Search

Precipitation/dissolution of insulating Li 2 S has long been recognized as the rate-determining step in lithium-sulfur (Li-S) batteries, which dramatically undermines sulfur utilization at elevated charging rates. Herein, we present an orientated Li 2 S deposition strategy to achieve extreme fast charging (XFC, ≤15 min) through synergistic control of porosity, electronic conductivity, and anchoring sites of electrode substrate. Via magnesiothermic reduction of a zeolitic imidazolate framework, a nitrogen-doped and hierarchical porous carbon with highly graphitic phase was developed. This design effectively reduces interfacial resistance and ensures efficient sequestration of polysulfides during deposition, leading to (110)-preferred growth of Li 2 S nanocrystalline between (002)-dominated graphitic layers. Our approach directs an alternative Li 2 S deposition pathway to the commonly reported lateral growth and 3D thickening growth mode, ameliorating the electrode passivation. Therefore, a Li-S cell capable of charging/discharging at 5C (12 min) while maintaining excellent cycling stability (82% capacity retention) for 1000 cycles is demonstrated. Even under high S loading (8.3 mg cm -2 ) and low electrolyte/sulfur ratio (3.8 mL mg -1 ), the sulfur cathode still delivers a high areal capacity of >7 mAh cm -2 for 80 cycles.

Stable and active oxygen reduction electrocatalysts are essential for practical fuel cells. Herein, we report a novel class of highly ordered platinum-cobalt (Pt-Co) alloys embedded with cobalt nitride. The intermetallic core-shell catalyst demonstrates an initial mass activity of 0.88 A mg Pt -1 at 0.9 V with 71% retention after 30,000 potential cycles of an aggressive square-wave accelerated durability test and loses only 9% of its electrochemical surface area, far exceeding the US Department of Energy 2025 targets, with unprecedented stability and only a minimal voltage loss under practical fuel cell operating conditions. We discover that regulating the atomic ordering in the core results in an optimal lattice configuration that accelerates the oxygen reduction kinetics. The presence of cobalt nitride decorated within PtCo superlattices guarantees a larger barrier to Co dissolution, leading to the excellent endurance of the electrocatalysts. This work brings up a transformative structural engineering strategy for rationally designing high-performing Pt-based catalysts with a unique atomic configuration for broad practical uses in energy conversion technology.

( S )-Methoprene has been widely applied as a powerful biochemical pesticide to control disease vectors and other pestiferous arthropods of economic importance. As a juvenile hormone analogue, many products based on ( S )-methoprene are developed and commercialized in the USA, Europe, and elsewhere. However, the agricultural use of ( S )-methoprene and its analogues remains underexplored. Here, based on an intermediate derivatization strategy and structural modification, a series of enantiopure ( S )-methoprene derivatives were designed for their expected bioactivity against two crop-threatening pests. Six compounds showed more than 2-fold stronger inhibition of emergence against Plutella xylostella than ( S )-methoprene, among which one that was designated as B2 showed even superior activity to the conventional chemical pesticide and biopesticide with IE 50 of 0.02 mg/L. Nine compounds exhibited over 2-fold higher bioactivity against Aphis craccivora growth than ( S )-methoprene. The physicochemical property evaluation and toxicological test showed that the potent ( S )-methoprene derivatives were low toxic to the nontarget organism and the environment. Molecular docking studies further demonstrated that the high bioactivity of B2 may be partially attributed to its great affinity for binding to juvenile hormone receptors of P. xylostella . The current study suggests that B2 is a biochemical pesticide candidate with potency to be developed as a new agrochemical for lepidopteran control.

Recent advancements in flexible triboelectric nanogenerators (TENGs) have widely focused on converting mechanical energy into electrical energy to power small wearable electronic gadgets and sensors. To effectively achieve this, an efficient energy-converted power management circuit is required. Herein, we report on Aurivillius-type strontium bismuth titanate (SrBi 4 Ti 4 O 15 ) nanoparticles (SBT NPs)-loaded polyglucosamine (PGA) composite film-based flexible TENG to be used for energy harvesting/storage and biomechanical applications. Initially, SBT NPs were synthesized and then, different weight concentrations were loaded into PGA. The TENG devices were fabricated using different wt % composite films (SBT/PGA) and polydimethylsiloxane as positive and negative triboelectric layers, respectively, and aluminum was used as a conductive electrode attached to two tribo films. To evaluate the electrical output from the device, contact-separation operation mode was used. An optimized TENG consisting of 2 wt % SBT/PGA composite film produced the maximum electrical output voltage and current of approximately ∼239 V and ∼7.5 μA, respectively. Efficient TENG energy harvesting and storage circuits have been proposed for storing charges in capacitors and for operating electronic gadgets. The optimized TENG was employed to generate electrical energy from various biomechanical movements. Thereafter, the biodegradability of the composite film was also tested. The fabricated films were completely biodegraded within a few hours. Furthermore, the TENG was utilized as a tap-indication transducer for multipurpose switching applications.

All-solid-state lithium-sulfur batteries (ASSLSBs) are promising next-generation battery technologies with a high energy density and excellent safety. Because of the insulating nature of sulfur/Li 2 S, conventional cathode designs focus on developing porous hosts with high electronic conductivities such as porous carbon. However, carbon hosts boost the decomposition of sulfide electrolytes and suffer from sulfur detachment due to their weak bonding with sulfur/Li 2 S, resulting in capacity decays. Herein, we propose a counterintuitive design concept of host materials in which nonconductive polar mesoporous hosts can enhance the cycling life of ASSLSBs through mitigating the decomposition of adjacent electrolytes and bonding sulfur/Li 2 S steadily to avoid detachment. By using a mesoporous SiO 2 host filled with 70 wt % sulfur as the cathode, we demonstrate steady cycling in ASSLSBs with a capacity reversibility of 95.1% in the initial cycle and a discharge capacity of 1446 mAh/g after 500 cycles at C/5 based on the mass of sulfur.

Targeted mass spectrometry is a powerful technique for quantifying specific proteins or metabolites in complex biological samples. Accurate peak picking is a critical step as it determines the absolute abundance of each analyte by integrating the area under the picked peaks. Although automated software exists for handling such complex tasks, manual intervention is often required to rectify potential errors like misclassification or mis-picking events, which can significantly affect quantification accuracy. Therefore, it is necessary to develop objective scoring functions to evaluate peak-picking results and to identify problematic cases for further inspection. In this study, we present targeted mass spectrometry quality encoder (TMSQE), a data-driven scoring function that summarizes peak quality in three types: transition level, peak group level, and consistency level across samples. Through unsupervised learning from large data sets containing 1,703,827 peak groups, TMSQE establishes a reliable standard for systematic and objective evaluations of chromatographic peak quality in targeted mass spectrometry. TMSQE shows a high degree of consistency with expert experiences and can efficiently capture problematic cases after the automated software. Furthermore, we demonstrate the generalizability of TMSQE by successfully applying it to various data sets, including both peptide and metabolite data sets. Our proposed scoring approach provides a reliable solution for consistent and accurate peak quality evaluation, facilitating peak quality control for targeted mass spectrometry.

