Direct conjugation of semiconductor nanoparticles with proteins

Nanocrystalline CdS particles directly conjugated with bovine serum albumin (BSA) protein were prepared by applying the supercritical fluid processing technique, rapid expansion of a supercritical solution into a liquid solvent. The direct conjugation takes advantage of the unique features of the process for nanoparticle formation. The BSA-conjugated CdS nanoparticles in stable aqueous suspension or in the solid state were characterized by using microscopy, X-ray diffraction, and optical spectroscopy methods. The results show that well-dispersed CdS nanoparticles are coated with BSA in a core-shell-like arrangement and that the protein species associated with the nanoparticles remain functional according to the modified Lowry assay. These BSA-conjugated CdS nanoparticles are also strongly luminescent, with the luminescence spectrum contributed to primarily by the exciton emission.     

Hydrothermal route to InAs semiconductor nanocrystals

Spherical InAs nanocrystals of 30-50 nm were hydrothermally synthesized at 120 degrees C, which showed a 100 meV-blueshift of band gap absorption and phonon confinement of optical vibration mode. The study of hydrothermal formation mechanism indicated that crystalline InAs could be obtained in an extended pH range (approximately -0.15 to 14).     

Examination of intermediates in globular protein unfolding by the tritium labeling method

Unfolding of polypeptide chain of ribonuclease A in urea and guanidinium chloride (GuCl) solutions under equilibrium conditions involves formation of intermediates whose properties (compactness and preservation of the most of the native hydrophobic core, secondary structures, and native-like folding of the polypeptide chain) correspond to the basic characteristics of the “molten globule” state. Intermediates are “damp” molten globules (with water molecules inside the globule). The examinations performed revealed pronounced distinctions in the properties of the intermediates, above all, in their compactness degrees.     

Nucleotide-directed growth of semiconductor nanocrystals

We engineer colloidal quantum dot nanocrystals through the choice of biomolecular ligands responsible for nanoparticle nucleation, growth, stabilization, and passivation. We systematically vary the presence of, and thereby elucidate the role of, phosphate groups and a multiplicity of functionalities on the mononucleotides used as ligands. The results provide the basis for synthesis of nanoparticles using precisely controlled synthetic oligonucleotide sequences.     

Optical properties of single semiconductor nanocrystals

We present an overview of the current progress in the understanding of the (steady state) optical properties of individual II-VI semiconductor nanocrystals. We begin with a presentation of the conceptual development of the theory required to model the electronic structure of these systems. This is followed by an overview of the current experimental results obtained from the spectroscopy of individual semiconductor nanocrystals, and in particular, we focus on the study of photoluminescence intermittency (blinking) and spectral diffusion. Where possible, we link the experimental observations to the predictions of current theories. We conclude that the surface of small semiconductor crystals plays an important role in determining their optical properties.     

Macromolecular crowding fails to fold a globular protein in cells

Proteins perform their functions in cells where macromolecular solutes reach concentrations of >300 g/L and occupy >30% of the volume. The volume excluded by these macromolecules stabilizes globular proteins because the native state occupies less space than the denatured state. Theory predicts that crowding can increase the ratio of folded to unfolded protein by a factor of 100, amounting to 3 kcal/mol of stabilization at room temperature. We tested the idea that volume exclusion dominates the crowding effect in cells using a variant of protein L, a 7 kDa globular protein with seven lysine residues replaced by glutamic acids; 84% of the variant molecules populate the denatured state in dilute buffer at room temperature, compared with 0.1% for the wild-type protein. We then used in-cell NMR spectroscopy to show that the cytoplasm of Escherichia coli does not overcome even this modest (～1 kcal/mol) free-energy deficit. The data are consistent with the idea that nonspecific interactions between cytoplasmic components can overcome the excluded-volume effect. Evidence for these interactions is provided by the observations that adding simple salts folds the variant in dilute solution but increasing the salt concentration inside E. coli does not fold the protein. Our data are consistent with the results of other studies of protein stability in cells and suggest that stabilizing excluded-volume effects, which must be present under crowded conditions, can be ameliorated by nonspecific interactions between cytoplasmic components.     

Architectural control of magnetic semiconductor nanocrystals.

Shape- and dopant-controlled magnetic semiconductor nanocrystals have been achieved by the thermolysis of nonpyrophoric and less reactive single molecular precursors under a monosurfactant system. Reaction parameters governing both the intrinsic crystalline phase and the growth regime (kinetic vs thermodynamic) are found to be important for the synthesis of various shapes of MnS nanocrystals that include cubes, spheres, 1-dimensional (1-D) monowires, and branched wires (bipods, tripods, and tetrapods). Obtained nanowires exhibit enhanced optical and magnetic properties compared to those of 0-D nanospheres. Proper choice of molecular precursors and kinetically driven low-temperature growth afford dopant controlled 1-D Cd1-xMn(x)S nanorods at high levels (up to approximately 12%) of Mn, which is supported by repeated surface exchange experiments and X-ray diffraction (XRD) and electron paramagnetic resonance (EPR) analyses.     

