Electrically-controlled near-infrared chiroptical switching of enantiomeric dinuclear ruthenium complexes

Enantiomerically pure dinuclear ruthenium complexes with 1,2-dicarbonylhydrazide as a bridging ligand are optically active in the visible and near infrared spectral regions depending on the oxidation states of the metal centers and are useful as an electrochemically driven near infrared chiroptical switch.

Synthesis of biodegradable thermo- and pH-responsive hydrogels for controlled drug release

Novel intelligent hydrogels composed of biodegradable and pH-sensitive poly(L-glutamic acid) (PGA) and temperature sensitive poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) (PNH) were synthesized and characterized for controlled release of hydrophilic drug. The influence of pH on the equilibrium swelling ratios of the hydrogels was investigated. A higher PNH content resulted in lower equilibrium swelling ratios. Although temperature had little influence on the swelling behaviors of the hydrogels, the changes of optical transmittance of hydrogels as a function of temperature were marked, which showed that the PNH part of hydrogel exhibited hydrophobic property at temperature above the lower critical solution temperature (LCST). The biodegradation rate of the stimuli-sensitive hydrogels in the presence of enzyme was directly proportional to the PGA content. Lysozyme was chosen as a model drug and loaded into the hydrogels.

Facile shape-controlled synthesis of luminescent europium benzene-1,3,5-tricarboxylate architectures at room temperature

The large-scale synthesis of the metal-organic framework Eu(1,3,5-BTC)center dot 6H(2)O nanocrystallites with delicate morphologies such as sheaflike, butterflylike, and flowerlike superstructures composed of nanowires have been realized via a simple solution phase method at room temperature. Time-dependent experiments indicate that these superstructures were constructed by the splitting crystal growth mechanism, as has been noted in some minerals in nature. The synthetic parameters such as reaction time, concentration and molar ratio of reactants, surfactant, and reaction temperature all affected the morphology of the Eu(1,3,5-BTC)center dot 6H(2)O architectures. These well-arranged architectures exhibit red emission corresponding to the D-5(0) -> F-7(2) transition of the Eu3+ ions under UV light excitation, and the lifetime is determined to be about 0.22 ms.

A novel urchinlike gold/platinum hybrid nanocatalyst with controlled size

In this paper, we have explored a simple and new strategy to obtain quasimonodisperse Au/Pt hybrid nanoparticles (NPS) with urchinlike morphology and controlled size and Pt shell thickness. Through changing the molar ratios of Au to Pt, the Pt shell thickness of urchinlike Au/Pt hybrid NPs could be easily controlled; through changing the size of Au NPs (the size was easily controlled from similar to 3 to similar to 70 nm via simple heating of HAuCl4-citrate aqueous solution), the size of urchinlike Au/Pt hybrid NPs could be facilely dominated. It should be noted that heating the solution (100 degrees C) was very necessary for obtaining three-dimensional (3D) urchinlike nanostructures while H2PtCl6 was added to gold NPs aqueous solution in the presence of reductant (ascorbic acid). The electrocatalytic oxygen reduction reaction (ORR, a reaction greatly pursued by scientists in view of its important application in fuel cells) and the electron-transfer reaction between hexacyanoferrate(III) ions and thiosulfate ions of urchinlike Au/Pt hybrid NPs were investigated. It is found that the as-prepared urchinlike Au/Pt hybrid NPs exhibited higher catalytic activities than that of similar to Pt NPs with similar size.

Rectangular Silver Nanorods: Controlled Preparation, Liquid-Liquid Interface Assembly, and Application in Surface-Enhanced Raman Scattering

In this paper, we for the first time report a polyol method for large-scale synthesis of rectangular silver nanorods in the presence of directing agent and seeds. This method has some clear advantages including simplicity, high quality, and ease of scaleup. Silver nanowires or silver nanorods with a submicrometer diameter could also be facilely prepared when the reaction parameters are slightly changed. Furthermore, a liquid-liquid assembly strategy has been employed to construct uniform rectangular silver nanorod arrays on a solid substrate which could be used as surface-enhanced Raman scattering (SERS) substrates with high SERS activity, stability, and reproducibility. It is found that the SERS spectra obtained from the probe molecules with the different concentrations show different SERS intensifies. As the concentration of 4-aminothiophenol (4-ATP) or rhodamine 6G (R6G) increases, the SERS intensities progressively increase. The enhancement factor for 4-ATP and R6G should be as large as 5.06 x 10(4) or much larger than the value of 5.06 x 10(8), respectively.

