Constructing self-organized structures on silicon and sapphire surfaces

We investigated methods to fabricate distinctive structures on silicon and sapphire substrates to grow a carbon nanotube (CNT) network using a solution from the Belousov-Zhabotinsky (BZ) reaction. The BZ reaction is a chemical system where chemical reactions and material diffusion coexist in a nonequilibrium state and generate spatiotemporal patterns in a petri dish. Precipitates from the reaction should also produce distinctive structures after being piled on the substrates. The structures have metal particles that act as catalysts for growing CNTs or quantum dots of nanodot devices. Therefore, such structures should be suitable to fabricate three-dimensional CNT networks or nanodot devices. To confirm this, we investigated the fabrication of distinctive structure using a BZ reaction solution. Results indicated that the BZ reaction solution produced interesting structures on the substrates. Moreover, we confirmed that the shape of the structure changed when the substrate used was changed. We believe that the developed methods are suitable to fabricate nanodevices, especially CNT network devices.     

Asymptotic formalism for ultraflat optical frequency comb generation using a Mach-Zehnder modulator

We theoretically prove that a conventional Mach-Zehnder modulator can generate an optical frequency comb with excellent spectral flatness. The modulator is asymmetrically dual driven by large amplitude sinusoidal signals with different amplitudes. The driving condition to obtain spectral flatness is analytically derived and optimized, yielding a simple formula. This formula also predicts the conversion efficiency and bandwidth of the generated frequency comb.     

Improved optical enrichment of SWNTs through extraction with chiral nanotweezers of 2,6-pyridylene-bridged diporphyrins

Chiral single-walled carbon nanotubes (SWNTs) have left- and right-handed helical structures (M and P, respectively, according to the IUPAC nomenclature). In this report, optically active SWNTs were obtained through preferential extraction of (M)- or (P)-SWNTs with 2,6-pyridylene-bridged chiral diporphyrins 1. In the circular dichroism (CD) spectra, the SWNTs extracted with 1 exhibit much larger intensity than those extracted with 1,3-phenylene-bridged chiral diporphyrins 2, indicating an improved chiral discrimination ability of 1. In particular, (6,5)-SWNTs display the most intensified CD signals among the SWNTs extracted with 1. In addition, the SWNT extraction ability of 1 has been shown to be considerably enhanced in comparison to 2. These improved discrimination and extraction abilities of 1 are attributed to the formation of its more stable SWNT complex. Computer-calculated energy minimized structures for 1:(6,5)-SWNT complexes show that (R)- and (S)-1 form complexes preferentially with (M)- and (P)-(6,5)-SWNTs, respectively. These calculations also predict that the 1:(6,5)-SWNT complex is approximately 1.6 kcal mol-1 more stable than the corresponding complex of 2, accounting for the improved abilities of 1 in the chiral discrimination and extraction.     

Synthesis of α‐maleimide‐ω‐dienyl heterotelechelic poly(methyl methacrylate) and its cyclization by the intramolecular Diels–Alder reaction

The synthesis of heterotelechelic poly(methyl methacrylate) (PMMA) containing α‐maleimide‐ω‐dienyl end‐groups and its subsequent intramolecular cyclization are described. The anionic polymerization of methyl methacrylate was carried out with 3‐tert‐butyldimethylsilyloxypropyl‐1‐lithium and 5‐bromo‐1,3‐pentadiene as the initiator and terminator, respectively, to synthesize α‐hydroxy‐ω‐dienyl‐PMMA. The introduction of the maleimide group to the α chain end by the reaction of the sodium salt of the polymer with N‐(3‐chloromethylphenyl)‐maleimide or N‐(3‐bromomethylphenyl)‐maleimide was not successful because of the nucleophilic addition of alkoxide to the carbon carbon double bond of the maleimide group. When 4,4′‐bismaleimidediphenylether was allowed to react with the alkoxide, the aimed α‐maleimide‐ω‐dienyl‐PMMA was obtained in a good yield. Ring closure by the intramolecular Diels–Alder reaction was carried out by the heating of the dilute polymer solution in tetrahydrofuran. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 237–246, 2000     

