Novel Perovskite Oxide Hybrid Nanofibers Embedded with Nanocatalysts for Highly Efficient and Durable Electrodes in Direct CO2 Electrolysis.

The unique characteristics of nanofibers in rational electrode design enable effective utilization and maximizing material properties for achieving highly efficient and sustainable CO2 reduction reactions (CO2RRs) in solid oxide electrolysis cells (SOECs). However, practical application of nanofiber-based electrodes faces challenges in establishing sufficient interfacial contact and adhesion with the dense electrolyte. To tackle this challenge, a novel hybrid nanofiber electrode, La0.6Sr0.4Co0.15Fe0.8Pd0.05O3-δ (H-LSCFP), is developed by strategically incorporating low aspect ratio crushed LSCFP nanofibers into the excess porous interspace of a high aspect ratio LSCFP nanofiber framework synthesized via electrospinning technique. After consecutive treatment in 100% H2 and CO2 at 700 °C, LSCFP nanofibers form a perovskite phase with in situ exsolved Co metal nanocatalysts and a high concentration of oxygen species on the surface, enhancing CO2 adsorption. The SOEC with the H-LSCFP electrode yielded an outstanding current density of 2.2 A cm-2 in CO2 at 800 °C and 1.5 V, setting a new benchmark among reported nanofiber-based electrodes. Digital twinning of the H-LSCFP reveals improved contact adhesion and increased reaction sites for CO2RR. The present work demonstrates a highly catalytically active and robust nanofiber-based fuel electrode with a hybrid structure, paving the way for further advancements and nanofiber applications in CO2-SOECs.

Lowering the Temperature of Solid Oxide Electrochemical Cells Using Triple-Doped Bismuth Oxides.

Despite the great potential of solid oxide electrochemical cells (SOCs) as highly efficient energy conversion devices, the undesirable high operating temperature limits their wider applicability. Herein, a novel approach to developing high-performance low-temperature SOCs (LT-SOCs) is presented through the use of an Er, Y, and Zr triple-doped bismuth oxide (EYZB). This study demonstrates that EYZB exhibits > 147 times higher ionic conductivity of 0.44 S cm-1 at 600 °C compared to commercial Y-stabilized zirconia electrolyte with excellent stability over 1000 h. By rationally incorporating EYZB in composite electrodes and bilayer electrolytes, the zirconia-based electrolyte LT-SOC achieves the unprecedentedly high performance of 3.45 and 2.02 W cm-2 in the fuel cell mode and 2.08 and 0.95 A cm-2 in the electrolysis cell mode at 700 °C and 600 °C, respectively. Further, a distinctive microstructural feature of EYZB that largely extends triple phase boundary at the interface is revealed through digital twinning. This work provides insights for developing high-performance LT-SOCs.

Enhancing the upconversion of Er3+ incorporated BaTiO3 by introducing oxygen vacancies.

Lanthanide-incorporated crystals display the phenomenon of upconversion (UC), wherein near-infrared (NIR) light is converted into ultraviolet-visible (UV-Vis) emission with a narrow bandwidth. This unique photophysical property renders lanthanide UC materials highly promising for diverse applications. However, the limited quantum efficiency (∼3%) hinders the broader utilization of UC materials. Consequently, numerous studies have focused on overcoming this low efficiency. Notably, it has been observed that manipulation of the site symmetry in UC materials significantly enhances their UC efficiency. In this study, we investigate the UC enhancement of Er3+ incorporated BaTiO3 (E-BT) crystals through the introduction of oxygen vacancies (OV). The OV were created using a post-heat treatment method, and the annealing time was varied to control the quantity of OV. An optimal annealing time of 6 hours was determined for efficient OV generation, beyond which the OV content decreased. Remarkably, E-BT crystals with OV exhibited up to three-fold greater UC compared to those without OV. This outcome suggests that OV induce symmetry changes in the E-BT crystal structure. Furthermore, the degree of UC enhancement in E-BT was found to be proportional to the amount of OV present.

Emerging strategies to fabricate polymeric nanocarriers for enhanced drug delivery across blood-brain barrier: An overview.