Agarperoxinols A and B ( 1-2 ), two naturally occurring humulene-type sesquiterpenoids with an unprecedented tricyclic 6/6/7 ring, were discovered from the agarwood of Aquilaria malaccensis . Their structures were unambiguously determined by various spectroscopic data, experimental ECD calculations, and single-crystal X-ray diffraction analysis. Agarperoxinol B showed significant and dose-dependent neuroinflammatory inhibitory effects on various proinflammatory mediators, including NO, TNF-α, IL-6, and IL-1β, and suppressed iNOS and COX-2 enzymes in LPS-activated microglial cells. A mechanistic study demonstrated that agarperoxinol B remarkably inhibited the phosphorylation of the Akt and JNK signaling pathways. Agarperoxinol B also significantly reduced the expression of the microglial markers Iba-1, COX-2, and TNF-α in the mouse cerebral cortex. Our findings introduce a bioactive compound from natural products that decreases proinflammatory factor production and has application for the treatment of neurodegenerative diseases., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The process of peak picking and quality assessment for multiple reaction monitoring (MRM) data demands significant human effort, especially for signals with low abundance and high interference. Although multiple peak-picking software packages are available, they often fail to detect peaks with low quality and do not report cases with low confidence. Furthermore, visual examination of all chromatograms is still necessary to identify uncertain or erroneous cases. This study introduces HeapMS, a web service that uses artificial intelligence to assist with peak picking and the quality assessment of MRM chromatograms. HeapMS applies a rule-based filter to remove chromatograms with low interference and high-confidence peak boundaries detected by Skyline. Additionally, it transforms two histograms (representing light and heavy peptides) into a single encoded heatmap and performs a two-step evaluation (quality detection and peak picking) using image convolutional neural networks. HeapMS offers three categories of peak picking: uncertain peak picking that requires manual inspection, deletion peak picking that requires removal or manual re-examination, and automatic peak picking. HeapMS acquires the chromatogram and peak-picking boundaries directly from Skyline output. The output results are imported back into Skyline for further manual inspection, facilitating integration with Skyline. HeapMS offers the benefit of detecting chromatograms that should be deleted or require human inspection. Based on defined categories, it can significantly reduce human workload and provide consistent results. Furthermore, by using heatmaps instead of histograms, HeapMS can adapt to future updates in image recognition models. The HeapMS is available at: https://github.com/ccllabe/HeapMS.

For realizing all-solid-state batteries (ASSBs), it is highly desirable to develop a robust solid electrolyte (SE) that has exceptional ionic conductivity and electrochemical stability at room temperature. While argyrodite-type Li 6 PS 5 Cl (LPSCl) SE has garnered attention for its relatively high ionic conductivity (∼3.19 × 10 -3 S cm -1 ), it tends to emit hydrogen sulfide (H 2 S) in the presence of moisture, which can hinder the performance of ASSBs. To address this issue, researchers are exploring approaches that promote structural stability and moisture resistance through elemental doping or substitution. Herein, we suggest using zeolite imidazolate framework-8 as a moisture absorbent in LPSCl without modifying the structure of the SE or the electrode configuration. By incorporating highly ordered porous materials, we demonstrate that ASSBs configured with LPSCl SE display stable cyclability due to effective and long-lasting moisture absorption. This approach not only improves the overall quality of ASSBs but also lays the foundation for developing a moisture-resistant sulfide electrolyte.

Elucidating the water-induced degradation mechanism of quantum-sized semiconductor nanocrystals is an important prerequisite for their practical application because they are vulnerable to moisture compared to their bulk counterparts. In-situ liquid-phase transmission electron microscopy is a desired method for studying nanocrystal degradation, and it has recently gained technical advancement. Herein, the moisture-induced degradation of semiconductor nanocrystals is investigated using graphene double-liquid-layer cells that can control the initiation of reactions. Crystalline and noncrystalline domains of quantum-sized CdS nanorods are clearly distinguished during their decomposition with atomic-scale imaging capability of the developed liquid cells. The results reveal that the decomposition process is mediated by the involvement of the amorphous-phase formation, which is different from conventional nanocrystal etching. The reaction can proceed without the electron beam, suggesting that the amorphous-phase-mediated decomposition is induced by water. Our study discloses unexplored aspects of moisture-induced deformation pathways of semiconductor nanocrystals, involving amorphous intermediates.

Recent advancements in wearable electronic technology demand advanced power sources to be flexible, deformable, durable, and sustainable. An ionic-solution-modified conductive hydrogel-based triboelectric nanogenerator (TENG) has advantages in wearable devices. However, fabricating a conductive hydrogel with better mechanical and electrical properties is still a challenge. Herein, a simple approach is developed to insert ion-rich pores inside the hydrogel, followed by ionic solution soaking. The suggested ionic conductive hydrogel is obtained by cross-linking the polyvinyl alcohol (PVA) hydrogel and carboxymethyl cellulose sodium salt (CMC), followed by soaking in the ionic solution. Furthermore, a flexible and shape-adaptable single-electrode TENG (S-TENG) is fabricated by combinations of ionic-solution-modified dual-cross-linked CMC/PVA hydrogel and silicone rubber. Additionally, the effects of the CMC concentration, type of ionic solution, and concentration of optimized ionic solutions on the hydrogel properties and S-TENG output performance are studied systematically. The well-dispersed CMC- and PVA-based hydrogel provides ion-rich pores with high ion migration, leading to enhanced conductivity. The fabricated S-TENG delivers maximum output performance in terms of voltage, current, and charge density of ∼584 V, 25 μA, and 120 μC/m 2 , respectively. The rectified S-TENG-generated energy is used to charge capacitors and to power a portable electronic display. In addition to energy harvesting, the S-TENG is successfully demonstrated as a touch sensor that can automatically control the light and the speaker based on human motions. This investigation provides a deep insight into the influence of the hydrogel on the device performance and gives a guidance for designing and fabrication of highly flexible and stretchable TENGs.

This study validates the beneficial role of residual Li compounds on the surface of Ni-rich cathode materials (LiNi x Co y Mn z O 2 , NCM). Residual Li compounds on Ni-rich NCM are naturally formed during the synthesis procedure, which degrades the initial Coulombic efficiency and generates slurry gelation during electrode fabrication in Li-ion batteries (LIBs) using liquid electrolytes. To solve this problem, washing pretreatment is usually introduced to remove residual Li compounds on the NCM surface. In contrast to LIBs, we found that residual Li compounds can serve as a functional layer that suppresses the interfacial side reactions of the NCM in all-solid-state batteries (ASSBs). The formation of resistive phosphate-based compounds from the undesirable side reaction during the initial charging step is suppressed by the residual Li compounds on the surface of the NCM, thereby reducing polarization growth in ASSBs and enhancing rate performances. The advantageous effects of the intrinsic residual Li compounds on the NCM surface suggest that the essential washing process of the NCM for the liquid-based LIB system should be reconsidered for ASSB systems.

