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PURPOSE: The aim of this prospective comparative trial was to evaluate whether patients treated with complete dentures with lingualized occlusion (LO) exhibited more positive results than patients treated with complete dentures with bilaterally balanced occlusion (BBO). MATERIALS AND METHODS: Twenty-eight completely edentulous patients, ranging in age from 60 to 82 years (mean age 70.9), consented in writing to be participants in this trial. The first 14 patients enrolled in the study protocol were treated with complete dentures with LO, and the next 14 patients were treated with complete dentures with BBO. Baseline characteristics were measured prior to the trial. Main outcome variables involved subjective outcomes of general satisfaction, ability to masticate, and stability and retention of the prostheses; these were quantified with a 100-mm visual analog scale. Objective outcomes were masticatory performance and the number of adjustments. Statistical assessments of the 2 groups were compared using multiple linear regression analysis. The baseline characteristics were analyzed by Student t test and chi-square test. RESULTS: There were no significant differences between the groups at baseline. The height of the alveolar ridge exhibited significant correlations with masticatory performance (P = .02). The occlusal scheme exhibited a significant correlation with only the patient's retention satisfaction rating (P = .03). CONCLUSION: Despite limitations of this study attributed to the small sample size and lack of randomization, this pilot study found that edentulous patients fitted with complete dentures with LO experienced and expressed greater satisfaction with their denture retention. In addition, it was observed that a higher alveolar ridge resulted in greater masticatory performance. [ABSTRACT FROM AUTHOR]

Abstract: High-pressure phase relations in the system NaAl3Si3O11–CaAl4Si2O11 were examined at 13–23GPa and 1600–1900°C, using a multianvil apparatus. A Ca-aluminosilicate with CaAl4Si2O11 composition, designated CAS phase, is stable above about 13GPa at 1600°C. In the system NaAl3Si3O11–CaAl4Si2O11, the CAS phase dissolving NaAl3Si3O11 component coexists with jadeite, corundum and stishovite below 22GPa, above which the CAS phase coexists with Na-rich calcium ferrite, corundum and stishovite. At 1600°C, the solubility of NaAl3Si3O11 component in the CAS solid solution increases with increasing pressure up to about 50mol% at about 22GPa, above which the solubility decreases with pressure. The maximum solubility of NaAl3Si3O11 component in the CAS phase increases with temperature up to around 70mol% at 1900°C at 22GPa. The dissociation of NaAlSi2O6 jadeite to NaAlSiO4 calcium ferrite plus stishovite occurs at about 22GPa. Lattice parameters of the CAS phase with the hexagonal Ba-ferrite structure change with increase of the NaAl3Si3O11 component: a-axis decreases and c-axis slightly increases, resulting in decrease of molar volume. Enthalpies of the CAS solid solutions were measured by high-temperature drop-solution calorimetry techniques. The results show that enthalpy of hypothetical NaAl3Si3O11 CAS phase is much higher than the mixture of NaAlSi2O6 jadeite, corundum and stishovite and is close to that of the mixture of NaAlSiO4 calcium ferrite, corundum and stishovite. When we adopt the Na:Ca ratio of 75:25 of the natural Na-rich CAS phase in a shocked Martian meteorite, Zagami, the phase relations determined above suggest that the natural CAS phase crystallized from melt at pressure around 22GPa and temperature close to or higher than 2000–2200°C. The inferred P, T conditions are consistent with those estimated using other high-pressure minerals in the shocked meteorite. [Copyright &y& Elsevier]

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. The chemical interactions and thermal properties of the new materials were evaluated using FT-IR and TGA, which revealed a shift in wavenumber and a decrease in T 10 . Incorporation of PTTG into CS significantly improved tensile strength, reaching up to 16.0 ± 2.6 MPa in the CS75PTTG25 formulation. The flexibility also increased to 55.9 ± 6.6 MPa in the simple blend of CS, PTMC copolymer, and N-methyl-D-glucamine. Additionally, the underlying mechanism is presented and thoroughly explained in this work. Consequently, CS/PTTG blend films, derived from biodegradable polymers with excellent mechanical properties, demonstrate potential for various applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

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. Our findings revealed that the specific presence of PEG-PPG-PEG, PAA, and PSAMA had a notable effect on delaying the suspension of sedimentation by the actual sediment weight as well as enhancing the uniformity of clay coating by the reflection efficiency of coating materials in PPFD units. To enhance sustainability in coating materials, it was essential to elucidate the optimal amounts of adjuvants and the pH levels as they are closely related to the efficacy of tree-coated spraying and soil conditions., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