Blood-brain barrier (BBB) serves as an essential interface between central nervous system (CNS) and its periphery, allowing selective permeation of ions, gaseous molecules, and other nutrients to maintain metabolic functions of brain. Concurrently, it restricts passage of unsolicited materials from bloodstream to CNS which could otherwise lead to neurotoxicity. Nevertheless, in the treatment of neurodegenerative diseases such as Parkinson's, Alzheimer's, diffuse intrinsic pontine glioma, and other brain cancers, drugs must reach CNS. Among various materials developed for this purpose, a few judiciously selected polymeric nanocarriers are reported to be highly prospective to facilitate BBB permeation. However, the challenge of transporting drug-loaded nanomaterials across this barrier remains formidable. Herein a concise analysis of recently employed strategies for designing polymeric nanocarriers to deliver therapeutics across BBB is presented. Impacts of 3Ss, namely, size, shape, and surface charge of polymeric nanocarriers on BBB permeation along with different ligands used for nanoparticle surface modification to achieve targeted delivery have been scrutinized. Finally, we elucidated future research directions in the context of designing smart polymeric nanocarriers for BBB permeation. This work aims to guide researchers engaged in polymeric nanocarrier design, helping them navigate where to begin, what challenges to address, and how to proceed effectively.

Correction: Visualization of intercellular cargo transfer using upconverting nanoparticles.

Correction for 'Visualization of intercellular cargo transfer using upconverting nanoparticles' by Yeongchang Goh et al., Nanoscale, 2022, https://doi.org/10.1039/d2nr01999j.

Visualization of intercellular cargo transfer using upconverting nanoparticles.

Cell-cell communication is important for cellular differentiation, organ function, and immune responses. In intercellular communication, the extracellular vesicles (EVs) play a significant role in delivering the cargo molecules such as genes, proteins, and enzymes, to regulate and control the ability of the recipient cells. In this study, the observation of intercellular cargo transfer via dual-colour imaging using upconverting nanoparticles (UCNPs) has been demonstrated. Using this technique, the intercellular transport via contact-dependent and contact-independent signaling in live HeLa cells was clearly visualized with real-time, long-term single-vesicle tracking. Furthermore, it was demonstrated that the endocytosed UCNPs can be transmitted with the encapsulation of EVs labelled with fluorescent proteins.

pH-responsive polyelectrolyte complexation on upconversion nanoparticles: a multifunctional nanocarrier for protection, delivery, and 3D-imaging of therapeutic protein.

The delicate tertiary structure of proteins, their susceptibility to heat- and enzyme-induced irreversible denaturation, and their tendency to get accumulated at the cell membrane during uptake are daunting challenges in proteinaceous therapeutic delivery. Herein, a polyelectrolyte complex having encapsulated therapeutic protein has been designed on the surface of upconverting luminescent nanoparticles (NaYF4:20%Yb3+,2%Er3+). This nanosized complex system has been found to overcome the challenges of protein aggregation at the cell membrane. It has also defended the cargo from denaturation against (a) enzymatic action of proteinase K and (b) heat (up to 60 °C). Additionally, the nanoparticles at the core of the loaded carrier served as near-infrared (980 nm) responsive probe to accomplish extended-duration 3D imaging during protein delivery. The outer layer of polymer played pivotal role to protect/retrieve the protein structure from denaturation as investigated by circular dichroism studies. Both the masked surface-charges of protein and the nanoscale size of the loaded carrier have facilitated their efficient passage through the cell membrane as observed through 3D images/videos. This nanocarrier is the first of its kind for direct delivery of protein. Thus, the findings can be useful to protect and transport various proteinaceous materials to overcome challenges of accumulation at the cell-membrane and low-temperature storage, as nature does.

Outstanding Strengthening and Toughening Behavior of 3D-Printed Fiber-Reinforced Composites Designed by Biomimetic Interfacial Heterogeneity.

