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.     

Preparation, structure and properties of novel 1,3-dithiol-2-ylidene derivatives containing bis(ethynylpyridine) units

1,3-Dithiol-2-ylidene derivatives containing bis(ethynylpyridine) units were synthesized using a Pd-catalyzed reaction of the corresponding dibromide. X-Ray crystal analysis revealed unique crystal structures depending on the aromatic groups. The absorption spectra and redox properties indicated intramolecular charge-transfer interactions between the 1,3-dithiole unit and the pyridyl parts.     

Facilitated sulfate transfer across the nitrobenzene-water interface as mediated by hydrogen-bonding ionophores.

Facilitated SO4(2-) transfers by hydrogen bond-forming ionophores are investigated across the nitrobenzene (NB)-water interface by using polarography with a dropping electrolyte electrode. Bis-thiourea 1, alpha,alpha'-bis(N'-p-nitrophenylthioureylene)-m-xylene, is found to significantly facilitate the transfer of the highly hydrophilic SO4(2-) whereas its counterpart, N-(p-nitrophenyl)-N'-propylthiourea (ionophore 2), cannot. In contrast to the predominant formation of a 1:1 complex with SO4(2-) in the bulk NB phase, the SO4(2-) transfer assisted by 1 is indeed based on the formation of a 1:2 complex between SO4(2-) and ionophore, even under the condition of [SO4(2-)]aq > [1]org. Such an exclusive formation of the 1:2 (SO4(2-) to ionophore) complex at the NB-water interface is not observed with structurally similar bis-thiourea 3, alpha,alpha'-bis(N'-phenylthioureylene)-m-xylene, where p-nitrophenyl moietes of bis-thiourea 1 are simply replaced by phenyl groups. The facilitated transfer of SO4(2-) with bis-thiourea 1 is further compared to that of HPO4(2-) and H2PO4- across the NB-water interface, which was previously shown to be assisted by 1 through the formation of the 1:1 and 2:1 (anion to ionophore) complexes, respectively. On the basis of these examinations, unique binding behaviors of hydrogen bond-forming ionophores at the NB-water interface are discussed, with a view towards development of ionophore-based anion-selective chemical sensors.     

An ASE Reduction Filter Using Cascaded Optical Fiber Grating Couplers in EDFA Repeater

A new configuration for an ASE reduction filter in EDFA repeaters for WDM optical transmission systems using optical fiber grating couplers (FGCs) was proposed and first demonstrated. The filtering characteristics of the proposed filter for amplified single wavelength signal and 2-channel WDM signals using EDFA were identified. It was found that the filter was effective to improve SNR in optical domain by reducing ASE noise. The required FGC characteristics for the filter were theoretically predicted under the condition that the total filter loss did not exceed 3 dB. More than 70% of drop efficiency was required in each FGC for the application of the proposed filter to an 8-channel WDM system using EDFA repeaters.     

Grothendieck groups of unbounded complexes of finitely generated modules

Let Λ be a left Artinian ring, D⁺(mod Λ) (resp., D⁻(mod Λ), D(mod Λ)) the derived category of bounded below complexes (resp., bounded above complexes, unbounded complexes) of finitely generated left Λ-modules. We show that the Grothendieck groups K₀(D⁺(mod Λ)), K₀(D⁻(mod Λ)) and K₀(D(mod Λ)) are trivial. Received: 7 April 2005     

Confirmation of sable QTL that modifies the effects of the Ay allele on yellow coat color on mouse chromosome 1

F₁-A^y mice between RR (aabbCC) and C57BL/6J-A^y (A^yaBBCC) have a much darker yellow coat color than do C57BL/6J-A^y. Quantitative trait locus (QTL) analysis was carried out to identify genes responsible for the darker modification of the yellow coat color (this has been traditionally termed “sable”). A significant sable QTL was identified on chromosome 1 (Dmyaq4, LOD score 15.5 for lightness, and 13.4 for color difference), in a chromosomal position similar to that of Dmyaq2, a sable QTL previously identified in C3H/HeJ. Another significant sable QTL was identified on chromosome 4 (Dmyaq5, LOD score 5.6 for lightness, and 4.3 for color difference) near the tyrosinase-related protein 1 (Tyrp1) locus. The effect of Dmyaq5 was significant only in the presence of the RR allele at Dmyaq4, suggesting that the Dmyaq4 (as well as Dmyaq2) is a novel coat color gene that may act up-stream of Tyrp1 signaling to increase eumelanin production.     

Synthesis of well‐defined syndiotactic poly(methyl methacrylate) with low‐temperature atom transfer radical polymerization in fluoroalcohol

The copper‐mediated atom transfer radical polymerization of methyl methacrylate (MMA) in 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) was studied to simultaneously control the molecular weight and tacticity. The polymerization using tris[2‐(dimethylamino)ethyl]amine (Me₆TREN) as a ligand was performed even at ?78°C with a number‐average molecular weight (M_n) of 13,400 and a polydispersity (weight‐average molecular weight/number‐average molecular weight) of 1.31, although the measured M_n's were much higher than the theoretical ones. The addition of copper(II) bromide (CuBr₂) apparently affected the early stage of the polymerization; that is, the polymerization could proceed in a controlled manner under the condition of [MMA]₀/[methyl α‐bromoisobutyrate]₀/[CuBr]₀/[CuBr₂]₀/[Me₆TREN]₀ = 200/1/1/0.2/1.2 at ?20°C with an MMA/HFIP ratio of 1/4 (v/v). For the field desorption mass spectrum of Cu^IBr/Me₆TREN in HFIP, there were [Cu(Me₆TREN)Br]⁺ and [Cu(Me₆TREN)OCH(CF₃)₂]⁺, indicating that HFIP should coordinate to the Cu^I/Me₆TREN complex. The syndiotacticity of the obtained poly(methyl methacrylate)s increased with the decreasing polymerization temperature; the racemo content was 84% for ?78°C, 77% for ?30°C, 75% for ?20°C, and 63% for 30°C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1436–1446, 2006     

Host-guest complexation effect of 2,3,6-tri-O-methyl-β-cyclodextrin on a C60-porphyrin light-to-photocurrent conversion system

In a light-to-photocurrent conversion system based on a C₆₀-porphyrin bilayer prepared by electrostatic alternate adsorption, porphyrin units in a porphyrin polymer have been isolated by cyclodextrin utilizing the host-guest interaction. In this system, a high quantum yield was achieved by suppression of self-quenching of porphyrin units.