An unprecedented tandem trifluoromethylsilylation/intramolecular S N 2 substitution sequence was realized by using bifunctional reagent Me 2 (CH 2 Cl)SiCF 3 , allowing efficient construction of valuable trifluoromethylated oxasilacyclohexanes that are difficult to access by known methods. Initial attempts into developing asymmetric variant reveal that using cinchonine-derived dimeric PTC catalyst could afford chiral oxasilacyclohexanes in up to 92% enantiomeric excess.

Over the last years, the development of highly active and durable Pt-based electrocatalysts has been identified as the main target for a large-scale industrial application of fuel cells. In this work, we make a significant step ahead in this direction by preparing a high-performance electrocatalyst and suggesting new structure-activity design concepts which could shape the future of oxygen reduction reaction (ORR) catalyst design. For this, we present a new one-dimensional nanowire catalyst consisting of a L1 0 ordered intermetallic PtCo alloy core and compressively strained high-index facets in the Pt-rich shell. We find the nanoscale PtCo catalyst to provide an excellent turnover for the ORR and hydrogen evolution reaction (HER), which we explain from high-resolution transmission electron microscopy and density functional theory calculations to be due to the high ratio of Pt(221) facets. These facets include highly active ORR and HER sites surprisingly on the terraces which are activated by a combination of sub-surface Co-induced high Miller index-related strain and oxygen coverage on the step sites. The low dimensionality of the catalyst provides a cost-efficient use of Pt. In addition, the high catalytic activity and durability are found during both half-cell and proton exchange membrane fuel cell (PEMFC) operations for both ORR and HER. We believe the revealed design concepts for generating active sites on the Pt-based catalyst can open up a new pathway toward the development of high-performance cathode catalysts for PEMFCs and other catalytic systems.

Molecular networking (MN) has become a popular data analysis method for untargeted mass spectrometry (MS)/MS-based metabolomics. Recently, MN has been suggested as a powerful tool for drug metabolite identification, but its effectiveness for drug metabolism studies has not yet been benchmarked against existing strategies. In this study, we compared the performance of MN, mass defect filtering, Agilent MassHunter Metabolite ID, and Agilent Mass Profiler Professional workflows to annotate metabolites of sildenafil generated in an in vitro liver microsome-based metabolism study. Totally, 28 previously known metabolites with 15 additional unknown isomers and 25 unknown metabolites were found in this study. The comparison demonstrated that MN exhibited performances comparable or superior to those of the existing tools in terms of the number of detected metabolites (27 known metabolites and 22 unknown metabolites), ratio of false positives, and the amount of time and effort required for human labor-based postprocessing, which provided evidence of the efficiency of MN as a drug metabolite identification tool.

Here, we report an unprecedented catalytic enantioselective cyanation of ketonitrones enabled by the bifunctional cyanating reagent Me 2 (CH 2 Cl)SiCN. This approach allows facile access to optically active N -hydroxyl-α-amino nitriles that are of high synthetic value but difficult to acquire by other methods. The use of bifunctional cyanating reagent Me 2 (CH 2 Cl)SiCN not only achieves an enantioselectivity higher than that with TMSCN but also enables various diversification reactions of the resulting silylated adducts. This represents the first enantioselective catalytic nucleophilic addition reaction of unactivated ketone-derived nitrones, exhibiting the potential of such tetrasubstituted C═N bonds for asymmetric synthesis of N -hydroxy α-amino acids and other N -hydroxy tertiary amines.

Mechanical energy is one of the freely available green energy sources that could be harvested to meet the small-scale energy demand. Piezoelectric nanogenerators can be used to harvest the biomechanical energy that is available in everyday human life and power various portable electronics. Herein, a ferroelectric material, i.e., lithium tantalate (LiTaO 3 ), was synthesized and used to fabricate a flexible piezoelectric nanogenerator (FPNG). Generally, ferroelectric materials display a strong electrostatic dipole moment and high piezoelectric coefficient, thus resulting in enhanced electrical performance. First, LiTaO 3 nanoparticles were synthesized and loaded into poly(vinylidene difluoride) (PVDF) to form a piezoelectric film and then, the piezoelectric composite film was sandwiched between two aluminum electrodes to fabricate an FPNG. The effect of the electrical performance of FPNG as a function of the concentration of LiTaO 3 loaded into PVDF was systematically investigated and optimized. The 2.5 wt % FPNG exhibited open-circuit voltage, short-circuit current, and power density values of ∼18 V, ∼1.2 μA, and ∼25 mW/m 2 , respectively. Furthermore, the FPNG revealed good electrical stability and mechanical durability. Finally, the FPNG was employed as a weight sensor to harvest various biomechanical energies and operate low-power- electronics.

An unprecedented catalyst-free reaction of benzo[ b ]thiophene-2,3-diones with difluoroenoxysilanes has been developed using either MeOH or H 2 O as the solvent, which constitutes a facile and efficient protocol for the solvent-controlled divergent synthesis of five- and seven-membered S -heterocycles featuring a gem -difluoromethylene group. A gram-scale synthesis and the diversification of the product transformations to other difluorinated S -heterocycles further highlight its utility.

The O -site reactivity of difluoroenoxysilanes is disclosed for the first time, which enabled the direct construction of versatile gem -difluoroalkenes through an unprecedented highly efficient addition reaction with ketenes. A series of valuable gem -difluoroenol esters were achieved in good to excellent yields. The synthetic versatility of this protocol is further demonstrated by the gram-scale synthesis and good functional group tolerance.

Transition-metal phosphides have gained great importance in the field of energy conversion and storage such as electrochemical water splitting, fuel cells, and Li-ion batteries. In this study, a rationally designed novel fluffy graphene (FG)-wrapped monophasic Ni 5 P 4 (Ni 5 P 4 @FG) is in-situ-synthesized using a chemical vapor deposition method as a Li-ion battery anode material. The porous and hollow structure of Ni 5 P 4 core is greatly helpful for lithium-ion diffusion, and at the same time, the cilia-like graphene nanosheet shell provides an electron-conducting layer and stabilizes the solid electrolyte interface formed on the Ni 5 P 4 surface. The Ni 5 P 4 @FG sample shows a high reversible capacity of 739 mAh g -1 after 300 cycles at a specific current density of 500 mA g -1 . The high capacity, superior cycling stability, and improved rate capability of Ni 5 P 4 @FG are ascribed to its unique hierarchical structure. Moreover, the present efficient fabrication methodology of Ni 5 P 4 @FG has potential to be developed as a general method for the synthesis of other transition-metal phosphides.

