Cu(2-x)S (x = 1, 0.2, 0.03) nanocrystals were synthesized with three different chemical methods: sonoelectrochemical, hydrothermal, and solventless thermolysis methods in order to compare their common optical and structural properties. The compositions of the Cu(2-x)S nanocrystals were varied from CuS (covellite) to Cu(1.97)S (djurleite) through adjusting the reduction potential in the sonoelectrochemical method, adjusting the pH value in the hydrothermal method and by choosing different precursor pretreatments in the solventless thermolysis approach, respectively. The crystallinity and morphology of the products were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), which shows that most of them might be of pure stoichiometries but some of them are mixtures. The obtained XRDs were studied in comparison to the XRD patterns of previously reported Cu(2-x)S. We found consistently that under ambient conditions the copper deficient Cu(1.97)S (djurleite) is more stable than Cu(2)S (chalcocite). Corroborated by recent computational studies by Lambrecht et al. and experimental work by Alivisatos et al. This may be the reason behind the traditionally known instability of the bulk Cu(2)S/CdS interface. Both Cu(2)S and the copper-deficient Cu(1.97)S have very similar but distinguishable electronic and crystal structure. The optical properties of these Cu(2-x)S NCs were characterized by UV-vis spectroscopy and NIR. All presented Cu(2-x)S NCs show a blue shift in the band gap absorption compared to bulk Cu(2-x)S. Moreover the spectra of these Cu(2-x)S NCs indicate direct band gap character based on their oscillator strengths, different from previously reported experimental results. The NIR spectra of these Cu(2-x)S NCs show a carrier concentration dependent plasmonic absorption.

Mercaptoacetic acid (RSH)-capped CdS nanocrystals (NCs) was demonstrated to be electrochemically reduced during potential scan and react with the coreactant S2O8(2-) to generate strong electrochemiluminescence (ECL) in aqueous solution. Based on the ECL of CdS NCs, a novel label-free ECL biosensor for the detection of low-density lipoprotein (LDL) has been developed by using self-assembly and gold nanoparticle amplification techniques. The biosensor was prepared as follows: The gold nanoparticles were first assembled onto a cysteamine monolayer on the gold electrode surface. This gold nanoparticle-covered electrode was next treated with cysteine and then reacted with CdS NCs to afford a CdS NC-electrode. Finally, apoB-100 (ligand of LDL receptor) was covalently conjugated to the CdS NC-electrode. The modification procedure was characterized by cyclic voltammetry, electrochemical impedance spectroscopy, and atomic force microscopy, respectively. The resulting modified electrode was tested as ECL biosensor for LDL detection. The LDL concentration was measured through the decrease in ECL intensity resulting from the specific binding of LDL to apoB-100. The ECL peak intensity of the biosensor decreased linearly with LDL concentration in the range of 0.025-16 ng mL-1 with a detection limit of 0.006 ng mL-1. The CdS NCs not only showed high ECL intensity and good biocompatibility but also could provide more binding sites for apoB-100 loading. In addition, the gold nanoparticle amplification for protein ECL analysis was applied to the improvement of the detection sensitivity. Thus, the biosensor exhibited high sensitivity, good reproducibility, rapid response, and long-term stability.

A versatile immunosensor using CdTe quantum dots as electrochemical and fluorescent labels has been developed for sensitive protein detection. This sandwich-type sensor is fabricated on an indium tin oxide chip covered with a well-ordered gold nanoparticle monolayer. Gel imaging systems were successfully introduced to develop a novel high-efficient optical immunoassay, which could perform simultaneous detection for the samples with a series of different concentrations of a target analyte. The linear range of this assay was between 0.1 and 500 ng/mL, and the assay sensitivity could be further increased to 0.005 ng/mL with the linear range from 0.005 to 100 ng/mL by stripping voltammetric analysis. The immunosensor showed good precision, high sensitivity, acceptable stability, and reproducibility and could be used for the detection of real sample with consistent results in comparison with those obtained by the ELISA method.

Copper I 7400 Plasmonic Cu2-xS Nanocrystals: Optical and Structural Properties of Copper--Deficient Copper(I) Sulfides. -Cu 2-x S (x = 1, 0.2, 0.03) nanocrystals are prepared by three different convenient and environmental benign techniques based on sonoelectrochemical, hydrothermal, and solventless thermolysis methods using CuSO4 as starting material. The samples are characterized by powder XRD, TEM, UV/VIS, and NIR spectroscopy. The compositions of the nanocrystals ranges from CuS to Cu1.97S by adjusting the reduction potential in the sonoelectrochemical method, from CuS to Cu 1.97 S by adjusting the pH values in the hydrothermal method, and from Cu1.8S to Cu1.97S in the thermolysis method. Cu2S is thermodynamically unstable under ambient conditions, compared to the Cu2-xS phase. All Cu2-xS nanocrystals show a blue shift in the band gap absorption compared to bulk Cu2-xS and are of direct band gap type, different from previously reported experimental results. Cu 2-x S nanocrystals show a plasmonic absorption, which depends on the carrier concentration. -(ZHAO, Y.; PAN, H.; LOU, Y.; QIU, X.; ZHU*, J.; BURDA, C.; J.

