Self-Reinforced Inductive Effect of Symmetric Bipolar Organic Molecule for High-Performance Rechargeable Batteries.

Herein, the self-reinforced inductive effect derived from coexistence of both p- and n-type redox-active motifs in a single organic molecule is presented. Molecular orbital energy levels of each motif are dramatically tuned, which leads to the higher oxidation and the lower reduction potentials. The self-reinforced inductive effect of the symmetric bipolar organic molecule, N,N'-dimethylquinacridone (DMQA), is corroborated, by both experimental and theoretical methods. Furthermore, its redox mechanism and reaction pathway in the Li+ -battery system are scrutinized. DMQA shows excellent capacity retention at the operating voltage of 3.85 and 2.09 V (vs Li+ /Li) when used as the cathode and anode, respectively. Successful operation of DMQA electrodes in a symmetric all-organic battery is also demonstrated. The comprehensive insight into the energy storage capability of the symmetric bipolar organic molecule and its self-reinforced inductive effect is provided. Thus, a new class of organic electrode materials for symmetric all-organic batteries as well as conventional rechargeable batteries can be conceived.

Linnaeite Mineral for NIR Light-Triggered Disruption of Alzheimer's Pore-Forming Aß Oligomers.

Minerals in the Earth's crust have contributed to the natural functioning of ecosystems via biogeochemical interactions. Linnaeite is a cobalt sulfide mineral with a cubic spinel structure that promotes charge transfer reactions with its surroundings. Here we report the hidden feature of linnaeite mineral to dissociate Alzheimer's ß-amyloid (Aß) oligomers under near-infrared (NIR) light irradiation. Alzheimer's disease (AD) is a neurodegenerative disorder caused by the abnormal accumulation of self-assembled Aß peptides in the elderly brain. The ß-sheet structured pore-forming Aß oligomer (ßPFO) is the most neurotoxic species exacerbating the symptoms of AD. However, a therapeutic agent that is capable of inactivating ßPFO has not yet been developed. Our microscopic and spectroscopic analysis results have revealed that NIR-excited linnaeite mineral can modulate the structure of ßPFO by inducing oxidative modifications. We have verified that linnaeite mineral is biocompatible with and has a mitigating effect on the neurotoxicity of ßPFO. This study suggests that minerals in nature have potential as drugs to reduce AD pathology.

Light-driven biocatalytic oxidation.

Enzymes are the catalyst of choice for highly selective reactions, offering nature-inspired approaches for sustainable chemical synthesis. Oxidative enzymes (e.g., monooxygenases, peroxygenases, oxidases, or dehydrogenases) catalyze a variety of enantioselective oxyfunctionalization and dehydrogenation reactions under mild conditions. To sustain the catalytic cycles of these enzymes, constant supply with or withdrawal of reducing equivalents (electrons) is required. Being redox by nature, photocatalysis appears a 'natural choice' to accomplish the electron-relay role, and many photoenzymatic oxidation reactions have been developed in the past years. In this contribution, we critically summarize the current developments in photoredoxbiocatalysis, highlight some promising concepts but also discuss the current limitations.

Metal-Organic Framework-Derived Carbon as a Photoacoustic Modulator of Alzheimer's ß-Amyloid Aggregate Structure.

Photoacoustic materials emit acoustic waves into the surrounding by absorbing photon energy. In an aqueous environment, light-induced acoustic waves form cavitation bubbles by altering the localized pressure to trigger the phase transition of liquid water into vapor. In this study, we report photoacoustic dissociation of beta-amyloid (Aß) aggregates, a hallmark of Alzheimer's disease, by metal-organic framework-derived carbon (MOFC). MOFC exhibits a near-infrared (NIR) light-responsive photoacoustic characteristic that possesses defect-rich and entangled graphitic layers that generate intense cavitation bubbles by absorbing tissue-penetrable NIR light. According to our video analysis, the photoacoustic cavitation by MOFC occurs within milliseconds in the water, which was controllable by NIR light dose. The photoacoustic cavitation successfully transforms robust, ß-sheet-dominant neurotoxic Aß aggregates into nontoxic debris by changing the asymmetric distribution of water molecules around the Aß's amino acid residues. This work unveils the therapeutic potential of NIR-triggered photoacoustic cavitation as a modulator of the Aß aggregate structure.

