Versatile PEG-derivatized phosphine oxide ligands for water-dispersible metal oxide nanocrystals

We report the simple synthesis of poly(ethylene glycol)(PEG)-derivatized phosphine oxide ligands for water-dispersible metal oxide nanocrystals.     

电感耦合等离子体原子发射光谱(ICP-AES)法测定铸造用硅砂中的Fe2O3、Al2O3、CaO、MgO、TiO2、K2O、Na2O

建立了电感耦合等离子体原子发射光谱(ICP-AES)法测定铸造用硅砂中Fe_2O_3、Al_2O_3、CaO、MgO、TiO_2、K_2O、Na_2O的方法。研究了溶样方法的选择优化,采用硝酸、氢氟酸溶样,冒高氯酸处理,通过元素分析线的选择,基体和共存元素影响的消除,在最佳的仪器分析条件下得出了方法的线性范围、相关系数及检出限。用硅砂3个梯度含量的标准物质的分析结果评价方法的准确度和精密度。方法的检出限Fe为0.012μg/mL、Al为0.032μg/mL、Ca为0.27μg/mL、Mg为0.003 2μg/mL、Ti为0.002 1μg/mL、K为0.16μg/mL,Na为0.000 44μg/mL。5次数据的相对标准偏差说明方法稳定性较好。方法适用于铸造用硅砂中Fe_2O_3、Al_2O_3、CaO、MgO、TiO_2、K_2O、Na_2O含量的测定。     

Thermodynamic stability of clusters of molybdenum oxide

We show that a single geometrical rule underlies the stability of "polyoxomolybdates", the variety of clusters of molybdenum(VI) oxide in (acidified) aqueous solution that are found experimentally. We predict that upon increasing the proton or total molybdenum oxide concentration, the average size of the clusters increases. We compare our predictions with results from ultracentrifugation experiments and with data in the literature. Finally, it is shown that the formation of metal oxide clusters is thermodynamically equivalent to the formation of surfactant micelles.     

Creation of thin oxide coatings and oxide nanopowders by anodic oxidation of metals in molten salts

We studied the feasibility of synthesizing ultrafine oxide powders by anodic oxidation of metals, such as zirconium and tantalum, in chloride + nitrate melts at temperatures above 830K. We showed that, varying the electrolyte composition, oxidation temperature, and anodic current density, one obtains either compact protective coatings on the specified metals or oxide powders with particle sizes of 50 to 200 nm.     

One-pot reduction of graphene oxide at subzero temperatures

We report a new reducing agent system: hydriodic acid with trifluoroacetic acid, which can chemically convert graphene oxide into reduced graphene oxide at temperatures below 0 °C in solution. This is the first achievement to produce reduced graphene oxide at subzero temperature with a mass production.     

Copper oxide nanocrystals

It is well-known that inorganic nanocrystals are a benchmark model for nanotechnology, given that the tunability of optical properties and the stabilization of specific phases are uniquely possible at the nanoscale. Copper (I) oxide (Cu(2)O) is a metal oxide semiconductor with promising applications in solar energy conversion and catalysis. To understand the Cu/Cu(2)O/CuO system at the nanoscale, we have developed a method for preparing highly uniform monodisperse nanocrystals of Cu(2)O. The procedure also serves to demonstrate our development of a generalized method for the synthesis of transition metal oxide nanocrystals. Cu nanocrystals are initially formed and subsequently oxidized to form highly crystalline Cu(2)O. The volume change during phase transformation can induce crystal twinning. Absorption in the visible region of the spectrum gave evidence for the presence of a thin, epitaxial layer of CuO, which is blue-shifted, and appears to increase in energy as a function of decreasing particle size. XPS confirmed the thin layer of CuO, calculated to have a thickness of approximately 5 A. We note that the copper (I) oxide phase is surprisingly well-stabilized at this length scale.     

Analysis of ethylene oxide sequences of the acetal copolymer from trioxane and ethylene oxide

An NMR method for the analysis of the ethylene oxide sequence of the acetal copolymer from trioxane and ethylene oxide has not yet been established. We found three novel cyclic compounds composed of 1 mol of ethyelene oxide and 1 mol of trioxane, 2 mol of ethylene oxide and 1 mol of trioxane, and 3 mol of ethylene oxide and 1 mol of trioxane. These compounds gave only one consecutive oxyethylene unit, two consecutive oxyethylene units, and three consecutive oxyethylene units in three consecutive oxymethylene units, respectively, and gave different ¹H NMR spectra for each oxyethylene unit. Considering these data, we synthesized three polymeric model compounds that have one consecutive oxyethylene sequence, two consecutive oxyethylene sequences, and three consecutive oxyethylene sequences in an oxymethylene main chain. By a linear combination of the ¹H NMR spectrum of each oxyethylene unit of the three polymeric model compounds, we succeeded in determining the ethylene oxide sequence by the ¹H NMR method for the copolymer from trioxane and ethylene oxide. Good agreement was observed between the ¹H NMR method and the hydrolysis method for the analysis of the ethylene oxide sequences. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3239–3245, 2001     

Zinc oxide quantum rods

Nanoscale zinc oxide (ZnO) rods of diameters close to the Bohr-exciton radius ( approximately 2 nm) can be prepared from a simple acetate precursor, resulting in ligand-capped rods of ZnO, highly dispersible in nonpolar solvents. Zinc oxide, ZnO, is a wide band-gap semiconductor with applications in blue/ultraviolet (UV) optoelectronic devices and piezoelectric devices. We observe self-assembly into uniform stacks of nanorods aligned parallel to each other with respect to the long axis, and photoluminescence measurements provide evidence for one-dimensional quantum confinement.     