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( N -vinyl pyrrolidone). This initial study using slow constant cooling (SCC) in rocking cells with a synthetic natural gas has now been expanded to further explore low molecular weight PVMOX homopolymers and VMOX copolymers as well as blends with nonpolymeric synergists. A PVMOX homopolymer with improved KHI performance was found using 3-mercaptoacetic acid as a chain transfer agent in the radical polymerization of VMOX. Among a range of copolymers, VMOX: n -butyl acrylate copolymers in particular gave good KHI performance, better than the PVMOX homopolymer. Among the potential synergists, trialkylamine oxides (alkyl = n -butyl or iso-pentyl) and tetra( n -pentyl)ammonium bromide to 2500 ppm were found to be antagonistic with PVMOX at the test concentrations while some alcohols and glycols were synergetic. The best synergist was 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD). For example, a mixture of 2500 ppm TMDD with 2500 ppm PVMOX ( M w 2400 g/mol) performed significantly better than 5000 ppm PVMOX. Addition of 1250 ppm TMDD to 2500 ppm VMOX: n -butyl acrylate 6:4 copolymer lowered the hydrate onset temperature in SCC tests by a further 3 °C compared to the copolymer alone giving hydrate onset at 4.2 °C., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

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. The developed skin model, LbL-3D Skin had a highly differentiated epidermis and dermis, similar to the validated reference methods (VRM) and native human skin. The quality parameters (cell survival in controls, tissue integrity, and barrier function) were similar to VRM and in accordance with OECD TG 439. The LbL-3D Skin SIT validation study was performed by three participating laboratories and consisted of three independent tests using 20 reference chemicals. The results obtained with the LbL-3D Skin demonstrated high within-laboratory and between-laboratory reproducibility, as well as high accuracy for use as a stand-alone assay to distinguish skin irritants from nonirritants. The predictive potency of LbL-3D Skin SIT using total 54 test chemicals were comparable to those in other RhE models in OECD TG 439. The validation study demonstrated that LbL-3D Skin has proven to be a robust and reliable method for predicting skin irritation., (© 2023 John Wiley & Sons Ltd.)

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. The proposed method first decomposes a spectrum into peaks with various widths by the wavelet transform. Subsequently, a sparse linear regression model is built using the wavelet coefficients. Models by the method are interpretable using the regression coefficients shown on Gaussian distributions with various widths. The interpretation is expected to reveal the relation of broad regions in spectra to the model prediction. In this study, we conducted the prediction of monomer concentration in copolymerization reactions of five monomers against methyl methacrylate by various chemometric approaches including conventional methods. A rigorous validation scheme revealed that the proposed method overall showed better predictive ability than various linear and non-linear regression methods. The visualization results were consistent with the interpretation obtained by another chemometric approach and qualitative evaluation. The proposed method is found to be useful for calculating the concentrations of monomers in copolymerization reactions and for the interpretation of spectra., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

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( N , N -dimethylaminoethyl methacrylate) was successfully prepared using reversible addition-fragmentation chain-transfer (RAFT) polymerization and was derived to carboxybetaine copolymers of poly(CBMA1- co -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). Further, we also evaluated nonspecific protein adsorption in fetal bovine serum and antibody immobilization on the substrate coated with P(CBMA1/CBMA3) copolymers using surface plasmon resonance (SPR) analysis. As the CBMA1 content increased, nonspecific protein adsorption on the P(CBMA1/CBMA3) copolymer surface decreased. Similarly, the immobilization amount of the antibody decreased as the CBMA1 content increased. However, the figure of merit (FOM), defined as the ratio of the amount of antibody immobilization to that of nonspecific protein adsorption, depended on the CBMA3 content; FOM was higher when the CBMA3 content was 20-40% than those of CBMA1 and CBMA3 homopolymers. These findings will help enhance the sensitivity of the analysis using molecular interaction measurement devices, such as SPR and quartz crystal microbalance.

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 3 particles were prepared using polymers with various M n values of 2400-4800 g/mol. PLLA-V6-OEG 3 was appropriated to achieve a pH-responsive behavior under physiological conditions within 3 min via the six-membered ring diol-ketone acetal. Moreover, it was found that the polymer chain length ( M n ) influenced the aggregation rate. TiO 2 was selected as the blending agent to improve the aggregation rate. The PLLA-V6-OEG 3 blended with TiO 2 was found to accelerate the aggregation rate compared with that without TiO 2 , and the best ratio of polymer/TiO 2 was 1:1. To study the effect of the chain end for stereocomplex polylactide (SC-PLA) particles, PLLA-V6-OEG 4 and PDLA-V6-OEG 4 were successfully synthesized. The obtained results of SC-PLA particle aggregation implied that the types of chain end and the molecular weight of polymer could influence the aggregation rate. The SC-V6-OEG 4 blended with TiO 2 could not make our target to aggregate under physiological conditions within 3 min. This study motivated us to control the particle aggregation rate under physiological conditions for applying as a target drug carrier which is significantly influenced by not only the molecular weight but also the hydrophilicity of the chain-end as well as the number of acetal bonds.

