The Bishop–Phelps–Bollobás theorem fails for bilinear forms on

In this paper we show that the Bishop–Phelps–Bollobás theorem fails for bilinear forms on l₁×l₁, while it holds for linear operators from l₁ to l_∞.     

Network single-walled carbon nanotube-field effect transistors (SWNT-FETs) with increased Schottky contact area for highly sensitive biosensor applications

Highly sensitive single-walled carbon nanotube-field effect transistor (SWNT-FET) devices, which detect protein adsorptions and specific protein-protein interactions at 1 pM concentrations, have been achieved. The detection limit has been improved 104-fold compared to the devices fabricated by photolithography. The substantially increased sensitivity is mainly due to the increased Schottky contact area which accommodates relatively more numbers of proteins even at very low concentration. The augmented number of proteins adsorbed on a device induces instant modulation of the work function of metal contact electrodes, which eventually changes the conductance of the device. Such devices have been attained by addressing metal electrodes on network-type SWNTs using a shadow mask on a tilted angle sample stage. The shadow mask allows metals to penetrate underneath the mask efficiently, therefore forming a thin and wide Schottky contact area on SWNT channels.     

Interactions of neutral and cationic transition metals with the redox system of hydroquinone and quinone: theoretical characterization of the binding topologies, and implications for the formation of nanomaterials

To understand the self-assembly process of the transition metal (TM) nanoclusters and nanowires self-synthesized by hydroquinone (HQ) and calix[4]hydroquinone (CHQ) by electrochemical redox processes, we have investigated the binding sites of HQ for the transition-metal cations TM(n+)=Ag(+), Au(+), Pd(2+), Pt(2+), and Hg(2+) and those of quinone (Q) for the reduced neutral metals TM(0), using ab initio calculations. For comparison, TM(0)-HQ and TM(n+)-Q interactions, as well as the cases for Na(+) and Cu(+) (which do not take part in self-synthesis by CHQ) are also included. In general, TM-ligand coordination is controlled by symmetry constraints imposed on the respective orbital interactions. Calculations predict that, due to synergetic interactions, silver and gold are very efficient metals for one-dimensional (1D) nanowire formation in the self-assembly process, platinum and mercury favor both nanowire/nanorod and thin film formation, while palladium favors two-dimensional (2D) thin film formation.     

Fully flexible unit cell simulation with recursive thermostat chains

The recursive thermostat chained fully flexible cell molecular dynamic simulation (NsigmaT ensemble) is performed. The ensemble is based on the metric tensor, whose components are used as extended variables. These variables are combined with Nosé-Poincaré recursive thermostat chains. This extended Hamiltonian approach preserves Hamiltonian in structure, and the partition function satisfies the NsigmaT ensemble state in phase space. In the present study, the generalized leap frog method was employed for time integration. The resulting molecular dynamics simulation was performed for bulk and thin film solid materials in the face-centered-cubic crystal structure. Uniaxial tension test and simple shear test are performed to predict the behaviors of a solid material in the bulk state and nanoscale thin film state. The proposed flexible cell method should serve as a powerful tool for the prediction of mechanical and thermal properties of solid materials including nanoscale behavior.     

ENDOR of NO-ligated cytochrome c'

The five-coordinate NO-bound heme in cytochrome c' from an overexpressing variant of denitrifying R. sphaeroides 2.4.3 was investigated by proton, nitrogen, and deuterium Q-band ENDOR (electron nuclear double resonance). ENDOR was a direct probe of the unpaired electron density on the nitrogen of NO and, as measured across the EPR line shape, showed a hyperfine coupling range from 36 to 44 MHz for 14NO and 51 to 63 MHz for 15NO. The smallest NO coupling occurred at an electronic g-tensor axis perpendicular to the FeNO plane, and the largest hyperfine coupling occurred in the FeNO plane where the highest nitrogen valence spin density is located. The isotropic component of the NO hyperfine coupling indicated that the electron spin on the NO is not simply in a pi orbital having only 2p character but is in an orbital having 2s and 2p character in a 1:2 ratio. ENDOR frequencies from heme meso-protons, assigned with reference to porphyrin models, were determined to result from an anisotropic hyperfine tensor. This tensor indicated the orientation of the heme with respect to the FeNO plane and showed that the FeNO plane bisects the heme N-Fe-N 90 degrees angle. ENDOR provided additional structural information through dipolar couplings, as follows: (1) to the nearest proton of the Phe14 ring, approximately 3.1 A away from the heme iron, where Phe14 is positioned to occlude binding of NO as a 6th (distal) ligand; (2) to exchangeable deuterons assigned to Arg127 which may H-bond with the proximal NO ligand.     

