Vacuum‐driven fluid manipulation by a piezoelectric diaphragm micropump for microfluidic droplet generation with a rapid system response time

Recently, we developed a convenient microfluidic droplet generation device based on vacuum‐driven fluid manipulation with a piezoelectric diaphragm micropump. In the present study built on our previous work, we investigate the influence of settings applied to the piezoelectric pump, such as peak‐to‐peak drive voltage (V_p‐p) and wave frequency, on droplet generation characteristics. Stepwise adjustments to the drive voltage in ±10‐V_p‐p increments over the range of 200?250 V_p‐p during droplet creation revealed that the droplet generation rate could be reproducibly controlled at a specific drive voltage. The droplet generation rate switched within <0.5 s after the input of a new voltage. Although the droplet generation rate depended on the drive voltage, this setting had almost no influence on droplet size. The frequency over the selected range (50?60 Hz) did not markedly influence the droplet generation rate or droplet size. We show that the current fluid manipulation system can be conveniently used for both droplet generation and for rapid droplet reading, which is required in many microfluidic‐based applications.     

Construction of self-assembled monolayer terminated with N-heterocyclic carbene-rhodium(I) complex moiety

Functionalization of self-assembled monolayer (SAM) of alkanethiolate with metal containing unit is one of the versatile methods to obtain functional surfaces such as heterogeneous catalysts. However, organic molecules that strongly bind to transition metals at SAM terminal are limited. Recently N-heterocyclic carbenes (NHCs) such as cyclic diaminocarbenes have emerged as strongly σ-donating ligands forming a robust bond with broad spectrum of transition metals. In the present study, for the purpose of establishment of a new robust basement for heterogeneous metal catalysts, a SAM of the alkanethiolate terminated with NHC-rhodium(I) complex moiety was prepared by utilizing a newly designed disulfide molecule bearing NHC-metal complex terminals. X-ray photoelectron spectroscopy (XPS) analysis and angle resolved XPS measurement revealed successful formation of the Rh-complex-terminated SAM on a gold substrate. Infrared reflection absorption spectroscopy (IRRAS) analysis suggested that the linker methylene chains connecting the rhodium complex moiety and the gold surface are in a loosely packed structure. This unique chemical species, NHC, would be a promising candidate as a basement for the construction of functional surface.     

Practical asymmetric synthesis of (S)-MA20565, a wide-spectrum agricultural fungicide

A practical asymmetric synthesis of a wide-spectrum agricultural fungicide, (S)-MA20565 (1), is described. The convergent synthesis was achieved starting from commercially available 3-(trifluoromethyl)aniline (7) in 44% overall yield through five steps and 2-bromobenzaldehyde (9) in 48% overall yield through four steps, respectively. (S)-O-[1-(3-Trifluoromethylphenyl)ethyl]hydroxylamine (2), a key intermediate of 1, was prepared via ruthenium(II)-catalyzed asymmetric transfer hydrogenation of 1-(3-trifluoromethylphenyl)ethanone (6) followed by chlorination using methanesulfonyl chloride and oxyamination using potassium acetohydroxamate with high level of stereocontrol.     

Second-order perturbational treatment of normal coordinates in the string model for the hydration reaction of formaldehyde

A perturbation theory for normal coordinates of nonadiabatic solvation is presented by means of the “string model” of chemical reactions. The dynamic normal coordinate is introduced for the perturbational treatment of the “intrinsic” normal coordinates that are orthogonal to the reaction path. The reaction is defined as the intrinsic reaction coordinate (IRC ) that is treated as a string. The string is thrown in the external force field that acts as a nonadiabatic source of perturbation. As an application of the present treatment, the effect of a water molecule for hydration reaction of formaldehyde is calculated. A second-order perturbation effect for the enhancement of the reaction rate is found.     