Photo-iniferter reversible addition-fragmentation chain transfer (PI-RAFT) polymerization of N-vinylformamide (NVF) is demonstrated by using purple light. PNVFs with predetermined molar masses and narrow molar mass distributions are obtained. High RAFT chain-end fidelity is confirmed by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) and electrospray-ionization time-of-flight mass spectrometry (ESI-TOF-MS), and chain extension experiment. To demonstrate the potential of this approach, an original poly(N-vinylpyrrolidone)-b-poly(N-vinylformamide) (PVP-b-PNVF) diblock copolymer is synthesized and characterized by aqueous size-exclusion chromatography (SEC), asymmetric flow field-flow fractionation (A4F), and 1 H diffusion-ordered spectroscopy nuclear magnetic resonance ( 1 H DOSY NMR). Finally, selective hydrolysis of PNVF block to corresponding pH-responsive poly(N-vinylpyrrolidone)-b-poly(N-vinylformamide) (PVP-b-PVAm) is performed., (© 2022 The Authors. Macromolecular Rapid Communications published by Wiley-VCH GmbH.)

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. The solubility of CDs is influenced to form the PPRX, resulting in differing numbers of CDs in the axle. PPRX structures were investigated by 1 H NMR, NOESY, and DOSY, and SC structures were investigated by FT-IR and XRD. Their thermal properties were also evaluated by DSC and TGA, to consider the physical properties of the simultaneous formation of PPRX and SC. This study gave insight into the complicated host-guest and polymer-polymer interactions.

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 N -vinylcaprolactam (VCap) are one of the most common KHI classes. Alternative classes of polymers containing caprolactam groups are rare. Here, we present a study on oxyvinylenelactam polymers and copolymers with pendant piperidone or caprolactam groups. Low-molecular-weight homo- and copolymers were obtained. The nonrotating vinylene groups impart rigidity to the polymer backbone. Poly(oxyvinylenecaprolactam) (POVCap) was insoluble in water, but poly(oxyvinylenepiperidone) (POVPip) and OVPip:OVCap copolymers with 60+ mol % OVPip were soluble with low cloud points. KHI screening tests were carried out using the slow constant cooling method in steel rocking cells. POVPip was water soluble with no cloud point up to 95 °C but showed a poor KHI performance. In contrast, OVPip:OVCap copolymers with about 60-70 mol % OVPip were also water soluble and showed a reasonable KHI performance, better than that of poly( N -vinylpyrrolidone) but not as good as that of poly( N -vinylcaprolactam). Surprisingly, several additives known to be good synergists for VCap-based polymers showed negligible synergy or were antagonistic with the 62:38 OVPip:OVCap copolymer with regard to lowering the onset temperature of hydrate formation. However, a blend with hexabutylguanidinium chloride showed a strong effect to delay the onset of rapid hydrate formation., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

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. The bioactivities were the antibacterial activity, cell viability, skin irritation, decomposability, and ability to attach ions for apatite nucleation. The results showed that all the composite hydrogels were completely decomposed within 2 days. The composite hydrogels had better antibacterial activity and higher efficiency to Gram-negative (Escherichia coli) than to Gram-positive (Staphylococcus epidermidis) bacteria. The composite hydrogels were studied for cell viability based on MTT assay and skin irritation on rabbit skin. The results indicated high cell survival more than 80% and no skin irritation. In addition, the results showed that calcium and phosphorous were preferentially attached to the composite hydrogel surface to grow apatite crystal (Ca/P ratio 1.86) compared to attaching to the chitosan hydrogel (Ca/P ratio 1.48) in 21 days of testing., (Copyright © 2022 Elsevier B.V. All rights reserved.)

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( N -alkylacrylamide)s without potential safety risks is of great importance. In this article, thermoresponsive poly( N -vinylisobutyramide) (PNVIBA) microgels of uniform size were synthesized with NVIBA as a monomer and N , N '-5-oxanonamethyene-bis- N -vinylacetamide as a cross-linker in the presence of sodium dodecyl sulfate by aqueous free radical precipitation polymerization. The introduction of cationic groups into PNVIBA microgels was also accomplished using N -vinylformamide (NVF) as a comonomer and the subsequent conversion of NVF into vinylamine by hydrolysis.