Fluoro-N,N,N',N'-tetramethylformamidinium hexafluorophosphate: a reagent for formation of interchain carboxylic anhydrides on self-assembled monolayers

In this paper, we report the reactivity of fluoro-N,N,N',N'-tetramethylformamidinium hexafluorophosphate (TFFH), a reagent for transformation of carboxylic acids into acid fluorides in solution, toward self-assembled monolayers (SAMs) of 16-mercaptohexadecanoic acid on gold. Contrary to the solution-based reactions, we found that only interchain carboxylic anhydrides (ICAs), not acid fluorides (AFs), were obtained at surfaces by the facile interchain reaction under most reaction conditions studied. AFs were found to be formed only when tetrabutylammonium fluoride, a reagent inducing fast decomposition of ICAs, was added to the reaction mixture. The reactivity of TFFH toward carboxylic acid-terminated SAMs was different from that of cyanuric fluoride, which has been reported previously (Langmuir 2005, 21, 11765-11772). This study provides more insight into the role of the proximity effect in SAM-based reactions as well as another approach to the formation of ICAs from carboxylic acid-terminated SAMs.     

Doped colloidal photonic crystal structure with refractive index chirping to the [111] crystallographic axis

A three-dimensionally ordered array of close-packed colloidal spheres, a photonic crystal structure in which the refractive index of the medium interstitial lattice in a colloidal crystal spatially changes in the [111] crystallographic axis, is demonstrated. The colloidal photonic crystal structure with refractive index chirping was produced by infiltration of a monomer and organic dopants with a high refractive index into a silica opal, followed by interfacial gel polymerization. The resulting photonic crystal structure has a gradually varying stop band at each different (111) plane in the face-centered cubic (fcc) crystal structure at a normal incidence. This novel structure exhibited optical characteristics that have band-gap broadening by the superposition of stop bands at each plane of the crystal with different dielectric functions. Moreover, the refractive index perturbation in the [111] fcc opal also showed a defect state within a pseudo-photonic band gap. This new type of photonic crystal structure should be useful for the band-gap engineering of photonic-band-gap materials.     

Polymerized rodlike nanoparticles with controlled surface charge density

Stable rodlike nanoparticles with highly controlled surface charge density have been developed by the free radical polymerization of the mixture of polymerizable cationic surfactant, cetyltrimethylammonium 4-vinylbenzoate (CTVB), and hydrotropic salt sodium 4-styrenesulfonate (NaSS) in aqueous solution. The surface charge of the polymerized CTVB/NaSS rodlike nanoparticles was controlled by varying the NaSS concentration during the polymerization process, and the charge variation was interpreted in terms of the overcharging effect in colloidal systems. The SANS measurements show that the diameter of the polymerized CTVB/NaSS rodlike nanoparticles is constant at 4 nm and the particle length ranges from 24 to 85 nm, depending on the NaSS concentration. The polymerized particles are longest when the NaSS concentration is 5 mol % which corresponds to the charge inversion or neutral point. The SANS and zeta potential measurements show that the Coulomb interactions between the particles are strongly dependent on the NaSS concentration and the zeta potential of the polymerized CTVB/NaSS nanoparticles changes from positive to negative (+12.8 approximately -44.2 mV) as the concentration of NaSS increases from 0 to 40 mol %. As the NaSS concentration is further increased, the zeta potential is saturated at approximately -50 mV.     

Theoretical prediction of heterogeneous molecular wires on the Si(001) surface

Using first-principles density-functional calculations, we propose a self-assembly technique for fabrication of the heterogeneous molecular wire on the dangling-bond wire generated on a H-passivated Si(001) surface. Here, we choose pyridine and borine as Lewis base and acid molecules, respectively, to demonstrate different behaviors in the chemical reactivity and selectivity on the dangling-bond wire, leading to formation of the heterogeneous pyridine-borine wire.