Size-dependent Raman red shifts of semiconductor nanocrystals

The size effects on Raman red shifts in low-dimensional semiconductor nanocrystals are investigated by considering the size-dependent root-mean-square average amplitude associated with the thermal vibration of atoms. The lower limit of vibrational frequency was obtained by matching the calculation results of Raman red shifts with the experimental data of Si, InP, CdSe, CdS0.65Se0.35, ZnO, CeO2, as well as SnO2 nanocrystals. The results indicate the following: (1) the Raman frequency decreases as the nanocrystal size decreases in both narrow and wide bandgap semiconductors; (2) the influence of crystal size on the Raman frequency of nanoparticles is more pronounced than that of nanowires and thin films; and (3) the Raman red shift is ascribed to the size-induced phonon confinement effect and surface relaxation. This model may provide new insights into the fundamental understanding of the underlying mechanism behind the Raman red shifts.     

Surface-functionalization-dependent optical properties of II-VI semiconductor nanocrystals

We report a study of the surface-functionalization-dependent optical properties of II-VI zinc-blende semiconductor nanocrystals on the basis of ligand-exchange chemistry, isomaterial core/shell growth, optical spectroscopy, transmission electron microscopy, and X-ray powder diffraction. Our results show that the transition energy and extinction coefficient of the 2S(h3/2)1S(e) excitonic band of these nanocrystals can be strongly modified by their surface ligands as well as ligand associated surface atomic arrangement. The oleylamine exchange of oleate-capped zinc-blende II-VI nanocrystals narrows the energy gap between their first and second excitonic absorption bands, and this narrowing effect is size-dependent. The oleylamine exchange results in the quenching, subsequent recovery, and even enhancing of the photoluminescence emission of these II-VI semiconductor nanocrystals. In addition, the results from our X-ray powder diffraction measurements and simulations completely rule out the possibility that oleate-capped zinc-blende CdSe nanocrystals can undergo zinc-blende-to-wurtzite crystal transformation upon ligand exchange with oleylamine. Moreover, our theoretical modeling results suggest that the surface-functionalization-dependent optical properties of these semiconductor nanocrystals can be caused by a thin type II isomaterial shell that is created by the negatively charged ligands (e.g., oleate and octadecyl phosphonate). Taking all these results together, we provide the unambiguous identification that II-VI semiconductor nanocrystals exhibit surface-functionalization-dependent excitonic absorption features.     

Fabrication of semiconductor nanowires by conjugation of quantum dots to actin filaments

We demonstrate the feasibility of fabrication of semiconducting nanowires (quantum dots) using F-actin as a template. Three different approaches of assembling quantum dots into nanowires are described. The nanowires were characterized by fluorescence microscopy.     

Internal dynamics of a globular protein in water

The frequency distributions of internal dynamics of a protein are calculated in solution using normal mode analysis. Our test case is bovine pancreatic trypsin inhibitor, consisting of 58 amino acid residues. Each water molecule surrounding the protein is treated as an internally rigid body that can move with the vibrating protein. The water molecules are redistributed around the protein, as dictated by the potential energy. It is shown that water molecules around the protein are essential for the protein to keep its tertiary structure close to the X-ray structure. The density of states calculated in this model is shifted toward high frequencies when compared with results previously obtained with a model in which the water molecules were not allowed to move with the protein. This shift toward high-frequency states originates from the stronger interactions of water molecules with the sidechain atoms in the protein. The present model is computationally demanding. So the previous (frozen water) model is suggested to be a reasonable approximation for expressing internal dynamics of a protein in solution. © 1996 by John Wiley & Sons, Inc.     

Localized surface plasmon resonances of anisotropic semiconductor nanocrystals

We demonstrate that anisotropic semiconductor nanocrystals display localized surface plasmon resonances that are dependent on the nanocrystal shape and cover a broad spectral region in the near-IR wavelengths. In-plane and out-of-plane dipolar resonances were observed for colloidal dispersions of Cu(2-x)S nanodisks, and the wavelengths of these resonances are in good agreement with calculations carried out in the electrostatic limit. The wavelength, line shape, and relative intensities of these plasmon bands can be tuned during the synthetic process by controlling the geometric aspect ratio of the disk or using a postsynthetic thermal-processing step to increase the free carrier densities.     

General synthesis of I-III-VI2 ternary semiconductor nanocrystals

Metastable orthorhombic phase of AgInS2 nanocrystals with various shapes, including particles, rods, and worms, have been obtained to demonstrate a facile and effective one-pot chemical route for the synthesis of high quality I-III-VI2 ternary semiconductor nanocrystals (AgInS2, CuInS2, AgInSe2) with controllable shape and size.     

Functionalized semiconductor nanocrystals for ultrasensitive detection of peptides

Semiconductor CdS nanoparticle have been prepared and modified with thiovanic acid. The functionalized nanoparticles are water-soluble. They were used as the fluorescence probes in the ultrasensitive detection of peptides. This method is based on the fluorescence enhancement of functionalized nano-CdS in the presence of peptide with mercapto groups (GN-9) and the fluorescence quenching of functionalized nano-CdS in the presence of peptide (GA-8 and MT-25). Excitation and emission wavelengths were 360 and 530 nm, respectively. Under optimum conditions, the calibration graphs are linear over the range of 0.15-3.5, 0.2-4.0, and 0.2-3.8 μg ml⁻¹ for GN-9, GA-8 and MT-25, respectively. The corresponding detection limits were 0.010 μg ml⁻¹ for GN-9, 0.018 μg ml⁻¹ for GA-8 and 0.022 μg ml⁻¹ for MT-25, respectively. This method has been proved to be a simple, rapid and sensitive method.     