3D printing of fiber-reinforced composites is expected to be the forefront technology for the next-generation high-strength, high-toughness, and lightweight structural materials. The intrinsic architecture of 3D-printed composites closely represents biomimetic micro/macrofibril-like hierarchical structure composed of intermediate filament assembly among the micron-sized reinforcing fibers, and thus contributes to a novel mechanism to simultaneously improve mechanical properties and structural features. Notably, it is found that an interfacial heterogeneity between numerous inner interfaces in the hierarchical structure enables an exceptional increase in the toughness of composites. The strong interfacial adhesion between the fibers and matrix, with accompanying the inherently weak interfacial adhesion between intermediate filaments and the resultant interfacial voids, provide a close representation of the toughness behavior of natural architectures relying on the localized heterogeneity. Given the critical embedment length of fiber reinforcement, extraordinary improvement has been attained not only in the strength but also in toughness taking advantage of the synergy effect from the aforementioned nature-inspired features. Indeed, the addition of a small amount of short fiber to the brittle bio-filaments results in a noticeable increase of more than 200% in the tensile strength and modulus with further elongation increment. This article highlights the inherent structural hierarchy of 3D-printed composites and the relevant sophisticated mechanism for anomalous mechanical reinforcement.

Near-Infrared-Triggered Upconverting Nanoparticles for Biomedicine Applications.

Due to the unique properties of lanthanide-doped upconverting nanoparticles (UCNP) under near-infrared (NIR) light, the last decade has shown a sharp progress in their biomedicine applications. Advances in the techniques for polymer, dye, and bio-molecule conjugation on the surface of the nanoparticles has further expanded their dynamic opportunities for optogenetics, oncotherapy and bioimaging. In this account, considering the primary benefits such as the absence of photobleaching, photoblinking, and autofluorescence of UCNPs not only facilitate the construction of accurate, sensitive and multifunctional nanoprobes, but also improve therapeutic and diagnostic results. We introduce, with the basic knowledge of upconversion, unique properties of UCNPs and the mechanisms involved in photon upconversion and discuss how UCNPs can be implemented in biological practices. In this focused review, we categorize the applications of UCNP-based various strategies into the following domains: neuromodulation, immunotherapy, drug delivery, photodynamic and photothermal therapy, bioimaging and biosensing. Herein, we also discuss the current emerging bioapplications with cutting edge nano-/biointerfacing of UCNPs. Finally, this review provides concluding remarks on future opportunities and challenges on clinical translation of UCNPs-based nanotechnology research.

Power-dependent photophysical pathways of upconversion in BaTiO3:Er3.

Lanthanide incorporated perovskite is one of the most promising systems for efficient energy conversion or light-emitting materials in terms of upconversion (UC). Investigation of the photophysical mechanism of UC in the lanthanide-doped system is here continued. However, research on the 4I13/2 energy state in Er3+ is rare and more is still needed. In our work, BaTiO3:Er3+ (E-BT) was irradiated by a 1532 nm laser which is a resonance to the energy between 4I13/2 and the ground 4I15/2 state in Er3+. Bright 1532 nm-pumped UC was generated, and the UC color changed from red to yellow under increasing laser power. In addition, pump-power-dependent UC contained interesting clues about the photophysical pathway of UC. By analyzing photon numbers for each UC (green: 2H11/2/4S3/2 → 4I15/2, red: 4F9/2 → 4I15/2, infrared: 4I9/2 → 4I15/2), we found that changes in photon number with pump-power increase contain three different phases (P). P1 is a red UC phase with a small cross-relaxation between Er3+ ions. However, in P2, there is a rapid decrease in the photon number with green UC generation, which is due to the enhancement of 4I13/2-populating cross-relaxation. Finally, in P3, a saturated 4I13/2 state causes little increase of photon number (compared with P2), with different mechanistic cross-relaxation enhancement. With these three different phases under 1532 nm pumping, photophysical mechanisms in E-BT are interpreted.

Upconversion properties in lanthanide doped layered-perovskite, CsBiNb2O7.

Despite advances of lanthanide-doped upconversion (UC) materials, the applications such as light-emitting diode and biological imaging are limited by low quantum efficiency. For this context, the understanding of unique interactions between the doped-lanthanides and the host crystals has attracted a huge amount of the researcher's interest. In particular, it was revealed that doping lanthanide ions in a non-centrosymmetric site of host lattice is the cause of relaxation of the Laporte selection rule in the 4f-4f transition of lanthanide ions. One of the layered perovskites CsBiNb2O7 is known to have non-centrosymmetric sites, which would lead to highly bright UC emission. Nevertheless, to our knowledge, there has been no research on the UC comparison between host materials of CsBiNb2O7 with other hosts. In this article, we present the UC intensity comparison of Yb3+-Er3+ ion doped CsBiNb2O7, NaYF4, BaTiO3, and SrTiO3 hosts (the UC in CsBiNb2O7:Er3+,Yb3+ was 2.4 times that of NaYF4:Er3+,Yb3+ and ∼70 times that of SrTiO3:Er3+,Yb3+). After that, we dig into UC, downshifting, and double beam system UC properties. The activator concentration was optimized by varying the doping ratio of Yb3+ and Er3+, and we found out the main reason for the concentration quenching behavior in Er3+ ion doped CsBiNb2O7 is dipole-dipole interaction. In addition, the double excitation experiment indicates that the absorption (4I15/2 → 4I13/2) factor is stronger than the stimulated emission (4I13/2 → 4I15/2) factor in CsBiNb2O7 under 1540 nm laser irradiation.