A styrylpyrone-fused ergosterol derivative, ergopyrone ( 1 ), was isolated and structurally characterized from a mushroom, Gymnopilus orientispectabilis , along with five biosynthetically related metabolites ( 2 - 6 ). Compound 1 features an unprecedented hexacyclic 6/5/6/6/6/5 skeleton that would be formed from ergosterol and styrylpyrone precursors via [3 + 2] cycloaddition. The chemical structure of 1 was elucidated by conventional spectroscopic and spectrometric data analysis coupled with computational methods including DP4+ probability and ECD simulation and an NOE/ROE-based interproton distance measurement technique via peak amplitude normalization for the improved cross-relaxation (PANIC) method. Plausible biosynthetic pathways of 1 - 6 are proposed, and compound 6 significantly regulated lipid metabolism in adipocytes through the upregulation of the mRNA expression of Adipsin , Fabp4 , SREBP1 , and ATGL .

Qualitative analysis of cucurbitane-type triterpenoids of bitter melon (fruit of Momordica charantia L.) using ultraperformance liquid chromatography quadrupole time-of-flight mass spectrometry revealed 27 promising cucurbitane-type triterpenoids, and LC/MS-guided chemical analysis of M. charantia fruit extract led to the isolation and structural characterization of 22 cucurbitane-type triterpenoids ( 1-22 ), including 8 new cucurbitane-type triterpenoidal saponins, yeojoosides A-H ( 1-8 ). The structures of the new compounds ( 1-8 ) were elucidated by spectroscopic methods, including 1D and 2D NMR and high-resolution electrospray ionization mass spectrometry. Their absolute configurations were assigned by quantum chemical electronic circular dichroism calculations, chemical reactions, and DP4+ analysis using gauge-including atomic orbital NMR chemical shift calculations. All isolated compounds ( 1-22 ) were examined for inhibitory activity against protein tyrosine phosphatases relevant to insulin resistance. Nine compounds ( 7 , 8 , 9 , 11 , 14 , 15 , 19 , 20 , and 21 ) showed selective inhibitory effects of over 70% against PTPN2. The present results suggested that these compounds would be potential antidiabetic agents.

Effective nonprecious metal catalysts are urgently needed for hydrogen evolution reaction (HER). The hybridization of N-doped graphene and a cost-effective metal is expected to be a promising approach for enhanced HER performance but faces bottlenecks in controllable fabrication. Herein, a silica medium-assisted method is developed for the high-efficient synthesis of single-layer N-doped graphene encapsulating nickel nanoparticles (Ni@SNG), where silica nanosheets molecule sieves tactfully assist the self-limiting growth of single-layer graphene over Ni nanoparticles by depressing the diffusion of gaseous carbon radical reactants. The Ni@SNG sample synthesized at 800 °C shows excellent activity for HER in alkaline medium with a low overpotential of 99.8 mV at 10 mA cm -2 , which is close to that of the state-of-the-art Pt/C catalyst. Significantly, the Ni@SNG catalyst is also developed as a binder-free electrode in magnetic field, exhibiting much improved performance than the common Nafion binder-based electrode. Therefore, the magnetism adsorption technique will be a greatly promising approach to overcome the high electron resistance and poor adhesive stability of polymer binder-based electrodes in practical applications.

Metal oxynitrides have been considered recently as emerging electrode materials for supercapacitors. Herein, we converted titanate nanotubes into a series of titanium oxynitride (TiON) nanorods at nitridation temperatures of 800, 900, and 1000 °C in ammonia gas and tested them as supercapacitor electrodes. TiON-800, TiON-900, and TiON-1000 showed capacities of 60, 140, and 71 F g -1 , respectively, at a current density of 1 A g -1 . However, because of TiON's low capacity, a heterostructure (TiON-900/MnCo 2 O 4 ) was designed based on the optimized TiON with MnCo 2 O 4 (MCO). The heterostructure TiON-900-MCO and MCO electrode materials showed specific capacities of 515 and 381 F g -1 , respectively, at a current density of 1 A g -1 . The cycling stability retention of TiON-900 and MCO were 75 and 68%, respectively; moreover, the heterostructure of TiON-900-MCO reached 78% at a current density of 5 A g -1 over 5000 cycles. The increased capacity and sustained cycling stability retention are attributable to the synergistic effect of TiON-900 and MCO. A coin cell (CC)-type symmetric supercapacitor prototype of TiON-900-MCO was fabricated and tested in the voltage range of 0.0-2.0 V in 1 M LiClO 4 in propylene carbonate/dimethyl carbonate electrolyte, and a 79% cycling retention capacity of TiON-900-MCO-CC was achieved over 10 000 cycles at a current density of 250 mA g -1 . We demonstrated a prototypical single cell of TiON-900-MCO-CC as a sustained energy output by powering a red-light emitting diode that indicated TiON-900-MCo electrode materials' potential application in commercial supercapacitor devices.

An efficient Fe(OTf) 3 -catalyzed nucleophilic substitution of cyclic or acyclic tertiary alcohols with difluoroenoxysilanes is developed, which provides a facile protocol for assembling structurally diverse α,α- gem -difluoroketones featuring a quaternary carbon center in good to excellent yields under mild conditions. Moreover, the diverse product elaborations highlight the utility of this protocol, as exemplified by the preparation of valuable difluorinated tricyclic indolines.

A diastereodivergent synthesis of α-chiral tertiary azides through catalytic enantioselective Michael addition of α-azido indanones to β,γ-unsaturated α-ketoesters is described. The merger of a newly designed bifunctional phosphoramide C4b and hexafluoroisopropanol (HFIP) affords syn -adducts, whereas the use of thiourea C6a provides anti -adducts without the aid of HFIP. Notably, additive HFIP proves to be the key control element to achieve diastereoselectivity reversal in the former case. The products are readily converted to enantioenriched spiro N -heterocycles.

Despite significant efforts to improve glioblastoma multiforme (GBM) treatment, GBM remains one of the most lethal cancers. Effective GBM treatments require sensitive intraoperative tumor visualization and effective postoperative chemotherapeutic delivery. Unfortunately, the diffusive and infiltrating nature of GBM limits the detection of GBM tumors, and current intraoperative visualization methods limit complete tumor resection. In addition, although chemotherapy is often used to eliminate any cancerous tissue remaining after surgery, most chemotherapeutic drugs do not effectively cross the brain-blood barrier (BBB) or enter GBM tumors. As a result, GBM has limited treatment options with high recurrence rates, and methods that improve its complete visualization during surgery and treatment are needed. Herein, we report a fluorescent nanoparticle platform for the near-infrared fluorescence (NIRF)-based tumor boundary visualization and image-guided drug delivery into GBM tumors. Our nanoplatform is based on ferumoxytol (FMX), an FDA-approved magnetic resonance imaging-sensitive superparamagnetic iron oxide nanoparticle, which is conjugated with hepthamethine cyanine (HMC), a NIRF ligand that specifically targets the organic anion transporter polypeptides that are overexpressed in GBM. We have shown that HMC-FMX nanoparticles cross the BBB and selectively accumulate in the tumor using orthotopic GBM mouse models, enabling NIRF-based visualization of infiltrating tumor tissue. In addition, HMC-FMX can encapsulate chemotherapeutic drugs, such as paclitaxel or cisplatin, and deliver these agents into GBM tumors, reducing tumor size and increasing survival. Taken together, these observations indicate that HMC-FMX is a promising nanoprobe for GBM surgical visualization and drug delivery.

