Quantum confinement effect of CdSe induced by nanoscale solvothermal reaction.

We report a novel method, nanoscale solvothermal reaction (NSR), to induce the quantum confinement effect of CdSe on nanostructured TiO(2) by solvothermal route. The time-dependent growth of CdSe is observed in solution at room temperature, which is found to be accomplished instantly by heat-treatment in the presence of solvent at 1 atm. However, no crystal growth occurs upon heat-treatment in the absence of solvent. The nanoscale solvothermal growth of CdSe quantum dot is realized on the nanocrystalline oxide surface, where Cd(NO(3))(2)·4H(2)O and Na(2)SeSO(3) solutions are sequentially spun on nanostructured TiO(2), followed by heat-treatment at temperatures ranging from 100 °C to 250 °C. Size of CdSe increases from 4.4 nm to 5.3 nm, 8.7 nm and 14.8 nm, which results in decrease in optical band gap from 2.19 eV to, 1.95 eV, 1.74 eV and 1.75 eV with increasing the NSR temperature from 100 °C to 150 °C, 200 °C and 250 °C, respectively, which is indicative of the quantum confinement effect. Thermodynamic studies reveal that increase in the size of CdSe is related to increase in enthalpy, for instance, from 3.77 J mg(-1) for 100 °C to 8.66 J mg(-1) for 200 °C. Quantum confinement effect is further confirmed from the CdSe-sensitized solar cell, where onset wavelength in external quantum efficiency spectra is progressively shifted from 600 nm to 800 nm as the NSR temperature increases, which leads to a significant improvement of power conversion efficiency by a factor of more than four. A high photocurrent density of 13.7 mA cm(-2) is obtained based on CdSe quantum dot grown by NSR at 200 °C.

A new PEG-lipid conjugate micelle for encapsulation of CdSe/ZnS quantum dots.

A new polymer conjugate of poly(ethylene glycol) (PEG) and 10,12-pentacosadiynoic acid (PCDA), PEG-PCDA conjugate, was synthesized by coupling reaction between carboxyl group of PCDA and hydroxyl group of PEG. Luminescent CdSe/ZnS QDs were encapsulated in the polymer micelles of mixtures of PEG-PCDA and PCDA using solid dispersion method to prepare water-soluble and biocompatible QD micelles. Upon UV-irradiation, the core of QD micelles was further stabilized by intramicellar crosslinking between neighboring PCDA moieties. The polymer conjugate was characterized by 1H-NMR, FT-IR, and GPC measurements, and thereof QD micelles observed using transmission electron microscopy (TEM) and dynamic light scattering (DLS). The QD micelles were spherical with diameters in the range of 30-190 nm. The encapsulated QDs in polymer micelles are water-soluble and have the high potential for applications in biomedical imaging and detection due to their good colloidal stability and biocompatible surface.

Preparation and characterization of CdSe/ZnS quantum dots encapsulated in poly(ethylene glycol)-b-poly(D,L-lactide) micelle nanoparticles.

The final goal of this study is to develop multi-functional organic/inorganic hybrid nanoparticles, which can be utilized as biomedical imaging probes and drug delivery carriers. As an initial step toward this goal, we encapsulated CdSe/ZnS quantum dots (QDs) into poly(ethylene glycol)-b-poly(D,L-lactide) (PEG-PLA) micelles using a solid dispersion method. The size and fluorescent intensity of QDs encapsulated in PEG-PLA micelles depended on the amount of incorporated QDs. For example, when the amount of QDs increased from 0.1 to 1.0 microg, the mean diameter increased from 24.2 +/- 6.0 to 211.2 +/- 6.5 nm and the fluorescent intensity changed from 10.2 +/- 1.0 to 469.9 +/- 15.6 (RFU). Stability studies showed that the size and zeta-potential (ZP) of QDs encapsulated in PEG-PLA micelles (QEMs) did not change significantly in response to a change in pH conditions or under a 10% serum condition. We also tested the cytotoxicity and cellular uptake of the QEMs. The viability of HeLa cells treated with micelles for 24 h was 80-100% in various concentration ranges of micelles. Confocal laser scanning microscopic images showed that the QEMs penetrated into the cells, particularly into the cytosolic compartments. Our results suggest that the QEMs may be a promising multi-functional nanocarrier for biomedical imaging and drug delivery.

Preparation of orthogonally functionalized surface using micromolding in capillaries technique for the control of cellular adhesion.

This study presents a simple method for the fabrication of an orthogonal surface that can be applied for cell patterning without the need to immobilize specific adhesive peptides, proteins, or extracellular matrix (ECM) for cell attachment. Micromolding in capillaries (MIMIC) produced two distinctive regions. One region contained poly(ethylene glycol)-poly(D,L-lactide) diblock copolymer (PEG-PLA) designed to provide a biological barrier to the nonspecific binding of proteins and fibroblast cells. The other region was coated with polyelectrolyte (PEL) to promote the adhesion of biomolecules including proteins and cells. Resistance to the adsorption of proteins increased with the length of PEG and PLA chains because the longer PEG chain increased the PEG layer thickness and the longer PLA chain induced stronger interaction with the PEL surface. The PEG5k-PLA2.5k (20mg/ml) was the most efficient candidate for the prevention of protein adhesion among the PEG-PLA copolymers examined. The orthogonal functionality of prepared surfaces having PEL regions and background PEG-PLA regions resulted in rapid patterning of biomolecules. Fluorescein isothiocyanate-tagged bovine serum albumin (FITC-BSA) and fibroblast cells successfully adhered to the exposed PEL surfaces. Although methods for cell patterning generally require an adhesive protein layer on the desired area, these fabricated surfaces without adhesive proteins provide a gentle microenvironment for cells. In addition, our proposed approach could easily control patterns, sizes, and shapes at micron scale.