Enhancing Bifunctional Electrocatalytic Activities of Oxygen Electrodes via Incorporating Highly Conductive Sm3+ and Nd3+ Double-Doped Ceria for Reversible Solid Oxide Cells.

Solid oxide cells (SOCs) are mutually convertible energy devices capable of generating electricity from chemical fuels including hydrogen in the fuel cell mode and producing green hydrogen using electricity from renewable but intermittent solar and wind resources in the electrolysis cell mode. An effective approach to enhance the performance of SOCs at reduced temperatures is by developing highly active oxygen electrodes for both oxygen reduction and oxygen evolution reactions. Herein, highly conductive Sm3+ and Nd3+ double-doped ceria (Sm0.075Nd0.075Ce0.85O2-δ, SNDC) is utilized as an active component for reversible SOC applications. We develop a novel La0.6Sr0.4Co0.2Fe0.8O3 -δ (LSCF)-SNDC composite oxygen electrode. Compared with the conventional LSCF-Gd-doped ceria oxygen electrode, the LSCF-SNDC exhibits ∼35% lower cathode polarization resistance (0.042 Ω cm2 at 750 °C) owing to rapid oxygen incorporation and surface diffusion kinetics. Furthermore, the SOC with the LSCF-SNDC oxygen electrode and the SNDC buffer layer yields a remarkable performance in both the fuel cell (1.54 W cm-2 at 750 °C) and electrolysis cell (1.37 A cm-2 at 750 °C) modes because the incorporation of SNDC promotes the surface diffusion kinetics at the oxygen electrode bulk and the activity of the triple phase boundary at the interface. These findings suggest that the highly conductive SNDC material effectively enhances both oxygen reduction and oxygen evolution reactions, thus serving as a promising material in reversible SOC applications at reduced temperatures.

Uptake of Polyelectrolyte Functionalized Upconversion Nanoparticles by Tau-Aggregated Neuron Cells.

Tauopathy is the aggregation phenomenon of tau proteins and associated with neurodegenerative diseases. It metastasizes via the transfer of tau aggregates to adjacent neuron cells; however, the mechanism has not yet been fully understood. Moreover, if the materials used for designing drug delivery system to treat such neurodegenerative diseases do not undergo biodegradation or exocytosis but remains in cells or tissues, they raise concerns about their possible negative impacts. In this study, the uptake and delivery mechanisms of nano-sized carriers in tau aggregated neuron cells were investigated employing polyelectrolyte-functionalized upconversion nanoparticles (UCNPs) of diameter ~100 nm. Investigation through bioimaging was carried out by irradiating the particles with near-infrared light. Here, forskolin and okadaic acid were employed to induce tau aggregation into healthy neuron cells. It was noticed that the tau-aggregated neuron cells, when treated with relatively large sized UCNPs, showed uptake efficiency similar to that of normal neuron cells however their intracellular transport and exocytosis were impacted, and most of the carriers remained accumulated around lysosome. This demonstrates that metastasis mechanisms of tauopathy can get influenced by the size of carriers and are to be considered during their pharmacokinetic studies which is often not addressed in many drug delivery studies.

Super-Gaussian, superdiffusive transport of multimode active matter.

