Publications by authors named "Hiroharu Ajiro"

In this study, a novel flexible material was fabricated by blending chitosan (CS) with a poly(trimethylene carbonate) (PTMC) copolymer. N-methyl-D-glucamine, which acts as a polyol, was grafted onto the PTMC copolymer to produce poly(TMC-co-TMC-glucamine) (PTTG), to enhance the hydrogen bonding interactions. The CS/PTTG blend films were then fabricated using solvent casting.

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Herein, we presented a comprehensive case study on the kaolin suspension derived from mining powder, with a specific emphasis on its mineral constituents within the size range of 2-5 μm and its suitability in spray applications. We have systematically investigated the influence of adjuvants, existing in both organic molecules and polymers, on the sedimentation behavior of clay suspensions. The investigations included the analysis of turbidity, dispersion weight, pH, and surface charge as key parameters.

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Kinetic hydrate inhibitors (KHIs) are used to prevent deposits and plugging of oil and gas production flow lines by gas hydrates. The key ingredient in a KHI formulation is a water-soluble amphiphilic polymer. Recently, polymers of a new commercially available 5-ring vinylic monomer 5-methyl-3-vinyl-2-oxazolidinone (VMOX) were investigated as KHIs and shown to perform better than some commercial KHI polymers such as poly(-vinyl pyrrolidone).

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Fourier-transform infrared (FTIR) spectroscopy can detect the presence of functional groups and molecules directly from a mixed solution of organic molecules. Although it is quite useful to monitor chemical reactions, quantitative analysis of FTIR spectra becomes difficult when various peaks of different widths overlap. To overcome this difficulty, we propose a chemometrics approach to accurately predict the concentration of components in chemical reactions, yet interpretable by humans.

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To enhance the pH-responsiveness of poly(lactic acid) (PLA) particles, desired vanillin acetal-based initiators were synthesized and functional PLA was initiated at the chain end. PLLA-V6-OEG particles were prepared using polymers with various values of 2400-4800 g/mol. PLLA-V6-OEG was appropriated to achieve a pH-responsive behavior under physiological conditions within 3 min via the six-membered ring diol-ketone acetal.

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Herein, we designed and synthesized a thermally stable carboxybetaine copolymer with a one- or three-carbon spacer between ammonium and carboxylate groups (CBMA1 and CBMA3) to create an anti-nonspecific adsorption surface with the ability to immobilize antibodies. A series of controlled poly(,-dimethylaminoethyl methacrylate) was successfully prepared using reversible addition-fragmentation chain-transfer (RAFT) polymerization and was derived to carboxybetaine copolymers of poly(CBMA1--CBMA3) [P(CBMA1/CBMA3)] with various CBMA1 contents, including the homopolymers of CBMA1 and CBMA3. Thermal stability of the carboxybetaine (co)polymers was higher than that of the carboxybetaine polymer with a two-carbon spacer (PCBMA2).

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The aim of this study is to validate an in vitro skin irritation test (SIT) using three-dimensional reconstructed human epidermal (RhE) skin equivalents prepared by layer-by-layer (LbL) method (LbL-3D Skin) in a series of interlaboratory studies. The goal of these validation studies is to evaluate the ability of this in vitro test to reliably discriminate skin irritant from nonirritant chemicals, as defined by OECD and UN GHS. This me-too validation study is to assess the within- and between-laboratory reproducibility, as well as the predictive capacity, of the LbL-3D Skin SIT in accordance with performance standards for OECD TG 439.

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Article Synopsis
  • The study showcases a new method for polymerizing N-vinylformamide (NVF) using purple light, resulting in polymers with specific weights and low variability.
  • High accuracy in the polymer's structure is confirmed through advanced mass spectrometry techniques and experiments that extend the polymer chain.
  • The process is demonstrated by creating and analyzing a new diblock copolymer, which can be further transformed into a pH-responsive material through selective hydrolysis.
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The ABA-type triblock-copolymers (BCPs) of polylactide (PLA) and poly(ethylene glycol) (PEG) were synthesized as axle components for rotaxane formation. It is known that α-cyclodextrin (CD) exists near the PEG moiety in pseudo-polyrotaxane (PPRX), and the PLA moiety can form a stereocomplex (SC), by mixing with L- and D-isomers. In this study, various CDs, including β-CD and γ-CD, were used as wheel components, and effects of CD structures on both PPRX and SC formations were studied.

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The deployment of kinetic hydrate inhibitors (KHIs) is a chemical method for the prevention of gas hydrate plugging in gas, condensate, and oil production flow lines. Polymers made using the monomer -vinylcaprolactam (VCap) are one of the most common KHI classes. Alternative classes of polymers containing caprolactam groups are rare.

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Recently, our group reported the synthesis and fabrication of composite hydrogels of chitosan (CS) and star-shaped polycaprolactone (stPCL). The co-crosslink of modified stPCL with carboxyl at the end chain (stPCL-COOH) provided good mechanical properties and stability to the composite hydrogels. This research presents the bioactivities of composite hydrogels showing a potential candidate to develop biomaterials such as wound dressing and bone tissue engineering.

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This study describes the long-distance diastereomeric effect on thermoresponsive properties in water-soluble diastereomeric polyurethanes (PUs) composed of an l-lysine ethyl ester diisocyanate and a trimethylene glycol l-/d-tartrate ester, which have differences in spatial arrangements of the ethyl esters in the mirror image. The PUs based on l-lysine and l-/d-tartrate ester, named l-PU and d-PU, were synthesized with various number average molecular weights from 4700 to 13 100. In turbidimetry, l-PU showed a steep phase transition from 100% to 0% within about 10 °C at 4 g L, whereas d-PU did not change completely to 0% transmittance even at 80 °C at 4 g L.