Highly luminescent zinc(II)-bis(8-hydroxyquinoline) (Znq(2)) complex nanorods have been synthesized via a sonochemical route from the microemulsion containing zinc acetate and 8-hydroxyquinoline. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed that the products were rod-like morphology with a diameter of about 200-450 nm and a length of about 1-3 microm. A possible mechanism for the formation of Znq(2) nanorods is proposed that the ultrasound wave might urge the collision and fusion of initial Znq(2) nuclei to form nanorods. The photoluminescence (PL) and resonance light scattering (RLS) of the products were also investigated. The Znq(2) nanorods were found to be sensitive to several proteins, such as human serum albumin (HSA), bovine serum albumin (BSA), bovine hemoglobin (Hb), and egg albumin (EA), displaying an increase in intensities of both PL and RLS. The protein-concentration dependence of the PL and RLS intensities can be well described as a Langmuir-type binding isotherm. This is the first report on the enhancement of PL and RLS intensities of Znq(2) nanorods by proteins. On the basis of enhanced PL and RLS intensities, the protein could be detected at the nanogram per milliliter level. The experimental results clearly showed that the Znq(2) nanorods were good protein probes for easy and highly sensitive detection.

Novel self-assembled V2O5 bundles with highly ordered superstructures and spindle-like morphology were synthesized by a rapid high-yielding sonochemical method. The as-prepared samples were characterized by X-ray diffraction, a field-emission scanning electron microscope, and a transmission electron microscope. The spindle-like V2O5 bundles are composed of several tens of homogeneous nanowires with diameters of 30-50 nm and lengths of 3-7 microm. A sensitive resonance light scattering method for the detection of bovine serum albumin (BSA) based on the self-assembled V2O5 bundles was developed. The results of the polarized resonance light scattering demonstrated that the Cabannes factor for the V2O5 bundles-BSA aggregates was BSA concentration-dependent.

In the medium of EDTA-NaOH, nanogold strongly catalyzed the slow reaction between hydrazine (N2H4) and Cu(II) to form Cu particles, which exhibited a strong resonance scattering (RS) peak at 602 nm. The increased RS intensity at 602 nm (DeltaI(RS)) was linear to the nanogold concentration in the range of 0.008-2.64 nM, with a detection limit of 1.0 pM Au. The rate equation obtained by the initial rate procedure was V(Cu) = K(Cu)[C(Cu(II))](2)C(OH)(1)C(Au)(1)C(N2)H4(1), with an apparent activation energy of 38 kJ x mol(-1), and the catalytic reaction mechanism was also discussed. An immunonanogold-catalytic resonance scattering spectral (RSS) assay was established for detection of microalbumin (Malb), using 10 nm nanogold to label goat antihuman Malb to obtain an immunonanogold probe (AuMalb) for Malb. In pH 5.0 citric acid-Na2HPO4 buffer solution, the AuMalb aggregated nonspecifically. Upon addition of Malb, it reacted with the probe to form dispersive AuMalb-Malb immunocomplex in the solution. After centrifugation, the supernatant containing AuMalb-Malb was obtained, and exhibited a catalytic effect on the reaction of N2H4-Cu(II) to produce large Cu particles that resulted in the I(602 nm) increasing. The increased RS intensity at 602 nm (DeltaI(602 nm)) was linear to Malb concentration (C(Malb)) in the range of 0.4 to 460 pg x mL(-1), with the regression equation of DeltaI(602 nm) = 0.3713 C(Malb) + 7.2, correlation coefficient of 0.9981 and detection limit of 0.1 pg x mL(-1) Malb. The proposed method was applied to detect Malb in healthy human urine samples, with satisfactory results.

A new molecularly imprinted electrochemical luminescence (MIP-ECL) sensor was developed for Gibberellin A3 (GA3) determination. This sensor is based on competitive binding between the GA3 and the Rhodamine B (RhB)-labeled GA3 (RhB-GA3) to the MIP film. After the competitive binding, the residual RhB-GA3 on the MIP was electro-oxidized to produce RhB oxide, which could greatly amplify the weak electrochemiluminescence (ECL) signal of luminol. The ECL intensity decreased when the RhB-GA3 was replaced by GA3 molecules in the samples. Accordingly, GA3 was determined in the concentration range from 1 × 10(-11) to 3 × 10(-9) mol/L with a detection limit of 3.45 × 10(-12) mol/L. The sensor shows high sensitivity and selectivity, wide response range, good accuracy, and fast response. Beer samples were assayed by using the sensors, and the recoveries ranging from 96.0% to 103.2% were obtained.