Synthesis of high aspect ratio quantum-size CdS nanorods and their surface-dependent photoluminescence

Colloidal CdS nanorods with diameters near 4 nm and narrow size distributions ( approximately +/-10%) were synthesized up to 300 nm long by a sequential reactant injection technique that utilizes phosophonic acids as capping ligands. The phosphonic acid strongly passivates the nonpolar CdS surfaces and sequential reactant injection provides controlled CdS formation kinetics to enable heterogeneous and facet-selective CdS deposition on the more reactive {002} surfaces. With this process, the nanorod length can be systematically increased by increasing reactant addition to extend nanorod growth. The phosphonic acid concentration, however, is quite important, as "low" concentrations allow radial deposition and branching to occur. These high aspect ratio (>100) CdS nanorods luminesce with relatively high efficiencies of 10.8% quantum yield at room temperature. The luminescence, however, mostly arises from trap-related recombination, and the emission is significantly red-shifted from the absorption edge. Various surface passivation treatments were explored to eliminate trap emission and increase the luminescence quantum yield. Thiol and amine passivation both significantly reduced trap emission and enhanced band-edge emission, but the total luminescence quantum yields dropped significantly, with a maximum measured value of 1.5% for the amine-passivated CdS nanorods.     

Shape selective growth of CdS one-dimensional nanostructures by a thermal evaporation process

CdS one-dimensional nanoforms such as nanowires, nanoribbons, network-like nanowires, pearl necklace type nanowires, helical-like nanowires, and nanowire arrays were formed on Si substrates by a simple thermal evaporation route. The shapes of the one-dimensional CdS nanoforms were controlled by varying the experimental parameters such as temperature and position of the substrates. Formation of the CdS one-dimensional nanoforms was initiated by the Au catalyzed vapor-liquid-solid technique, whereas the vapor-solid process played a crucial role in defining the shapes of the nanoforms. Different optical characterizations such as optical absorbance, photoluminescence, and Raman spectroscopy were adopted to explore the physical and structural quality of these CdS nanoforms.     

Synthesis, photoluminescence, and adsorption of CdS/dendrimer nanocomposites

CdS/dendrimer nanocomposites can be synthesized from methanolic Cd(2+) and S(2-) with amine-terminated polyamidoamine dendrimers of generation 8 (G8NH(2)) as stabilizers. By controlling the preparation conditions, nanoparticles with diameters < or = 2 nm can be obtained with a narrow size distribution. They show blue photoluminescence at approximately 450 nm. We studied the effects of various additives on the photoluminescence and elucidated its mechanism. Stable aggregates of two to three G8NH(2) molecules with several CdS nanoparticles form; the particles are located at the surface of the G8NH(2) molecules. The adsorption of the CdS/G8NH(2) nanocomposites on flat substrate surfaces is determined by the substrate chemistry. The hydrophilic nature of G8NH(2) results in weak affinity to graphite but strong affinity to hydroxy-terminated substrates such as mica, oxidized silicon wafers, and carboxylate-terminated monolayers. Patterning of nanocomposites on these hydrophilic substrates is achieved by the microcontact printing method. We propose to use only one molecule, a large dendrimer, to control the nanoparticle formation and also the immobilization of the synthesized nanoparticle/dendrimer composites.     

Synthesis of modified uracil and cytosine nucleobases using a microwave-assisted method

Modified nucleobases and nucleic acids have found many biological and pharmaceutical applications. Here we report a microwave-directed synthesis of a variety of modified uracil and cytosine nucleobases with high yields under solvent-free conditions. The reaction yields were further improved by addition of Lewis acid. The crystal structures of 5-isopropyl-6-methyluracil and 6-phenyluracil were also determined.     

巯基修饰寡聚DNA包覆的CdS纳米粒子

用5'－端的1－C,2-C位之间磷酸根上修饰有巯基的寡聚胞嘧啶(oligoC10-SH)和矣鸟嘌呤(oligoG10-SH)作为包覆剂直接合成了CdS半导体纳米粒子。实验结果表明CdS的表面的寡聚DNA仍可进行正常的复性,并且复性后CdS的荧光发生了有利于DNA分子标识的显著增强。     

Synthesis and evolution of novel hollow ZnO urchins by a simple thermal evaporation process

Delicate hollow ZnO urchins have been fabricated by thermal evaporation of metallic zinc powders in a tube furnace without the use of additive, high temperature, or low pressure. The phase transformation, morphologies, and photoluminescence evolution of the ZnO products were carefully studied and investigated with X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), and photoluminescence (PL) spectra. These studies indicated that the growth of hollow ZnO urchins involves the vaporization of Zn powder, solidification of liquid droplets, surface oxidation, sublimation, and self-catalytic growth of one-dimensional nanowires.     