Heat-fueled enzymatic cascade for selective oxyfunctionalization of hydrocarbons.

Heat is a fundamental feedstock, where more than 80% of global energy comes from fossil-based heating process. However, it is mostly wasted due to a lack of proper techniques of utilizing the low-quality waste heat (<100 °C). Here we report thermoelectrobiocatalytic chemical conversion systems for heat-fueled, enzyme-catalyzed oxyfunctionalization reactions. Thermoelectric bismuth telluride (Bi2Te3) directly converts low-temperature waste heat into chemical energy in the form of H2O2 near room temperature. The streamlined reaction scheme (e.g., water, heat, enzyme, and thermoelectric material) promotes enantio- and chemo-selective hydroxylation and epoxidation of representative substrates (e.g., ethylbenzene, propylbenzene, tetralin, cyclohexane, cis-ß-methylstyrene), achieving a maximum total turnover number of rAaeUPO (TTNrAaeUPO) over 32000. Direct conversion of vehicle exhaust heat into the enantiopure enzymatic product with a rate of 231.4 µM h-1 during urban driving envisions the practical feasibility of thermoelectrobiocatalysis.

Siloxane Hybrid Material-Encapsulated Highly Robust Flexible µLEDs for Biocompatible Lighting Applications.

Flexible micro-light-emitting diodes (f-µLEDs) have been regarded as an attractive light source for the next-generation human-machine interfaces, thanks to their noticeable optoelectronic performances. However, when it comes to their practical utilizations fulfilling industrial standards, there have been unsolved reliability and durability issues of the f-µLEDs, despite previous developments in the high-performance f-µLEDs for various applications. Herein, highly robust flexible µLEDs (f-HµLEDs) with 20 × 20 arrays, which are realized by a siloxane-based organic-inorganic hybrid material (SHM), are reported. The f-HµLEDs are created by combining the f-µLED fabrication process with SHM synthesis procedures (i.e., sol-gel reaction and successive photocuring). The outstanding mechanical, thermal, and environmental stabilities of our f-HµLEDs are confirmed by a host of experimental and theoretical examinations, including a bending fatigue test (105 bending/unbending cycles), a lifetime accelerated stress test (85 °C and 85% relative humidity), and finite element method simulations. Eventually, to demonstrate the potential of our f-HµLEDs for practical applications of flexible displays and/or biomedical devices, their white light emission due to quantum dot-based color conversion of blue light emitted by GaN-based f-HµLEDs is demonstrated, and the biocompatibility of our f-HµLEDs is confirmed via cytotoxicity and cell proliferation tests with muscle, bone, and neuron cell lines. As far as we can tell, this work is the first demonstration of the flexible µLED encapsulation platform based on the SHM, which proved its mechanical, thermal, and environmental stabilities and biocompatibility, enabling us to envisage biomedical and/or flexible display applications using our f-HµLEDs.

Magnetoelectric dissociation of Alzheimer's ß-amyloid aggregates.

The abnormal self-assembly of ß-amyloid (Aß) peptides and their deposition in the brain is a major pathological feature of Alzheimer's disease (AD), the most prevalent chronic neurodegenerative disease affecting nearly 50 million people worldwide. Here, we report a newly discovered function of magnetoelectric nanomaterials for the dissociation of highly stable Aß aggregates under low-frequency magnetic field. We synthesized magnetoelectric BiFeO3-coated CoFe2O4 (BCFO) nanoparticles, which emit excited charge carriers in response to low-frequency magnetic field without generating heat. We demonstrated that the magnetoelectric coupling effect of BCFO nanoparticles successfully dissociates Aß aggregates via water and dissolved oxygen molecules. Our cytotoxicity evaluation confirmed the alleviating effect of magnetoelectrically excited BCFO nanoparticles on Aß-associated toxicity. We found high efficacy of BCFO nanoparticles for the clearance of microsized Aß plaques in ex vivo brain tissues of an AD mouse model. This study shows the potential of magnetoelectric materials for future AD treatment using magnetic field.

Unbiased Photoelectrode Interfaces for Solar Coupling of Lignin Oxidation with Biocatalytic C═C Bond Hydrogenation.

