Phase separation of Lal3 inside single-walled carbon nanotubes.

Simple binary solids can be found to adopt unprecedented structures when confined into nanometre-sized cavities, such as the inner cylindrical bore of single-walled carbon nanotubes (SWNT). In the case of the discussed Lal(x)@SWNT encapsulation composite, the Lal2 "crystal" fragment adopts the structure of bulk Lal3, with one third of the iodine positions unoccupied. A complete characterisation of the encapsulation composite was achieved using an enhanced digital restoration approach of high-resolution transmission electron microscopy (HRTEM) images. The resulting complex exit surface wave provides information about the precise structural data of both filling material and host SWNT, establishing the SWNT's chirality and thus enabling a prediction of the composite's overall electron-transport properties.     

Single Atoms of Iron on MoS2 Nanosheets for N2 Electroreduction into Ammonia

Efforts have been devoted to achieving a highly efficient artificial synthesis of ammonia (NH₃). Reported herein is a novel Fe-MoS₂ catalyst with Fe atomically dispersed onto MoS₂ nanosheets, imitating natural nitrogenase, to boost N₂ electroreduction into NH₃ at room temperature. The Fe-MoS₂ nanosheets exhibited a faradic efficiency of 18.8 % with a yield rate of 8.63 μg mg_cat.⁻¹ h⁻¹ for NH₃ at −0.3 V versus the reversible hydrogen electrode. The mechanism study revealed that the electroreduction of N₂ was promoted and the competing hydrogen evolution reaction was suppressed by decorating the edge sites of S in MoS₂ with the atomically dispersed Fe, resulting in high catalytic performance for the electroreduction of N₂ into NH₃. This work provides new ideas for the design of catalysts for N₂ electroreduction and strengthens the understanding about N₂ activation over Mo-based catalysts.     

Microscale sample deposition onto hydrophobic target plates for trace level detection of neuropeptides in brain tissue by MALDI-MS

A sample preparation method that combines a modified target plate with a nanoscale reversed-phase column (nanocolumn) was developed for detection of neuropeptides by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). A gold-coated MALDI plate was modified with an octadecanethiol (ODT) self-assembled monolayer to create a hydrophobic surface that could concentrate peptide samples into a approximately 200-500-microm diameter spot. The spot sizes generated were comparable to those obtained for a substrate patterned with 200-microm hydrophilic spots on a hydrophobic substrate. The sample spots on the ODT-coated plate were 100-fold smaller than those formed on an unmodified gold plate with a 1-microl sample and generated 10 to 50 times higher mass sensitivity for peptide standards by MALDI-TOF MS. When the sample was deposited on an ODT-modified plate from a nanocolumn, the detection limit for peptides was as low as 20 pM for 5-microl samples corresponding to 80 amol deposited. This technique was used to analyze extracts of microwave-fixed tissue from rat brain striatum. Ninety-eight putative peptides were detected including several that had masses matching neuropeptides expected in this brain region such as substance P, rimorphin, and neurotensin. Twenty-three peptides had masses that matched peaks detected by capillary liquid chromatography with electrospray ionization MS.     

Shape-controlled synthesis of metal nanostructures: the case of silver

The concept of shape-controlled synthesis is discussed by investigating the growth mechanisms for silver nanocubes, nanowires, and nanospheres produced through a polymer-mediated polyol process. Experimental parameters, such as the concentration of AgNO(3) (the precursor to silver), the molar ratio between poly(vinylpyrrolidone) (PVP, the capping agent) and AgNO(3), and the strength of chemical interaction between PVP and various crystallographic planes of silver, were found to determine the crystallinity of seeds (e.g., single crystal versus decahedral multiply twinned particles). In turn, the crystallinity of a seed and the extent of the PVP coverage on the seed were both instrumental in controlling the morphology of final product. The ability to generate silver nanostructures with well-defined morphologies provides a great opportunity to experimentally and systematically study the relationship between their properties and geometric shapes.     

