Injectable and biodegradable piezoelectric hydrogel for osteoarthritis treatment.

Osteoarthritis affects millions of people worldwide but current treatments using analgesics or anti-inflammatory drugs only alleviate symptoms of this disease. Here, we present an injectable, biodegradable piezoelectric hydrogel, made of short electrospun poly-L-lactic acid nanofibers embedded inside a collagen matrix, which can be injected into the joints and self-produce localized electrical cues under ultrasound activation to drive cartilage healing. In vitro, data shows that the piezoelectric hydrogel with ultrasound can enhance cell migration and induce stem cells to secrete TGF-ß1, which promotes chondrogenesis. In vivo, the rabbits with osteochondral critical-size defects receiving the ultrasound-activated piezoelectric hydrogel show increased subchondral bone formation, improved hyaline-cartilage structure, and good mechanical properties, close to healthy native cartilage. This piezoelectric hydrogel is not only useful for cartilage healing but also potentially applicable to other tissue regeneration, offering a significant impact on the field of regenerative tissue engineering.

Enhancing Efficiency of Low-Grade Heat Harvesting by Structural Vibration Entropy in Thermally Regenerative Electrochemical Cycles.

The majority of waste-heat energy exists in the form of low-grade heat (<100 °C), which is immensely difficult to convert into usable energy using conventional energy-harvesting systems. Thermally regenerative electrochemical cycles (TREC), which integrate battery and thermal-energy-harvesting functionalities, are considered an attractive system for low-grade heat harvesting. Herein, the role of structural vibration modes in enhancing the efficacy of TREC systems is investigated. How changes in bonding covalency, influenced by the number of structural water molecules, impact the vibration modes is analyzed. It is discovered that even small amounts of water molecules can induce the A1g stretching mode of cyanide ligands with strong structural vibration energy, which significantly contributes to a larger temperature coefficient (ɑ) in a TREC system. Leveraging these insights, a highly efficient TREC system using a sodium-ion-based aqueous electrolyte is designed and implemented. This study provides valuable insights into the potential of TREC systems, offering a deeper understanding of the intrinsic properties of Prussian Blue analogs regulated by structural vibration modes. These insights open up new possibilities for enhancing the energy-harvesting capabilities of TREC systems.

Manipulation and Direct Characterization of Polymer/Small-Molecule Interface Morphology in Bulk-Heterojunction Solar Cell.

To investigate the effect of miscibility between conjugated polymers (CPs) and Y6 on bulk-heterojunction (BHJ) type morphology, we propose three different CPs with similar chemical structures but different miscibility with Y6. After selectively removing Y6 from the CP/Y6 blend films, their interface morphology and interlocked dimensions are quantitatively compared using a square-wave model. As CP-Y6 miscibility increases, a higher intermixed interface is formed, providing an enlarged CP-Y6 interface area. Conversely, as the miscibility between CP and Y6 decreases, the height and width of the interlocked dimensions formed by phase separation gradually decrease and increase, respectively. Additionally, when the CP-Y6 interface morphology and electrical properties of the corresponding organic photovoltaic (OPV) device are correlated, as the highly intermixed CP-Y6 interface develops, the exciton dissociation efficiency increases owing to the reduced exciton diffusion length to be dissociated, but the bimolecular recombination tends to deteriorate simultaneously. Furthermore, if the miscibility between CP and Y6 is excessive, the formation of a charge transport pathway through phase separation is interrupted, deteriorating the charge transport capability in BHJ-type OPVs. However, it was confirmed that introducing F atoms into the conjugated backbone of CP can reduce the bimolecular recombination, providing ameliorated light-harvesting efficiency.

Engineering of Solvation Entropy by Poly(4-styrenesulfonic acid) Additive in an Aqueous Electrochemical System for Enhanced Low-Grade Heat Harvesting.