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In the coronavirus disease 2019 pandemic, protective clothing is required for medical staff at risk of infection. This study proposes functional smart fabrics with antimicrobial and water-repellent properties, using titanium dioxide (TiO) and fluoropolymer-based precursors as coating materials. Experimental results indicated a uniform distribution of TiO particles with an average size below 200 nm throughout the fabric.

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Cellulose nanofibrils (CNFs) have attracted attention as building blocks for sustainable materials owing to their high performance and the advantages of their abundant natural resources. Bioinspired CNF/polymer nanocomposites, consisting of a soft polymer phase and a high fraction (>50 wt %) of CNF reinforcement, have been focused on excellent mechanical properties, including Young's modulus, mechanical strength, and toughness, mimicking the energy dissipation system in nature. However, efficient softening and toughening with a small amount of the soft phase is still a challenge because a large amount of the polymer phase (nearly 50%) is still required to provide ductility and toughness.

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Microgels are soft, adaptive materials exhibiting various properties not only like hydrogels and microparticles but also like macromolecules, colloids, and surfactants. To widen the range of their biomedical and environmental applications, the exploration of an alternative for poly(-alkylacrylamide)s without potential safety risks is of great importance. In this article, thermoresponsive poly(-vinylisobutyramide) (PNVIBA) microgels of uniform size were synthesized with NVIBA as a monomer and ,'-5-oxanonamethyene-bis--vinylacetamide as a cross-linker in the presence of sodium dodecyl sulfate by aqueous free radical precipitation polymerization.

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Poly(ethylene terephthalate) (PET) is a widely used plastic in bottles and fibers; its waste products pollute the environment owing to its remarkable durability. Recently, Ideonella sakaiensis 201-F6 was isolated as a unique bacterium that can degrade and assimilate PET, thus paving the way for the bioremediation and bioconversion of PET waste. We found that this strain harbors a poly(hydroxyalkanoate) (PHA) synthesis gene cluster, which is highly homologous with that of Cupriavidus necator, an efficient PHA producer.

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Thermoresponsive degradable polyurethane (PU) hydrogels are expected as the next-generation biomedical devices, although they have an important trade-off relationship between toughness and thermoresponsive properties. Tough and thermoresponsive comb PU hydrogels are prepared by one-shot poly-addition between hexamethylene diisocyanate, triethylene glycol tartrate ester, poly(ethylene glycol) 300 (PEG300), and glycerol. The swelling ratio change between 4 and 40 °C decreases as the proportion of PEG300 increases and is maintained at 600% switching within 30% PEG300.

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Stimuli-responsive materials have been actively researched over the past few decades. Among such materials, spiropyran is one of the most attractive compounds because the structure and polarity of the material are dramatically changed after photo irradiation, unlike other materials. In this work, we designed and synthesized a spiropyran derivative (SpMA) with a methacryloyl group on the nitrobenzene ring of a spiropyran skeleton.

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d-limonene, a terpene and natural compound, has been found to be an excellent penetration enhancer for transdermal drug delivery (TDD). It hence has been incorporated within various transdermal formulations. Herein, we report the application of polystyrene gel swollen with d-limonene and its derivatives for TDD.

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In order to prepare thermoresponsive polyurethane gels, a novel polyurethane bearing oligo(ethylene glycol) (OEG) as the side chain is successfully synthesized with hexamethylene diisocyanate and OEG tartrate ester. The aqueous solution of the polyurethane shows sharp and clear lower critical solution temperature behavior at 34 °C. Furthermore, a hydrogel based on the same polyurethane is also successfully prepared using glycerol as the crosslinker.

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Thermal and photo responsive copolymer based on N-vinylamide backbone was designed. Methoxyethyl group and azobenzene were selected to improve hydrophilicity and photoresponsive moieties, respectively. The N-(methoxyethyl)-N-vinylformamide was synthesized and copolymerized with N-vinylformamide by free radical polymerization.

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In regenerative medicine, it has become increasingly important to collect cultured tissues using non-invasive methods. Enzymatic deadhesion is normally used to collect cells, but this method cannot be used when trying to collect whole tissues in order to avoid damaging cell-cell interactions. In order to resolve this issue, a thermoresponsive culture dish with poly(N-isopropyl acrylamide) (PNIPAAm) has been employed.

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Hydrogel preparations using poly(N-vinylformamide) (PNVF) and poly(N-vinylacetamide) (PNVA), which are composed of non-conjugated vinyl monomers, N-vinylformamide (NVF) and N-vinylacetamide (NVA), were investigated without chemical crosslinkers. Hydrogen bonding interaction between the polymers and poly(ethylene glycol) have been firstly attempted to result in unstable film, which is easily soluble in water. On the other hand, the simple thermal treatment of the PNVF films at 200 °C for several hours produced the hydrogels after water immersion, although PNVA did not produce any hydrogels under the same condition.

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Herein, we present the first induced chirality of vanillin and its phenolic analogs attached to the chain ends of poly(l,l-lactide) and poly(d,d-lactide). Vanillin analogs were used as chromophoric and luminophoric, but achiral, ring-opening initiators of corresponding chiral cyclic lactides. Induced chirality was evident from clear circular dichroism bands at 270-320 nm due to π-π* and n-π* transitions at the vanillin moiety.

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