Rational design of anode materials comprising rich benefits of high capacity, superior rate capability, and exalted lifetime is of considerable significance in the progress of high-performance Li-ion batteries (LIBs) and supercapatteries. Herein, highly porous cobalt vanadate (Co 2 VO 4 ) nanospheres encapsulated with reduced graphene oxide (rGO) nanosheets (rGO@CoV PNSs) were prepared by a facile hydrothermal method and employed as a hybrid composite-based anode material for energy storage devices. The nanocavities and porous features of CoV nanospheres, and the laminated rGO nanosheets over CoV PNSs can significantly surpass the volume changes and enhance the surface electrokinetics, respectively. With benefits of rich redox activity and constructive traits, the rGO@CoV PNSs as an electrode material in LIBs exhibited superior reversible capacity of 780.6 mAh/g after 100 cycles with remarkable rate performance. Moreover, the hybrid composite displayed an excellent reversible capacity of 531.8 mAh/g even after 1000 cycles performed at 1000 mA/g. Utilizing the synergistic features, the rGO@CoV PNSs composite was also explored as a battery-type electrode for supercapatteries. The fabricated supercapattery device with rGO@CoV PNSs and rGO demonstrated good rate performance including superior areal energy (0.048 mWh/cm 2 ) and power (9.96 mW/cm 2 ) densities. Therefore, the graphene sheathed metal vanadates would be an ultrahigh rate electrode candidates for energy storage devices.

Dysregulation of the inflammatory response is a key driver of many debilitating and costly diseases including immune disorders, cancer, and infection. Pyroptosis is a highly inflammatory form of programmed cell death, triggered by various stimuli and meditated by the activation of inflammatory caspases. Pharmacologic agents that provide strategies to modulate pyroptosis for research and clinical practice are still very limited. In current study, we identify 3-difluoroalkyl quaternary oxindoles as chemical inhibitors of caspase-1, the pyroptosis driving caspase. Our results demonstrated compound 6 could directly bind to the CARD domain of pro-caspase-1 to inhibit its infammasome recruitment and pharmacologic inhibition of pyroptotic cell death by compound 6 is partially efficacious in sepsis models. Compound 6 is thus a potential therapeutic for inflammatory disorders and a tool for further study of the inflammation in human health and disease., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

The tunable properties of materials originate from variety of structures; however, it is still a challenge to give an accurate and fast evaluation of stabilities for screening numerous candidates. Herein, we propose an atom classification model to describe the multicomponent materials based on the structural recognition, in which the atoms are classified to estimate the total energies. Taking two-dimensional planar C 1- x B x and C 1-2 x (BN) x as examples, we have found that the test error of total energies is about 3 meV per atom. Notably, the distributions of classified atoms demonstrate the evolution of configurations as a function of temperature, providing a clearer picture of phase transition. In addition, our method is universal, which can be flexibly extended to the bulk structures with more components.

We report that phosphorane can activate (salen)TiCl 2 complex to achieve unprecedented excellent enantioselectivity and a broad substrate scope in the cyanation of nitroolefins. Our cyanating reagent Me 2 (CH 2 Cl)SiCN proves to be more active than TMSCN in this reaction, allowing 11 β-aliphatic nitrolefins and 12 β-CF 3 nitroolefins (either β-aryl or aliphatic) to work well to give the corresponding tertiary or quaternary β-nitronitriles with high to excellent enantioselectivity.

Surface-enhanced Raman scattering (SERS) is an ultrasensitive molecular screening technique with greatly enhanced Raman scattering signals from trace amounts of analytes near plasmonic nanostructures. However, research on the development of a sensor that balances signal enhancement, reproducibility, and uniformity has not yet been proposed for practical applications. In this study, we demonstrate the potential of the practical application for detecting or predicting asymptomatic breast cancer from human tears using a portable Raman spectrometer with an identification algorithm based on multivariate statistics. This potentiality was realized through the fabrication of a plasmonic SERS substrate equipped with a well-aligned, gold-decorated, hexagonal-close-packed polystyrene (Au/HCP-PS) nanosphere monolayer that provided femtomole-scale detection, giga-scale enhancement, and <5% relative standard deviation for reliability and reproducibility, regardless of the measuring site. Our results can provide a first step toward developing a noninvasive, real-time screening technology for detecting asymptomatic tumors and preventing tumor recurrence.

Designing binder-free and core-shell-like electrode materials with synergistic effects has attracted widespread attention for the development of high energy density hybrid supercapacitors (HSCs). Herein, binder-free cobalt molybdate nanosheet-laminated cobalt phosphate micropetals on nickel foam (CoM NS@CoP/NF) were facilely prepared for use as an effective battery-type electrode in HSCs. With the multifunctional features, the rationally combined core-shell-like CoM NS@CoP/NF electrode exhibited a maximum capacity of 886.8 μA h/cm 2 at a current density of 5 mA/cm 2 with a good rate capability of 64.2% and cycling stability of 87.4% (after 10 000 cycles). The high electrochemical performance of the hybrid composite could be attributed to the synergistic effects of hierarchical architectures and large accessible electroactive area, which facilitates the fast electron/transportation within the active material and accelerates the redox chemistry process. Utilizing the superior energy-storage properties, a pouch-type HSC was fabricated with core-shell-like CoM NS@CoP-6 h architectures as a battery-type electrode and activated carbon as a capacitive-type electrode in an aqueous alkaline electrolyte. The miniature hybrid device exhibited maximum energy and power densities of 0.44 mW h/cm 2 and 40.35 mW/cm 2 , respectively, with good cycling stability. Moreover, the HSCs can energize various portable electronic equipments, which demonstrates their suitability for real-time applications.

Electrophilic aminations involve an umpolung of a nitrogen atom, providing an alternate, distinctive synthetic strategy. The recent advent of various designed O-substituted hydroxylamines has significantly advanced this research field. An underappreciated issue is atom economy of the transformations: The necessary activating group on the oxygen atom is left in coproduced waste. Herein, we describe Rh-catalyzed electrophilic amination of substituted isoxazolidin-5-ones for the synthesis of unprotected, cyclic β-amino acids featuring either benzo-fused or spirocyclic scaffolds. Using the cyclic hydroxylamines allows for retaining both nitrogen and oxygen functionalities in the product. The traceless, redox neutral process proceeds on a gram scale with as little as 0.1 mol % catalyst loading. In contrast to related electrophilic aminations in the literature, a series of mechanistic experiments suggests a unique pathway involving spirocyclization, followed by the skeletal rearrangement. The insights provided herein shed light on a nuanced reactivity of the active species, Rh-nitrenoid generated from the activated hydroxylamine, and extend the knowledge on electrophilic aromatic substitutions.

