Publications by authors named "Shin-ichi Yusa"

Extracellular vesicles (EVs) have been widely recognized as a heterogeneous group of membrane-coated submicrometer particles released by different types of cells, including stem cells (SCs). Due to their ability to harbor and transfer bioactive cargo into the recipient cells, EVs have been reported as important paracrine factors involved in the regulation of a variety of biological processes. Growing data demonstrate that EVs may serve as potential next-generation cell-free therapeutic factors.

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Double hydrophilic diblock copolymers (GA and GA), composed of non-charged poly(glycosyloxyethyl methacrylate) (PGEMA, G) and cationic poly((3-acrylamidopropyl)trimethylammonium chloride), were synthesized via reversible addition-fragementation chain transfer (RAFT) radical polymerization. Likewise, diblock copolymers (GS and GS), composed of PGEMA and anionic poly(2-acrylamido-2-methylpropanesulfonate) were synthesized via RAFT. The subscripts in these abbreviations indicate the degree of polymerization (DP) of each block.

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Article Synopsis
  • FDA-approved anticoagulants can increase bleeding risks, including serious intracranial hemorrhages, but the specific effectiveness and safety of sulfonate polymers as alternatives have not been thoroughly studied.
  • Researchers synthesized and evaluated various sulfonated copolymers, finding that PSSS-based copolymers showed stronger anticoagulant effects compared to PAMPS-based ones, with the effectiveness influenced by sulfonate concentration and molecular weight.
  • The PEG-PSSS copolymer demonstrated significant anticoagulant activity in animal models and can be reversed by Heparin Binding Copolymer (HBC), targeting specific factors in the blood coagulation process, indicating potential for use in medical applications related to blood contact.
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A dual zwitterionic diblock copolymer (MC) consisting of poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC, M) and poly(3-((2-(methacryloyloxy)ethyl) dimethylammonio) propionate) (PCBMA, C) is synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. A double hydrophilic diblock copolymer (MS) consist of PMPC and anionic poly(3-sulfopropyl methacrylate potassium salt) (PMPS, S) is synthesized via RAFT. The degrees of polymerization of each block are 100.

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The effects of two ionic liquids (ILs), 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF) and 1-butyl-1-methyl pyrrolidinium tetrafluoroborate ([bmp]BF), on a mixture of phospholipids (PLs) 1,2-dipalmitoyl--glycero-3-phosphatidylcholine (DPPC), 1,2-dipalmitoyl--glycero-3-phosphoethanolamine (DPPE), and 1,2-dipalmitoyl--glycero-3-phosphoglycerol (DPPG) (6:3:1, M/M/M, 70% PL) in combination with 30 mol % cholesterol (CHOL) were investigated in the form of a solvent-spread monolayer and bilayer (vesicle). Surface pressure (π)-area () isotherm studies, using a Langmuir surface balance, revealed the formation of an expanded monolayer, while the cationic moiety of the IL molecules could electrostatically and hydrophobically bind to the PLs on the palisade layer. Turbidity, dynamic light scattering (size, ζ-potential, and polydispersity index), electron microscopy, small-angle X-ray/neutron scattering, fluorescence spectroscopy, and differential scanning calorimetric studies were carried out to evaluate the effects of IL on the structural organization of bilayer in the vesicles.

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Dicarboxylate metallosurfactants (AASM), synthesized by mixing N-dodecyl aminomalonate, -aspartate and -glutamate with CaCl, MnCl and CdCl, were characterized by XRD, FTIR, and NMR spectroscopy. Layered structures, formed by metallosurfactants, were evidenced from differential scanning calorimetry and thermogravimetric analyses. Solvent-spread monolayer of AASM in combination with soyphosphatidylcholine (SPC) and cholesterol (CHOL) were studied using Langmuir surface balance.