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. Here, we describe a topological strategy in the polymer phase for efficient toughening of bioinspired CNF nanocomposites with a water-soluble comb polyurethane (PU). The comb PU provided higher elongation at break and more efficient flexibility for the nanocomposite than the linear PU, even at a small content. Moreover, CNF nanocomposites with 30 wt % of PU content and tetrabutylammonium as bulky counterions showed enhanced toughness (180% higher) and strain at break (250% higher) when compared to pure CNF due to the promotion of slippage between nanofibrils. Scanning electron microscopy (SEM) images of the fracture surface for CNF/comb PU nanocomposites displayed the pull-out of mesoscale layers and nanofibrils, supporting that the comb topology promotes the slippage between fibrils. Furthermore, the rheological study revealed that the comb PU has an entanglement plateau modulus lower than linear PU by 1 order of magnitude, related to the loosened entanglements. Our study establishes an efficient softening and toughening strategy while using small amounts of polymer phase addition, promoting interfibrillar slippage with the loosely entangled comb PU phase.

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 2 ) and fluoropolymer-based precursors as coating materials. Experimental results indicated a uniform distribution of TiO 2 particles with an average size below 200 nm throughout the fabric. A zone of inhibition test revealed that the fabric inhibited bacterial growth, specifically of Staphylococcus aureus and Klebsiella pneumoniae , before and after 10 wash cycles of the fabric. In wetting angle measurements, the contact angles of water droplets on the fabric ranged from 120° to 139°. A water repellency test confirmed that the coated fabrics retained their water-repellent property after 10 wash cycles., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

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% T to 0% T within about 10 °C at 4 g L -1 , whereas d-PU did not change completely to 0% T transmittance even at 80 °C at 4 g L -1 . In addition, the thermoresponsive properties of l-PU were less affected by concentration than those of d-PU. This long-distance diastereomeric effect on thermoresponsive behavior between l-PU and d-PU appeared in common among 6 samples with 4700 to 13 100 number average molecular weight. In the dynamic light scattering experiments at each transmittance, the hydrodynamic diameter ( D h ) of l-PU increased up to 1000 nm, while the D h of d-PU remained almost at 200-300 nm. The C[double bond, length as m-dash]O stretching vibration of FT-IR spectra showed that d-PU has more hydrogen-bonded ester groups than L-PU. Thus, we speculated that the difference in the retention of polymer chains in the micelle to promote intermicellar bridging generates the long-distance diastereomeric effect., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

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. Cells grown on PET accumulated intracellular PHA at high levels. Collectively, our findings in this study demonstrate that I. sakaiensis can mediate the direct conversion of non-biodegradable PET into environment-friendly plastic, providing a new approach for PET recycling., (© 2021. The Author(s).)

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. Moreover, the one-shot preparation of comb PU hydrogel with PEG300 improves toughness up to 100 times compared to the original comb PU hydrogel. Rheological analysis suggests that the bimodal toughening phenomenon for the proportion of PEG300 is due to the network structure and the hydrophobic aggregation domain. This simple toughening method using a heteronetwork based on the kinetic difference of step-growth PU is expected to apply to other chemical structures., (© 2021 Wiley-VCH GmbH.)

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. The UV spectra of the newly synthesized SpMA showed the photo-isomerization of spiropyran. The maximum absorption wavelength (λmax) of SpMA was 616 nm in n-hexane, a nonpolar solvent, although λmax of SpMA was 532 nm in methanol, a polar protic solvent, which resulted in an 84 nm blue-shift. SpMA was successfully polymerized by ruthenium (Ru)-catalyzed living radical polymerization. Poly(SpMA) (PSpMA) was then spin-coated on a PET substrate in order to control the surface properties of water repellency and cell adhesion. The water repellency was decreased approximately 10° under UV irradiation, because of the polarity change of PSpMA caused by photo-isomerization from the spiropyran (SP) type to the merocyanine (MC) type. In addition, NIH3T3 cells were spread only on 6% of the surface of the PSpMA thin film after UV irradiation compared with no UV irradiation. The polarity change of PSpMA by photo-isomerization is also believed to be the reason for this behavior. As a result, we successfully synthesized a photo-controllable cell culture scaffold.

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. Poly(styrene- co -divinylbenzene) (PS gel), poly(styrene- co -divinylbenzene- co -4-vinylpyridine) (PS-4VP) gel and poly(styrene- co -divinylbenzene- co -(vinylbenzyl) trimethylammonium chloride) (PS-VBAC gel) were employed as chemical gels to improve the stability of the TDD substrates. The drug permeation properties from the PS gels swollen in limonene were examined, regarding the effect of its network density as well as their rheological properties. The lowest density of the network showed the highest steady flux of the permeation at 43.7 ± 0.3 μg/cm². FT-IR spectra were confirmed for PS-4VP and PS-VBAC, bearing cationic moieties and they could control the release of ibuprofen by the electrostatic interaction at the interface of organogel and skin. The steady state flux of skin permeation got low values from 55.2 ± 0.8 to 11.6 ± 2.0 μg/cm², when the cationic moieties were increased. Moreover, the chemical network of PS gel swollen in limonene showed high mechanical stability illustrated by elastic modulus (G') of about 98 kPa for 10% cross-linked PS gel. The developed PS gels swollen in limonene show highly promising results, suggesting their possible application in TDD.