Wurtzite Cu2ZnSnS4 nanocrystals: a novel quaternary semiconductor

A new wurtzite phase Cu(2)ZnSnS(4) was discovered and the corresponding nanocrystals have been successfully synthesized. They have been characterized in detail and showed the photoelectric response, which demonstrated their potential in the application of photovoltaic devices.     

The kinetics of growth of semiconductor nanocrystals in a hot amphiphile matrix

The first comprehensive study on the kinetics of nanocrystal growth in a hot amphiphile medium is presented. An example is given with CdSe semiconductor nanocrystals grown after the injection of precursor (a mixture of Cd- and Se-reagents) in concentrated tri-octylphosphine oxide matrix (heated to more than 300 degrees C). The particle size distribution is reconstructed as a function of time from the absorption and photoluminescence spectra collected during the synthesis process. For this purpose a new expression is used relating the exciton energy due to quantum confinement with the nanocrystal radius. The growth kinetics is considered as a two-stage process in order to describe the time variation of nanoparticle size. During the first stage, called reaction-limited growth, the size of initial nucleus rapidly increases due to a sort of surface reaction exhausting the precursor in the nanoparticle vicinity. The growth in such conditions favors also a remarkable narrowing of the size distribution. The nanocrystal develops further on account of a slow precursor transfer from a distant space driven by the concentration gradient--classical diffusion-limited growth. The width of size distribution also increases proportional to the average particle size. Any growth will stop after the precursor concentration reaches a minimum value defining the limit for the final nanocrystal size in a batch. Solving the kinetic equations for the growth rate in each case of kinetics derives analytical expressions for the mean radius and variance of size distribution. Then the respective expressions are matched in a uniform solution valid during the entire synthesis. The theoretical model is in a good quantitative agreement with the experimental data for independent syntheses. Important characteristic scales of the processes (time-constant and length) and microscopic parameters of the reacting system (interfacial energy and reaction rate constant) are estimated from the data. It turns out that the fast reaction-limited growth is important to obtain well-defined nanocrystals of high optical quality by using less energy, time and consumable. However, to make them reproducibly uniform one should control also the ultra-fast nucleation process preceding the nanocrystal growth, which is still unknown. Nevertheless, our current findings allow the conceptual design of a new continuos-flow reactor for the manufacturing of a large amount of uniform nanocrystals.     

A spray-based method for the production of semiconductor nanocrystals

We present a spray based-method for the formation and production of semiconductor nanocrystals that provides an attractive alternative to the commonly used epitaxial and colloidal procedures. According to this spray-based method, mainly thermospray, solutions of semiconductor salts are first sprayed into monodispersed droplets, which subsequently become solid nanocrystals by solvent evaporation. A semiconductor nanocrystal is produced from a single spray droplet upon the full vaporization of the solvent. The average diameter and size distribution of the final nanocrystals are controlled and determined by the solute concentration of the sprayed solution and by the droplet size, hence by the spray production parameters. The spray-produced nanocrystals are collected on any selected solid support. Representative results, shown in this letter, reveal the formation of CdS nanocrystals in the size range of 3 to 6 nanometers and with a size distribution of as low as five percent. A further structural analysis of these nanocrystals showed that they were formed in the zinc blend phase with a high degree of crystallinity.     

Controlled chemical doping of semiconductor nanocrystals using redox buffers

Semiconductor nanocrystal solids are attractive materials for active layers in next-generation optoelectronic devices; however, their efficient implementation has been impeded by the lack of precise control over dopant concentrations. Herein we demonstrate a chemical strategy for the controlled doping of nanocrystal solids under equilibrium conditions. Exposing lead selenide nanocrystal thin films to solutions containing varying proportions of decamethylferrocene and decamethylferrocenium incrementally and reversibly increased the carrier concentration in the solid by 2 orders of magnitude from their native values. This application of redox buffers for controlled doping provides a new method for the precise control of the majority carrier concentration in porous semiconductor thin films.     

Thermodynamic study of the thermal denaturation of a globular protein in the presence of different ligands

By means of difference UV-Vis spectra, the thermal denaturation of catalase has been studied in the presence of different surfactants: sodium perfluorooctanoate, sodium octanoate and sodium dodecanoate. These results indicate that hydrogenated surfactants play two opposite roles in the folding and stability of catalase, they act as a structure stabiliser at a low molar concentrations (enhancing T _m) and as a destabilizer at a higher concentrations (diminishing T _m). Meanwhile sodium perfluorooctanoate enhances T _m in the whole concentration range. An approach for the determination of the heat capacity, enthalpy and entropy has been made, finding that for the three studied surfactants, at all concentrations, the enthalpy term dominates the entropy term.