One-nanometer-scale size-controlled synthesis of monodisperse magnetic iron oxide nanoparticles.
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Biomedical subjects
Publications and source records attributed to Taeghwan Hyeon.
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Quantum-sized ZnS nanocrystals with quasi-spherical and rod shapes were synthesized by the aging reaction mixtures containing diethylzinc, sulfur, and amine. Uniform-sized ZnS nanorods with the average dimension of 5 nm x 21 nm, along with a small fraction of 5 nm-sized quasi-spherical nanocrystals, were synthesized by adding diethylzinc to a solution containing sulfur and hexadecylamine at 125 degrees C, followed by aging at 300 degrees C. Subsequent secondary aging of the nanocrystals in oleylamine at 60 degrees C for 24 h produced nearly pure nanorods. Structural characterizations showed that these nanorods had a cubic zinc blende structure, whereas the fabrication of nanorods with this structure has been known to be difficult to achieve via colloidal chemical synthetic routes. High-resolution TEM images and reaction studies demonstrated that these nanorods are formed from the oriented attachment of quasi-spherical nanocrystals. Monodisperse 5 nm-sized quasi-spherical ZnS nanocrystals were separately synthesized by adding diethylzinc to sulfur dissolved in a mixture of hexadecylamine and 1-octadecene at 45 degrees C, followed by aging at 300 degrees C. When oleic acid was substituted for hexadecylamine and all other procedures were unchanged, we obtained 10 nm-sized quasi-spherical ZnS nanocrystals, but with broad particle size distribution. These two different-sized quasi-spherical ZnS nanocrystals showed different proportions of zinc blende and wurtzite crystal structures. The UV absorption spectra and photoluminescence excitation spectra of the 5 nm ZnS quasi-spherical nanocrystals and of the nanorods showed a blue-shift from the bulk band-gap, thus showing a quantum confinement effect. The photoluminescence spectra of the ZnS nanorods and quasi-spherical nanocrystals showed a well-defined excitonic emission feature and size- and shape-dependent quantum confinement effects.
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Hierarchically ordered mesocellular mesoporous silica materials (HMMS) were synthesized using a single structure-directing agent. The mesocellular pores are synthesized without adding any pore expander; the pore walls are composed of SBA-15 type mesopores. Small-angle X-ray scattering revealed the presence of uniform pore structures with two different sizes. Using HMMS as a nanoscopic template, hierarchically ordered mesocellular mesoporous carbon (HMMC) and polymer (HMMP) materials were synthesized. HMMS was used as a host for enzyme immobilization. To improve the retention of enzymes in HMMS, we adsorbed enzymes, and then employed crosslinking using glutaraldehyde (GA). The resulting crosslinked enzyme aggregates (CLEAs) show an impressive stability with extremely high enzyme loadings. For example, 0.5 g alpha-chymotrypsin (CT) could be loaded in 1 g of silica with no activity decrease observed with rigorous shaking over one month. In contrast, adsorbed CT without GA treatment resulted in a lower loading, which further decreased due to continuous leaching of adsorbed CT under shaking. The activity of crosslinked CT aggregates in HMMS was approximately 10 times higher than that of the adsorbed CT, which represents a 74-fold increase in activity per unit weight of HMMS due to higher CT loading.
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The development of nanocrystals has been intensively pursued, not only for their fundamental scientific interest, but also for many technological applications. The synthesis of monodisperse nanocrystals (size variation <5%) is of key importance, because the properties of these nanocrystals depend strongly on their dimensions. For example, the colour sharpness of semiconductor nanocrystal-based optical devices is strongly dependent on the uniformity of the nanocrystals, and monodisperse magnetic nanocrystals are critical for the next-generation multi-terabit magnetic storage media. For these monodisperse nanocrystals to be used, an economical mass-production method needs to be developed. Unfortunately, however, in most syntheses reported so far, only sub-gram quantities of monodisperse nanocrystals were produced. Uniform-sized nanocrystals of CdSe (refs 10,11) and Au (refs 12,13) have been produced using colloidal chemical synthetic procedures. In addition, monodisperse magnetic nanocrystals such as Fe (refs 14,15), Co (refs 16-18), gamma-Fe(2)O(3) (refs 19,20), and Fe(3)O(4) (refs 21,22) have been synthesized by using various synthetic methods. Here, we report on the ultra-large-scale synthesis of monodisperse nanocrystals using inexpensive and non-toxic metal salts as reactants. We were able to synthesize as much as 40 g of monodisperse nanocrystals in a single reaction, without a size-sorting process. Moreover, the particle size could be controlled simply by varying the experimental conditions. The current synthetic procedure is very general and nanocrystals of many transition metal oxides were successfully synthesized using a very similar procedure.
We successfully synthesized monodisperse chromium nanoparticles from the thermolysis of a Fischer carbene complex.
We synthesized Ni/Pd core/shell nanoparticles from the consecutive thermal decomposition of metal-surfactant complexes. The nanoparticle catalyst was atom-economically applied for various Sonogashira coupling reactions.
