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In this study, poly(butylene adipate‐co‐terephthalate) (PBAT) biocomposites were generated from spent coffee grounds (SCGs) or torrefied SCG (TSCGs) using a melt compounding process. TSCGs were obtained at torrefaction temperatures of 230, 245, 260, 275, or 290°C for a duration of 60 min. Torrefaction enhanced the hydrophobicity, grindability, and biomass stability of the resulting composites by eliminating hemicellulose. Various concentrations of SCGs (10 and 20 wt.%) and TSCGs (10, 20, and 30 wt.%) were compounded into PBAT. The thermal, mechanical, and degradation properties of PBAT biocomposites were investigated. As SCGs and TSCGs were introduced, the crystallization temperature drastically increased. Compared with PBAT biocomposites with SCGs, PBAT biocomposites with TSCGs exhibited higher thermal stability and hydrophobicity, and improved mechanical properties. Further, alkaline hydrolysis occurred at a faster rate for biocomposites with biofillers than for neat PBAT. Therefore, this study demonstrated the improved compatibility between SCGs and PBAT by torrefaction. [ABSTRACT FROM AUTHOR]

Poly(butylene sebacate-co-terephthalate) (PBSeT) copolyesters are prepared by melt polymerization via two-step transesterification and polycondensation using pentaerythritol (PE) as a branching agent. The effects of the incorporated PE on its chemical, thermal, mechanical, and degradation properties, along with the rheological properties of its melt, are investigated. The highest molecular weight and intrinsic viscosity along with the lowest melt flow index were achieved at a PE content of 0.2 mol%, with minimal reduction in the tensile strength and the highest tear strength. The addition of PE did not significantly influence the thermal behavior and stability of the PBSeT copolyesters; however, the elongation at break decreased with increasing PE content. The sample with 0.2 mol% PE exhibited a higher storage modulus and loss modulus as well as a lower loss angle tangent than the other samples, indicating improved melt elasticity. The incorporation of more than 0.2 mol% PE enhanced the enzymatic degradation of copolyesters. In summary, including within 0.2 mol%, PE effectively improved both the processability-related characteristics and degradation properties of PBSeT copolyesters, suggesting their potential suitability for use in agricultural and packaging materials. [ABSTRACT FROM AUTHOR]

Solid polymer electrolytes (SPEs) are a key component of solid-state lithium metal batteries. For attaining high ionic conductivity and high mechanical strength simultaneously, nanostructured SPEs are designed to have functionally separated ion transporting channels and solid-phase walls. Here, we report ion-conductive bicontinuous solid polymer electrolytes (Bi-SPEs) from thermodynamically stable bicontinuous microemulsions of ionic liquids and diacrylates in the presence of amphiphilic ionic liquids and lithium salt. From stable bicontinuous microemulsions with 10–30 wt% amphiphilic ionic liquids, free-standing Bi-SPE films were successfully obtained by photopolymerization and then implemented in lithium metal batteries. At 10 wt% of amphiphilic ionic liquids, the ionic conductivity increased up to 1.4 mS cm−1 keeping the mechanical strength at 0.8 MPa. A LiFePO4-paired lithium metal cell exhibits a stable discharge capacity of 121.9 mA h g−1 with 90.3% capacity retention (CE = 99.9%) over 300 cycles at 0.5 C and 30 °C. [ABSTRACT FROM AUTHOR]

