Ice/Salt-Assisted Synthesis of Ultrathin Two-Dimensional Micro/Mesoporous Iron and Nitrogen Co-Doped Carbon as an Efficient Electrocatalyst for Oxygen Reduction

An ice/salt-assisted strategy has been developed to achieve the green and efficient synthesis of ultrathin two-dimensional (2D) micro/mesoporous carbon nanosheets (CNS) with the dominant active moieties of Fe−N₄ (Fe-N-CNS) as high-performance electrocatalysts for the oxygen reduction reaction (ORR). The strategy involves freeze-drying a mixture of iron porphyrin and KCl salt using ice as template followed by a confined pyrolysis with KCl as an independent sealed nanoreactor to facilitate the formation of 2D carbon nanosheets, N incorporation, and porosity creation. The well-defined assembly of ultrathin 2D carbon nanosheets ensures high utilization of D1 and D3 Fe−N₄ active sites, and effectively promotes the mass transport of ORR reactants by virtue of the pronounced mesoporous structure. The resulting Fe-N-CNS electrocatalyst was shown to exhibit superior ORR activity, better electrochemical durability, and methanol tolerance towards ORR in alkaline electrolyte relative to the commercial Pt/C electrocatalyst.     

Improved synthetic routes to methylene-bridged P-chiral diphosphine ligands via secondary phosphine–boranes

Improved methods for the preparation of methylene-bridged diphosphine ligands are described. Both enantiomers of the key intermediate tert-butylmethylphosphine–borane were prepared via resolution or by the conversion of one enantiomer into the opposite enantiomer. The precursor borane complexes of bis(tert-butylmethylphosphino)methane (t-Bu-MiniPHOS), bis((1,1,3,3-tetramethylbutyl)methylphosphino)methane (t-Oct-MiniPHOS), and (tert-butylmethylphosphino)(di-tert-butylphosphino)methane (trichickenfootphos) were prepared in good yields and enantiopure form.     

Transition-metal-free controlled polymerization for poly(p-aryleneethynylene)s

A transition-metal-free controlled polymerization for the attainment of poly(p-aryleneethynylene)s is developed. The polymerization of 1-pentafluorophenyl-4-[(trimethylsilyl)ethynyl]benzene with a catalytic amount of fluoride anions proceeds in a chain-growth-like manner to afford polymers with controlled molecular weights and low polydispersity indexes. The mechanism involves a pentacoordinated fluorosilicate as a key intermediate. The anionic “living” nature of this process is applied to block copolymerization and also surface-terminated polymerization.     

Topographic, electrochemical, and optical images captured using standing approach mode scanning electrochemical/optical microscopy

We developed a high-resolution scanning electrochemical microscope (SECM) for the characterization of various biological materials. Electrode probes were fabricated by Ti/Pt sputtering followed by parylene C-vapor deposition polymerization on the pulled optical fiber or glass capillary. The effective electrode radius estimated from the cyclic voltammogram of ferrocyanide was found to be 35 nm. The optical aperture size was less than 170 nm, which was confirmed from the cross section of the near-field scanning optical microscope (NSOM) image of the quantum dot (QD) particles with diameters in the range of 10-15 nm. The feedback mechanism controlling the probe-sample distance was improved by vertically moving the probe by 0.1-3 microm to reduce the damage to the samples. This feedback mode, defined as "standing approach (STA) mode" (Yamada, H.; Fukumoto, H.; Yokoyama, T.; Koike, T. Anal. Chem. 2005, 77, 1785-1790), has allowed the simultaneous electrochemical and topographic imaging of the axons and cell body of a single PC12 cell under physiological conditions for the first time. STA-mode feedback imaging functions better than tip-sample regulation by the conventionally available AFM. For example, polystyrene beads (diameter approximately 6 microm) was imaged using the STA-mode SECM, whereas imaging was not possible using a conventional AFM instrument.     

Adsorption and aggregation properties of heterogemini surfactants containing a quaternary ammonium salt and a sugar moiety

A novel heterogemini surfactant comprising two hydrocarbon chains and two different hydrophilic groups such as a quaternary ammonium cation and gluconamide nonion N,N-dimethyl-N-[2-(N'-alkyl-N'-gluconamide)ethyl]-1-alkylammonium bromides (2CnAmGlu, where n represents hydrocarbon chain lengths of 8, 10, 12, and 14) was synthesized by reacting N,N-dimethylethylenediamine with alkyl bromide, followed by a reaction with 1,5-D(+)-gluconolactone. The adsorption properties of 2CnAmGlu were characterized by surface tension measurements made using the Wilhelmy plate method, and their aggregation properties were investigated by dynamic light scattering and cryogenic transmission electron microscopy techniques. The relationship between the hydrocarbon chain length and the logarithm of the critical micelle concentration (cmc) for 2CnAmGlu exhibited a linear decrease when the chain length was increased up to 12 and then a departure from linearity at n=14. The surface tension reached 24-26 mN m-1 at each cmc, indicating high efficiency in lowering the surface tension of water. Furthermore, it was found that the structure of the aggregate formed for 2CnAmGlu in solution was influenced by the hydrocarbon chain length; that is, for n=10 and 12, micelles with a hydrodynamic radius of 2-5 nm were formed, whereas vesicles were also observed for n=14.     