The pulp and paper manufacturers generate approximately 50 million metric tons of lignin per annum, most of which has been abandoned or incinerated because of lignin's recalcitrant nature. Here, we report bias-free photoelectrochemical (PEC) oxidation of lignin coupled with asymmetric hydrogenation of C═C bonds. The PEC platform consists of a hematite (α-Fe2O3) photoanode and a silicon photovoltaic-wired mesoporous indium tin oxide (Si/mesoITO) photocathode. We substantiate a new function of photoelectroactivated α-Fe2O3 to extract electrons from lignin. The extracted electrons are transferred to the Si/mesoITO photocathode for regenerating synthetic nicotinamide cofactor analogues (mNADHs). We demonstrate that the reduction kinetics of mNAD+s depend on their reduction peak potentials. The regenerated mNADHs activate ene-reductases from the old yellow enzyme (OYE) family, which catalyze enantioselective reduction of α,ß-unsaturated hydrocarbons. This lignin-fueled biocatalytic PEC system exhibits an excellent OYE's turnover frequency and total turnover number for photobiocatalytic trans-hydrogenation through cofactor regeneration. This work presents the first example of PEC regeneration of mNADHs and opens up a sustainable route for bias-free chemical synthesis using renewable lignin waste as an electron feedstock.

Light-Stimulated Carbon Dot Hydrogel: Targeting and Clearing Infectious Bacteria In Vivo.

Infectious bacteria evolve fast into resistance to conventional antimicrobial agents, whereas treatments for drug resistance bacteria progress more slowly. Here, we report a universally applicable photoactivated antimicrobial modality through light-responsive carbon dot-embedding soft hyaluronic acid hydrogel (CDgel). Because of the innate nature of the infectious bacteria that produce hyaluronidase, applied hyaluronic acid-based CDgel breaks down via bacteria and releases carbon dots (CDs) into the infectious sites. The released CDs possess photodynamic capabilities under light irradiation, inducing 1O2 generation and growth inhibition of the infectious bacteria, S. aureus and E. coli (∼99% and ∼97%, respectively), in vitro. In particular, these photodynamic effects of CDs from CDgel have been shown to accelerate the healing of infected wounds in vivo, showing a higher wound regeneration rate as compared to that of untreated wounds. Our work demonstrates that the biocompatible and shape-controllable CDgel possesses therapeutic potential as a treatment modality for the light-driven control of drug-resistant bacterial infections.

Lignin-Induced CaCO3 Vaterite Structure for Biocatalytic Artificial Photosynthesis.

The vaterite phase of CaCO3 exhibits unique characteristics, such as high porosity, surface area, dispersivity, and low specific gravity, but it is the most unstable polymorph. Here, we report lignin-induced stable vaterite as a support matrix for integrated artificial photosynthesis through the encapsulation of key active components such as the photosensitizer (eosin y, EY) and redox enzyme (l-glutamate dehydrogenase, GDH). The lignin-vaterite/EY/GDH photobiocatalytic platform enabled the regeneration of the reduced nicotinamide cofactor under visible light and facilitated the rapid conversion of α-ketoglutarate into l-glutamate (initial conversion rate, 0.41 mM h-1; turnover frequency, 1060 h-1; and turnover number, 39,750). The lignin-induced vaterite structure allowed for long-term protection and recycling of the active components while facilitating the photosynthesis reaction due to the redox-active lignin. Succession of stability tests demonstrated a significant improvement of GDH's robustness in the lignin-vaterite structure against harsh environments. This work provides a simple approach for solar-to-chemical conversion using a sustainable, integrated light-harvesting system.

Near-Infrared-Active Copper Molybdenum Sulfide Nanocubes for Phonon-Mediated Clearance of Alzheimer's ß-Amyloid Aggregates.

