NA and HSA. Furthermore, the decrease in the K_a value with the extent of modification was indicative of the involvement of lysine residues in NA-HSA interaction.     

Spectroscopic studies on the interaction between human hemoglobin and CdS quantum dots

The interaction between human adult hemoglobin (Hb) and bare CdS quantum dots (QDs) was investigated by fluorescence, synchronous fluorescence, circular dichroism (CD), and Raman spectroscopic techniques under physiological pH 7.43. The intrinsic fluorescence of Hb is statically quenched by CdS QDs. The quenching obeys the Stern-Volmer equation, with an order of magnitude of binding constant (K) of 10(7). The electrostatic adsorption of Hb on the cationic CdS QDs surface is energetically favorable (DeltaS(0)=70.22 Jmol(-1)K(-1), DeltaH(0)=-23.11 kJmol(-1)). The red shift of synchronous fluorescence spectra revealed that the microenvironments of tryptophan and tyrosine residues at the alpha(1)beta(2) interface of Hb are disturbed by CdS QDs, which are induced from hydrophobic cavities to a more exposed or hydrophilic surrounding. The secondary structure of the adsorbed Hb has a loose or extended conformation for which the content of alpha-helix has decreased from 72.5 to 60.8%. Moreover, Raman spectra results indicated that the sulfur atoms of the cysteine residues form direct chemical bonds on the surface of the CdS QDs. The binding does not significantly affect the spin state of the heme iron, and deoxidation is not expected to take place on the coated oxyhemoglobin. The change of orientation of heme vinyl groups was also detected.     

Cadmium sulfide quantum dots modified by chitosan as fluorescence probe for copper (II) ion determination

CdS quantum dots (QDs) have been prepared and modified with chitosan. Based on the quenching of fluorescence signals of the functionalized CdS QDs at 531 nm wavelength and enhancement of signals the 400–700 nm wavelength range by Cu²⁺ at pH 4.2, a simple, rapid and specific method for Cu²⁺ determination is presented. Under optimum conditions, the relative fluorescence intensity of CdS QDs is linearly proportional to copper concentration from 8.0 nmol L^?1 to 3.0 μmol L^?1 with a detection limit of 1.2 nmol L^?1. The mechanism can be explained in terms of strong binding of Cu²⁺ onto the surface of CdS, resulting in a chemical displacement of Cd²⁺ ions and the formation of CuS on the surface of the QDs.     

光谱法研究核壳量子点CdTe/CdS与牛血清白蛋白的相互作用

应用荧光光谱、圆二色光谱和紫外吸收光谱等技术研究核壳量子点CdTe/CdS与牛血清白蛋白(BSA)相互作用的结果表明,CdTe/CdS对BSA的荧光猝灭机理为静态猝灭。根据不同温度下量子点对BSA的荧光猝灭作用计算了结合常数、热力学参数,证明了量子点与BSA相互作用力主要是范德华力或氢键作用力。探讨了量子点对BSA构象的影响。     

Energy Relay from an Unconventional Yellow Dye to CdS/CdSe Quantum Dots for Enhanced Solar Cell Performance

A new design for a quasi‐solid‐state Forster resonance energy transfer (FRET) enabled solar cell with unattached Lucifer yellow (LY) dye molecules as donors and CdS/CdSe quantum dots (QDs) tethered to titania (TiO₂) as acceptors is presented. The Forster radius is experimentally determined to be 5.29 nm. Sequential energy transfer from the LY dye to the QDs and electron transfer from the QDs to TiO₂ is followed by fluorescence quenching and electron lifetime studies. Cells with a donor–acceptor architecture (TiO₂/CdS/CdSe/ZnS‐LY/S^2?‐multi‐walled carbon nanotubes) show a maximum incident photon‐to‐current conversion efficiency of 53 % at 530 nm. This is the highest efficiency among Ru‐dye free FRET‐enabled quantum dot solar cells (QDSCs), and is much higher than the donor or acceptor‐only cells. The FRET‐enhanced solar cell performance over the majority of the visible spectrum paves the way to harnessing the untapped potential of the LY dye as an energy relay fluorophore for the entire gamut of dye sensitized, organic, or hybrid solar cells.     

