Phase behavior of aqueous solutions of copolymers of N,N'-diisopropylfumaramide and N-isopropylacrylamide: effect of the density of side chains

This letter describes the phase behavior of aqueous solutions of an N-isopropylacrylamide (NIPAM) homopolymer and copolymers of N,N'-diisopropylfumaramide (DIPFAM) and NIPAM as studied by transmittance measurements, infrared spectroscopy, and differential scanning calorimetry to reveal the effect of the density of N-isopropylamide side chain upon the phase behavior. The clouding-point and clearing-point temperatures decreased with increasing the mole fraction of DIPFAM (x(D)). It was noteworthy that only an extra side chain per ca. 7 NIPAM units had a remarkable effect on the phase behavior; the interactions between side chains were stronger, the intrapolymer contraction was less favorable, and the cooperativity of phase transition was lower at x(D) = 0.15 presumably because of the steric hindrance of dense side chains.     

A dimethoxytriazine type glycosyl donor enables a facile chemo-enzymatic route toward α-linked N-acetylglucosaminyl-galactose disaccharide unit from gastric mucin

An efficient chemo-enzymatic process for construction of the α-linked disaccharide unit (GlcNAcα1-4Gal) found in gastric mucin has been developed. The process consists of a one-step preparation of a novel triazine type glycosyl donor in water and the subsequent transglycosylation to a galactose derivative catalysed by α-N-acetylglucosaminidase.     

Retinal Photodamage Mediated by All‐trans‐retinal†

Accumulation of all‐trans‐retinal (all‐trans‐RAL), reactive vitamin A aldehyde, is one of the key factors in initiating retinal photodamage. This photodamage is characterized by progressive retinal cell death evoked by light exposure in both an acute and chronic fashion. Photoactivated rhodopsin releases all‐trans‐RAL, which is subsequently transported by ATP‐binding cassette transporter 4 and reduced to all‐trans‐retinol by all‐trans‐retinol dehydrogenases located in photoreceptor cells. Any interruptions in the clearing of all‐trans‐RAL in the photoreceptors can cause an accumulation of this reactive aldehyde and its toxic condensation products. This accumulation may result in the manifestation of retinal dystrophy including human retinal degenerative diseases such as Stargardt’s disease and age‐related macular degeneration. Herein, we discuss the mechanisms of all‐trans‐RAL clearance in photoreceptor cells by sequential enzymatic reactions, the visual (retinoid) cycle, and potential molecular pathways of retinal photodamage. We also review recent imaging technologies to monitor retinal health status as well as novel therapeutic strategies preventing all‐trans‐RAL‐associated retinal photodamage.     

Worst-Case Violation of Sampled Convex Programs for Optimization with Uncertainty

A deterministic approach called robust optimization has been recently proposed to deal with optimization problems including inexact data, i.e., uncertainty. The basic idea of robust optimization is to seek a solution that is guaranteed to perform well in terms of feasibility and near-optimality for all possible realizations of the uncertain input data. To solve robust optimization problems, Calafiore and Campi have proposed a randomized approach based on sampling of constraints, where the number of samples is determined so that only a small portion of the original constraints is violated by the randomized solution. Our main concern is not only the probability of violation, but also the degree of violation, i.e., the worst-case violation. We derive an upper bound of the worst-case violation for the sampled convex programs and consider the relation between the probability of violation and the worst-case violation. The probability of violation and the degree of violation are simultaneously bounded by a prescribed value when the number of random samples is large enough. In addition, a confidence interval of the optimal value is obtained when the objective function includes uncertainty. Our method is applicable to not only a bounded uncertainty set but also an unbounded one. Hence, the scope of our method includes random sampling following an unbounded distribution such as the normal distribution.     