Pd/Light‐Accelerated Atom‐Transfer Carbonylation of Alkyl Iodides: Applications in Multicomponent Coupling Processes Leading to Functionalized Carboxylic Acid Derivatives

The atom‐transfer carbonylation reaction of various alkyl iodides thereby leading to carboxylic acid esters was effectively accelerated by the addition of transition‐metal catalysts under photoirradiation conditions. By using a combined Pd/hν reaction system, vicinal C‐functionalization of alkenes was attained in which α‐substituted iodoalkanes, alkenes, carbon monoxide, and alcohols were coupled to give functionalized esters. When alkenyl alcohols were used as acceptor alkenes, three‐component coupling reactions, which were accompanied by intramolecular esterification, proceeded to give lactones. Pd‐dimer complex [Pd₂(CNMe)₆][PF₆]₂, which is known to undergo homolysis under photoirradiation conditions, worked quite well as a catalyst in these three‐ or four‐component coupling reactions. In this metal/radical hybrid system, both Pd radicals and acyl radicals are key players and a stereochemical study confirmed the carbonylation step proceeded through a radical carbonylation mechanism.     

Iron-catalyzed decarbonylation reaction of aliphatic carboxylic acids leading to α-olefins

The catalytic decarbonylation reaction of aliphatic carboxylic acids can be carried out in the presence of an iron complex, and it proceeds smoothly to give α-olefins with high selectivity.     

Radical carbonylation of ω-alkynylamines leading to α-methylene lactams. Synthetic scope and the mechanistic insights

Tin hydride mediated radical carbonylation and cyclization reaction was investigated using a variety of ω-alkynyl amines as substrates. In this reaction α-methylene and α-stannylmethylene lactams having five to eight membered rings were obtained as principal products. In cases where the nitrogen has a substituent capable of giving stable radicals, such as an α-phenethyl group, the lactam ring formation again took place with extrusion of an α-phenethyl radical. Coupled with the subsequent protodestannylation procedure (TMSCl plus MeOH), these reactions provide a useful entry to α-methylene lactams with incorporation of CO as a lactam carbonyl group. In cases where the amines do not have a substituent acting as a radical leaving group, a reaction course involving a 1,4-H shift is chosen so as to liberate tin radicals ultimately. Thus the proposed mechanism involves (i) nucleophilic attack of amine nitrogen onto a carbonyl group of α,β-unsaturated acyl radicals/α-ketenyl radicals via lone pair-π* interaction, which leads to zwitterionic radical species, (ii) the subsequent proton shift from N to O to give hydroxyallyl radicals, (iii) 1,4-hydrogen shift from O to C, and (iv) β-scission to give lactams with liberation of tin radicals. DFT calculations reveal that the 1,4-hydrogen shifts, the key step of the reaction mechanism, can proceed under usual reaction conditions. On the other hand, an S(H)i type reaction to give lactams may be the result of the β-scission of the similar zwitterionic radical intermediates. DFT calculations also predict that an S(H)i type reaction would result when the intermediate has a good (radical) leaving group such as a phenethyl group.     

Synthesis of (3S)-(tert-butyldimethylsilyloxy)methylcyclopentan-1-one as a key intermediate of sphingosine 1-phosphate-1 receptor agonists

Herein we report the asymmetric synthesis of (3S)-(tert-butyldimethylsilyloxy)methylcyclopentan-1-one (S)-3 as a practical chiral synthon for a wide range of pharmaceutical and/or natural products, using Lipshutz’s asymmetric copper-catalyzed conjugate reduction. This method makes it feasible to prepare a conformationally constrained cyclopentane analogue 12, which is one of the key intermediates for the synthesis of novel sphingosine 1-phosphate-1 receptor agonists.     

Flow of a single magnetic vortex in a submicron-size superconducting Al disk controlled by radio-frequency currents

We report the first observation of a single-vortex flow in a mesoscopic superconductor. A flow of a single vortex is successfully controlled by an rf current superimposed on a dc current, evidence of which is provided by voltage steps in current-voltage (I-V) characteristics. Irrespective of the number of vortices confined to the disk, we unambiguously observe that when a single vortex inside the disk is driven out of the disk, another vortex enters the disk similarly to two balls colliding in billiards: only one vortex passes through the Al disk at the same time in mesoscopic systems.