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. This polyurethane hydrogel including 10 mol% of glycerol presents a large swelling ratio change between 4 °C and 37 °C from 250% to 40%., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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. In order to control the nanosized structures, poly(N-vinylformamide) derivatives bearing azobenzene at the N-position near to the vinyl polymer main chain were synthesized by polymer reaction with the poly(N-vinylformamide-co-N-(methoxyethyl)-N-vinylformamide) and azobenzene. Aggregation size of the multi-stimuli-responsive polymer was controlled by preparation of the hydrophobic interaction at around N-position.

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. This system can change its hydrophobicity depending on temperature. Thus, tissues can attach above 37 °C and be detached below 20 °C. However, the PNIPAAm system has some issues related to cost and detachment time. In this study, we developed a novel thermoresponsive detachment system using a polysaccharide derivative. We chose hydroxy butyl chitosan (HBC) as the thermoresponsive polymer because of its high biocompatibility and rapid phase transition. We developed a novel method of HBC synthesis in conditions that were milder than previously reported. We used spin-coating to make a thin coating on two kinds of culture dishes with various concentrations of HBC solution. Seeded cells attached to the surface at less than 0.5 mg/ml HBC coating concentration, and they could be successfully detached by simply lowering the temperature of the suspension dishes without enzymatic treatment; the cells took only 5-20 min to detach. To evaluate this system, we measured three metrics related to cell culturing on culture dishes: initial attachment rate, detachment rate and tissue detachment time. The study revealed that tissues could be detached faster on the suspension dishes used in this study than on PNIPAAm grafted dishes when HBC was coated at 0.5 mg/ml. We successfully developed a novel tissue detachment system using HBC. These results suggest that smart polymers may be useful in regenerative medicine.

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. The swelling ratios of the formed hydrogel ranged from 100 to 250. The analysis of the supernatant reveals the structural change at alpha proton of PNVF. Furthermore, the decrease of molecular weights were observed by SEC analysis when the hydrogels formed. The possible mechanism of the crosslinking reaction is also discussed. The present study provides the novel method to prepare PNVF hydrogels without the use of chemical crosslinkers.

The stereocomplex formation of poly(l,l-lactide) (PLLA) and poly(d,d-lactide) (PDLA) was selected in order to investigate the interaction of the two surfaces including hydrogen bonding and van der Waals interaction. Adhesion force measurement using surface force apparatus (SFA) equipped with an optical microscope was conducted on the PLLA and PDLA spin-coated films. The adhesion forces, Fad, phenomenologically followed the linear relation with the applied normal load, L. For the force Fad between PLLA and PDLA films with low molecular weights (PLLA, Mn = 2800; PDLA, : Mn = 2100), the slope of linear fitting of Fad vs L was significantly larger for the heterointerface (PLLA/PLDA) compared with that for the homointerface (PLLA/PLLA and PDLA/PDLA). However, when polymers with higher molecular weights (PLLA, Mn = 8500; PDLA, Mn = 8300) were measured, the slopes of linear fitting lines were almost the same for hetero- and homointerfaces. This indicated that the mobility of the lower molecular weight PLLA/PDLA films promoted the selective interaction of PLLA and PDLA under the applied normal loads. The adhesion between the outermost PLLA layer and PDLA layer prepared by layer-by-layer (LbL) assembly was also measured. It is interesting that the adhesion force was very weak in this case. This weak adhesion could be explained by the much less mobility of the polymer chain due to the stereocomplex formation within the LbL layers. This study demonstrated that the adhesion force due to the selective interaction of PLLA and PDLA between PLLA/PDLA films could be directly measured, and depended on the mobility of the outermost polymer chains, which reflected the different structures of polymer chains in the organized complex films.

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. However, no circularly polarized luminescence band was detected. Density functional theory (DFT) and time-dependent DFT calculations suggested the existence of multiple through-space intramolecular CH/O interactions between the ortho -methoxy moiety of vanillin and nearest-neighbor lactic acid units. The terminus sensitively indicated whether the main-chain chirality was l or d.