Ternary chalcogenide materials have attracted significant interest in recent years because of their unique physicochemical and optoelectronic properties without relying on precious metals, rare earth metals, or toxic elements. Copper molybdenum sulfide (Cu2MoS4, CMS) nanocube is a biocompatible ternary chalcogenide nanomaterial that exhibits near-infrared (NIR) photocatalytic activity based on its low band gap and electron-phonon coupling property. Here, we study the efficacy of CMS nanocubes for dissociating neurotoxic Alzheimer's ß-amyloid (Aß) aggregates under NIR light. The accumulation of Aß aggregates in the central nervous system is known to cause and exacerbate Alzheimer's disease (AD). However, clearance of the Aß aggregates from the central nervous system is a considerable challenge due to their robust structure formed through self-assembly via hydrogen bonding and side-chain interactions. Our spectroscopic and microscopic analysis results have demonstrated that NIR-excited CMS nanocubes effectively disassemble Aß fibrils by changing Aß fibril's nanoscopic morphology, secondary structure, and primary structure. We have revealed that the toxicity of Aß fibrils is alleviated by NIR-stimulated CMS nanocubes through in vitro analysis. Moreover, our ex vivo evaluations have suggested that the amount of Aß plaques in AD mouse's brain decreased significantly by NIR-excited CMS nanocubes without causing any macroscopic damage to the brain tissue. Collectively, this study suggests the potential use of CMS nanocubes as a therapeutic ternary chalcogenide material to alleviate AD in the future.

Extremely Stable Luminescent Crosslinked Perovskite Nanoparticles under Harsh Environments over 1.5 Years.

Organic-inorganic hybrid perovskite nanoparticles (NPs) are a very strong candidate emitter that can meet the high luminescence efficiency and high color standard of Rec.2020. However, the instability of perovskite NPs is the most critical unsolved problem that limits their practical application. Here, an extremely stable crosslinked perovskite NP (CPN) is reported that maintains high photoluminescence quantum yield for 1.5 years (>600 d) in air and in harsher liquid environments (e.g., in water, acid, or base solutions, and in various polar solvents), and for more than 100 d under 85 °C and 85% relative humidity without additional encapsulation. Unsaturated hydrocarbons in both the acid and base ligands of NPs are chemically crosslinked with a methacrylate-functionalized matrix, which prevents decomposition of the perovskite crystals. Counterintuitively, water vapor permeating through the crosslinked matrix chemically passivates surface defects in the NPs and reduces nonradiative recombination. Green-emitting and white-emitting flexible large-area displays are demonstrated, which are stable for >400 d in air and in water. The high stability of the CPN in water enables biocompatible cell proliferation which is usually impossible when toxic Pb elements are present. The stable materials design strategies provide a breakthrough toward commercialization of perovskite NPs in displays and bio-related applications.

Photomodulating Carbon Dots for Spatiotemporal Suppression of Alzheimer's ß-Amyloid Aggregation.

Extracellular deposition of ß-amyloid (Aß) peptide aggregates is a major characteristic of Alzheimer's disease (AD) brain. Because Aß peptide aggregates aggravate neuropathy and cognitive impairment for AD patients, numerous efforts have been devoted to suppressing Aß self-assembly as a prospective AD treatment option. Here, we report Aß-targeting, red-light-responsive carbon dots (CDs), and their therapeutic functions as a light-powered nanomodulator to spatiotemporally suppress toxic Aß aggregation both in vitro and in vivo. Our aptamer-functionalized carbon dots (Apta@CDs) showed strong targeting ability toward Aß42 species. Moreover, red LED irradiation induced Apta@CDs to irreversibly denature Aß peptides, impeding the formation of ß-sheet-rich Aß aggregates and attenuating Aß-associated cytotoxicity. Consequently, Apta@CDs-mediated photomodualtion modality achieved effective suppression of Aß aggregation in vivo, which significantly reduced the Aß burden at the targeted sites in the brain of 5xFAD mice by ∼40% and ∼25% according to imaging and ELISA analyses, respectively. Our work demonstrates the therapeutic potential of photomodulating CDs for light-driven suppression against Aß self-assembly and related neurotoxicity.

Chemical sensing platforms for detecting trace-level Alzheimer's core biomarkers.