Living matter often exhibits multimode transport that switches between an active, self-propelled motion and a seemingly passive, random motion. Here, we investigate an exactly solvable model of multimode active matter, such as living cells and motor proteins, which alternatingly undergoes active and passive motion. Our model study shows that the reversible transition between a passive mode and an active mode causes super-Gaussian transport dynamics, observed in various experiments. We find the non-Gaussian character of the matter's displacement distribution is essentially determined by the population ratio between active and passive motion. Interestingly, under a certain population ratio of the active and passive modes, the displacement distribution changes from sub-Gaussian to super-Gaussian as time increases. The mean-square displacement of our model exhibits transient superdiffusive dynamics, yet recovers diffusive behavior at both the short- and long-time limits. We finally generalize our model to encompass complex, multimode active matter in an arbitrary spatial dimension.

High-Performance Perovskite Light-Emitting Diodes with Surface Passivation of CsPbBrxI3-x Nanocrystals via Antisolvent-Triggered Ion-Exchange.

Inorganic lead halide perovskite nanocrystals (PeNCs) have intensively drawn attention as efficient light-emitting materials for optoelectronic applications due to their fine optoelectronic properties with a high photoluminescence quantum yield and easily tunable saturated emission color. However, the poor stability of the red-emitting PeNCs has become an obstacle because of the uncontrollable iodine substitution from the PeNCs due to weak Pb-I bonding. In this work, we have demonstrated a ligand-mediated post-treatment (LMPT) method using a halide ion-pair ligand, tridodecylmethyl ammonium iodide (TrDAI), for the air stable and high-quality red-emitting PeNCs. Through the LMPT method, the optoelectronic properties of red-emitting PeNCs are dramatically improved resulting in a PLQY of 88.7% at 637 ± 2 nm emission with an increased carrier lifetime from 20.77 to 31.52 ns. We achieve highly efficient red perovskite light-emitting diodes exhibiting a maximum current efficiency of 7.69 cd A-1 and an external quantum efficiency of 6.36% at 637 ± 2 nm electroluminescence emission with a sharp full-width at half maximum of 31 nm.

Structural basis for the inhibition of PDK2 by novel ATP- and lipoyl-binding site targeting compounds.

Pyruvate dehydrogenase kinase (PDK) controls the activity of pyruvate decarboxylase complex (PDC) by phosphorylating key serine residues on the E1 subunit, which leads to a decreased oxidative phosphorylation in mitochondria. Inhibition of PDK activity by natural/synthetic compounds has been shown to reverse the Warburg effect, a characteristic metabolism in cancer cells. PDK-PDC axis also has been associated with diabetes and heart disease. Therefore, regulation of PDK activity has been considered as a promising strategy to treat related diseases. Here we present the X-ray crystal structure of PDK2 complexed with a recently identified PDK4 inhibitor, compound 8c, which has been predicted to bind at the lipoyl-binding site and interrupt intermolecular interactions with the E2-E3bp subunits of PDC. The co-crystal structure confirmed the specific binding location of compound 8c and revealed the remote conformational change in the ATP-binding pocket. In addition, two novel 4,5-diarylisoxazole derivatives, GM10030 and GM67520, were synthesized and used for structural studies, which target the ATP-binding site of PDK2. These compounds bind to PDK2 with a sub-100nM affinity as determined by isothermal titration calorimetry experiments. Notably, the crystal structure of the PDK2-GM10030 complex displays unprecedented asymmetric conformation of human PDK2 dimer, especially in the ATP-lids and C-terminal tails.

Correlation of Time-Dependent Oxygen Surface Exchange Kinetics with Surface Chemistry of La0.6Sr0.4Co0.2Fe0.8O3-δ Catalysts.

The Sr segregation at the surface of a perovskite La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) oxygen electrode is detrimental to the electrochemical performance and durability of energy conversion devices such as solid oxide fuel cells. However, a quantitative correlation of degradation of the oxygen surface exchange kinetics with Sr precipitation formation at the LSCF surface is not clearly understood yet. Herein, the correlation of the time-dependent degradation mechanisms of the LSCF catalysts with respect to Sr segregation phenomenon at the surface were investigated at 800 °C for a prolonged annealing time (∼800 h) by combining in situ electrochemical measurements, and ex situ chemical and structural analyses at the multiscale. The in situ monitored surface exchange coefficient (kchem) was found to drastically drop by ∼86% over the 800 h, and it was accompanied by the formation of Sr-containing secondary phases on the bulk LSCF surface, as expected. However, the estimated coverage of Sr segregation on the LSCF surface was only ∼15%, even after 800 h of aging time, showing significant deviation from the kchem degradation rate (∼86%). The surface chemistry evolution at the clean surface area, which is believed to be electrochemically active, was further analyzed on the nanoscale. The quantified results showed that the Sr elemental fraction of the A-site at the outermost surface of the LSCF samples was becoming deficient from ∼4.0 at 0 h to ∼0.27 at 800 h annealing. Interestingly, the time-dependent behavioral tendencies between kchem degradation and surface Sr fractional changes were highly analogous. Thus, our results suggest that this Sr deficiency at the clean surface region more dominantly impacts the degradation process rather than an electrochemical activity passivation by the SrOx precipitates, which has been shown to be a major degradation mechanism of LSCF performance.