The thermally regenerative electrochemical cycle (TREC) is a reliable and efficient approach to converting low-grade heat into electricity. A high temperature coefficient (α) is the key to maximize the energy conversion efficiency of the TREC system. In this study, we present significant improvement of α of a Prussian blue analogue (PBA)-based electrochemical cell by adding poly(4-styrenesulfonic acid) (PSS) to the electrolyte. Raman spectra showed that water-soluble charged polymers strongly affect the ion hydration structure and increase the entropy change (ΔS) during ion intercalation in PBA. A large α of -2.01 mV K-1 and high absolute heat-to-electricity conversion efficiency up to 1.83% was achieved with a TREC cell in the temperature range 10-40 °C. This study provides a fundamental understanding of the origin of α and a facile method to boosting the temperature coefficient for building a highly efficient low-grade heat harvesting system.

Comparison between internal jugular vein access using midline catheter and peripheral intravenous access during cardiopulmonary resuscitation in adults.

Objectives: Vascular access is an important procedure for drug administration during the resuscitation of a patient with cardiac arrest; however, it can be challenging under emergent conditions. This study aimed to investigate the efficiency of ultrasound-guided internal jugular venous access using a midline catheter versus peripheral intravenous access during cardiopulmonary resuscitation. Methods: This was a prospective single-center observational study among patients who received cardiopulmonary resuscitation. The primary outcomes were the success rate of first attempt and the time taken for vascular access via the internal jugular and peripheral veins. We also measured the diameter of the internal jugular and peripheral veins at the access point and the distance from the access point to the heart. Results: In all, 20 patients were included in the study. Internal jugular and peripheral venous access had a first-attempt success rate of 85% and 65%, respectively (p = 0.152). The time to access the internal jugular and peripheral veins was 46.4 ± 40.5 s and 28.8 ± 14.7 s, respectively (p = 0.081). The diameter of the internal jugular and peripheral veins was 10.8 ± 2.6 mm and 2.8 ± 0.8 mm, respectively (p < 0.001). The distance from the vascular access point to the heart was 20.3 ± 4.7 cm and 48.8 ± 13.1 cm for the internal jugular and peripheral veins, respectively (p < 0.001). Conclusions: There was a trend toward higher success rates in the internal jugular vein rather than the peripheral intravenous approach, which was not statistically significant.

Effect of Chlorine Substituents on the Photovoltaic Properties of Monocyanated Quinoxaline-Based D-A-Type Polymers.

A string of monocyanated quinoxaline (Qx)-based D-A-type polymers systematically decorated with electron-attracting chlorine (Cl) atoms was created for use in non-fullerene polymer solar cells (PSCs). First, coupling of the benzodithiophene (BDT) donor and Qx acceptor with the strong electron-attracting cyano (CN) unit at its 5-position yielded the monocyanated reference polymer PB-CNQ. Subsequently, the additional Cl atoms were separately or simultaneously incorporated into the thiophene side groups of the BDT donor and Qx acceptor to create other objective polymers, PBCl-CNQ, PB-CNQCl, and PBCl-CNQCl. The Cl substituents on the BDT donor and Qx acceptor are represented by the names of the polymers. Owing to the favorable contributions of Cl substituents, the inverted-type non-fullerene PSCs based on partially chlorinated PBCl-CNQ (12.80%) and PB-CNQCl (13.93%) exhibited better power conversion efficiencies (PCEs) than the device based on unchlorinated reference PB-CNQ (11.19%). However, a significantly reduced PCE of 9.84% was observed for the device based on PBCl-CNQCl, in which Cl atoms were loaded on both the BDT donor and Qx acceptor at the same time. Hence, these results reveal that optimization of the number and position of Cl substituents in monocyanated Qx-based polymers is essential for enhancing their photovoltaic nature through the synergistic effects between two strong electron-attracting CN and Cl substituents.

Temperature-Dependent Fracture Resistance of Silicon Nanopillars during Electrochemical Lithiation.