Interactions of Quercetin with Casein and Bovine Serum Albumin as well as the Effects of Coexisting Carbon Nanotubes

Fluorescence quenching and synchronous fluorescence methods were used to study the interactions of fluore-scence-active quercetin (Qct) with casein (Cas) and bovine serum albumin (BSA) in phosphate buffer solution (PBS, pH=7.4) with or without coexisting carbon nanotubes (CNTs). Formulae for binding constant (K) and molar binding ratio (n) were established for methods 1 (fixing protein concentration, changing Qct concentration, and monitoring the fluorescence of protein) and 2 (fixing Qct concentration, changing protein concentration, and monitoring the fluorescence of Qct), to which values of K and n were calculated via nonlinear least-square fitting of the experimental data, and the “optical inner filtering induced fluorescence quenching” effect was thus quantitatively evaluated. The quenching effects of coexisting CNTs on the fluorescence of Qct, BSA, and Cas, as well as the effects of coexisting CNTs on Qct-BSA and Qct-Cas interactions, were examined. Synchronous fluorescence was also used to examine the effects of coexisting CNTs and Qct on the conformations of BSA and Cas, with relevant K and n values for tyrosine (Tyr) and tryptophan (Trp) residues estimated. It was concluded that the CNTs mainly interacted with the Trp residues locating near the protein surfaces, but small-sized Qct molecules could further interact with the Tyr residues locating inside the protein molecules.     

Study of caffeine binding to human serum albumin using optical spectroscopic methods

The binding of caffeine to human serum albumin (HSA) under physiological conditions has been studied by the methods of fluorescence, UV-vis absorbance and circular dichroism (CD) spectroscopy. The mechanism of quenching of HSA fluorescence by caffeine was shown to involve a dynamic quenching procedure. The number of binding sites n and apparent binding constant K _b were measured by the fluorescence quenching method and the thermodynamic parameters ΔH, ΔG, ΔS were calculated. The results indicate that the binding is mainly enthalpy-driven, with van der Waals interactions and hydrogen bonding playing major roles in the reaction. The distance r between donor (HSA) and acceptor (caffeine) was obtained according to the Förster theory of non-radiative energy transfer. Synchronous fluorescence, CD and three-dimensional fluorescence spectroscopy showed that the microenvironment and conformation of HSA were altered during the reaction.     

Study of the interactions between fluoroquinolones and human serum albumin by affinity capillary electrophoresis and fluorescence method

The interactions between fluoroquinolones and human serum albumin (HSA) were investigated by affinity capillary electrophoresis (ACE) and fluorescence quenching technique. Based on the efficient separation of several fluoroquinolones using a simple phosphate buffer, the binding constants of fluoroquinolones with HSA were determined simultaneously during one set of electrophoresis by ACE method. The thermodynamic parameters were obtained from data at different temperatures, and the negative ΔH and ΔS values showed that both hydrogen bonds and van der Waals interaction played major roles in the binding of fluoroquinolones to HSA. The interactions were also studied by fluorescence quenching technique. The results of fluorescence titration revealed that fluoroquinolones had the strong ability to quenching the intrinsic fluorescence of HSA through the static quenching procedure. The binding site number n, apparent binding constant K_b and the Stern-Volmer quenching constant K_sv were determined. The thermodynamic parameters were also studied by fluorescence method, and the results were consonant with that of ACE.     

