meso–meso‐Linked Diarylamine‐Fused Porphyrin Dimers

A meso–meso‐linked diphenylamine‐fused porphyrin dimer and its methoxy‐substituted analogue were synthesized from a meso–meso‐linked porphyrin dimer by a reaction sequence involving Ir‐catalyzed β‐selective borylation, iodination, meso‐chlorination, and S_NAr reactions with diarylamines followed by electron‐transfer‐mediated intramolecular double C?H/C?I coupling. While these dimers commonly display characteristic split Soret bands and small oxidation potentials, they produced different products upon oxidation with tris(4‐bromophenyl)aminium hexachloroantimonate. Namely, the diphenylamine‐fused porphyrin dimer was converted into a dicationic closed‐shell quinonoidal dimer, while the methoxy‐substituted dimer gave a meso–meso, β‐β doubly linked porphyrin dimer.     

III–V quantum devices and circuits based on nanoscale Schottky gate control of hexagonal quantum wire networks

The concept, the present status, key issues and future prospects of a novel hexagonal binary decision diagram (BDD) quantum circuit approach for III–V quantum large-scale integrated circuits (QLSIs) are presented and discussed. In this approach, the BDD logic circuits are implemented on III–V semiconductor-based hexagonal nanowire networks controlled by nanoscale Schottky gates. The hexagonal BDD QLSIs can operate at delay-power products near the quantum limit in the quantum regime as well as in the many-electron classical regime. To demonstrate the feasibility of the present approach, GaAs Schottky wrap gate (WPG)-based single-electron BDD node devices and their integrated circuits were fabricated and their proper operations were confirmed. Selectively grown InGaAs sub-10 nm quantum wires and their hexagonal networks have been investigated to form high-density hexagonal BDD QLSIs operating in the quantum regime at room temperature.     

Strongly nonlinear luminescence in oxidized porous silicon films

Partially oxidized free-standing porous silicon films show a strongly superlinear increase in photoluminescence (PL) intensity above a threshold cw excitation intensity of 10 W/cm². The PL-intensity increase can be expressed by a power law with n9 as a function of the excitation intensity. The PL-peak wavelength of this emission is slightly redshifted from that at low-excitation levels. These changes are fully reversible and reproducible, but not observed in samples on substrate. We attribute this behavior to thermal reexcitation of carriers trapped at the dangling bond states in initially nonluminescent Si nanocrystallites.     

High-energy quasi-phase-matched optical parametric oscillation in a periodically poled MgO:LiNbO3 device with a 5 mm x 5 mm aperture

Fabrication of a 5 mm thick periodically poled MgO-doped LiNbO3 device with a 32.1 microm period for mid-infrared generation was demonstrated. The periodic structure was evaluated by measurement of second-harmonic generation with the d31 coefficient. Optical parametric oscillation using this device with an uncoated 5 mm x 5 mm aperture and a 36 mm effective length realized a high-energy output of 77 mJ for both signal (wavelength 1.83 microm) and idler (2.54 microm) waves with a 72% slope efficiency at 110 mJ pumping of a Q-switched Nd:YAG laser with a 12 ns pulse duration.     

Preparation and microstructural studies on hydrothermally prepared hematite

A 0.1 M FeCl3 aqueous solution was hydrothermally treated in a 1.5-dm3 stainless steel autoclave at varied temperatures (Th: 110-200 degrees C). Highly ordered cubic particles with uniform micropores 0.8 nm in diameter are produced at Th = 115 degrees C, although the cubic particles become less uniform with wide pore size distribution by raising the Th.     

High-energy quasi-phase-matched optical parametric oscillation in a 3-mm-thick periodically poled MgO:LiNbO3 device

We have demonstrated high-energy quasi-phase-matched optical parametric oscillation in a 3-mm-thick periodically poled 5-mol. % MgO-doped LiNbO3 device with a 32.1-microm grating period and a 30-mm length. With a large-spot-size pump laser of 2.2-mm diameter, we obtained a total output pulse energy of 22 mJ for both the signal (wavelength 1.82 microm) and the idler (2.56 microm) waves at an input pump energy of 46 mJ.     

Strongly red-fluorescent novel donor-pi-bridge-acceptor-pi-bridge-donor (D-pi-A-pi-D) type 2,1,3-benzothiadiazoles with enhanced two-photon absorption cross-sections

Novel donor-pi-bridge-acceptor-pi-bridge-donor (D-pi-A-pi-D) type 2,1,3-benzothiadiazole fluorescent dyes connected to the N,N-diarylamino terminus via various type pi-conjugate spacers exhibits large two-photon absorption cross-sections and high fluorescent quantum yields in orange-red color.     

Plasma production by helicon and slow waves

The observation of slow-wave sustained (SW) discharge in a whistler- or helicon-wave range of frequency is made using high-frequency and very-high-frequency bands of rf. The SW discharge occurs at an extremely low rf power and plasma density, which are lower than a capacitive-coupling discharge region.     

A new strategy for the design of water-soluble synthetic receptors: specific recognition of DNA intercalators and diamines

Water-soluble zinc bisporphyrin receptors 1 and 2 having two Lewis acidic sites (zinc) in the hydrophobic environment consisting of alkyl chains and a bisporphyrin framework, and covered with hydrophilic exterior (twelve or eighteen carboxyl groups) were prepared. The receptors show high affinity for diamines and DNA intercalators in water where the binding constants K(a) are of the order of 10(7) and 10(8) M(-1), respectively. Diamines and DNA intercalators are bound to the receptor through different mechanisms. Diamines are bound through hydrophobic interactions and zinc-nitrogen interactions, while DNA intercalators are bound through hydrophobic interactions and charge-transfer interactions. Flexible alkyl chains can make van der Waals contact with guests and create a hydrophobic environment around the bound guest by an induced-fit-type mechanism. For the binding of DNA intercalators, the following features are noteworthy: 1). Binding constants are similar between the zinc porphyrins and zinc-free porphyrins; 2). the binding constant is larger for the guest having the lower LUMO; this indicates the important contribution of charge-transfer interactions to binding; 3). the hydrophobic and cationic nature of DNA intercalators is substantially important, and 4). higher ionic strength reduced the binding affinities; this shows a moderate contribution of electrostatic interactions. The conformational instability of the receptors also contributes to the tight binding: hydrophobic and electrostatic interactions cannot both be favorable at the same time in the guest-free receptor. Enthalpy-entropy compensation observed for the binding of diamines and DNA intercalators is characterized by a relatively small slope (alpha=0.74) and a large intercept (beta=7.75 kcal mol(-1)) in the DeltaH degrees versus TDeltaS degrees plot; this shows that a conformational change of receptors and a significant desolvation occur upon binding. The receptor can competitively bind to propidium iodide to deprive DNA of the intercalated propidium iodide. These features of water-soluble receptors consisting of a rigid framework and flexible side chains with a large solvent-accessible area are in contrast to highly preorganized rigid receptors, and they can provide useful guidelines for rational design of induced-fit artificial receptors in water.     

Construction of a square-planar hydroperoxo-copper(II) complex inducing a higher catalytic reactivity

A novel hydroperoxo-copper(II) complex with a square-planar geometry has been prepared, which has exhibited a higher selectivity and catalytic reactivity for dimethyl sulfide, in contrast to that with a trigonal-bipyramidal one.