Poly (lactic acid) (PLA) is an important biodegradable plastic with unique properties. However, its widespread application is hindered by its low miscibility and suboptimal degradation properties. To overcome these limitations, we investigated the mechanical, thermal, and degradation properties of PLA and poly (butylene sebacate‐co‐terephthalate) (PBSeT) blends in the presence of poly (ethylene oxide) (PEO). Specifically, this study aimed to identify the effects of PEO as a compatibilizer and hydrolysis accelerator in PLA/PBSeT blends. PLA (80%) and PBSeT (20%) were melt blended with various PEO contents (2–10 phr), and their mechanical, thermal, and hydrolytic properties were analyzed. All PEO‐treated blends exhibited a higher elongation at break than that of the control sample, and the tensile strength was slightly reduced. In the PEO 10% sample, the elongation at break increased to 800% of that of the control sample. Differential scanning chromatography (DSC) analysis confirmed that when PEO was added to the PLA/PBSeT blends, the two glass transition temperatures (Tg) narrowed, resulting in improved miscibility of PLA and PBSeT. In addition, the hydrolytic degradation of the PLA/PBSeT/PEO blend accelerated as the PEO content increased. It was confirmed that PEO can act as a compatibilizer and hydrolysis‐accelerating agent for PLA/PBSeT blends. [ABSTRACT FROM AUTHOR]

Extracellular vesicles (EVs) are nano‐sized membranous structures involved in intercellular communication and various physiological and pathological processes. Here, we present a novel method for rapid (within 15 min), large‐scale production of high‐purity EVs using eMTDΔ4, a peptide derived from Noxa. The treatment of mesenchymal stem cells derived from human Wharton's jelly after trypsinization and subsequent eMTDΔ4 stimulation in a chemically defined sucrose buffer with orbital shaking led to a substantial increase (approximately 30‐fold) in EV production with markedly high purity (approximately 45‐fold). These EVs (TS‐eEVs) showed higher regenerative and immunomodulatory potential than natural EVs obtained from the culture media after 48 h. The calcium chelator BAPTA‐AM and calpain inhibitor ALLM, but not the natural EV biogenesis inhibitor GW4869, blocked the TS‐eEV production induced by eMTDΔ4, indicating that the eMTDΔ4‐mediated regulation of intracellular calcium levels and calpain activity are closely associated with the rapid, mass production of TS‐eEVs. The present study may lead to considerable advances in EV‐based drug development and production of stem cell‐derived EVs for cell therapy. [ABSTRACT FROM AUTHOR]

Poly(butylene sebacate-co-terephthalate) (PBSeT) is a biodegradable flexible polymer suitable for melt blending with other biodegradable polymers. Melt blending with a compatibilizer is a common strategy for increasing miscibility between polymers. In this study, PBSeT polyester was synthesized, and poly(lactic acid) (PLA) was blended with 25 wt% PBSeT by melt processing with 3–6 phr PLA-grafted maleic anhydride (PLA-g-MAH) compatibilizers. PLA-g-MAH enhanced the interfacial adhesion of the PLA/PBSeT blend, and their mechanical and morphological properties confirmed that the miscibility also increased. Adding more than 6 phr of PLA-g-MAH significantly improved the mechanical properties and accelerated the cold crystallization of the PLA/PBSeT blends. Furthermore, the thermal stabilities of the blends with PLA-g-MAH were slightly enhanced. PLA/PBSeT blends with and without PLA-g-MAH were not significantly different after 120 h, whereas all blends showed a more facilitated hydrolytic degradation rate than neat PLA. These findings indicate that PLA-g-MAH effectively improves PLA/PBSeT compatibility and can be applied in the packaging industry. [ABSTRACT FROM AUTHOR]

Purpose: An electric field (EF) can be used to change the mechanical properties of cells and skin tissues. We demonstrate EF‐induced elasticity changes in human dermal fibroblasts (HDFs) and a human skin equivalent and identify the underlying principles related to the changes. Methods: HDFs and human skin equivalent were stimulated with electric fields of 1.0 V/cm. Change in cellular elasticity was determined by using atomic force microscopy. Effects of EF on the biomechanical and chemical properties of a human skin equivalent were analyzed. In cells and tissues, the effects of EF on biomarkers of cellular elasticity were investigated at the gene and protein levels. Results: In HDFs, the cellular elasticity was increased and the expression of biomarkers of cellular elasticity was regulated by the EF. Expression of the collagen protein in the human skin equivalent was changed by EF stimulation; however, changes in density and microstructure of the collagen fibrils were not significant. The viscoelasticity of the human skin equivalent increased in response to EF stimulation, but molecular changes were not observed in collagen. Conclusions: Elasticity of cells and human skin equivalent can be regulated by electrical stimulation. Especially, the change in cellular elasticity was dependent on cell age. [ABSTRACT FROM AUTHOR]