Hydrothermal synthesis of single-crystal CeCO3OH and their thermal conversion to CeO2

Hexagonal single-crystalline cerium carbonate hydroxide （CeCO3OH） precursors with dendrite morphologies have been synthesized by a facile hydrothermal method at 180 C using CeCl3-7H2O as the cerium source, triethylenetetramine as both an alkaline and carbon source, with triethylenete- tramine also playing an important role in the formation of the dendrite structure. Polycrystalline ceria （CeO2） have been obtained by calcining the precursor at 500 C for 4 h. Tile morphology of the precursor was partly maintained during the heating process. The optical absorption spectra indicate the CeO2 nano/microstructures have a direct band gap of 2.92 eV, which is lower than values of the bulk powder due to the quantum size effect. The high absorption in the UV region for CeO2 nano/microstructure indicated that this material was expected to be used as UV-blocking materials.     

Synthesis of CdS and ZnS nanowires using single-source molecular precursors

Single-source molecular precursors were used to synthesize II-VI compound semiconductor nanowires for the first time. Cadmium sulfide and zinc sulfide nanowires were prepared using cadmium diethyldithiocarbamate, Cd(S2CNEt2)2, and zinc diethyldithiocarbamate, Zn(S2CNEt2)2, respectively, as precursors in a gold nanocluster-catalyzed vapor-liquid-solid growth process. High-resolution transmission electron microscopy studies show that the CdS and ZnS nanowires are single-crystal wurtzite structures with stoichiometric compositions. In addition, photoluminescence measurements demonstrate that these nanowires exhibit high-quality optical properties. The applicability of our approach to the synthesis of other compound and alloy semiconductors nanowires as well as nanowire heterostructures of these materials is discussed.     

Synthesis and photoluminescence properties of 8-hydroxyquinoline derivatives and their metallic complexes

Three new 8-hydroxyquinoline derivatives, i.e. 5-[(4-styryl-benzylidene)-amino]-quinolin-8-ol (1), 5-[(4-bromo-2-fluoro-benzylidene)-amino]-quinoline-8-ol (2) and 2-[2-(9-ethyl-9H-carbazol-2yl)-vinyl]-quinolin-8-ol (3), and their metallic complexes were synthesized and identified by ultraviolet-visible (UV-Vis), ¹H nuclear magnetic resonance (¹H NMR), Fourier transform infrared spectrometer (FTIR), mass spectrometry (MS) spectra and elemental analyses. Their fluorescence properties were studied by photoluminescence, which indicated that the luminescence wavelength of 5-and 2-substitued-8-hydroxyquinoline derivatives shifted to red in comparison with that of 8-hydroxyquinoline. Meanwhile, the fluorescence lifetime of 2-[2-(9-ethyl-9H-carbazol-2yl)-vinyl]-quinolin-8-ol and its zinc complex showed long lifetime in benzene solution. __________ Translated from Chinese Journal of Organic Chemistry, 2007, 27(3): 402–408 [译自: 有机化学]     

Partial solubility parameters of lactose, mannitol and saccharose using the modified extended Hansen method and evaporation light scattering detection

The modified extended Hansen method was tested for the first time to determine partial solubility parameters of non-polymeric pharmaceutical excipients. The method was formerly tested with drug molecules, and is based upon a regression analysis of the logarithm of the mole fraction solubility of the solute against the partial solubility parameters of a series of solvents of different chemical classes. Two monosaccharides and one disaccharide (lactose monohydrate, saccharose and mannitol) were chosen. The solubility of these compounds was determined in a series of solvents ranging from nonpolar to polar and covering a wide range of the solubility parameter scale. Sugars do not absorb at the UV-vis region, and the saturated solutions were assayed with a recent chromatographic technique coupled to an evaporative light scattering detector. This technique was suitable to determine the concentration dissolved in most solvents. The modified extended Hansen method provided better results than the original approach. The best model was the four parameter equation, which includes the dispersion delta d, dipolar delta p, acidic delta a and basic delta b partial solubility parameters. The partial solubility parameters obtained, expressed as MPa1/2, were delta d = 17.6, delta p = 28.7, delta h = 19, delta a = 14.5, delta b = 12.4, delta T = 32.8 for lactose, delta d = 16.2, delta p = 24.5, delta h = 14.6, delta a = 8.7, delta b = 12.2, delta T = 32.8 for mannitol and delta d = 17.1, delta p = 18.5, delta h = 13, delta a = 11.3, delta b = 7.6, delta T = 28.4 for saccharose. The high total solubility parameters delta T obtained agree with the polar nature of the sugars. The dispersion parameters delta d are quite similar for the three sugars indicating that the polar delta p and hydrogen bonding parameters (delta h, delta a, delta b) are responsible for the variation in the total solubility parameters delta T obtained, as also found for drugs. The results suggest that the method could be extended to determine the partial solubility parameters of other non-polymeric pharmaceutical excipients.     