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We synthesized uniform Cu2O coated Cu nanoparticles from the thermal decomposition of copper acetylacetonate followed by air oxidation and used these nanoparticles as catalysts for Ullmann type amination coupling reactions of aryl chlorides
Mesocellular polymer foams with uniform approximately 17 nm cellular pores were fabricated using mesocellular silica foams as inorganic templates. The mesocellular polymer foams have high surface areas up to approximately 600 m(2)g(-1) and pore volumes of 1.6 cm(3)g(-1).
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We report on the synthesis of semiconductor nanocrystals of PbS, ZnS, CdS, and MnS through a facile and inexpensive synthetic process. Metal-oleylamine complexes, which were obtained from the reaction of metal chloride and oleylamine, were mixed with sulfur. The reaction mixture was heated under appropriate experimental conditions to produce metal sulfide nanocrystals. Uniform cube-shaped PbS nanocrystals with particle sizes of 6, 8, 9, and 13 nm were synthesized. The particle size was controlled by changing the relative amount of PbCl(2) and sulfur. Uniform 11 nm sized spherical ZnS nanocrystals were synthesized from the reaction of zinc chloride and sulfur, followed by one cycle of size-selective precipitation. CdS nanocrystals that consist of rods, bipods, and tripods were synthesized from a reaction mixture containing a 1:6 molar ratio of cadmium to sulfur. Spherical CdS nanocrystals (5.1 nm sized) were obtained from a reaction mixture with a cadmium to sulfur molar ratio of 2:1. MnS nanocrystals with various sizes and shapes were synthesized from the reaction of MnCl(2) and sulfur in oleylamine. Rod-shaped MnS nanocrystals with an average size of 20 nm (thickness) x 37 nm (length) were synthesized from a 1:1 molar ratio of MnCl(2) and sulfur at 240 degrees C. Novel bullet-shaped MnS nanocrystals with an average size of 17 nm (thickness) x 44 nm (length) were synthesized from the reaction of 4 mmol of MnCl(2) and 2 mmol of sulfur at 280 degrees C for 2 h. Shorter bullet-shaped MnS nanocrystals were synthesized from a 3:1 molar ratio of MnCl(2) and sulfur. Hexagon-shaped MnS nanocrystals were also obtained. All of the synthesized nanocrystals were highly crystalline.
A new and simple method has been developed to synthesize large quantities of highly monodisperse tetragonal zirconia nanocrystals. In this synthesis, a nonhydrolytic sol-gel reaction between zirconium(IV) isopropoxide and zirconium(IV) chloride at 340 degrees C generated 4 nm sized zirconia nanoparticles. A high-resolution transmission electron microscopic (HRTEM) image showed that the particles have a uniform particle size distribution and that they are highly crystalline. These monodisperse nanoparticles were synthesized without any size selection process. X-ray diffraction studies combined with Rietveld refinement revealed that the ZrO(2) nanocrystals are the high-temperature tetragonal phase, and very close to a cubic phase. When zirconium(IV) bromide is used as a precursor instead of zirconium chloride, zirconia nanoparticles with an average size of 2.9 nm were obtained. The UV-visible absorption spectrum of 4 nm sized zirconia nanoparticles exhibited a strong absorption starting at around 270 nm. A fluorescence spectrum with excitation at 300 nm showed a broad fluorescence band centered around 370 nm. FTIR spectra showed indication of TOPO binding on the ZrO(2) nanoparticle surface. These optical studies also suggest that the nanoparticles are of high quality in terms of narrow particle size distribution and relatively low density of surface trap states.
Bimodal mesoporous silica material composed of 30-40 nm sized nanoparticles with 3.5 nm sized three-dimensionally interconnected mesopores was synthesized under neutral conditions using sodium silicate as a silica source. Using the bimodal mesoporous silica as a template, bimodal mesoporous carbon having 4 nm sized framework mesopores and approximately 30 nm sized textural pores was synthesized.
Recent advances in the synthesis of various magnetic nanoparticles using colloidal chemical approaches are reviewed. Typically, these approaches involve either rapid injection of reagents into hot surfactant solution followed by aging at high temperature, or the mixing of reagents at a low temperature and slow heating under controlled conditions. Spherical cobalt nanoparticles with various crystal structures have been synthesized by thermally decomposing dicobalt octacarbonyl or by reducing cobalt salts. Nanoparticles of Fe-Pt and other related iron or cobalt containing alloys have been made by simultaneously reacting their constituent precursors. Many different ferrite nanoparticles have been synthesized by the thermal decomposition of organometallic precursors followed by oxidation or by low-temperature reactions inside reverse micelles. Rod-shaped iron nanoparticles have been synthesized from the oriented growth of spherical nanoparticles, and cobalt nanodisks were synthesized from the thermal decomposition of dicobalt octacarbonyl in the presence of a mixture of two surfactants.
Hollow silica tubes with mesoporous wall structure were synthesized through the sol-gel reactions of tetraethoxysilane and n-octadecyltrimethoxysilane (TEOS/C18-TMS) on the surface of ammonium dl-tartrate crystals. Novel hollow carbon tubes with mesoporous walls and rectangular-shaped channels were fabricated using the silica tubes as templates.
Mesocellular carbon foam composed of nanometer sized primary particles was synthesized using hydrothermally synthesized MSU-F silica as a template and poly(furfuryl alcohol) as a carbon source.