Formation of Supramolecular Nanostructures through in Situ Self-Assembly and Post-Assembly Modification of a Biocatalytically Constructed Dipeptide Hydrazide**

Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging.     

Hydrophobic Monomers Recognize Microenvironments in Hydrogel Microspheres during Free-Radical-Seeded Emulsion Polymerization

The three-dimensional structure of nanocomposite microgels was precisely determined by cryo-electron micrography. Several nanocomposite microgels that differ with respect to their nanocomposite structure, which were obtained from seeded emulsion polymerization in the presence of microgels, were used as model nanocomposite materials for cryo-electron micrography. The obtained three-dimensional segmentation images of these nanocomposite microgels provide important insights into the interactions between the hydrophobic monomers and the microgels, that is, hydrophobic styrene monomers recognize molecular-scale differences in polarity within the microgels during the emulsion polymerization. This result led to the formation of unprecedented multi-layered nanocomposite microgels, which promise substantial potential in colloidal applications.     

Site-Selective Supramolecular Complexation Activates Catalytic Ethane Oxidation by a Nitrido-Bridged Iron Porphyrinoid Dimer

Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 ⁵⁺, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 ⁵⁺ catalyzed ethane oxidation in the presence of H₂O₂ at a relatively low temperature. The site-selective complexation of 3 ⁵⁺ with an additional anionic porphyrin (TPPS⁴⁻) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 ⁵⁺ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS⁴⁻ to 3 ⁵⁺ enhanced the catalytic activity.     

An optically clocked transistor array with dual serial-to-parallel and parallel-to-serial conversion capability for optical label swapping

We propose an optically clocked transistor array optoelectronic integrated circuit (OEIC) for both serial-to-parallel and parallel-to-serial conversion (demux/mux), enabling an interface between high-speed asynchronous burst optical labels and CMOS circuitry for optical label swapping. Dual functionality of the OEIC reduces size, power, and cost of the optical label swapper. The capability for greater than 20-Gb/s conversion operation is demonstrated.     

Planar lightwave integrated circuits with embedded actives for board and substrate level optical signal distribution

This paper explores design options for planar optical interconnections integrated onto boards, discusses fabrication options for both beam turning and embedded interconnections to optoelectronic devices, describes integration processes for creating embedded planar optical interconnections, and discusses measurement results for a number of integration schemes that have been demonstrated by the authors. In the area of optical interconnections with beams coupled to and from the board, the topics covered include integrated metal-coated polymer mirrors and volume holographic gratings for optical beam turning perpendicular to the board. Optical interconnections that utilize active thin film (approximately 1-5 /spl mu/m thick) optoelectronic components embedded in the board are also discussed, using both Si and high temperature FR-4 substrates. Both direct and evanescent coupling of optical signals into and out of the waveguide are discussed using embedded optical lasers and photodetectors.     

10 Gbit/s optical soliton transmission over 7200 km by using amonolithically integrated MQW-DFB-LD/MQW-EA modulator light source

The authors demonstrate 10 Gbit/s optical soliton transmission in a recirculating loop through the use of a monolithically integrated MQW-DFB-LD/MQW-EA modulator light source. The timing jitter due to the Gordon-Haus effect is successfully reduced by the optical bandpass filters conventionally used in the cascaded EDFAs to avoid the accumulation of amplified spontaneous emission. The transmission distance of 7200 km is achieved at a bit error rate of 10^-9     

OTDM transmitter using WDM-TDM conversion with an electroabsorptionwavelength converter

An all-optical multiplexing technique using wavelength division multiplexing (WDM)-time division multiplexing (TDM) conversion with an electroabsorption wavelength converter has been proposed and demonstrated. The effectiveness of this WDM-TDM conversion technique for various pulsewidth settings was experimentally investigated. The fluctuation of the signal performance, which was inevitably caused by the coherent crosstalk between adjacent pulses in the conventional optical time division multiplexing (OTDM) technique, were successfully suppressed, even in the case of wide pulse duration. High Q-factor performance has been maintained for a wide range of duty ration from 36% to 74%. By introducing this technique to the optical time division multiplexer, a highly stable and high-quality 40-Gb/s optical signal can be effectively produced without generating the short pulse or setting two tributaries at orthogonal polarization states, and without introducing high-speed electronics for signal multiplexing. The WDM-TDM conversion with an electroabsorption wavelength converter was extended to 60-Gb/s operation by using three 20-Gb/s tributaries. A clear eye opening was confirmed for a waveform after the WDM-TDM conversion of the 60-Gb/s signal     

To-and-fro motion of W5Si3 on a beta-Si3N4 substrate at elevated temperatures.

Behavior of fine crystalline particles of W5Si3 on a beta-Si3N4 substrate at high temperatures was observed by an in situ heating experiment in a transmission electron microscope. Some of the fine particles of W5Si3 moved in a to-and-fro manner.     

A Necessary and Sufficient Condition for the Existence of a Heterochromatic Spanning Tree in a Graph

We prove the following theorem. An edge-colored (not necessary to be proper) connected graph G of order n has a heterochromatic spanning tree if and only if for any r colors (1≤r≤n−2), the removal of all the edges colored with these r colors from G results in a graph having at most r+1 components, where a heterochromatic spanning tree is a spanning tree whose edges have distinct colors.     

Selective Propargylation of Carbonyl Compounds and Imines with Barium Reagents

A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.