During the lithation of silicon anodes, the solid-state diffusion of lithium into LixSi follows the Arrhenius law, the resulting morphology and fracture behavior are determined by the silicon anode operation temperature. Here, we reveal the temperature dependence of the lithiation mechanics of crystalline silicon nanopillars (SiNPs) via microscopic observations of the anisotropic growth and fracture behavior. We fabricated 1D SiNP structures with various orientations (⟨100⟩, ⟨110⟩, and ⟨111⟩) as working electrodes and operated them at temperatures ranging from -20 to 40 °C. The lithiation of crystalline silicon at low temperatures exhibited preferential volume expansion along ⟨110⟩ and decreased fracture resistance. Furthermore, low temperatures caused the catastrophic fracture of amorphous silicon after the second lithiation. Our findings demonstrate the importance of silicon anode temperature control to prevent mechanical fracture during the cycle of lithium-ion batteries in harsh environments (e.g., electric vehicles in winter).

Editorial for Special Issue: Highly Efficient Energy Harvesting Based on Nanomaterials.

Energy-harvesting systems generate electricity or produce fuels such as hydrogen from various energy sources such as thermal energy, kinetic energy, and renewable energy [...].

Association between oral health and frailty: results from the Korea National Health and Nutrition Examination Survey.

BACKGROUND: Previous research has suggested that poor oral health is positively associated with frailty. The objective of this study was to explore associations of key oral diseases (periodontal disease, tooth loss), and oral hygiene and management behaviors with the level of frailty in community-dwelling older Korean adults using national representative survey data. METHODS: This study used cross-sectional, 6th and 7th Korea National Health and Nutrition Examination Survey (KNHANES VI, VII) data. Adults aged 50+ years were included. Frailty was measured using frailty phenotype (FP) and frailty index (FI). FP was determined using five frailty criteria, i.e., weight loss, weakness, exhaustion, slowness, or low physical activity, and the level of frailty was classified with the number of criteria present (robust, none; pre-frail, 1-2; frail, 3+). FI was determined using a 44-item FI constructed according to a standard protocol, and the level of frailty was classified as robust (FI: ≤ 0.08), pre-frail (FI: 0.08-0.25), and frail (FI: ≥ 0.25). Multiple ordinal regression analyses were conducted with each type of frailty as the outcome variable. Independent variables of interest were the periodontal status, number of teeth, and practices on oral hygiene and management. Analyses were additionally adjusted for participants' socioeconomic, diet, and behavioral characteristics. RESULTS: The prevalence of frailty was 4.38% according to the FP classification (n = 4156), 10.74% according to the FI classification (n = 15,073). In the final adjusted model, having more teeth and brushing after all three meals were significantly associated with lower odds of being more frail (in both frailty models); no significant association was observed between periodontal disease and frailty. CONCLUSIONS: Findings from this study show having more teeth and practicing adequate brushing are significantly associated with frailty. Due to limitations of the study design, well-designed longitudinal studies are needed to confirm these findings.

Effect of Electron-Withdrawing Chlorine Substituent on Morphological and Photovoltaic Properties of All Chlorinated D-A-Type Quinoxaline-Based Polymers.

The choice of the chlorine (Cl) atom as an electron-withdrawing substituent in conjugated polymers leads to a higher potential in the commercialization of polymer solar cells than its fluorine counterpart because of the versatility and cost-effectiveness of the chlorination process. In addition, the population and location of Cl substituents can significantly influence the photovoltaic characteristics of polymers. In this study, three chlorinated quinoxaline-based polymers were invented to examine the numerical and positioning effects of the Cl atom on their photovoltaic characteristics. The number of Cl substituents in the reference polymer, PBCl-Qx, was adjusted to three: two Cl atoms in the benzodithiophene-type D unit and one Cl atom in the quinoxaline-type A unit. Subsequently, two more Cl atoms were selectively introduced at the 4- and 5-positions of the alkylated thiophene moieties at the 2,3-positions of the quinoxaline moiety in PBCl-Qx to obtain the additional polymers PBCl-Qx4Cl and PBCl-Qx5Cl, respectively. The conventional PBCl-Qx4Cl device exhibited a better power conversion efficiency (PCE) of 12.95% as compared to those of PBCl-Qx (12.44%) and PBCl-Qx5Cl (11.82%) devices. The highest PCE of the device with PBCl-Qx4Cl was ascribed to an enhancement in the open-circuit voltage and fill factor induced by the deeper energy level of the highest occupied molecular orbital and the favorable morphological features in its blended film with Y6.