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Gas marbles are a new family of particle-stabilized soft dispersed system with a soap bubble-like air-in-water-in-air structure. Herein, stimulus-responsive character is successfully introduced to a gas marble system for the first time using polymer particles carrying a poly(tertiary amine methacrylate) (pK ≈7) steric stabilizer on their surfaces as a particulate stabilizer. The gas marbles exhibited long-term stability when transferred onto the planar surface of liquid water, provided that the solution pH of the subphase is basic and neutral.

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Liquid marbles (LMs) can be prepared by adsorption of hydrophobic particles at the air-liquid interface of a water droplet. LMs have been studied for their application as microreaction vessels. However, their opaqueness poses challenges for internal observation.

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AB-type and BAB-type betaine block copolymers composed of a carboxybetaine methacrylate and a sulfobetaine methacrylate, PGLBT--PSPE and PSPE--PGLBT--PSPE, respectively, were synthesized by one-pot RAFT polymerization. By optimizing the concentration of the monomer, initiator, and chain transfer agent, block extension with precise ratio control was enabled and a full conversion (~99%) of betaine monomers was achieved at each step. Two sets (total degree of polymerization: ~300 and ~600) of diblock copolymers having four different PGLBT:PSPE ratios were prepared to compare the influence of block ratio and molecular weight on the temperature-responsive behavior in aqueous solution.

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Article Synopsis
  • Polymeric drug delivery technology has significantly improved, making it easier for medicines to enter cells, with highlighted applications of biodegradable and bio-reducible polymers.
  • Natural polymers like chitosan and hyaluronic acid, along with synthetic options such as dendritic and bioabsorbable polymers, are being utilized in innovative drug delivery methods.
  • The combination of synthetic and biological materials is leading to advanced micro- and nano-drug delivery systems, which have shown potential in treating diseases, including cancer.
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Block copolymers (PM; PM and PM) comprising poly(2-(methacryloyloxy)ethylphosphorylcholine) (PMPC, P) containing biocompatible phosphorylcholin pendants and cationic poly((3-acryloylaminopropyl) trimethylammonium chloride) (PMAPTAC, M) were synthesized via a controlled radical polymerization method. The degrees of polymerization of the PMPC and PMAPTAC segments are denoted by subscripts (PM). The mixture of cationic PM and anionic sodium chondroitin sulfate C (CS) with the pendant anionic carboxylate and sulfonate groups formed polyion complex (PIC) aggregates in phosphate-buffered saline.

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Highly positively charged poly(vinyl benzyl trimethylammonium chloride) (PVBMA) was successfully synthesized with approximately 82% of yield. The PVBMA was characterized by the molecular weight (M ) of 343.45 g mol and the molecular weight distribution, (Đ) of 2.

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It has been 100 years since the first article on polymerization was published by Hermann Staudinger [...

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Cationic random copolymers (PC) consisting of 2-(methacryloyloxy)ethyl phosphorylcholine (MPC; P) with methacroylcholine chloride (MCC; C) and anionic random copolymers (PS) consisting of MPC and potassium 3-(methacryloyloxy)propanesulfonate (MPS; S) were prepared via a reversible addition-fragmentation chain transfer method. "" and "" represent the compositions (mol %) of the MCC and MPS units in the copolymers, respectively. The degrees of polymerization for the copolymers were 93-99.

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Solvent extraction has been ubiquitously used to recover valuable metals from wastes such as spent batteries and electrical boards. With increasing demands for energy transition, there is a critical need to improve the recycling rate of critical metals, including copper. Therefore, the sustainability of reagents is critical for the overall sustainability of the process.

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A laboratory-synthesized triblock copolymer poly(ethylene oxide--acrylic acid--styrene) (PEG-PAA-PS) was used as a template to synthesize hollow BaCO nanoparticles (BC-NPs). The triblock copolymer was synthesized using reversible addition-fragmentation chain transfer radical polymerization. The triblock copolymer has a molecular weight of 1.