Functionalized cadmium sulfide quantum dots as fluorescence probe for silver ion determination

CdS quantum dots (QDs) modified with l-cysteine has been prepared by one step. They are water-soluble and biocompatible. To improve CdS QDs stability and interaction between silver ion and functionalized CdS QDs in aqueous solution, some amounts of fresh l-cysteine were added to functionalized CdS solution. Based on the characteristic fluorescence enhancement of CdS QDs at 545 nm by silver ions in the presence of some amounts of fresh l-cysteine, simultaneously, a gradual red shift of fluorescence emission bands of CdS QDs from 545 to 558 nm was observed. A simple, rapid, sensitive and specific detection method for silver ion was proposed. Under optimum conditions, the fluorescence intensity of CdS QDs is linearly proportional to silver concentration from 2.0 × 10⁻⁸ to 1.0 × 10⁻⁶ mol/L with a detection limit of 5.0 × 10⁻⁹ mol/L. In comparison with single organic fluorophores, functionalized CdS quantum dots are brighter, more stable against photobleaching, and don’t suffer from blinking. Furthermore, owing to the fluorescence enhancement effect of CdS QDs by silver ion, the proposed method showed lower detection blank and higher sensitivity. Possible fluorescence enhancement mechanism was also studied.     

Reverse micelle-derived Cu-doped Zn1−xCdxS quantum dots and their core/shell structure

Reverse micelle chemistry-derived Cu-doped Zn_1?xCd_xS quantum dots (QDs) with the composition (x) of 0, 0.5, 1 are reported. The Cu emission was found to be dependent on the host composition of QDs. While a dim green/orange emission was observed from ZnS:Cu QDs, a relatively strong red emission could be obtained from CdS:Cu and Zn_0.5Cd_0.5S:Cu QDs. Luminescent properties of undoped QDs versus Cu-doped ones and quantum yields of alloyed ZnCdS versus CdS QDs are compared and discussed. To enhance Cu-related red emission of CdS:Cu and Zn_0.5Cd_0.5S:Cu core QDs, core/shell structured QDs with a wider band gap of ZnS shell are also demonstrated.     

Binding behavior of DEHP to albumin: spectroscopic investigation

Bis(2-ethylhexyl)phthalate (DEHP) is one of the biggest selling synthetic plasticizers which can migrate to environment and enter human body via air, water, medical apparatus, and food. In this paper, three-dimensional fluorescence (3D-FL) spectroscopy, UV–visible absorption spectroscopy and circular dichroism (CD) spectroscopy were employed to explore the binding of DEHP to bovine serum albumin (BSA) at the physiological conditions. The number of binding sites n and observed binding constant K _b was measured by fluorescence quenching method. It was found that the fluorescence quenching was static quenching mechanism and caused by the formation of DEHP–BSA complex at ground state. The enthalpy change (ΔH ^θ), Gibbs free energy change (ΔG ^θ) and entropy change (ΔS ^θ) were calculated at four different temperatures. Site marker competitive displacement experiments were carried out to identify the binding location. The results demonstrated that DEHP bound primarily on Sudlow’s site I in domain IIA of BSA molecule. The distance r (2.95?nm) between donor (BSA) and acceptor (DEHP) was obtained based on F?rster’s non-radiation fluorescence resonance energy transfer (FRET) theory. Furthermore, the CD spectral results indicated that the secondary structure of BSA changed in presence of high concentration of DEHP, which implied that high level of DEHP in plasma was potentially poisonous. The study is helpful to evaluating the health risk of DEHP and understanding its functional effects on protein during the blood transportation process.     

Determination of Hydrocortisone in Cosmetics by CdSe/CdS Quantum Dots-Based Fluoroimmunoassay Using Magnetic Fe3O4/Au Nanoparticles as Solid Carriers