Alzheimer's disease (AD) is the most prevalent neurodegenerative disorder and affects more than 10% of the population aged over 65 worldwide. Despite considerable global efforts, AD patients can only be diagnosed after the onset of symptoms based on neuropsychological tests and neuroimaging. Because the changes in the levels of biomarkers associated with Aß deposits and tau tangles precede the appearance of the first cognitive symptoms, accurate measurements of AD core biomarkers is critical for identifying asymptomatic AD patients and predicting disease progression. In this regard, significant efforts have been made to develop novel AD biomarker-targeting sensor platforms that have superb sensitivity and high accessibility. This review provides an overview of recent advances in optical and electrical sensing of core AD biomarkers in clinically relevant fluids such as the cerebrospinal fluid and human blood. We have summarized current challenges and future strategies for translating the sensing techniques discovered in the academic laboratories into clinical analytic platforms for early diagnosis of AD.

Metallic Woodpile Nanostructures for Femtomolar Sensing of Alzheimer's Neurofilament Lights.

Alzheimer's disease (AD), the most common age-related neurodegenerative disorder, accompanies a massive degradation of neurons including axonal injury. Being an axonal neuron-specific protein, neurofilament light (NfL) is a blood biomarker that reflects the neurodegeneration in AD, but no attempt has been made yet to develop sensing platforms that target NfLs in blood serum or plasma. Here, we report three-dimensional cross-stacked Pt nanowire arrays for the ultrasensitive photoelectrochemical (PEC) detection of NfLs. We constructed a woodpile-like Pt nanowire array (PtWP)-based biocathode by printing multilayer Pt nanowire arrays in an orthogonal configuration and conjugating them with NfL-specific DA2 antibodies. According to our collective electrochemical analyses, the five-layered PtWP electrode modified with DA2 antibodies exhibited high oxygen reduction activities due to the large electrochemical active surface area and the effective electron transfer properties. We have combined the DA2-PtWP biocathode with a water-oxidizing, iron oxyhydroxide-deposited bismuth vanadate (FeOOH/BiVO4) photoanode to assemble a bias-free PEC detection system. Powered by a white-light-emitting diode, the unbiased PEC platform accurately recognizes NfLs in blood plasma with the limit-of-detection of 38.2 fg/mL and limit-of-quantification of 853 fg/mL, which is 40 times lower than the NfL levels in AD patients' blood.

Solar-Assisted eBiorefinery: Photoelectrochemical Pairing of Oxyfunctionalization and Hydrogenation Reactions.

Inspired by natural photosynthesis, biocatalytic photoelectrochemical (PEC) platforms are gaining prominence for the conversion of solar energy into useful chemicals by combining redox biocatalysis and photoelectrocatalysis. Herein, we report a dual biocatalytic PEC platform consisting of a molybdenum (Mo)-doped BiVO4 (Mo:BiVO4 ) photoanode and an inverse opal ITO (IO-ITO) cathode that gives rise to the coupling of peroxygenase and ene-reductase-mediated catalysis, respectively. In the PEC cell, the photoexcited electrons generated from the Mo:BiVO4 are transferred to the IO-ITO and regenerate reduced flavin mononucleotides to drive ene-reductase-catalyzed trans-hydrogenation of ketoisophrone to (R)-levodione. Meanwhile, the photoactivated Mo:BiVO4 evolves H2 O2 in situ via a two-electron water-oxidation process with the aid of an applied bias, which simultaneously supplies peroxygenases to drive selective hydroxylation of ethylbenzene into enantiopure (R)-1-phenyl-1-hydroxyethane. Thus, the deliberate integration of PEC systems with redox biocatalytic reactions can simultaneously produce valuable chemicals on both electrodes using solar-powered electrons and water.

Piezoelectric materials for ultrasound-driven dissociation of Alzheimer's ß-amyloid aggregate structure.

Piezoelectric materials can evoke electrochemical reactions by transferring charge carriers to reactants upon receiving mechanical stimuli. We report a newly discovered function of piezoelectric bismuth oxychloride (BiOCl) nanosheets for dissociating Alzheimer's ß-amyloid (Aß) aggregates through ultrasound-induced redox reactions. The accumulation of Aß aggregates (e.g., Aß fibrils, plaques) in the central nervous system is a major pathological hallmark of Alzheimer's disease (AD). Thus, clearing Aß aggregates is considered a key for treating AD, but the dissociation of Aß aggregates is challenging due to their extremely robust structure consisting of ß-sheets. BiOCl nanosheets are a biocompatible piezoelectric material with piezocatalytic activity in response to ultrasound. Our analyses using multiple spectroscopic and microscopic tools have revealed that BiOCl nanosheets effectively disassemble Aß fibrils under ultrasound stimulation. Sono-activated BiOCl nanosheets produce piezo-induced oxidative stress, which effectively destabilizes the ß-sheets in Aß fibrils. In vitro evolution has also shown that sono-activated BiOCl nanosheets can effectively alleviate the neuro-toxicity of Aß fibrils. Furthermore, ex vivo evolution demonstrated that amount of Aß plaques in AD mouse's brain slices was drastically reduced by treatment with sono-activated BiOCl nanosheets.

