Daisaku Kaneko

Gelation Behavior by the Lanthanoid Adsorption of the Cyanobacterial Extracellular Polysaccharide

The self-organization behavior of an extracellular polysaccharide (sacran) extracted from the cyanobacterium Aphanothece sacrum in response to lanthanoid ion adsorption was investigated. Consequently, cryogenic TEM images revealed that sacran could be cross-linked by Nd(3+) trivalent ions and formed a fibrous nanostructural network containing water. Furthermore, sacran adsorbed trivalent metal ions at a 3:1 ratio, which was the theoretical ionic adsorption and showed more efficient adsorption than alginate based on electric conductivity titration. The critical gelation concentrations, Cg, where sacran formed tough gels upon metal ion binding were estimated. The Cg for trivalent metal ions was lower than that for divalent ions, and the Cg for lanthanoid ions was particularly low at 10(-3) to 10(-4) M, changing every four elemental numbers. The extracellular matrix of Aphanothece sacrum, sacran, may adsorb metal ions to create fibrous nanostructures that reinforce the jelly matrix.

Hyperbranched Polycoumarates with Photofunctional Multiple Shape Memory

In good shape: The films of hyperbranched polycoumarate derivatives can undergo a reversible [2+2] cycloaddition under irradiation of UV light and behave like photomechanical elastomers. From a predetermined original shape A the photonically and thermally memorized shapes B and C were obtained. The original shape was recovered by photoirradiation (see picture; Tg =glass transition temperature).

Syntheses of hyperbranched liquid-crystalline biopolymers with strong adhesion from phenolic phytomonomers

A novel thermotropic liquid-crystalline (LC) biocopolymer, poly{trans-3-methoxyl-4-hydroxycinnamic acid (MHCA: ferulic acid)-co-trans-3,4-dihydroxycinnamic acid (DHCA: caffeic acid)}, was synthesized by a thermal acidolysis-polycondensation of MHCA and DHCA, efficiently catalyzed by Na2HPO4. When the MHCA composition of poly(MHCA-co-DHCA) was 60, 75, and 90 mol %, the copolymers showed a nematic LC phase although individual homopolymers such as polyMHCA and polyDHCA did not exhibit LC phase. Poly(MHCA-co-DHCA)s showed high molecular weight (Mw) ranged between Mn 2.6 × 104 to 3.7 × 104 and Mw 8.2 × 104 to 13.1 × 104, respectively, high glass-transition temperature (Tg) with the range of 115 to 140 °C and high degradation temperature T10, from 315 to 356 °C. In the adhesive test of copolymers against the surface of carbon substrate, the copolymers showed high shear strength at fracture.

Mass spectrometry imaging of the capsaicin localization in the capsicum fruits

We succeeded in performing mass spectrometry imaging (MSI) of the localization of capsaicin in cross-sections of the capsicum fruits at a resolution of 250 µm using matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. Post source decay of protonated capsaicin ion revealed structural information of the corresponding acid amide of vanillylamide and C 9 chain fatty acid. MALDI-TOF-MSI confirmed that localization of capsaicin in the placenta is higher than that in the pericarp. In addition, it revealed no localization of capsaicin in seed and the higher localization of capsaicin at placenta surface compared with that in the internal region. A quantitative difference was detected between localizations of capsaicin at placenta, pericarp and seed in the capsicum fruits. This imaging approach is a promising technique for rapid quality evaluation general food as well as health food and identification of medicinal capsaicin in plant tissues.

Oligonucleotide analysis by nanoparticle-assisted laser desorption/ionization mass spectrometry

We analyzed oligonucleotides by nanoparticle-assisted laser desorption/ionization (nano-PALDI) mass spectrometry (MS). To this end, we prepared several kinds of nanoparticles (Cr-, Fe-, Mn-, Co-based) and optimized the nano-PALDI MS method to analyze the oligonucleotides. Iron oxide nanoparticles with diammonium hydrogen citrate were found to serve as an effective ionization-assisting reagent in MS. The mass spectra showed both [M - H](-) and [M + xMe(2+)- H](-) (Me: transition metal) peaks. The number of metal-adducted ion signals depended on the length of the oligonucleotide. This phenomenon was only observed using bivalent metal core nanoparticles, not with any other valency metal core nanoparticles. Our pilot study demonstrated that iron oxide nanoparticles could easily ionize samples such as chemical drugs and peptides as well as oligonucleotides without the aid of an oligonucleotide-specific chemical matrix (e.g., 3-hydroxypicolinic acid) used in conventional MS methods. These results suggested that iron-based nanoparticles may serve as the assisting material of ionization for genes and other biomolecules.