Gravitational compression dynamics of charged colloidal crystals

We examine the compression of charged colloidal crystals under the influence of gravitational force by monitoring the spatiotemporal variations of Bragg diffraction from the crystal lattice. We use the dilute aqueous dispersions of colloidal silica particles (diameter=216 nm, charge number=733, a particle volume fraction φ=0.06) in the presence of 5-15 μM sodium chloride. The sedimentation profiles of the colloidal crystals along the crystal height are determined by in situ fiber optics reflection spectroscopy. The time evolutions of the sedimentation profiles are calculated by numerical simulations based on a phenomenological continuum model that explicitly incorporates the electrostatic interparticle interactions. The simulation results correctly describe the experiments at sufficiently high ionic strength.     

Charge ordering and carrier generation by air oxidation of a nickel complex with selenium-containing extended-tetrathiafulvalenedithiolate ligands

The structures and electrical properties of ((n)Bu(4)N)[Ni(dmstfdt)(2)] (1), ((n)Bu(4)N)(2)[Ni(dmstfdt)(2)] (2), and ((n)Bu(4)N)(3)[Ni(dmstfdt)(2)](2) (3), where dmstfdt = extended-tetrathiafulvalenedithiolate ligand, were examined. The fresh crystal of 1 was found to be a Mott insulator, but the crystal gradually became highly conducting because of air oxidation. Compound 3 exhibited a semiconducting charge-ordering state.     

Experimental study of internal flow structures in cylindrical rotating detonation engines

The internal flow structures of detonation wave were experimentally analyzed in an optically accessible hollow rotating detonation combustor with multiple chamber lengths. The cylindrical RDC has a glass chamber wall, 20 mm in diameter, which allowed us to capture the combustion self-luminescence. A chamber 70 mm in length was first tested using C₂H₄O₂ and H₂–O₂ as propellants. Images with a strong self-luminescence region near the bottom were obtained, confirming the small extent of the region where most of the heat release occurs as found in our previous research. Based on the visualization experiments, we tested RDCs with shorter chamber walls of 40 and 20 mm. The detonation wave was also observed in the shorter chambers, and its velocity was not affected by the difference in chamber length. Thrust performance was also maintained compared to the longer chamber, and the short cylindrical RDC had the same specific impulse tendency as the cylindrical (hollow) or annular 70-mm chamber RDC. Finally, we calculated the pressure distributions of various chamber lengths, and found they were also consistent with the measured pressure at the bottom and exit. We concluded that the short-chamber cylindrical RDC with equal length and diameter maintained thrust performance similar to the longer annular RDC, further expanding the potential of compact RDCs.     

Photocontrol of cell adhesion and proliferation by a photoinduced cationic polymer surface

In this study photoinduced cation generation, based on the photochemical properties of malachite green (MG), was used for the surface design and in vitro photochemical control of cell adhesion and proliferation. The MG-derivatized surface was prepared by coating a photoreactive polymer as a substrate onto a poly(ethylene terephthalate) (PET) sheet. The photoreactive polymer was radical copolymer of styrene with the MG-derivatized monomer diphenyl(4-vinylphenyl)methane leucohydroxide (degree of substitution of MG unit: 12.4 mol%). Water contact angle measurements and X-ray photoelectron spectroscopy revealed high hydrophobicity and homogeneous distribution of the MG groups on the outermost surface of the coated film, respectively. When the coated film was exposed to ultraviolet light (UV) irradiation at wavelengths of 290-410 nm, a time-dependent color change of the film was observed from pale yellow, before irradiation, to green. These results indicated generation of cations on the film surface by photochemical cation generation of the MG groups, which was quantitatively characterized by force versus distance curves measurements in atomic force microscopic (AFM) observation using a carboxylated AFM tip. The seeding and culture of endothelial cells showed a marked reduction in adhesion on the nonirradiated coated film surface, whereas the UV-irradiated surface promoted cell adhesion and proliferation except for incubation in serum-free medium, which was similar to commercial tissue culture PET sheet. These observations may be due to adsorption of cell adhesive proteins, typified by fibronectin, in serum-containing medium onto the cationized photoreactive copolymer surface by electrostatic interactions.     

Cobalt-catalyzed benzyl-alkynyl coupling

Benzylic halides coupled with 1-alkynylmagnesium halides in the presence of a catalytic amount of Co(acac)₃ to provide 1-aryl-2-alkynes in moderate to good yield.