Malaria is a pathogenic disease in mammal species and typically causes destruction of red blood cells (RBCs). The malaria‐infected RBCs undergoes alterations in morphology and its rheological properties, and the altered rheological properties of RBCs have a significant impact on disease pathophysiology. In this study, we investigated detailed topological and biomechanical properties of RBCs infected with malaria Plasmodium berghei ANKA using atomic force microscopy. Mouse (BALB/c) RBCs were obtained on Days 4, 10, and 14 after infection. We found that malaria‐infected RBCs changed significantly in shape. The RBCs maintained a biconcave disk shape until Day 4 after infection and then became lopsided on Day 7 after infection. The central region of RBCs began to swell beginning on Day 10 after infection. More schizont stages were present on Days 10 and 14 compared with on Day 4. The malaria‐infected RBCs also showed changes in mechanical properties and the cytoskeleton. The stiffness of infected RBCs increased 4.4–4.6‐fold and their cytoskeletal F‐actin level increased 18.99–67.85% compared with the control cells. The increase in F‐actin depending on infection time was in good agreement with the increased stiffness of infected RBCs. Because more schizont stages were found at a late period of infection at Days 10 and 14, the significant changes in biomechanical properties might contribute to the destruction of RBCs, possibly resulting in the release of merozoites into the blood circulation. [ABSTRACT FROM AUTHOR]

Monolayer (ML)-molybdenum disulfide (MoS 2 ) with a direct band gap of ~1.8 eV exhibits considerable potential for advanced electronic and optical device applications. The surface electronic properties of ML-MoS 2 need to be controlled for developing novel MoS 2 -based devices. In this study, we investigated the work function variation of chemical vapor deposition-grown ML-MoS 2 that was controlled by proton irradiation. The crystallinity of the ML-MoS 2 was confirmed by micro-Raman and Photoluminescence measurements. The work functions of the ML-MoS 2 irradiated with varying proton beam flux were measured by Kelvin probe force microscopy. As the ML-MoS 2 were exposed to the proton beam flux ranging from 1 × 10 12 to 1 × 10 14 protons/cm 2 at the same beam energy of 10 MeV, the contact potential difference of the MoS 2 increased up to about 0.108 V with increased proton beam flux. Based on the referenced value of the Au work function (≈5.1 eV), the work functions of non-treated ML-MoS 2 and proton-irradiated ML-MoS 2 with a proton beam flux of 1 × 10 14 protons/cm 2 were determined to be 5.031 eV and 4.992 eV, respectively. The decrease of the work function of the MoS 2 with increased proton beam flux is due to the defect formation induced by proton irradiation. We suggest the possibility of engineering the surface potential and electronic properties of ML-MoS 2 through controlling proton irradiation conditions. [ABSTRACT FROM AUTHOR]

Poly (lactic acid) (PLA) is the most widely available commercial bioplastic that is used in various medical and packaging applications and three-dimensional filaments. However, because neat PLA is brittle, it conventionally has been blended with ductile polymers and plasticizers. In this study, PLA was blended with the high-ductility biopolymer poly (butylene-sebacate–co–terephthalate) (PBSeT), and hexamethylene diisocyanate (HDI) was applied as a crosslinking compatibilizer to increase the miscibility between the two polymers. PLA (80%) and PBSeT (20%) were combined with various HDI contents in the range 0.1–1.0 parts-per-hundred rubber (phr) to prepare blends, and the resulting physical, thermal, and hydrolysis properties were analyzed. Fourier-transform infrared analysis confirmed that –NH–C=OO− bonds had formed between the HDI and the other polymers and that the chemical bonding had influenced the thermal behavior. All the HDI-treated specimens showed tensile strengths and elongations higher than those of the control. In particular, the 0.3-phr-HDI specimen showed the highest elongation (exceeding 150%) and tensile strength. In addition, all the specimens were hydrolyzed under alkaline conditions, and all the HDI-treated specimens degraded faster than the neat PLA one. [ABSTRACT FROM AUTHOR]