Photonic Carbon Dots as an Emerging Nanoagent for Biomedical and Healthcare Applications.

As a class of carbon-based nanomaterials, carbon dots (CDs) have attracted enormous attention because of their tunable optical and physicochemical properties, such as absorptivity and photoluminescence from ultraviolet to near-infrared, high photostability, biocompatibility, and aqueous dispersity. These characteristics make CDs a promising alternative photonic nanoagent to conventional fluorophores in disease diagnosis, treatment, and healthcare managements. This review describes the fundamental photophysical properties of CDs and highlights their recent applications to bioimaging, photomedicine (e.g., photodynamic/photothermal therapies), biosensors, and healthcare devices. We discuss current challenges and future prospects of photonic CDs to give an insight into developing vibrant fields of CD-based biomedicine and healthcare.

Near-Infrared-Active Copper Bismuth Oxide Electrodes for Targeted Dissociation of Alzheimer's ß-Amyloid Aggregates.

The abnormal accumulation of ß-amyloid (Aß) aggregates in the brain is a major pathological hallmark of Alzheimer's disease. We report a near-infrared (NIR)-active CuBi2O4-based photocathodic platform that can target intact Aß aggregates and dissociate them into nontoxic species. Because of its relatively narrow band gap, CuBi2O4 exhibits strong absorption of NIR light, which allows for deeper tissue penetration and causes less photodamage to tissues compared to visible light. Furthermore, its high stability in aqueous media, biocompatibility, and robustness against photocorrosion make CuBi2O4 an ideal material for medical applications. For the targeted clearance of Aß aggregates, we have conjugated the KLVFF peptide which specifically recognizes and captures Aß aggregates on the surface of silver-doped CuBi2O4 (Ag:CuBi2O4). Upon illumination of NIR light under a cathodic bias, the KLVFF-immobilized Ag:CuBi2O4 (KLVFF-Ag:CuBi2O4) effectively dissociated ß-sheet-rich, long, and entangled Aß fibrillary aggregates into small fragmented, soluble species through photo-oxygenation. We also verified that the KLVFF-Ag:CuBi2O4 photocathode is biocompatible and effective in reducing Aß aggregate-induced neurotoxicity. Our work demonstrates the potential of the KLVFF-Ag:CuBi2O4 platform for the targeted disassembly of cytotoxic, robust Aß aggregates with the aid of NIR energy and cathodic bias.

"Waste to Wealth": Lignin as a Renewable Building Block for Energy Harvesting/Storage and Environmental Remediation.

Lignin is the second most earth-abundant biopolymer having aromatic unit structures, but it has received less attention than other natural biomaterials. Recent advances in the development of lignin-based materials, such as mesoporous carbon, flexible thin films, and fiber matrix, have found their way into applications to photovoltaic devices, energy-storage systems, mechanical energy harvesters, and catalytic components. In this Review, we summarize and suggest another dimension of lignin valorization as a building block for the synthesis of functional materials in the fields of energy and environmental applications. We cover lignin-based materials in the photovoltaic and artificial photosynthesis for solar energy conversion applications. The most recent technological evolution in lignin-based triboelectric nanogenerators is summarized from its fundamental properties to practical implementations. Lignin-derived catalysts for solar-to-heat conversion and oxygen reduction are discussed. For energy-storage applications, we describe the utilization of lignin-based materials in lithium-ion rechargeable batteries and supercapacitors (e.g., electrodes, binders, and separators). We also summarize the use of lignin-based materials as heavy-metal adsorbents for environmental remediation. This Review paves the way to future potentials and opportunities of lignin as a renewable material for energy and environmental applications.