Fluorination is an effective process to open the band gap of graphene (Gr), which is beneficial to the development of optoelectronic devices working in wide wavelength. Herein, we report a dual-mode broadband photodetector (PD) by integrating fluorinated graphene (F-Gr) with silicon (Si). It is found that when working in photoconductive mode, the F-Gr/Si heterojunction exhibited a remarkable photoresponse over a wide spectral region from ultraviolet (UV), visible to near infrared (NIR) light with a high responsivity ( R) of 1.9 × 10 7 A W -1 and specific detectivity ( D*) of 4.4 × 10 12 Jones at 650 nm. Nonetheless, both parameters will be considerably reduced when the F-Gr/Si heterojunction works in the photodiode mode. In this mode, the I light / I dark ratio is as high as 2.0 × 10 5 and the response speed is accelerated by more than 3 orders of magnitude from about 5 ms to 6.3 μs. Notably, the responsivity of the device in the UV and NIR regions was remarkably enhanced in comparison with that of pristine Gr/Si-heterojunction-based devices. Considering the F-coverage-dependent band gap of the F-Gr revealed by the first-principle calculations, we believe that the enhancement was ascribed to the opening of the band gap in the partially fluorinated Gr, which is stabilized due to the configuration entropy as the temperature increases. The dual-mode PD enabled the simultaneous weak light detection and fast photodetection, which overcome the limitation of the traditional monomode PD.

The NBOMe family is a group of new psychoactive substances (NPSs). In this study, the fragmentation patterns of NBOMe derivatives were analyzed using liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF/MS). The MS/MS spectral data was used to establish a molecular networking map for NBOMe derivatives. The fragmentation patterns of nine NBOMe derivatives were interpreted on the basis of their product ion spectral data. NBOMe derivatives generally showed similar product ion spectral patterns; among them, the halogen-substituted methoxybenzyl ethanamine type derivatives showed a characteristic product ion of a radical cation. Molecular network analysis of the MS/MS data revealed that all NBOMe derivatives formed one integrated networking cluster that discriminated them from other types of NPSs. NBOMe derivatives were spiked into human urine and identified by connection to the NBOMe database network. Furthermore, the NBOMe compounds that were not registered in the database were also recognized as an NBOMe-related substance by molecular networking. These results demonstrate the potential of using molecular networking-based screening methods for designer drugs, and the proposed method would be useful in forensic or doping analysis.

A facile Mn surface doping process is proposed to improve the thermal and structural stabilities of Ni-rich layered cathode materials (Ni ≥ 80%) for lithium-ion batteries in electric vehicles. Herein, we demonstrate that the surface structure of the Ni-rich layered cathode materials can be stabilized by the introduction of a thin Mn-rich surface layer. This layer effectively reduces the direct exposure of the highly reactive Ni on the surface of the cathode materials, thus enhancing thermal stability and mitigating side reactions associated with highly reactive Ni that causes the loss of reversible capacity. In practice, the Mn surface-doped Ni-rich layered cathode material exhibits a high specific capacity with an improved cycling stability even at a high temperature (60 °C). We believe that our simple approach offers more opportunities to upscale production without any extra caution.

We facilely prepared silver nanoparticle-decorated Ce 6 Mo 10 O 39 marigold flower-like structures (Ag NPs@CM MFs) for use as an effective positive material in hybrid supercapacitors (HSCs). With the aid of ethylenediaminetetraacetic acid (EDTA) as a chelating agent, self-assembled CM MFs were synthesized by a single-step hydrothermal method. When the electrochemical properties were tested in an aqueous alkaline electrolyte, the synthesized CM MFs with 0.15 g of EDTA exhibited a relatively high charge storage property (55.3 μA h/cm 2 at 2 mA/cm 2 ) with a battery-type redox behavior. The high capacity performance is mainly because of the large surface area of the CM MFs, and the hierarchically connected nanoflakes provide wide open wells for rapid accessibility of electrolyte ions and enable fast transportation of electrons. A further improvement in electrochemical performance was achieved (62 μA h/cm 2 at 2 mA/cm 2 ) by decorating Ag NPs on the surface of the CM MFs (i.e., Ag NPs@CM MFs), which is attributed to the increased electric conductivity. Considering the synergistic effect and the high electrochemical activity, Ag NPs@CM MFs were further employed as an effective positive electrode for the fabrication of pouch-type HSC with porous carbon (negative electrode) in an alkaline electrolyte. The HSC exhibited a high cell potential (1.5 V) with maximum energy and power densities of 0.0183 mW h/cm 2 and 10.237 mW/cm 2 , respectively. The potency of HSC in practical applications was also demonstrated by energizing red and yellow light-emitting diodes as well as a three-point pattern torch light.

We report the development of a surface-enhanced Raman spectroscopy sensor chip by decorating gold nanoparticles (AuNPs) on ZnO nanorod (ZnO NR) arrays vertically grown on cellulose paper (C). We show that these chips can enhance the Raman signal by 1.25 × 10 7 with an excellent reproducibility of <6%. We show that we can measure trace amounts of human amniotic fluids of patients with subclinical intra-amniotic infection (IAI) and preterm delivery (PTD) using the chip in combination with a multivariate statistics-derived machine-learning-trained bioclassification method. We can detect the presence of prenatal diseases and identify the types of diseases from amniotic fluids with >92% clinical sensitivity and specificity. Our technology has the potential to be used for the early detection of prenatal diseases and can be adapted for point-of-care applications.

Triboelectric nanogenerator (TENG) technology is an emerging field to harvest various kinds of mechanical energies available in our living environment. Nowadays, for industrial and large-scale area applications, developing the TENG with low device processing cost and high electrical output is a major issue to be resolved. Herein, we designed a TENG with low cost by employing the microgrooved architectured (MGA)-poly(tetrafluoroethylene) (PTFE; Teflon) and aluminum as triboelectric materials with opposite tendencies. Moreover, the MGA-PTFE was fabricated by a single-step, facile, and cost-effective thermal imprinting lithography technique via micropyramidal textured silicon as a master mold, fabricated by a wet-chemical etching method. Therefore, designing the TENG device by following these techniques can definitely reduce its manufacturing cost. Additionally, the electrical output of TENG was enhanced by adjusting the imprinting parameters of MGA-PTFE. Consequently, the MGA-PTFE was optimized at an imprinting pressure and temperature of 5 MPa and 280 °C, respectively. Thus, the TENG with an optimal MGA-PTFE polymer exhibited the highest electrical output. A robustness test of TENG was also performed, and its output power was used to drive light-emitting diodes and portable electronic devices. Finally, the real application of TENG was also examined by employing it as a smart floor and object-falling detector.