Using different type of initiators, the antibacterial moieties are introduced at the chain end of poly(L,L-lactide) (PLLA) and poly(D,D-lactide) (PDLA), and the thermal properties are simultaneously improved using the stereocomplex approach. The physical interaction of polymers and antibacterial compounds is investigated. The double bonds at the chain end are utilized for the interaction of silver ion; however, the silver ions are not detected after stereocomplexation of PLLA and PDLA. On the other hand, catechin (CT) is selected as an initiator precursor of lactide polymerization, protecting the phenolic hydroxyl groups. The linear PLLA and PDLA are obtained by the initiator, resulting in CT conjugated PLAs at the chain end groups after deprotection of phenolic hydroxyl groups. The antibacterial properties are determined by proliferation tests of staphylococcus aureus. The results suggest that the antibacterial properties of CT modified PLAs are derived from the original CT parts., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The stereocomplex formation of poly(L,L-lactide) (PLLA) and poly(D,D-lactide) (PDLA) using an inkjet system was expanded to the amphiphilic copolymers, using poly(ethylene glycol) (PEG) as a hydrophilic polymer. The diblock copolymers, which are composed of PEG and PLLA (MPEG-co-PLLA) and PEG and PDLA (MPEG-co-PDLA), were employed for thin-film preparation using an aqueous inkjet system. The solvent and temperature conditions were optimized for the stereocomplex formation between MPEG-co-PLLA and MPEG-co- PDLA. As a result, the stereocomplex was adequately formed in acetonitrile/water (1:1, v/v) at 40 °C. The aqueous conditions improved the stereocomplex film preparation, which have suffered from clogging when using the organic solvents in previous work. The triblock copolymers, PLLA-co-PEG-co-PLLA and PDLA-co-PEG-co-PDLA, were employed for square patterning with the inkjet system, which produced thin films. The amphiphilic polymer film was able to retain hydrophobic compounds inside. The present result contributed to the rapid film preparation by inkjet, retaining drugs with difficult solubility in water, such as paclitaxel within the films.

Layer-by-layer (LbL) assembly based on hydrogen-bonding interactions is generating great interest for biomedical applications because it is composed of neutral polymers, while LbL assembly based on electrostatic interaction requires polycations which may induce toxicity issues. As a neutral polymer, poly(N-vinylamide), which has low toxicity compared to poly(acrylamide), has the potential to fabricate LbL thin films via hydrogen-bonding interactions. Herein we report interpolymer complexes of poly(N-vinylamide)s and natural polyphenol tannic acid to form the multilayered thin film. Poly(N-vinylformamide) and poly(N-vinylacetamide), which are water-soluble and insoluble in acetonitrile, could not form complexes with TA in water. On the other hand, N-alkylated poly(N-vinylamide) such as poly(N-ethyl-N-vinylformamide) and poly(N-methyl-N-vinylacetamide) was soluble in acetonitrile and allowed the LbL assembly to proceed with TA. Furthermore, the QCM frequency shift with films composed of poly(N-ethyl-N-vinylformamide) and TA were stable in water, while those of poly(N-methyl-N-vinylacetamide) and TA were instable in water, possibly because formamide has lower steric hindrance compared to acetamide to allow stronger hydrogen-bonding interactions to take place. Thus, LbL assembly reactions with alkylated poly(N-vinylamide)s and TA were investigated and revealed that poly(N-ethyl-N-formamide) and TA, which are water-soluble, effectively interacted with one another to generate water-stable hydrogen-bonded multilayered films.

Advanced bioactive systems with defined macroscopic properties and spatio-temporal sequestration of extracellular biomacromolecules are highly desirable for next generation therapeutics. Here, chitosan (CT) hydrogels were prepared with neutral or negatively charged cross-linkers in order to promote selective electrostatic complexation with charged drugs. CT was functionalized with varied dicarboxylic acids, such as tartaric acid, poly(ethylene glycol) bis(carboxymethyl) ether, 1,4-phenylenediacetic acid and 5-sulfoisophthalic acid monosodium salt (PhS), whereby PhS was hypothesized to act as a simple mimetic of heparin. Attenuated total reflectance Fourier transform infrared spectroscopy showed the presence of CO amide I, N-H amide II and CO ester bands, providing evidence of covalent network formation. The cross-linker content was reversely quantified by proton nuclear magnetic resonance on partially degraded network oligomers, so that 18 mol.% PhS was exemplarily determined. Swellability (SR: 299 ± 65-1054 ± 121 wt.%), compressibility (E: 2.1 ± 0.9-9.2 ± 2.3 kPa), material morphology and drug-loading capability were successfully adjusted based on the selected network architecture. Here, hydrogel incubation with model drugs of varied electrostatic charge, i.e. allura red (AR, doubly negatively charged), methyl orange (MO, negatively charged) or methylene blue (MB, positively charged), resulted in direct hydrogel-dye electrostatic complexation. Importantly, the cationic compound, MB, showed different incorporation behaviours, depending on the electrostatic character of the selected cross-linker. In light of this tunable drug-loading capability, these CT hydrogels would be highly attractive as drug reservoirs towards e.g. the fabrication of tissue models in vitro., (Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