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An amphiphilic diblock copolymer (PChM-PNIPAM), composed of poly(cholesteryl 6-methacryloyloxy hexanoate) (PChM) and poly(-isopropyl acrylamide) (PNIPAM) blocks, was prepared via reversible addition-fragmentation chain transfer radical polymerization. The PChM and PNIPAM blocks exhibited liquid crystalline behavior and a lower critical solution temperature (LCST), respectively. PChM-PNIPAM formed water-soluble polymer micelles in water below the LCST because of hydrophobic interactions of the PChM blocks.

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A New Year's Message 2023.

Polymers (Basel)

February 2023

We wish you all happiness, health and progress in the new year [...

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Development of molecules that can be effectively used for killing cancer cells remains a research topic of interest in drug discovery. However, various limitations of small molecules and nanotechnology-based drug-delivery systems hinder the development of chemotherapeutics. To resolve this issue, this study describes the potential application of polymeric molecules as anticancer drug candidates.

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Poly(4-((3-methacrylamidopropyl)dimethylammonium)butane-1-sulfonate) (PSBP) was prepared via controlled radical polymerization. PSBP showed upper critical solution temperature (UCST) behavior in aqueous solutions, which could be controlled by adjusting the polymer and NaCl concentrations. Owing to its pendant sulfonate anions, PSBP exhibited a negative zeta potential of -7.

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There has been increasing interest in colloidal particles adsorbed at the air-water interface, which lead to stabilization of aqueous foams and liquid marbles. The wettability of the particles at the interface is known to play an important role in determining the type of air/water dispersed system. Foams are preferably formed using relatively hydrophilic particles, and liquid marbles tend to be formed using relatively hydrophobic particles.

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Poly(2-methoxyethyl acrylate) (PMEA) and poly(ethylene oxide) (PEO) have protein-antifouling properties and blood compatibility. ABA triblock copolymers (PMEA-PEO-PMEA (MEOM; is average value of and )) were prepared using single-electron transfer-living radical polymerization (SET-LRP) using a bifunctional PEO macroinitiator. Two types of MEOM composed of PMEA blocks with degrees of polymerization (DP = ) of 85 and 777 were prepared using the same PEO macroinitiator.

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A diblock copolymer (P(VBTAC/NaSS)--PAPTAC; P(VS)A) composed of amphoteric random copolymer, poly(vinylbenzyl trimethylammonium chloride--sodium -styrensunfonate) (P(VBTAC/NaSS); P(VS)) and cationic poly(3-(acrylamidopropyl) trimethylammonium chloride) (PAPTAC; A) block, and poly(acrylic acid) (PAAc) were prepared via a reversible addition-fragmentation chain transfer radical polymerization. Scrips V, S, and A represent VBTAC, NaSS, and PAPTAC blocks, respectively. Water-soluble polyion complex (PIC) vesicles were formed by mixing P(VS)A and PAAc in water under basic conditions through electrostatic interactions between the cationic PAPTAC block and PAA with the deprotonated pendant carboxylate anions.

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Double-hydrophilic diblock copolymers, PMPC--PGEMA (MG), were synthesized via reversible addition-fragmentation chain transfer radical polymerization using glycosyloxyethyl methacrylate and 2-(methacryloyloxy)ethyl phosphorylcholine. The degree of polymerization (DP) of the poly(2-(methacryloyloxy) ethylphosphorylcholine) (PMPC) block was 100, whereas the DPs () of the poly(glycosyloxyethyl methacrylate) PGEMA block were 18, 48, and 90. Water-soluble complexes of C/MG and fullerene (C) were prepared by grinding MG and C powders in a mortar and adding phosphate-buffered saline (PBS) solution.

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Hydrophilic poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) shows biocompatibility because the pendant phosphorylcholine group has the same chemical structure as the hydrophilic part of phospholipids that form cell membranes. Hollow particles can be used in various fields, such as a carrier in drug delivery systems because they can encapsulate hydrophilic drugs. In this study, vinyl group-decorated silica particles with a radius of 150 nm were covered with cross-linked PMPC based on the graft-through method.

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