Herein, we develop a binder-free copper molybdate nanocone array with a prism-like morphology on nickel foam (Cu 3 Mo 2 O 9 NCAs/Ni foam) using a single-step hydrothermal method. With an optimal growth time (10 h) under hydrothermal conditions, the prism-like Cu 3 Mo 2 O 9 NCAs are uniformly decorated on Ni foam with good adhesion and crystallinity. The prepared Cu 3 Mo 2 O 9 NCAs/Ni foam has been directly used as a binder-free electrode to examine its suitability as a positive electrode in hybrid supercapacitors. In an aqueous 1 M KOH electrolyte, the binder-free Cu 3 Mo 2 O 9 NCAs/Ni foam showed battery-type behavior with a high areal capacity of 449.5 μAh cm -2 at a discharge current density of 2 mA cm -2 and also exhibited a good cycling stability. In addition, the pouch-type hybrid supercapacitor is assembled using the prism-like Cu 3 Mo 2 O 9 NCAs/Ni foam as a positive electrode and the activated carbon as a negative electrode in a 1 M KOH electrolyte. The hybrid supercapacitor achieves a maximum cell potential of 1.6 V with superior energy storage properties, including a high areal capacitance of 609.7 mF cm -2 at 3.5 mA cm -2 , a high areal energy (0.21 mWh cm -2 ), and a high power density (2.73 mW cm -2 ). The obtained results suggest that the facilely synthesized Cu 3 Mo 2 O 9 NCAs/Ni foam electrode has great potential in high-performance energy storage devices.

Biomimetic microarchitectured polymer layers, such as inverted hemispherical architectured (IHSA)-polydimethylsiloxane (PDMS) and hemispherical architectured (HSA)-PDMS layers, were prepared by a simple and cost-effective soft-imprinting lithography method via a hexagonal close-packed polystyrene microsphere array/silicon mold. The IHSA-PDMS/glass possessed superior antireflection (AR) characteristics with the highest/lowest average transmittance/reflectance ( T avg / R avg ) values of approximately 89.2%/6.4% compared to the HSA-PDMS/glass, flat-PDMS/glass, and bare glass ( T avg / R avg ∼88.8%/7.5%, 87.5%/7.9%, and 87.3%/8.8%, respectively). In addition, the IHSA-PDMS/glass also exhibited a relatively strong light-scattering property with the higher average haze ratio ( H avg ) of ∼38% than those of the bare glass, flat-PDMS/glass, and HSA-PDMS/glass (i.e., H avg ≈ 1.1, 1.7, and 34.2%, respectively). At last, to demonstrate the practical feasibility under light control of the solar cells, the IHSA-PDMS was laminated onto the glass substrates of perovskite solar cells (PSCs) as an AR layer, and their device performances were explored. Consequently, the short-circuit current density of the PSCs integrated with the IHSA-PDMS AR layer was improved by ∼17% when compared with the device without AR layer, resulting in the power conversion efficiency (PCE) up to 19%. Therefore, the IHSA-PDMS is expected to be applied as an AR layer for solar cells to enhance their light absorption as well as the PCE.

We report a flexible battery-type electrode based on binder-free nickel cobalt layered double hydroxide nanosheets adhered to nickel cobalt layered double hydroxide nanoflake arrays on nickel fabric (NC LDH NFAs@NSs/Ni fabric) using facile and eco-friendly synthesis methods. Herein, we utilized discarded polyester fabric as a cost-effective substrate for in situ electroless deposition of Ni, which exhibited good flexibility, light weight, and high conductivity. Subsequently, the vertically aligned NC LDH NFAs were grown on Ni fabric by means of a hot-air oven-based method, and fluffy-like NC LDH NS branches are further decorated on NC LDH NFAs by a simple electrochemical deposition method. The as-prepared core-shell-like nanoarchitectures improve the specific surface area and electrochemical activity, which provides the ideal pathways for electrolyte diffusion and charge transportation. When the electrochemical performance was tested in 1 M KOH aqueous solution, the core-shell-like NC LDH NFAs@NSs/Ni fabric electrode liberated a maximum areal capacity of 536.96 μAh/cm 2 at a current density of 2 mA/cm 2 and excellent rate capability of 78.3% at 30 mA/cm 2 (420.5 μAh/cm 2 ) with a good cycling stability. Moreover, a fabric-based hybrid supercapacitor (SC) was assembled, which achieves a stable operational potential window of 1.6 V, a large areal capacitance of 1147.23 mF/cm 2 at 3 mA/cm 2 , and a high energy density of 0.392 mWh/cm 2 at a power density of 2.353 mW/cm 2 . Utilizing such high energy storage abilities and flexible properties, the fabricated hybrid SC operated the wearable digital watch and electric motor fan for real-time applications.

Herein, a smart strategy is proposed to tailor unique interwoven nanocable architecture consisting of MnCoO x nanoparticles embedded in one-dimensional (1D) mesoporous N-doped carbon nanofibers (NCNFs) by using electrospinning technique. The as-prepared network mat of N-doped carbon nanofibers with embedded MnCoO x nanoparticles (MnCoO x @NCNFs) is tested as a current collector-free and binder-free flexible anode, which eliminates slurry preparation process during electrode fabrication in the Li-ion battery (LIB). The MnCoO x @NCNFs possess versatile structural characteristics that can address simultaneously different issues such as poor conductivity, low cycling stability, volume variation, flexibility, and binder issue associate with the metal oxide. The free-standing mat electrode shows not only high initial discharge and charge capacities but also reversible discharge cycling stability of almost 80% retention up to 100 cycles and 60% retention up to 500 cycles at 1.0 A/g. Such high Li storage capacity and excellent cycling stability are attributed to the unique flexible and free-standing spider network-like architecture of the 1D MnCoO x @NCNFs that provides the platform for bicontinuous electron/ion pathways for superior electrochemical performance. Along with excellent electrochemical performance, simple synthesis procedure of unique binder-free MnCoO x @NCNFs can achieve cost-effective scalable mass production for practical use in a flexible mode, not merely in LIBs but also in a wide spectrum of energy storage fields., Competing Interests: The authors declare no competing financial interest.

Despite extensive study on single-layer layered double hydroxides (SL-LDHs) with NO 3 - counterions, SL-LDHs with CO 3 2- counterions (CO 3 2- SL-LDHs) have never been prepared before. Herein, a CoAl-CO 3 2- SL-LDH which stays stable in water and powdery state is first synthesized using ethylene glycol as a reaction medium. The SL-LDH, with thickness of ∼0.85 nm, is composed of one Co(Al)O 6 layer sandwiched between two CO 3 2- layers. The SL-LDH powder shows high specific surface area (∼289 m 2 /g) and excellent electrocatalytic oxygen evolution efficiency. This work provides the first simple way to prepare CO 3 2- SL-LDHs and will open an avenue for synthesizing other SL-LDHs.