Controlled synthesis of nanoporous Au microsheet via surfactant emulsion template

A facile and wet-chemical approach was employed to control synthesis of self-organizing, hyperbranched nanoporous Au microsheet with high quality in bulk quantity. This method produced nanoporous Au microsheets with a thickness of 7-15 nm. The microsheets were composed of irregularly interconnected planar Au nanoplates with interstices, i.e. nanopores of 10-50 nm. And the nanoporous Au microsheets were enveloped in 10-30 nm thick polyaniline (PANI) sheaths. The morphology of the nanostructured Au composites could also be easily tuned by changing the concentration of aniline and chlorauric acid. The dendritic and epitaxial growth of nanoporous Au microsheet was believed as the diffusion-limited process confined in the lamellar emulsion phase through self-assembly of aniline and dodecylsulfate. The solution reaction proceeded at a mild condition (room temperature and aqueous solutions), and less toxic reagents were employed instead of extreme toxic and corrosive chemicals.

Templateless, surfactantless, simple electrochemical route to rapid synthesis of diameter-controlled 3D flowerlike gold microstructure with "clean" surface

We report for the first time a simple low-cost electrochemical route to synthesis of diameter-controlled hierarchical flowerlike gold microstructures with "clean'' surfaces using gold nanoplates or nanopricks as building blocks without introducing any template or surfactant.

One-pot, high-yield synthesis of size-controlled gold particles with narrow size distribution

Here, we first report a facile one-step one-phase synthetic route to achieve size-controlled gold micro/nanoparticles with narrow size distribution by using o-diaminobenzene as a reducing agent in the presence of poly(N-vinyl-2-pyrrolidone) via a simple wet-chemical approach. All experimental data including that from scanning-electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction techniques indicates that the gold micro/nanoparticles with a narrow size distribution were produced in high yield (similar to 100%).

Soluble neodymium chloride 2-ethylhexanol complex as a highly active catalyst for controlled isoprene polymerization

Soluble NdCl3 center dot 3EHOH (2-ethyl hexanol) in hexane combined with AlEt3 is highly active for isoprene polymerization in hexane. The NdCl3 center dot 3EHOH/AlEt3 has higher activity than the typical binary catalyst NdCl3 center dot 3(i)PrOH (isopropanol)/AlEt3 and ternary catalyst NdV3 (neodymium versatate)/AlEt2Cl/Al(i-Bu)(2)H. The molecular weight of polyisoprenes can be controlled by variation of [Nd], [Al]/[Nd] ratio and polymerization temperature and time. The NdCl3 center dot 3EHOH/AlEt3 catalyst polymerized isoprene to afford products featuring high cis-1,4 stereospecificity (ca. 96%), high molecular weight (ca. 10(5)) and relatively narr ow molecular weight distributions (M-w/M-n = 2.0-2.8) simultaneously. More importantly, some living polymerization characteristics were demonstrated: (a) absence of chain termination; (b) linear correlation between M-n and polymer yield; (c) increment of molecular weight in the 'seeding' polymerization. Though some deviation from the typical living polymerization such as molecular weight distribution is not narrow enough and the line of M-n and polymer yield does not extrapolate to zero, controlled polymerization with the current catalyst can still be concluded.

Design of polymeric stabilizers for size-controlled synthesis of monodisperse gold nanoparticles in water

A new methodology is described for the one-step aqueous preparation of highly monodisperse gold nanoparticles with diameters below 5 nm using thioether- and thiol-functionalized polymer ligands. The particle size and size distribution was controlled by subtle variation of the polymer structure. It was shown that poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) were the most effective stabilizing polymers in the group studied and that relatively low molar mass ligands (similar to 2500 g/mol) gave rise to the narrowest particle size distributions. Particle uniformity and colloidal stability to changes in ionic strength and pH were strongly affected by the hydrophobicity of the ligand end group. "Multidentate" thiol-terminated ligands were produced by employing dithiols and tetrathiols as chain-transfer agents, and these ligands gave rise to particles with unprecedented control over particle size and enhanced colloidal stability. It was found throughout that dynamic light scattering (DLS) is a very useful corroboratory technique for characterization of these gold nanoparticles in addition to optical spectroscopy and TEM.