Anionic Complexes of MWCNT with Supergiant Cyanobacterial Polyanions

Multi-walled carbon nanotubes (MWCNTs) were well dispersed in an aqueous solution of the cyanobacterial polysaccharide, sacran, with an ultra-high molecular weight >10 million g/mol. MWCNTs powder was put into aqueous solutions of various polysaccharides including sacran and was dispersed under sonication. As a result of the turbidity measurement of the supernatant, it was found that sacran showed the highest MWCNT-dispersion efficiency of all the polysaccharides used here. Cryogenic transmission electron microscopic (Cryo-TEM) studies directly demonstrated the existence of MWCNTs in the supernatant, and high-resolution TEM observation revealed that MWCNTs covered by sacran chains made their efficient dispersion in water. Raman spectroscopy demonstrated the existence of MWCNT in dried sample from supernatant and the interaction between MWCNT and sacran. The ζ-potential measurement of the dispersion indicated the negative surface charges of the sacran/MWCNT complexes. Then the MWCNT complexes were able to fabricate by ionic interaction; electrophoresis of the anionic complex formed the sacran/MWCNT gels on the anode while the droplet of sacran/MWCNT dispersion formed gel beads in the presence of the lanthanoid cations.

Surface Friction of Poly(dimethyl Siloxane) Gel and Its Transition Phenomenon

The surface sliding friction of chemically cross-linked poly(dimethyl siloxane) (PDMS) swollen with linear PDMS as an oligomer is investigated. The friction force f increases with the normal pressure P in a power-law relation f∝Pα, where the exponent α changes in a range of 0-1, depending on the degree of polymerization, Npoly, of the linear PDMS oligomer. When Npoly is in a range of 240-320, a dramatic decrease in friction force is observed at a critical normal pressure, Pc, leading to a very low friction coefficient on the order of 10−3 at high-pressure ranges. The Pc increases with decreasing network size Nnetof the gel and also with increasing polymer length related to Npoly. One possible explanation for this transition phenomenon in friction is that linear PDMS molecules are exuded from the gel network beyond a certain pressure and behave as polymer brushes, which are able to reduce the friction.

Mussel‐mimetic, bioadhesive polymers from plant‐derived materials

AIM Mussel-mimetic, bioadhesive polymers are synthesized from plant-derived sources. The strong adhesive action is caused by interactions between the catechol groups at the end of the polymer terminal chains and the substrate surface. Here, we present a preliminary study of the adhesion properties and a discussion of the adhesion mechanism. METHODS Two bioadhesive polymers were synthesized from natural plant-derived monomers by the transesterification of: (a) caffeic acid (3,4-dihydroxycinnamic acid; DHCA) and p-coumaric acid (4-hydroxycinnamic acid; 4HCA) to produce poly(DHCA-co-4HCA); and (b) 4-dihydroxyhydrocinnamic acid (DHHCA) and 3-(3-hydroxyphenyl) propionic acid (3HPPA) to produce poly(DHHCA-co-3HPPA). Thermoplastic poly(DHCA-co-4HCA) or poly(DHHCA-co-3HPPA) was placed between glass, carbon, steel, or bovine dentin substrates, and a lap shear adhesion test was conducted to compare them using conventional cyanoacrylate glue and epoxy resin. RESULTS The greatest adhesion for all tested substrates was exhibited by poly(DHHCA-co-3HPPA), followed by epoxy resin adhesive, poly(DHCA-co-4HCA), and cyanoacrylate adhesive. The adhesive strength of poly(DHHCA-co-3HPPA) was greater than 25.6 MPa for glass, 29.6 MPa for carbon, 15.7 MPa for steel, and 16.3 MPA for bovine dentin. CONCLUSION The adhesion of poly(DHHCA-co-3HPPA) might be the strongest reported for a mussel-mimic adhesive system, and could be a feasible alternative to petroleum adhesives.

Mass Spectrometry Imaging Analysis of Location of Procymidone in Cucumber Samples.

The localization of procymidone fungicide residue in cucumbers was investigated by mass spectrometry imaging (MSI). Cucumbers were grown, harvested, and then divided into two groups that were either sprayed or not sprayed with procymidone. The content of procymidone in the cucumbers was quantitatively determined by chromatographic techniques. Subsequently, the spatial distribution of procymidone was imaged by MSI. Procymidone reached the central part of the cucumbers following spraying compared with the control.

Contact Dynamics in the Adhesion Process between Spherical Polydimethylsiloxane Rubber and Glass Substrate

The contact dynamics between a soft sphere and a rigid substrate on the micron scale was studied experimentally. The time evolution of the contact radius, contact angle, and the force acting on the sphere were measured simultaneously in the loading and the unloading cycle. There is little effect of repetition: the experimental results obtained in the second and third cycles agree completely with those of the first cycle. The contact angle changes dynamically in the loading and the unloading processes, and there are regions where the advancing angle and the receding angle remain constant. The experimental results were analyzed in terms of the extended Johnson-Kendall-Roberts theory, and it was found, to our surprise, that the theory works well: the theory predicts the force curve quite accurately if the apparent surface energy obtained from the contact radius is used. The apparent surface energy was experimentally obtained as a function of the contact line velocity, and it was found that (1) the curve agrees qualitatively with that predicted by Greenwood and Johnson, and (2) certain modification is needed when the velocity of the contact line changes the sign.