Porous carbons were prepared from a metal-organic framework (MOF, named ZIF-8), with or without modification, via high-temperature pyrolysis. Porous carbons with high nitrogen content were obtained from the calcination of MOF after introducing an ionic liquid (IL) (IL@MOF) via the ship-in-bottle method. The MOF-derived carbons (MDCs) and IL@MOF-derived carbons (IMDCs) were characterized using various techniques and used for liquid-phase adsorptions in both water and hydrocarbon to understand the possible applications in purification of water and fuel, respectively. Adsorptive performances for the removal of organic contaminants, atrazine (ATZ), diuron, and diclofenac, were remarkably enhanced with the modification/conversion of MOFs to MDC and IMDC. For example, in the case of ATZ adsorption, the maximum adsorption capacity of IMDC (Q 0 = 208 m 2 /g) was much higher than that of activated carbon (AC, Q 0 = 60 m 2 /g) and MDC (Q 0 = 168 m 2 /g) and was found to be the highest among the reported results so far. The results of adsorptive denitrogenation and desulfurization of fuel were similar to that of water purification. The IMDCs are very useful in the adsorptions since these new carbons showed remarkable performances in both the aqueous and nonaqueous phases. These results are very meaningful because hydrophobic and hydrophilic adsorbents are usually required for the adsorptions in the water and fuel phases, respectively. Moreover, a plausible mechanism, H-bonding, was also suggested to explain the remarkable performance of the IMDCs in the adsorptions. Therefore, the IMDCs derived from IL@MOF might have various applications, especially in adsorptions, based on high porosity, mesoporosity, doped nitrogen, and functional groups.

Gold-decorated, vertically grown ZnO nanorods (NRs) on a flexible graphite sheet (Au/ZnONRs/G) were developed for surface-enhanced Raman scattering (SERS)-based biosensing to identify trace amounts of human aqueous humors. This Au/ZnONRs/G SERS-functionalized sensor was fabricated via two steps: hydrothermal synthesis-induced growth of ZnO NRs on graphite sheets for nanostructure fabrication, followed by e-beam evaporator-induced gold metallization on ZnONRs/G for SERS functionalization. The thickness of the Au layer and the height of the ZnO NRs for enhancing SERS performance were adjusted to maximize Raman intensity, and the optimized Au/ZnONRs/G nanostructures were verified by the electric finite element computational models to maximize the electric fields. The proposed Au/ZnONRs/G SERS sensor showed an enhancement factor of 2.3 × 10 6 via rhodamine 6G Raman probe and excellent reproducibility (relative standard deviation of <10%) via Raman mapping of a SERS active area with a square of 100 × 100 μm 2 . To evaluate the actual bioapplicability of point-of-care-testing (POCT) analysis in clinics, SERS data acquisition was performed with an integration time of 1 s from a 1 μL analytic droplet of the sample. The performance of this Au/ZnONRs/G sensor was evaluated using human aqueous humors with cataract and two oxidative stress-induced eye diseases, age-related macular degeneration, and diabetic macular edema. These three eye diseases could be identified without any labeling or modification using the Au/ZnONRs/G SERS sensor and the computational algorithm incorporating a support vector machine and multivariate statistical prediction. Therefore, these findings indicate that our label-free, highly reproducible and flexible Au/ZnONRs/G SERS-functionalized sensor supported by a multivariate statistics-derived bioclassification method has great potential in POCT applications for identifying eye diseases.

We report the creation of hybrid energy cells based on hierarchical nano/micro-architectured polydimethylsiloxane (HNMA-PDMS) films with multifunctionality to simultaneously harvest mechanical, solar, and wind energies. These films consist of nano/micro dual-scale architectures (i.e., nanonipples on inverted micropyramidal arrays) on the PDMS surface. The HNMA-PDMS is replicable by facile and cost-effective soft imprint lithography using a nanoporous anodic alumina oxide film formed on the micropyramidal-structured silicon substrate. The HNMA-PDMS film plays multifunctional roles as a triboelectric layer in nanogenerators and an antireflection layer for dye-sensitized solar cells (DSSCs), as well as a self-cleaning surface. This film is employed in triboelectric nanogenerator (TENG) devices, fabricated by laminating it on indium-tin oxide-coated polyethylene terephthalate (ITO/PET) as a bottom electrode. The large effective contact area that emerged from the densely packed hierarchical nano/micro-architectures of the PDMS film leads to the enhancement of TENG device performance. Moreover, the HNMA-PDMS/ITO/PET, with a high transmittance of >90%, also results in highly transparent TENG devices. By placing the HNMA-PDMS/ITO/PET, where the ITO/PET is coated with zinc oxide nanowires, as the top glass substrate of DSSCs, the device is able to add the functionality of TENG devices, thus creating a hybrid energy cell. The hybrid energy cell can successfully convert mechanical, solar, and wind energies into electricity, simultaneously or independently. To specify the device performance, the effects of external pushing frequency and load resistance on the output of TENG devices are also analyzed, including the photovoltaic performance of the hybrid energy cells.

Li metal batteries such as Li-air and Li-S systems have increasingly attracted the attention of researchers because of their high energy densities, which are enhanced by the use of Li metal negative electrodes. However, poor cycle efficiency and safety concerns, which are mainly related to dendritic Li growth during cycling, need to be addressed. Here we propose a solution to the Li dendrite problems. We distributed chemically prepared nitrogen-doped few-layer graphene (N-FLG) sheets on Cu substrates to create island structures. The island-type FLG on the Cu electrode was prepared via spin-coating using slurries that included a polymer binder. When the electrode was used for Li deposition, Li ions were first inserted into the graphene layers. Then, Li metal nucleation occurred at the N-FLG sheets owing to their high electrical conductivity; meanwhile, an insulating polymer layer on the Cu prevented the growth of metallic Li there. Lastly, Li metal grew from the edges of N-FLG sheets in both the lateral and vertical direction, and Li metal deposits filled the gaps between the N-FLG islands as well as covering the remainder of the electrode surface. Thus, stable cycling with flat voltage profiles was demonstrated over 100 cycles at a current density of 2 mA cm -2 . The materials and electrochemical characterization results highlight the effectiveness of this method, which paves the way for the development of robust, dendrite-free Li metal electrodes.

The mean power conversion efficiency (PCE) of quantum-dot-sensitized solar cells (QDSCs) is mainly limited by the low photovoltage and fill factor (FF), which are derived from the high redox potential of polysulfide electrolyte and the poor catalytic activity of the counter electrode (CE), respectively. Herein, we report that this problem is overcome by adopting Ti mesh supported mesoporous carbon (MC/Ti) CE. The confined area in Ti mesh substrate not only offers robust carbon film with submillimeter thickness to ensure high catalytic capacity, but also provides an efficient three-dimension electrical tunnel with better conductivity than state-of-art Cu2S/FTO CE. More importantly, the MC/Ti CE can down shift the redox potential of polysulfide electrolyte to promote high photovoltage. In all, MC/Ti CEs boost PCE of CdSe0.65Te0.35 QDSCs to a certified record of 11.16% (Jsc = 20.68 mA/cm(2), Voc = 0.798 V, FF = 0.677), an improvement of 24% related to previous record. This work thus paves a way for further improvement of performance of QDSCs.