Novel block copolymers using the monomers 5-(2-methoxyethyoxymethyl)-5-methyl-[1,3]-dioxa-2-one (TMCM-MOE1OM) as a hydrophilic segment and lactides as a hydrophobic segment were designed in order to prepare controllable degradation polymers by dynamic polymer rearrangement based on the hydrophilicity. When the copolymer film contacted water, the hydrophobic polylactide (PLA) segments tend to be buried under the TMCM-MOE1OM segments due to the hydrophilicity of the methoxyethoxy groups. The copolymers were hardly degraded by both proteinase K and lipase, while both of their homopolymers, poly(trimethylene carbonate) and PLA, were degraded, which suggests that the rearrangement of the TMCM-MOE1OM segments at the outermost surface significantly improved the degradation ratio., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The simultaneous improvement of the melting temperature (T(m) = 224 °C) and the decomposition temperature (T(10) = 359 °C) of poly(lactide)s was achieved by the stereocomplex formation of poly(l-lactide) and poly(d-lactide) with bio-based aromatic groups at both initiating and terminating chain ends.

The stereoregular synthetic polymer isotactic polystyrene bearing partially sulfonated groups (SiPS) was used as a layer-by-layer assembled thin film for the first time. When a low molecular weight compound was employed as the pair for the alternative layer-by-layer (LbL) assembly, the frequency shift was very small using quartz crystal microbalance (QCM) analysis, whereas poly(vinylamine) (PVAm) formed an effective pair for the construction of LbL films with SiPS. When it was neutralized, SiPS was not assembled, probably due to the loss of effective polymer-polymer interactions. The ionic strength conditions revealed a slight difference of the assembly behavior on the isotactic polymer as compared to the atactic one. The assembled LbL film showed the same peaks over the range from 1141 to 1227 cm(-1) and 700 cm(-1) in the FT-IR/ATR spectra as the bulk complex of SiPS/PVAm, and the thickness on one side was calculated at 76 nm by QCM analysis. The surface roughness of the film was also observed by AFM., (© 2012 American Chemical Society)

The surface design and control of substrates with nanometer- or micrometer-sized polymer films are of considerable interest for both fundamental and applied studies in the biomedical field because of the required surface properties. The layer-by-layer (LbL) technique was discovered in 1991 by Decher and co-workers for the fabrication of polymer multilayers constructed mainly through electrostatic interaction. The scope and applicability of this LbL assembly has been extended by introducing molecularly regular conformations of polymers or proteins by employing, for the first time, weak interactions such as van der Waals interactions and biological recognition. Since these weak interactions are the sum of the attractive or repulsive forces between parts of the same molecule, they allow macromolecules to be easily arranged into the most stable conformation in a LbL film. By applying this characteristic feature, the template polymerization of stereoregular polymers, stereoregular control of surface biological properties, drastic morphological control of biodegradable nano materials, and the development of three-dimensional cellular multilayers as a tissue model were successfully achieved. It is expected that LbL assembly using weak interactions will promote further interest into fundamental and applied studies on the design of surface chemistry in the biomedical field., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The swelling behaviors of IPN with poly(N-vinylacetamide) (PNVA), which possibly converts from nonionic gel to cationic gel, and the stimuli responsive polymers, such as poly(acrylic acid) (PAAc) and poly(N-isopropylacrylamide) (PNIPAm) were investigated in order to prepare the stimuli responsive amphiphilic gel. When the monomer concentrations were uniformed at the IPN preparation, the obtained PNVA/PAAc IPN showed the pH responsivity with around 100 of swelling ratio at pH 4 to around 1 of swelling ratio at pH 2, although it lost the amphiphilicity due to the lack of swelling in ethanol. On the other hand, the gelation of N-vinylacetamide at 2 M in PNIPAM gel resulted in thermosensitive and amphiphilic hydrogel, that the swelling ratio in EtOH/water (3/7, v/v) also decreased, compared to the value in water at 25 degrees C.