Characterization and demulsification of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) copolymers

Four poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) copolymers with different molecular weights and PPO/PEO composition ratios were synthesized. The characterization of the PEO-PPO-PEO triblock copolymers was studied by surface tension measurement, UV-vis spectra, and surface pressure method. These results clearly showed that the CMC of PEO-PPO-PEO was not a certain value but a concentration range, in contrast to classical surfactant, and two breaks around CMC were reflected in both surface tension isotherm curves and UV-vis absorption spectra. The range of CMC became wider with increasing PPO/PEO composition ratio. Surface pressure Pi-A curves revealed that the amphiphilic triblock copolymer PEO-PPO-PEO molecule was flexible at the air/water interface. We found that the minimum area per molecule at the air/water interface increased with the proportion of PEO chains. The copolymers with the same mass fractions of PEO had similar slopes in the isotherm of the Pi-A curve. From the demulsification experiments a conclusion had been drawn that the dehydration speed increased with decreased content of PEO, but the final dehydration rate of four demulsifiers was approximate. We determined that the coalescence of water drops resulted in the breaking of crude oil emulsions from the micrograph.     

High-efficiency surface-induced dissociation on a rhenium oxide surface

We report on the high-efficiency surface-induced dissociation of benzene and cyclohexane polyatomic ions after scattering from a rhenium oxide surface with a kinetic energy of 5–290 eV. Rhenium oxide was prepared by directly heating a rhenium metal foil, under 10^?5 mbar partial oxygen pressure, at about 1000 K. Rhenium oxide is characterized by a very high work function of 6.4 eV and thus minimizes ion reneutralization probabilities. The catalytic combustion of surface organic impurities with oxygen ensures good long-term stability. We found that the surface-induced dissociation ion current is 70 times larger on rhenium oxide than on bare rhenium or stainless steel. Absolute scattered ion yields of about 50% were measured. The implications of surface-induced dissociation on mass spectrometry in supersonic molecular beams are mentioned.     

Protein-directed reduction of graphene oxide and intracellular imaging

We demonstrate a facile, one-step, protein-directed approach to preparing a new functional reduced graphene oxide via simultaneous reduction and surface functionalization of graphene oxide sheets with herceptin and show its potential application as a novel biological imaging agent.     

A cast-mold approach to iron oxide and Pt/iron oxide nanocontainers and nanoparticles with a reactive concave surface

We report the synthesis of various iron oxide nanocontainers and Pt-iron oxide nanoparticles based on a cast-mold approach, starting from nanoparticles having a metal core (either Au or AuPt) and an iron oxide shell. Upon annealing, the particles evolve to asymmetric core-shells and then to heterodimers. If iodine is used to leach Au out of these structures, asymmetric core-shells evolve into "nanocontainers", that is, iron oxide nanoparticles enclosing a cavity accessible through nanometer-sized pores, while heterodimers evolve into particles with a concave region. When starting from a metal domain made of AuPt, selective leaching of the Au atoms yields the same iron oxide nanoparticle morphologies but now encasing Pt domains (in their concave region or in their cavity). We found that the concave nanoparticles are capable of destabilizing Au nanocrystals of sizes matching that of the concave region. In addition, for the nanocontainers, we propose two different applications: (i) we demonstrate loading of the cavity region of the nanocontainers with the antitumoral drug cis-platin; and (ii) we show that nanocontainers encasing Pt domains can act as recoverable photocatalysts for the reduction of a model dye.     

The molecular structures of gaseous cyclopentene oxide,cyclohexene oxide and cycloheptene oxide as determined by electron diffraction

The molecular structures of gaseous cyclopentene oxide, cyclohexene oxide and cycloheptene oxide are investigated by electron diffraction. The boat conformation of cyclopentene oxide is confirmed, while a half-chair conformer is determined for cyclohexene oxide. Cycloheptene oxide is found to exist in a 66(2):34(2) conformational mixture of two chair forms.     

Adsorption of nitrous oxide on the(6,0) magnesium oxide nanotube

Nitrous oxide adsorption on the pristine（6,0） magnesium oxide nanotube was studied by using density functional theory calculations.We present the nature of the N₂O interaction in selected sites of the nanotube.Adsorption energies corresponding to adsorption of the N₂O on the nanotube were calculated to be in the range -11.67 to -22.21 kJ mol^-1.Our results indicate that the N₂O molecule has a weak physical adsorption on the pristine models due to weak Van der Waals interaction between the nanotubes and N₂O molecule.The important results can be useful in production of the N₂O sensors.     