Exercise-induced piezoelectric stimulation for cartilage regeneration in rabbits.

More than 32.5 million American adults suffer from osteoarthritis, and current treatments including pain medicines and anti-inflammatory drugs only alleviate symptoms but do not cure the disease. Here, we have demonstrated that a biodegradable piezoelectric poly(L-lactic acid) (PLLA) nanofiber scaffold under applied force or joint load could act as a battery-less electrical stimulator to promote chondrogenesis and cartilage regeneration. The PLLA scaffold under applied force or joint load generated a controllable piezoelectric charge, which promoted extracellular protein adsorption, facilitated cell migration or recruitment, induced endogenous TGF-ß via calcium signaling pathway, and improved chondrogenesis and cartilage regeneration both in vitro and in vivo. Rabbits with critical-sized osteochondral defects receiving the piezoelectric scaffold and exercise treatment experienced hyaline-cartilage regeneration and completely healed cartilage with abundant chondrocytes and type II collagen after 1 to 2 months of exercise (2 to 3 months after surgery including 1 month of recovery before exercise), whereas rabbits treated with nonpiezoelectric scaffold and exercise treatment had unfilled defect and limited healing. The approach of combining biodegradable piezoelectric tissue scaffolds with controlled mechanical activation (via physical exercise) may therefore be useful for the treatment of osteoarthritis and is potentially applicable to regenerating other injured tissues.

Nitrogen Plasma-Assisted Functionalization of Silicon/Graphite Anodes to Enable Fast Kinetics.

The practical use of silicon anodes is interfered by the following key factors: volume expansion, slow kinetics, and low electrical and ionic conductivities. Many studies have focused on surface engineering from the particle to electrode level to achieve stability and energy density. Herein, simple nitrogen gas plasma is introduced as a surface treatment method for silicon-based electrodes to avoid the problems of material synthesis-based functionalizations (e.g., high cost, time consuming, and low quality). The introduction of activated nitrogen gas on electrode surfaces changes the binding energy and resistance of silicon, increasing the reversibility of the charge/discharge reaction of silicon-based anodes. In addition, such doping and dehydrogenation of the electrode surface improve reaction kinetics to 876 mA h g-1 specific capacity at 8.5 A g-1 in silicon/graphite anodes even with a high silicon content of 40%. The proposed strategy, through nitrogen plasma, offers advantages for direct functionalization on electrode surfaces by a simple method.

Cation Composition-Dependent Device Performance and Positive Bias Instability of Self-Aligned Oxide Semiconductor Thin-Film Transistors: Including Oxygen and Hydrogen Effect.

Amorphous oxide semiconductor transistors control the illuminance of pixels in an ecosystem of displays from large-screen TVs to wearable devices. To satisfy application-specific requirements, oxide semiconductor transistors of various cation compositions have been explored. However, a comprehensive study has not been carried out where the influence of cation composition, oxygen, and hydrogen on device characteristics and stability is systematically quantified, using commercial-grade process technology. In this study, we fabricate self-aligned top-gate structure thin-film transistors with three oxide semiconductor materials, InGaZnO (In/Ga/Zn = 1:1:1), In-rich InGaZnO, and InZnO, having mobility values of 10, 27, and 40 cm2/V·s, respectively. Combinations of varied amounts of oxygen and hydrogen are incorporated into each transistor by controlling the fabrication process to study the effect of these gaseous elements on the physical nature of the channel material. Electrons can be captured by peroxy linkage (O22-) or undercoordinated In (In* to become In+), which are manifested in the extracted subgap density-of-states profile and first-principles calculations. Energy difference between electron-trapped In+ and O22- σ* is the smallest for IGZO, and In+-O22- annihilation occurs by electron excitation from the subgap In+ state to the O22- σ*. Furthermore, characteristic time constants during positive bias stress and recovery reveal the various microscopic physical phenomena within the transistor structure between different cation compositions.