Vivid and Fully Saturated Blue Light-Emitting Diodes Based on Ligand-Modified Halide Perovskite Nanocrystals.

CsPbX3 (X = I, Br, Cl) perovskite nanocrystals (NCs) have recently emerged as emitting materials for optoelectronic and display applications owing to their easily tunable emissions, high photoluminescence quantum yield (PLQY), and vivid color purity (full width at half maximum of approximately 20 nm). However, the lagging quantum yields of blue-emitting perovskite NCs have resulted in low efficiency compared to green or red perovskite light-emitting diodes (PeLEDs); moreover, the long insulating ligands (such as oleylamine and oleic acid) inhibit charge carrier injection. In this study, we demonstrated a facile ligand-mediated post-treatment (LMPT) method for high-quality perovskite NCs with changing optical properties to allow fine-tuning of the target emission wavelength. This method involves the use of a mixed halide ion-pair ligand, di-dodecyl dimethyl ammonium bromide, and chloride, which can induce a reconstruction through a self-anion exchange. Using the LMPT method, the PLQY of the surface-passivated blue-emitting NCs was dramatically enhanced to over 70% within the 485 nm blue emission region and 50% within the 467 nm deep-blue emission region. Through this treatment, we achieved highly efficient blue-PeLED maximum external quantum efficiencies of 0.44 and 0.86% within the 470 and 480 ± 2 nm electroluminescence emission regions, respectively.

Anomalous Dynamics of in Vivo Cargo Delivery by Motor Protein Multiplexes.

Vesicle transport conducted by motor protein multiplexes (MPMs), which is ubiquitous among eukaryotes, shows anomalous and stochastic dynamics qualitatively different from the dynamics of thermal motion and artificial active matter; the relationship between in vivo vesicle-delivery dynamics and the underlying physicochemical processes is not yet quantitatively understood. Addressing this issue, we perform accurate tracking of individual vesicles, containing upconverting nanoparticles, transported by kinesin-dynein-multiplexes along axonal microtubules. The mean-square-displacement of vesicles along the microtubule exhibits unusual dynamic phase transitions that are seemingly inconsistent with the scaling behavior of the mean-first-passage time over the travel length. These paradoxical results and the vesicle displacement distribution are quantitatively explained and predicted by a multimode MPM model, developed in the current work, where ATP-hydrolysis-coupled motion of MPM has both unidirectional and bidirectional modes.

Siloxane-Encapsulated Upconversion Nanoparticle Hybrid Composite with Highly Stable Photoluminescence against Heat and Moisture.

Herein, we report a siloxane-encapsulated upconversion nanoparticle hybrid composite (SE-UCNP), which exhibits excellent photoluminescence (PL) stability for over 40 days even at an elevated temperature, in high humidity, and in harsh chemicals. The SE-UCNP is synthesized through UV-induced free-radical polymerization of a sol-gel-derived UCNP-containing oligosiloxane resin (UCNP-oligosiloxane). The siloxane matrix with a random network structure by Si-O-Si bonds successfully encapsulates the UCNPs with chemical linkages between the siloxane matrix and organic ligands on UCNPs. This encapsulation results in surface passivation retaining the intrinsic fluorescent properties of UCNPs under severe conditions (e.g., 85 °C/85% relative humidity) and a wide range of pH (from 1 to 14). As an application example, we fabricate a two-color binary microbarcode based on SE-UCNP via a low-cost transfer printing process. Under near-infrared irradiation, the binary sequences in our barcode are readable enough to identify objects using a mobile phone camera. The hybridization of UCNPs with a siloxane matrix provides the capacity for highly stable UCNP-based applications in real environments.