In this study, poly(butylene sebacate-co-terephthalate) (PBSeT) was successfully synthesized using various ratios of sebacic acid (Se) and dimethyl terephthalate (DMT). The synthesized PBSeT showed a high molecular weight (Mw, 88,700–154,900 g/mol) and good elastomeric properties. In particular, the PBSeT64 (6:4 sebacic acid/dimethyl terephthalate mole ratio) sample showed an elongation at break value of over 1600%. However, further increasing the DMT content decreased the elongation properties but increased the tensile strength due to the inherent strength of the aromatic unit. The melting point and crystallization temperature were difficult to observe in PBSeT64, indicating that an amorphous copolyester was formed at this mole ratio. Interestingly, wide angle X-ray diffraction (WAXD) curves was shown in the cases of PBSeT46 and PBSeT64, neither the crystal peaks of PBSe nor those of poly(butylene terephthalate) (PBT) are observed, that is, PBSeT64 showed an amorphous form with low crystallinity. The Fourier-transform infrared (FT-IR) spectrum showed C–H peaks at around 2900 cm−1 that reduced as the DMT ratio was increased. Nuclear magnetic resonance (NMR) showed well-resolved peaks split by coupling with the sebacate and DMT moieties. These results highlight that elastomeric PBSeT with high molecular weight could be synthesized by applying DMT monomer and showed promising mechanical properties. [ABSTRACT FROM AUTHOR]

Block copolymer self-assembly affords diverse nanostructures, spanning from spheres and cylinders to networks, offering meticulous control over properties and functionalities at the nanoscale. However, creating thermodynamically stable network structures with high packing frustration remains a challenge. In this study, we report a methodology to access diverse network structures such as gyroid, diamond, and primitive phases from diblock copolymers using end group and linker chemistry. The stability of the medial packing of polymer chain ends (plumber's nightmare structure) over skeletal aggregation (gyroid) is attributed to the interplay between the strength of the end-end interactions and the initial shape of the curvature. Our study establishes an approach to develop tailored network structures from block copolymers, providing an important platform for using block copolymers in nanotechnology applications.

Poly(butylene sebacate-co-terephthalate) (PBSeT) copolyesters are prepared by melt polymerization via two-step transesterification and polycondensation using pentaerythritol (PE) as a branching agent. The effects of the incorporated PE on its chemical, thermal, mechanical, and degradation properties, along with the rheological properties of its melt, are investigated. The highest molecular weight and intrinsic viscosity along with the lowest melt flow index were achieved at a PE content of 0.2 mol%, with minimal reduction in the tensile strength and the highest tear strength. The addition of PE did not significantly influence the thermal behavior and stability of the PBSeT copolyesters; however, the elongation at break decreased with increasing PE content. The sample with 0.2 mol% PE exhibited a higher storage modulus and loss modulus as well as a lower loss angle tangent than the other samples, indicating improved melt elasticity. The incorporation of more than 0.2 mol% PE enhanced the enzymatic degradation of copolyesters. In summary, including within 0.2 mol%, PE effectively improved both the processability-related characteristics and degradation properties of PBSeT copolyesters, suggesting their potential suitability for use in agricultural and packaging materials.