Printed Zinc Paper Batteries.

Paper electronics offer an environmentally sustainable option for flexible and wearable systems and perfectly fit the available printing technologies for high manufacturing efficiency. As the heart of energy-consuming devices, paper-based batteries are required to be compatible with printing processes with high fidelity. Herein, hydrogel reinforced cellulose paper (HCP) is designed to serve as the separator and solid electrolyte for paper batteries. The HCP can sustain higher strain than pristine papers and are biodegradable in natural environment within four weeks. Zinc-metal (Ni and Mn) batteries printed on the HCP present remarkable volumetric energy density of ≈26 mWh cm-3 , and also demonstrate the feature of cuttability and compatibility with flexible circuits and devices. As a result, self-powered electronic system could be constructed by integrating printed paper batteries with solar cells and light-emitting diodes. The result highlights the feasibility of hydrogel reinforced paper for ubiquitous flexible and eco-friendly electronics.

Prussian Blue Nanolayer-Embedded Separator for Selective Segregation of Nickel Dissolution in High Nickel Cathodes.

Transition metal layered oxides (LiNixCoyMn1-x-yO2, NCM) have been considered as one of the most promising cathodes for lithium-ion batteries used in long-mileage electric vehicles and energy storage systems. Despite its potential interest, dissolved transition metal (TM) ions toward anode sides can catalyze parasitic reactions such as electrolytic decomposition and dendritic Li growth, ultimately leading to catastrophic safety hazards. In this study, we demonstrate that Prussian Blue (PB) nanoparticles anchored to a commercial PE separator significantly reduce cell resistance and effectively suppress TM crossover during cycling, even under harsh conditions that accelerate Ni dissolution. Therefore, using a PB-coated separator in a harsh condition to intentionally dissolve Ni2+ ions at a high cutoff potential of 4.6 V, NCM||graphite full cells maintain 50.8% of their initial capacity at the 150th cycle. Scalable production of PB-coated separator through the facile synthetic methods can help establish a new research direction for the design of high-energy-density batteries.

Effect of electron-withdrawing fluorine and cyano substituents on photovoltaic properties of two-dimensional quinoxaline-based polymers.

In this study, strong electron-withdrawing fluorine (F) and cyano (CN) substituents are selectively incorporated into the quinoxaline unit of two-dimensional (2D) D-A-type polymers to investigate their effects on the photovoltaic properties of the polymers. To construct the 2D polymeric structure, electron-donating benzodithiophene and methoxy-substituted triphenylamine are directly linked to the horizontal and vertical directions of the quinoxaline acceptor, respectively. After analyzing the structural, optical, and electrochemical properties of the resultant F- and CN-substituted polymers, labeled as PBCl-MTQF and PBCl-MTQCN, respectively, inverted-type polymer solar cells with a non-fullerene Y6 acceptor are fabricated to investigate the photovoltaic performances of the polymers. It is discovered that the maximum power conversion efficiency of PBCl-MTQF is 7.48%, whereas that of PBCl-MTQCN is limited to 3.52%. This significantly reduced PCE of the device based on PBCl-MTQCN is ascribed to the formation of irregular, large aggregates in the active layer, which can readily aggravate the charge recombination and charge transport kinetics of the device. Therefore, the photovoltaic performance of 2D quinoxaline-based D-A-type polymers is significantly affected by the type of electron-withdrawing substituent.

Pseudoelasticity of SrNi2P2 Micropillar via Double Lattice Collapse and Expansion.