Microencapsulation of capsaicin by solvent evaporation method and thermal stability study of microcapsules

With polylactic acid (PLA) as shell and capsaicin as core substances, microcapsules were prepared based on solvent evaporation method. The orthogonal test was used to analyze the effects of the process conditions such as polyvinyl alcohol and PLA concentrations, stirring rate, and oil/water ratio on the particle size of the microencapsulated capsaicin (MC) agents. The chemical composition, morphology and size distribution of the microcapsules prepared by the most satisfactory conditions were analyzed by Fourier transform infrared spectroscopy, laser light scattering, and scanning electron microscopy. The MC agents had a mean diameter of 3–5 μm. The thermal properties of the MC agents were measured by differential scanning calorimetry and thermogravimetric analysis, it was demonstrated that the thermal stability of the MC agents was changed or even improved by the encapsulated PLA over the surface, when compared with similar parameters of the uncovered capsaicin. The in vitro release profile suggested that the microcapsules could be a suitable material for controlled release of capsaicin.     

Studies on optical absorption and photoluminescence of thioglycerol-stabilized CdS quantum dots

Nanoparticles of CdS were prepared at 303 K by aqueous precipitation method using CdSO4 and (NH4)2S in presence of the stabilizing agent thioglycerol. Adjustment of the thioglycerol (T) to ammonium sulphide (A) ratio (T:A) from 1:25 to 1:3.3 was done during synthesis and nanoparticles of different size were obtained. The prepared colloids were characterized by UV-vis and photoluminescence (PL) spectroscopic studies. Prominent first and second excitonic transitions are observed in the UV-vis spectrum of the colloid prepared with a T:A ratio of 1:3.3. Particle size analysis was done using XRD, high resolution TEM and dynamic light scattering and found to be approximately 3 nm. UV-vis and PL spectral features also agree with this particle size in colloid with T:A of 1:3.3. The band gap of CdS quantum dots has increased from the bulk value 2.4-2.9 eV. PL spectra show quantum size effect and the peak is shifted from 628 to 556 nm when the ratio of T:A was changed from 1:25 to 1:3.3. Doping of CdS with Zn2+ and Cu2+ is found to enhance the PL intensity. PL band shows blue-shift and red-shift on doping with Zn2+ and Cu2+, respectively. UV and PL spectral features of the CdS/Au hybrid nanoparticles obtained by a physical mixing of CdS and Au nanoclusters in various volume ratios is also discussed. Au red-shifts and rapidly quenches the PL of CdS. An additional low energy band approximately 650 nm is observed in the UV visible spectrum of the hybrid nanoparticles.     

Synthesis and thermal studies of flexible polyurethane nanocomposite foams obtained using nanoclay modified with flame retardant compound

This work presents thermal studies of nanocomposites based on the flexible polyurethane (PU) matrix and filled using montmorillonite organically modified with organophosphorus flame retardant compound. Flexible PU nanocomposite foams were prepared in the reaction carried out between reactive alcoholic hydroxyl and isocyanate groups with the ratio of NCO to OH groups equal to 1.05. The amount of an organoclay ranging from 3 to 9 vol% was added to the polyol component of the resin before mixing with isocyanate. The apparent density of PU foams was ranging from 0.066 to 0.077 g cm^?1. Thermal properties of the flexible PU nanocomposite foams were investigated by thermogravimetry and dynamical mechanical analysis. Glass transition temperatures (T _g) were defined as maximum peak on tanδ curve. Thermal decomposition was observed at 310–320 °C (calculated from the onset of TG curve). Tensile strength of the PU foams was determined using mechanical test. The microstructure of the nanoparticles and the composites was investigated by X-ray diffraction. Finally, it was confirmed that the thermal and mechanical properties of flexible PU nanocomposite depend on the amount of nanoclay.     