Reactivity of hydrogen species on oxide surfaces

Hydrogen species on oxides are widely involved in oxides-catalyzed reactions such as H_2/hydrocarbon oxidation, hydrogenation/dehydrogenation, water-gas shift, and water-splitting reactions. Thus identifications of hydrogen species on oxide surfaces and their reactivity are important for fundamental understanding of these oxides-catalyzed reactions. In this Feature Article, we briefly review our research progress on the reactivity of various hydrogen species on oxides, including surface hydroxyl species,hydride species and hydrated protons. We have successfully developed effective strategies of using gas-phase atomic H to controllably create oxygen vacancies and prepare various hydrogen species on oxide model catalysts under ultra-high vacuum(UHV) conditions and using well-defined oxide nanocrystals with different surface structures and oxygen vacancy concentrations to study the H_2-oxide interaction under ambient or even higher H_2 pressures. Reactivity of various hydrogen species on oxide surfaces has been identified, including local oxygen vacancy-controlled reactivity of OH species, oxygen vacancystabilized hydride species, homolytic dissociation of H2 at oxygen vacancies of reduced oxide surfaces into hydride species accompanied by surface oxidation, photoexcited holes-stimulated desorption of hydride species, electron-stimulated desorption of hydride and OH species, and photoexcited electrons-stimulated desorption of hydrated protons. Strong influences of oxygen vacancies in oxides on both stability and reactivity of various hydrogen species on oxide surfaces are highlighted.     

Gas-bubble effects on the formation of colloidal iron oxide nanocrystals

This paper reports that gas bubbles can be used to tailor the kinetics of the nucleation and growth of inorganic-nanocrystals in a colloidal synthesis. We conducted a mechanistic study of the synthesis of colloidal iron oxide nanocrystals using gas bubbles generated by boiling solvents or artificial Ar bubbling. We identified that bubbling effects take place through absorbing local latent heat released from the exothermic reactions involved in the nucleation and growth of iron oxide nanocrystals. Our results show that gas bubbles display a stronger effect on the nucleation of iron oxide nanocrystals than on their growth. These results indicate that the nucleation and growth of iron oxide nanocrystals may rely on different types of chemical reactions between the iron-oleate decomposition products: the nucleation relies on the strongly exothermic, multiple-bond formation reactions, whereas the growth of iron oxide nanocrystals may primarily depend upon single-bond formation reactions. The identification of exothermic reactions is further consistent with our results in the synthesis of iron oxide nanocrystals with boiling solvents at reaction temperatures ranging from 290 to 365 °C, by which we determined the reaction enthalpy in the nucleation of iron oxide nanocrystals to be -142 ± 12 kJ/mol. Moreover, our results suggest that a prerequisite for effectively suppressing secondary nucleation in a colloidal synthesis is that the primary nucleation must produce a critical amount of nuclei, and this finding is important for a priori design of colloidal synthesis of monodispersed nanocrystals in general.     

Magnetic control of bioelectrocatalytic processes based on assembled iron oxide particles

A facile magnetic control system was designed in bioelectrocatalytic process based on functionalized iron oxide particles. The iron oxide particles were modified with glucose oxidase, and ferrocene dicarboxylic acid was used as electron transfer mediator. Functionalized iron oxide particles can assemble along the direction of applied magnetic field, and the directional dependence of the assembled iron oxide particles can be utilized for device purposes. We report here how such functionalized magnetic particles are used to modulate the bioelectrocatalytic signal by changing the orientation of the applied magnetic field.     

Structures of oxide nanobelts and nanowires.

We have recently reported the synthesis of one-dimensional nanobelt structures of ZnO, SnO2, In2O3, CdO, Ga2O3, and PbO2 by evaporating the desired commercial metal oxide powders at high temperatures (Science (2001), 291, 1947). The as-synthesized oxide nanobelts are pure, structurally uniform, single crystalline, and most of them free from dislocations. The beltlike morphology appears to be a unique and common structural characteristic for the family of semiconducting oxides. In the present article, we focus on the twin and stacking fault planar defects found in oxide nanobelts and nanowires although they are rarely observed. Some interesting and unique growth morphologies are presented to illustrate the roles played by surface energy and kinetics in growth. It is shown that the surfaces of the oxide nanobelts are enclosed by the low-index, low-energy crystallographic facets. The growth morphology is largely dominated by the growth kinetics.     

A Useful Poly(ethylene oxide)‐poly(propylene oxide)‐poly(ethylene oxide) Triblock Crosslinker in a Diffusion‐Controlled Polymerization Method

Monodisperse micron‐sized polystyrene particles crosslinked with a novel poly(ethylene oxide)‐poly(propylene oxide)‐poly(ethylene oxide) triblock diol diacrylate (t‐BDDA) were produced via simple dispersion polymerization. It was established that the monomer‐diffusible surface characteristics of primary particles played a decisive role in producing the monodisperse crosslinked polymer particles. We named this concept a diffusion‐controlled polymerization method, DPM. Here in this study, particularly, t‐BDDA is proposed as a very useful crosslinker capable of self‐assembling and crosslinking in the process of particle formation and particle growth.