The maximum recoverable strain of most crystalline solids is less than 1% because plastic deformation or fracture usually occurs at a small strain. In this work, we show that a SrNi2P2 micropillar exhibits pseudoelasticity with a large maximum recoverable strain of ∼14% under uniaxial compression via unique reversible structural transformation, double lattice collapse-expansion that is repeatable under cyclic loading. Its high yield strength (∼3.8 ± 0.5 GPa) and large maximum recoverable strain bring out the ultrahigh modulus of resilience (∼146 ± 19 MJ/m3), a few orders of magnitude higher than that of most engineering materials. The double lattice collapse-expansion mechanism shows stress-strain behaviors similar to that of conventional shape-memory alloys, such as hysteresis and thermo-mechanical actuation, even though the structural changes involved are completely different. Our work suggests that the discovery of a new class of high-performance ThCr2Si2-structured materials will open new research opportunities in the field of pseudoelasticity.

Copper Hexacyanoferrate Thin Film Deposition and Its Application to a New Method for Diffusion Coefficient Measurement.

The use of Prussian blue analogues (PBA) materials in electrochemical energy storage and harvesting has gained much interest, necessitating the further clarification of their electrochemical characteristics. However, there is no well-defined technique for manufacturing PBA-based microelectrochemical devices because the PBA film deposition method has not been well studied. In this study, we developed the following deposition method for growing copper hexacyanoferrate (CuHCFe) thin film: copper thin film is immersed into a potassium hexacyanoferrate solution, following which the redox reaction induces the spontaneous deposition of CuHCFe thin film on the copper thin film. The film grown via this method showed compatibility with conventional photolithography processes, and the micropattern of the CuHCFe thin film was successfully defined by a lift-off process. A microelectrochemical device based on the CuHCFe thin film was fabricated via micropatterning, and the sodium ion diffusivity in CuHCFe was measured. The presented thin film deposition method can deposit PBAs on any surface, including insulating substrates, and it can extend the utilization of PBA thin films to various applications.

Tear-Based Aqueous Batteries for Smart Contact Lenses Enabled by Prussian Blue Analogue Nanocomposites.

Batteries for contact lenses fabricated by conventional methods could cause severe damage to the eyes if broken. Herein, we present flexible aqueous batteries that operate in tears and provide a safe power supply to smart contact lenses. Nanocomposite flexible electrodes of carbon nanotubes and Prussian blue analogue nanoparticles for cathode and anode were embedded in UV-polymerized hydrogel as not only a soft contact lens but also an ion-permeable separator. The battery exhibited a discharging capacity of 155 µAh in an aqueous electrolyte of 0.15 M Na-ions and 0.02 M K-ions, equivalent to the ionic concentration of tears. The power supply was enough to operate a low-power static random-access memory. In addition, we verified the mechanical stability, biocompatibility and compatibility with a contact lens cleaning solution. It could ultimately enable a safe power supply for smart contact lenses without risk of injury due to the leakage or breakage of the battery.

Efficient Low-Grade Heat Harvesting Enabled by Tuning the Hydration Entropy in an Electrochemical System.

Harvesting of low-grade heat (<100 °C) is promising, but its application is hampered by a lack of efficient and low-cost systems. The thermally regenerative electrochemical cycle (TREC) is a potential alternative system with high energy-conversion efficiency. Here, the temperature coefficient (α), which is a key factor in a TREC, is studied by tuning the hydration entropy of the electrochemical reaction. The change of α in copper hexacyanoferrate (CuHCFe) with intercalation of different monovalent cations (Na+ , K+ , Rb+ , and Cs+ ) and a larger α value of -1.004 mV K-1 being found in the Rb+ system are observed. With a view to practical application, a full cell is constructed for low-grade heat harvesting. The resultant ηe is 4.34% when TREC operates between 10 and 50 °C, which further reaches 6.21% when 50% heat recuperation is considered. This efficiency equals to 50% of the Carnot efficiency, which is thought to be the highest ηe reported for low-grade heat harvesting systems. This study provides a fundamental understanding of the mechanisms governing the TREC, and the demonstrated efficient system paves the way for low-grade heat harvesting.