席夫碱自组装单分子膜的电化学行为

利用自组装技术将席夫碱硫醇衍生物在金表面形成自组装单分子膜,并初步研究了此自组装单分子膜的电化学行为,发现该席夫碱分子在0.1 mol•L－1的KCl溶液中具有电化学不可逆氧化还原行为，且随着自组装时间的增加表观电极反应速率常数值显著减小,最后减小为0,并对此进行了解释.     

Electrochemical Studies of Thiol Self‐Assembled Monolayers at a Heated Gold‐Wire Microelectrode

Mercaptoundecanoic acid (MUA) and glutathione (GSH) self‐assembled monolayers were prepared on gold‐ wire microelectrode. Cyclic voltammetry was used to investigate the influence of temperature on electrochemical behaviors of Fe(CN)₆^3?/4? and Ru(NH₃)₆^3+/2+ at these SAMs modified electrodes in aqueous solution. It is found that temperature shows great influence on electron transfer (ET) and mass transport (MT) for the two SAMs modified electrodes and the influence of temperature depends on the charge properties of the redox couples and terminal groups of SAMs and the structure of the monolayer on gold surface. The temperature can greatly increase MT rate of Fe(CN)₆^3?/4? at both MUA and GSH modified electrodes. However, the increased MT rate doesn't have any effect on the CV's for Fe(CN)₆^3?/4? /MUA system. For Ru(NH₃)₆^3+/2+ , temperature can greatly improve the electrochemical reaction in both MUA and GSH modified electrodes, which is ascribed to temperature‐induced diffusion and convection and the electrostatic interaction between Ru(NH₃)₆^3+/2+ and negatively charged carboxyl groups on the electrode surface.     

Rigid nanoscopic containers for highly dispersed, stable metal and bimetal nanoparticles with both size and site control

We demonstrate a novel strategy for the preparation of mesoporous silica-supported, highly dispersed, stable metal and bimetal nanoparticles with both size and site control. The supporting mesoporous silica, functionalized by polyaminoamine (PAMAM) dendrimers, is prepared by repeated Michael addition with methyl acrylates (MA) and amidation reaction with ethylenediamine (EDA), by using aminopropyl-functionalized mesoporous silica as the starting material. The encapsulation of metal nanoparticles within the dendrimer-propagated mesoporous silica is achieved by the chemical reduction of metal-salt-impregnated dendrimer-mesoporous silica by using aqueous hydrazine. The site control of the metal or bimetal nanoparticles is accomplished by the localization of inter- or intradendrimeric nanoparticles within the mesoporous silica tunnels. The size of the encapsulated nanoparticles is controlled by their confinement to the nanocavity of the dendrimer and the mesopore. For Cu and Pd, particles locate at the lining of mesoporous tunnels, and have diameters of less than 2.0 nm. For Pd/Pt, particles locate at the middle of mesoporous tunnels and have diameters in the range of 2.0-4.2 nm. The Pd and Pd/Pt nanoparticles are very stable in air, whereas the Cu nanoparticles are stable only in an inert atmosphere.     

Nanostructured pure gamma-Fe2O3 via forced precipitation in an organic solvent

Pure maghemite, gamma-Fe(2)O(3), was prepared as ultra fine particles in the nanometer-sized range via the forced precipitation method in an organic solvent. The precipitation of iron(III) ions, from iron(III) chloride in 2-propanol led selectively to highly dispersed particles of ferrihydrite, which upon treatment with temperatures higher than 200 degrees C under dynamic vacuum resulted in high-surface-area particles of gamma-Fe(2)O(3). Precipitation in water also led to ferrihydrite, but the final product, after heating at 300 degrees C, contained a mixture of gamma-Fe(2)O(3) and alpha-Fe(2)O(3) (hematite). The precipitation from iron(III) nitrate in water resulted in goethite which was converted to hematite upon heating. On the other hand, the final product in 2-propanol was a mixture of maghemite and hematite. The products were characterized by FTIR, TGA, XRD, and gas sorption analysis. Nitrogen gas adsorption studies for the pure gamma-Fe(2)O(3) samples revealed mesoporous particles with high surface areas in the range of 70-120 m(2) g(-1) after heat treatment at 300 degrees C. The gamma-Fe(2)O(3) particles retained their gamma-phase as well as their mesoporous structure at relatively high temperatures, as high as 400 degrees C.