Formation and stabilization model of the 42-mer Abeta radical: implications for the long-lasting oxidative stress in Alzheimer's disease

Amyloid fibrils mainly consist of 40-mer and 42-mer peptides (Abeta40, Abeta42). Abeta42 is believed to play a crucial role in the pathogenesis of Alzheimer's disease because its aggregative ability and neurotoxicity are considerably greater than those of Abeta40. The neurotoxicity of Abeta peptides involving the generation of free radicals is closely related to the S-oxidized radical cation of Met-35. However, the cation's origin and mechanism of stabilization remain unclear. Recently, structural models of fibrillar Abeta42 and Abeta40 based on systematic proline replacement have been proposed by our group [Morimoto, A.; et al. J. Biol. Chem. 2004, 279, 52781] and Wetzel's group [Williams, A. D.; et al. J. Mol. Biol. 2004, 335, 833], respectively. A major difference between these models is that our model of Abeta42 has a C-terminal beta-sheet region. Our biophysical study on Abeta42 using electron spin resonance (ESR) suggests that the S-oxidized radical cation of Met-35 could be generated by the reduction of the tyrosyl radical at Tyr-10 through a turn structure at positions 22 and 23, and stabilized by a C-terminal carboxylate anion through an intramolecular beta-sheet at positions 35-37 and 40-42 to form a C-terminal core that would lead to aggregation. A time-course analysis of the generation of radicals using ESR suggests that stabilization of the radicals by aggregation might be a main reason for the long-lasting oxidative stress of Abeta42. In contrast, the S-oxidized radical cation of Abeta40 is too short-lived to induce potent neurotoxicity because no such stabilization of radicals occurs in Abeta40.     

The discovery of polymer‐clay hybrids

The first successful example of a polymer‐clay hybrid was nylon‐clay hybrid (NCH), which is a nano‐meter‐sized composite of nylon‐6 and 1‐nm‐thick exfoliated aluminosilicate layers of the clay mineral. NCH was found and developed at Toyota Central Research and Development Laboratories over 17 years ago. The NCH containing a few weight percentages of clay exhibits superior properties such as high modulus, high strength, and good gas‐barrier properties. The key for the discovery of NCH was the polymerization of a nylon monomer in the interlayer space of the clay. This highlight presents the development of NCH from its discovery to its commercialization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 819–824, 2004     

Localization of Iα and Iβ phases in algal cellulose revealed by acid treatments

Highly crystalline I-rich type Cladophora cellulose, which had been kept in never-dried condition, was treated in 60wt% sulfuric acid at 100°C, for 1–48h. The cellulose microcrystals thus obtained were analysed by X-ray diffractometry, FT-IR, and transmission electron microscopy. The I component was found to be more degraded than the I component. The cellulose I/I ratios of the samples acid-treated for 0, 24, and 48 h were about 8:2, 6:4, and 4:6, respectively. After the acid treatment, the microcrystals became narrower in width, and very sharp at their ends. These results indicate that the I phase is mostly located at the surface of the microcrystals, which is morphologically more susceptible to the acid treatment.     

Counterion Exchange Selectivity in Detergent–Polymer Aggregates

In aqueous solution, the interaction between sodium dodecyl sulfate (SDS) and poly(ethylene glycol) (PEG) results in the formation of small aggregates or clusters of SDS attached to the PEG polymer chain. Selectivity coefficients for exchange of two monovalent (N-methyl-4-cyanopyridinium cation and Tl⁺) and two divalent (methylviologen cation and Cu²⁺) counterions at the surface of SDS–PEG clusters, determined employing photophysical techniques, are similar, but not identical, to those for exchange at the surface of SDS micelles in the absence of PEG. The principal factor affecting ion exchange selectivity in SDS–PEG clusters does not appear to be aggregate size or surface charge density but rather the presence of poly(oxyethylene) subunits at the aggregate surface.     

Identification of beta-decay of150La

The -decay of¹⁵⁰La, the heaviest isotope of lanthanum, has been identified by observing -rays from mass separated activities obtained at KUR-ISOL. From the decay curves of 97.0 and 208.7 keV -rays in¹⁵⁰Ce and of Ce-K X-ray, the half-life of¹⁵⁰La has been determined as 0.51(3) s. This value is in agreement with theoretical predictions from microscopic theory.