Benefiting from the demixing of substances in the two-phase region, a smart polymer laminate film system that exhibits direction-controlled phase separation behavior was developed in this study. Here, nanoemulsion films (NEFs) in which liquid nanodrops were uniformly confined in a polymer laminate film through the layer-by-layer deposition of oppositely charged emulsion nanodrops and polyelectrolytes were fabricated. Upon reaching a critical temperature, the NEFs exhibited a micropore-guided demixing phenomenon. A simulation study based on coarse-grained molecular dynamics revealed that the perpendicular diffusion of oil droplets through the micropores generated in the polyelectrolyte layer is crucial for determining the coarsening kinetics and phase separation level, which is consistent with the experimental results. Considering the substantial advantages of this unique and tunable two-dimensional demixing behavior, the viability of using the as-proposed NEF system for providing an efficient route for the development of smart drug delivery patches was demonstrated.

Supramolecular polymerization offers a fascinating opportunity to develop dynamic soft materials by associating monomeric building blocks via noncovalent interactions. We report that polymerization can spontaneously drive the supramolecular polymerization of nanoscale micellar objects. We constructed the patchy micelles via two-step polymerization-induced self-assembly. A horizontal association between the patches results in a 1D supermicellar chain in situ by minimizing the enthalpic penalty of exposing the growing chains to solvent. Its length grows with increasing degree of polymerization, confirming that the supramolecular polymerization was triggered and controlled by polymerization. Our results highlight the observation that (1) the entire self-assembly process of forming, compartmentalizing, and associating the micelles can be driven by polymerization in a concerted manner and that (2) polymerization-induced self-assembly now can use compartmentalized nanoobjects as substrates beyond block copolymer chains. Polymerization-induced supramolecular polymerization could be useful for the autonomous preparation of hierarchical nanostructures.

Lower cellular elasticity is a distinguishing feature of cancer cells compared with normal cells. To determine whether cellular elasticity differs based on cancer cell type, cells were selected from three different cancer types including breast, cervix, and lung. For each cancer type, one counterpart normal cell and three types of cancer cells were selected, and their elasticity was measured using atomic force microscopy (AFM). The elasticity of normal cells was in the order of MCF10A > WI-38 ≥ Ect1/E6E7 which corresponds to the counterpart normal breast, lung, and cervical cancer cells, respectively. All cancer cells exhibited lower elasticity than their counterpart normal cells. Compared with the counterpart normal cells, the difference in cellular elasticity was the greatest in cervical cancer cells, followed by lung and breast cancer cells. This result indicates lower elasticity is a unique property of cancer cells; however, the reduction in elasticity may depend on the histological origin of the cells. The F-actin cytoskeleton of cancer cells was different in structure and content from normal cells. The F-actin is mainly distributed at the periphery of cancer cells and its content was mostly lower than that seen in normal cells., Competing Interests: Competing Interests: The authors have declared that no competing interest exists., (© The author(s).)

We report the patterned growth of Au nanoparticles (NPs) on polarity-patterned polycrystalline lead zirconate titanate (PZT) as a template through photochemical reaction. The photochemical deposition of the Au NPs includes ultraviolet (UV) light illumination of the patterned PZT while immersed in a HAuCl4 solution. In particular, the influence of the UV wavelength, and the influence of the solution with the stabilizer and reducer on the growth selectivity of the Au NPs on the polarity-patterned regions was investigated. For a UV light of 365 nm wavelength, corresponding to a band-gap excitation of the PZT, more Au NPs were deposited on the + z polar region than on the other non-polar regions. However, no deposition of the Au NPs was observed for UV light wave-lengths longer than - 365 nm. When ascorbic acid (AA) as a reducer and cetyl-trimethylammonium bromide (CTAB) as a stabilizer were added to the HAuCl4 solution, the Au NPs on the + z polar region were observed to be deposited with a UV light of 435 nm, which is larger than the optical band gap wavelength of the PZT. Also, the growth selectivity and size uniformity on the + z region was significantly improved. These results could be due to the defect-induced photo-excitation of electrons and enhanced reduction process of Au+ ions by adding the reducer and the stabilizer in the photo-chemical process. This study suggests the possibility of the patterned growth of Au NPs on a ferroelectric surface through polarity patterning and photochemical reaction by optimizing the UV wavelength and employing reduction potential agents in a metal salt solution.