Adsolubilization of 2-naphthol into adsorbed layer of PEO-PPO-PEO triblock copolymers on hydrophilic silica

Adsolubilization of 2-naphthol into an adsorbed layer of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers (Pluronics) on hydrophilic silica has been investigated. Four kinds of Pluronics (P103, P105, P123, and F108) were used in order to understand the effect of the hydrophobicity of surfactant on the adsolubilization. The order of the adsorption in the saturation level was found to be P123 approximately P103 > P105 > F108, meaning that Pluronics with higher hydrophobicity can adsorb preferentially to the silica surface. Indeed, this order was parallel to the order of the adsolubilization amount of 2-naphthol. In the case of co-addition of the Pluronics and 2-naphthol, the adsolubilization amount increased gradually at lower surfactant concentration regions, reached a maximum, and then decreased with increasing concentration of the Pluronics. The maximum amount appeared at critical polymolecular micelle concentration of each Pluronics. On the other hand, the final decrement was not observed when 2-naphthol was added after replacement of the Pluronics supernatant by the Pluronics free solution. These results suggest that adsolubilization behavior is influenced by the existence of the polymolecular micellar aggregates in the solution phase.     

Photoinduced alignment of nanocylinders by supramolecular cooperative motions

A linearly polarized laser beam was used to control nanocylinders self-assembled in an amphiphilic diblock liquid-crystalline copolymer consisting of flexible poly(ethylene oxide) as a hydrophilic block and poly(methacrylate) containing an azobenzene moiety in the side chain as a hydrophobic liquid-crystalline segment. The perfect array of poly(ethylene oxide) nanocylinders was achieved, aligned perpendicularly to the polarization direction of the actinic light by supramolecular cooperative motions between the ordered azobenzene and microphase separation. By the simple and convenient way of photocontrol, the macroscopic parallel patterning of nanocylinders can be easily obtained in an arbitrary area.     

Synthesis and photophysical properties of electron-rich perylenediimide-fullerene dyad

An electron-rich perylenediimide-C60 dyad has been prepared to explore a new type of donor-acceptor system. Time-resolved absorption measurements in benzonitrile revealed unambiguous evidence for the formation of a charge-separated state consisting of perylene diimide radical cation and C60 radical anion via photoinduced electron transfer, showing a new class of artificial photosynthetic models in terms of charge separation.     

In vivo isotropic 3D diffusion tensor mapping of the rat brain using diffusion-weighted 3D MP-RAGE MRI

The purpose of this study was to examine the potential of diffusion-weighted (DW) three-dimensional (3D) MP-RAGE MRI for diffusion-tensor mapping of the rat brain in vivo. A DW-3D-MP-RAGE (3D-DWI) sequence was implemented at 2.0 T using six gradient orientations and a b value of 1000 s/mm2. In this sequence, the preparation sequence with a "90 degrees RF-motion proving gradient (MPG): MPG-180 degrees RF-MPG-90 degrees RF" pulse train (DW driven equilibrium Fourier transform) was used to sensitize the magnetization to diffusion. A centric k-space acquisition order was necessary to minimize saturation effects (T1 contamination) from tissues with short relaxation time. The image matrix was 128x128x128 (interpolated from 64x64x64 acquisitions), which resulted in small isotropic DW image data (voxel size: 0.273x0.273x0.273 mm3). Moreover, 3D-DWI-derived maps of the fractional anisotropy (FA), relative anisotropy (RA) and main-diffusion direction were completely free of susceptibility-induced signal losses and geometric distortions. Two well-known commissural fibers, the corpus callosum and anterior commissure, were indicated and shown to be in agreement with the locations of these known stereotaxic atlases. The experiment took 45 min, and shorter times should be possible in clinical application. The 3D-DWI sequence allows for in vivo 3D diffusion-tensor mapping of the rat brain without motion artifacts and susceptibility to distortion.     

Ultrafast photosynthetic reduction of elemental sulfur by Au nanoparticle-loaded TiO2

Nanometer-sized gold particles with varying mean size from 3.2 to 12.2 nm were loaded on the surfaces of TiO2 particles in a highly dispersed state with the loading amount maintained constant (0.46 +/- 0.02 mass %) using the deposition-precipitation method. Light irradiation (lambda(ex) > 300 nm) to a deaerated ethanol TiO2 particle suspension containing elemental sulfur (S8) led to the energetically uphill reduction of S8 to H2S. It has been found that this reaction is dramatically enhanced with such a low level of Au loading on TiO2 and that the zero-order rate constant of reaction increases with decreasing mean size of Au nanoparticles (d). The effects of reaction parameters (substrate concentration, light intensity, temperature) on the rate of reaction were studied to infer the essential reaction mechanism. Further, a kinetic analysis has led to a conclusion that the increase in the rate of reaction with decreasing d results from the improvement of the charge separation efficiency.