Neutron activation analysis using a modified absolute calibration method

Journal of Radioanalytical and Nuclear Chemistry - In this work a modified absolute calibration method of neutron activation analysis (NAA) was proposed. Reaction rates per atom of elements of...     

Polymer-anchoring Schiff base ligands and their metal complexes: Investigation of their electrochemical,photoluminescence, thermal and catalytic properties

In this study, we prepared three polymer-anchored Schiff base ligands and their Cu(II), Co(II) and Ni(II) transition metal complexes. For this purpose, we synthesized three Schiff base ligands from the reaction of 2,4-dihydroxybenzaldehyde with diamines in the ethanol solution and characterized by the analytical and spectroscopic methods. We investigated the electrochemical and photophysical properties of the free Schiff base ligands in different solvents and concentrations. In the electrochemical studies, we found that the ligands show the reversible and irreversible redox processes. In order to obtain the polymer-anchored ligands, we used Merrifield’s peptide resin (PS) as solid support. The surface morphologies of the polymer anchored Schiff base ligands were done with the scanning electron microscopy (SEM). We did alkene epoxidation and alkane oxidation reactions of the metal complexes and used the cyclohexene, styrene, cyclohexane and cyclooctane as the substrate and they show the low catalytic activity. The metal complexes have no selectivity in the oxidation reactions. The polymer anchored Schiff base ligands and their metal complexes have high thermal stability at the higher temperatures.     

Preparation of LaPO4 nanowires with high aspect ratio by a facile hydrothermal method and their photoluminescence

LaPO₄ nanowires (NWs) measuring 10–15 nm in diameter and up to 4 μm long were prepared by a 200 °C and 12 h hydrothermal reaction of LaCl₃ and Na₃PO₄·12H₂O solution with pH adjusting by 37 % HNO₃ to 1, without using any surfactants or templates. The as-prepared LaPO₄ NWs were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning and transmission electron microscopy, and UV–visible and photoluminescent spectroscopy. In the present research, photonic luminescence and absorbance of LaPO₄ NWs show the maximum emission at 397.60 nm in the violet region and a band gap of 2.87 eV.     

Silica coating of silver nanoparticles using a modified Stober method

Silver nanoparticles prepared through a borohydride-reduction method were directly coated with silica by means of a seeded polymerization technique based on the Stober method. Various amine catalysts were used for initialization of a sol-gel reaction of TEOS with no need for a prior surface modification. Use of dimethylamine (DMA) as a catalyst was found to be necessary to obtain a proper coating. The silica shell thickness was varied from 28 to 76 nm for TEOS concentrations of 1-15 mM at 11.1 M water and 0.8 M DMA. The optical spectra of the core-shell silver-silica composite particles show a qualitative agreement with predictions by Mie theory.     

溶剂热合成片状介孔CeO2及光致发光性能

本文以乙二醇为溶剂,Ce(NO3)3·6H2O为铈源,尿素为沉淀剂,采用了溶剂热法一步合成了二维片状结构的介孔CeO2,同时讨论了不同反应时间对晶型的影响。通过SEM、TEM、XRD、EDS和N2吸附-脱附等检测手段进行了表征,结果表明所合成CeO2是由大量较规整的片状结构单元组成,在片状结构上分布着均匀有序的介孔,产物具有立方萤石型结构,并考察了相应的光致发光性能。     

Synthesis of mercaptoethylamine-coated CdSe/CdS nanocrystals and their use for DNA probe.

CdSe/CdS nanocrystals (NCs) have been synthesized in aqueous solution by using mercaptoethylamine as a stabilizer. The results of TEM, UV-Vis and FL spectra show that the product is of excellent crystal structure, uniform in radius, with extraordinary fluorescence characters. These CdSe/CdS NCs allow the ultrasensitive quantitative detection of DNA. Under the optimum conditions, linear relationships have been found between the relative fluorescence intensity and the DNA concentration in the ranges 0 - 10 and 10 - 100 microg mL(-1); the linear equations are DeltaF = 210 + 80.91 C and DeltaF = 946 + 10.57 C (C, microg mL(-1)), respectively. The detection limits are 0.251 and 1.920 microg mL(-1), correspondingly. The proposed method has been applied to the determination of DNA in pig liver. It is indicated that these NCs could become a newly kind of DNA probe. In addition, the mechanism of the binding reaction has also been explored. It is considered that the binding reaction is mainly due to static electricity forces.