Structures of silica nanoparticles coated with stereocomplex thin films composed of isotactic (it) poly(methyl methacrylate) (PMMA) and syndiotactic (st) poly(methacrylic acid) (PMAA) and with porous it-PMMA thin films under gentle stirring or static conditions were analyzed by dynamic light scattering (DLS) and scanning electron microscopy (SEM), respectively. The porous it-PMMA films were fabricated by stepwise stereocomplex assembling of it-PMMA and st-PMAA, and subsequent extraction of the st-PMAA from the films. From DLS results, an evident difference was not observed between the it-PMMA films and the stereocomplex films, whereas the it-PMMA films after 10 h of stirring in acetonitrile/water (4/6, v/v) and drying on a SEM stage fused to form nanostructured networks. The fusion of the it-PMMA films on the silica nanoparticles occurred not by the dissolution of it-PMMA in the mixed solvent, but rather by an interaction of the it-PMMA chains driven by the slight solvation of acetonitrile without dissolution. Thus, leaving the solution at rest would be important for film fusion on the particles, and multiple spherical substrates could promote the crosslinking of the it-PMMA chains on the particles.

Stereoregular isotactic-poly(propylene oxide) (it-PPO) was investigated for use as a biomaterial surface. The conventional characteristic of nonstereoregular atactic PPO was altered to a hydrophobic solid nature (contact angle: 95.6 ± 3.8°), which resulted in the potential solid surface applications. The high crystallinity of it-PPO created both smooth and microsized, random crater-shaped surfaces using the spin coating and dip coating approaches, respectively. The results of protein adsorption with bovine serum albumin (BSA), bovine gamma globulin (BγG), and bovine plasma fibrinogen (BPF) showed multilayered adsorption onto it-PPO. Mouse fibroblast L929 cells adhered onto the it-PPO surfaces, and cultured well as compared with commercially available Cell Desk LF1 as a control surface. These unique physical characteristics of it-PPO were due to the configuration of the polymer chain backbone structure, which maintained the polyether chemical structure.

A novel approach is employed to produce core-corona nanospheres, which introduces a stereoregular hydrophilic part to an amphiphilic block copolymer. The resultant morphology is reported using isotactic-poly(methacrylic acid)-block-poly(butyl acrylate). Infrared spectroscopy revealed a supramolecular interaction, and X ray diffraction revealed the crystallization of the outer isotactic-poly(methacrylic acid) part. The nanostructure, which looks like a nanosized 'grape', was formed when nanospheres and nanofibers coexisted simultaneously and partially fused., (Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Mechanistic studies have revealed that the isospecific polymerization of epoxides by a discrete salen cobalt(III) catalyst occurs at the surface of the undissolved, crystalline complex.

The solvent effects on the crystallization of porous isotactic (it) poly(methyl methacrylate) (PMMA) thin films as well as the incorporation behavior of syndiotactic (st) poly(methacrylic acid) (PMAA) into the porous films were investigated. The porous it-PMMA thin films were prepared by the extraction of st-PMAA from a stepwise layer-by-layer (LbL) assembly composed of it-PMMA and st-PMAA. The X-ray diffraction pattern of the it-PMMA thin films after immersion in acetonitrile/water (4/6, v/v) showed two characteristic peaks of a crystalline it-PMMA double-stranded helix (2theta = 9 degrees and 14 degrees , d = 0.96 and 0.62 nm). This suggested that acetonitrile promoted the crystallization of the thin films, because water is a nonsolvent for PMMA. The surface structural change of the it-PMMA films was also analyzed by atomic force microscopy. The it-PMMA conformation was maintained after crystallization as observed by infrared spectroscopy. The incorporation percentages of st-PMAA into the porous it-PMMA thin films under various solvent conditions were estimated using a quartz crystal microbalance. The incorporation of st-PMAA decreased as the it-PMMA films crystallized or with growing thickness of the porous it-PMMA films. This suggested that the polymer-polymer interactions and the entanglement of the it-PMMA chains played an important role. The incorporation was promoted as the acetonitrile content in the st-PMAA solution increased, indicating that it was necessary for st-PMAA incorporation to solvate it-PMMA.

Poly(N-vinylacetamide) hydrogels (PNVA gels) were synthesized to investigate their basic characteristics for biomedical applications such as water contact angles, protein uptake, and mouse fibroblasts (L-929) cell adhesion. Because PNVA gels show hydrophilic features, double network (DN) hydrogels were prepared by the secondary polymerization of N-vinylacetamide (NVA) or acrylamide (AAm) in PNVA gels (NVA/NVA DN gels and NVA/AAm DN gels, respectively), in order to vary PNVA gel features for biocompatibility. Contact angles for both DN gels decreased to around 20 degrees, whereas both PNVA and PAAm gels were over 30 degrees. On the other hand, more protein tended to adsorb to DN gels than single network hydrogels. Compared to PNVA gel, cell adhesion and proliferation on NVA/NVA DN gel were improved with less swelling ratio and much protein uptake, while no significant difference was observed on NVA/AAm DN gel, probably due to more hydrophilic character, supported by lowest water contact angle. These complicated structure change in DN gels would provide a new methodology for tuning the biocompatibility of hydrogels and for controlling surface hydrophilic characteristics and network structures.