This work demonstrated the feasibility of detecting hydrocortisone in cosmetics using a novel CdSe/CdS quantum dots‐based competitive fluoroimmunoassay with magnetic core/shell Fe₃O₄/Au nanoparticles (MCFN) as solid carriers. Hydrocortisone antigen was labeled with the synthesized core/shell CdSe/CdS quantum dots (QDs) to form the antigen‐QDs conjugate. Meanwhile, hydrocortisone antibody was incubated with MCFN and the immobilized antibody was obtained. The immobilized antibody was then mixed sequentially with hydrocortisone and a slightly excess amount of the QDs‐labeled hydrocortisone antigen, allowing their competition for binding with the antibody immobilized on MCFN. The bound hydrocortisone and the antigen‐QDs conjugates on MCFN were removed subsequently after the mixture was applied to a magnetic force. The analyte concentration was obtained by measuring the fluorescence intensity of the unbound hydrocortisone antigen‐QDs conjugates. The proposed method was characterized by simplicity, rapidity, and high sensitivity with a wide linear working range of 0.5 to 15000 pg·mL^?1 and a low detection limit of 0.5 pg·mL^?1. The proposed method was successfully applied to the determination of hydrocortisone in cosmetics with satisfactory results.     

Voltammetric and spectroscopic investigations of 4-nitrophenylferrocene interacting with DNA

Cyclic voltammetry (CV) coupled with UV–vis and fluorescence spectroscopy were used to probe the interaction of potential anticancer drug, 4-nitrophenylferrocene (NFC) with DNA. The electrostatic interaction of the positively charged NFC with the anionic phosphate of DNA was evidenced by the findings like negative formal potential shift in CV, ionic strength effect, smaller bathochromic shift in UV–vis spectroscopy, incomplete quenching in the emission spectra and decrease in viscosity. The diffusion coefficients of the free and DNA bound forms of the drug were evaluated from Randles–Sevcik equation. The binding parameters like binding constant, ratio of binding constants (K_red/K_ox), binding site size and binding free energy were determined from voltammetric data. The binding constant was also determined from UV–vis and fluorescence spectroscopy with a value quite close to that obtained from CV.     

水溶性的CdSe/CdS/ZnS量子点的合成及表征

用L-半胱氨酸盐(Cys)作为稳定剂,合成了水溶性的双壳结构的CdSe/CdS/ZnS半导体量子点。吸收光谱和荧光光谱结果表明,双壳结构的CdSe/CdS/ZnS纳米微粒比单一的CdSe核纳米粒子和单核壳结构的CdSe/CdS纳米粒子具有更优异的发光特性。用透射电子显微镜(TEM)、ED、XRD、XPS和FTIR等方法对CdSe核和双壳层的CdSe/CdS/ZnS纳米微粒的结构、分散性及形貌分别进行了表征。     

Dual-functional photocatalysis boosted by electrostatic assembly of porphyrinic metal-organic framework heterojunction composites with CdS quantum dots

Photocatalytic dual-functional reaction under visible light irradiation represents a sustainable development strategy. In detail, H₂ production coupled with benzylamine oxidation can remarkably lower the cost by replacing sacrificial agents. In this work, Cd S quantum dots(Cd S QDs) were successfully loaded onto the surface of a porphyrinic metal-organic framework(Pd-PCN-222) by the electrostatic selfassembly at room temperature. The consequent Pd-PCN-222/CdS heterojunction composites...     

Fe3O4/PEI/Au@CdSe/CdS多功能复合材料的制备与表征

以共沉淀法制备出Fe₃O₄纳米粒子,通过聚乙烯亚胺(PEI)修饰Fe₃O₄纳米粒子,再原位复合上Au纳米粒子,制得Fe₃O₄/PEI/Au纳米颗粒微球。再将Fe₃O₄/PEI/Au纳米颗粒与巯基乙酸修饰的量子点CdSe/CdS连接,成功制备了Fe₃O₄/PEI/Au@CdSe/CdS多功能复合微球。经过傅里叶变换红外光谱仪(FTIR)、荧光分光光度计、荧光显微镜、X射线衍射(XRD)、透射电子显微镜(TEM)及振动样品磁强计(VSM)的表征。结果表明:多功能复合微球的粒径在40nm左右,具有超顺磁性,剩磁,矫顽力近似等于零,饱和磁化强度为28.83A·m₂·kg^-1,同时兼有优越的荧光性能和金纳米粒子的特性。