Notes

Improved Shelf-Life as well as Consumer Endorsement involving Fresh-Cut and Deep-fried Potato Strips by simply a great Passable Layer associated with Garden Cress Seeds Mucilage.
In this report, we describe an alkynyl halo-aza-Prins cyclization of 3-hydroxyisoindolones to prepare aza-Prins products. These Prins adducts undergo oxidation at the 3-isoindolone position after activation of the amide by triflic anhydride and 2-chloropyridine to form a pentadienyl cation capable of undergoing a halo-Nazarov cyclization. Using this methodology, angular-fused N-heterocyclic small molecules with two new rings, two new carbon-carbon bonds, a vinyl halide, and an aza-tertiary stereocenter can be obtained in good yields.A general synthesis of 1-vinyltetrahydro-β-carbolines (THBCs) has been achieved via palladium(0)-catalyzed cyclocondensation between allenyltryptamines and aryl iodides. Aza-spiroindolenines could also be accessed from the N-unsubstituted indole substrates by simply tweaking the reaction conditions. DDQ-mediated oxidation of THBCs easily afforded β-carbolines, which could be synthetically transformed into 1-aroyl-β-carbolines of pharmacological interest. Formal total syntheses of eudistomins Y1 and Y2 have also been achieved.Monolayer transition metal dichalcogenides bear great potential for photodetection and light harvesting due to high absorption coefficients. However, these applications require dissociation of strongly bound photogenerated excitons. The dissociation can be achieved by vertically stacking different monolayers to realize band alignment that favors interlayer charge transfer. In such heterostructures, the reported recombination times vary strongly, and the charge separation and recombination mechanisms remain elusive. We use two color pump-probe microscopy to demonstrate that the charge separation in a MoSe2/WSe2 heterostructure is ultrafast (∼200 fs) and virtually temperature independent, whereas the recombination accelerates strongly with temperature. Ab initio quantum dynamics simulations rationalize the experiments, indicating that the charge separation is temperature-independent because it is barrierless, involves dense acceptor states, and is promoted by higher-frequency out-of-plane vibrations. The strong temperature dependence of the recombination, on the other hand, arises from a transient indirect-to-direct bandgap modulation by low-frequency shear and layer breathing motions.Control of materials properties has been the driving force of modern technologies. So far, materials properties have been modulated by their composition, structure, and size. Here, by using cathodoluminescence in a scanning transmission electron microscope, we show that the optical properties of stacked, >100 nm thick hexagonal boron nitride (hBN) films can be continuously tuned by their relative twist angles. Due to the formation of a moiré superlattice between the two interface layers of the twisted films, a new moiré sub-band gap is formed with continuously decreasing magnitude as a function of the twist angle, resulting in tunable luminescence wavelength and intensity increase of >40×. Our results demonstrate that moiré phenomena extend beyond monolayer-based systems and can be preserved in a technologically relevant, bulklike material at room temperature, dominating optical properties of hBN films for applications in medicine, environmental, or information technologies.MXenes, transition metal carbides or nitrides, have gained great attention in recent years due to their high electrical conductivity and catalytic activity, hydrophilicity, and diverse surface chemistry. However, high hydrophilicity and negative ζ potential of the MXene nanosheets limit their processability and interfacial assembly. Previous examples for modifying the dispersibility and wettability of MXenes have focused on the use of organic ligands, such as alkyl amines, or covalent modification with triethoxysilanes. Here, we report a simple method to access MXene-stabilized oil-in-water emulsions by using common inorganic salts (e.g., NaCl) to flocculate the nanosheets and demonstrate the use of these Pickering emulsions to prepare capsules with shells of MXene and polymer. Ti3C2Tz nanosheets are used as the representative MXene. The salt-flocculated MXene nanosheets produce emulsions that are stable for days, as determined by optical microscopy imaging. The incorporation of a diisocyanate in the discontinuous oil phase and diamine in the continuous water phase led to interfacial polymerization and the formation of capsules. The capsules were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM), confirming the presence of both polymer and nanosheets. The addition of ethanol to the capsules led to the removal of the toluene core and retention of the shell structure. The ability to assemble MXene nanosheets at fluid-fluid interfaces without the use of ligands or cosurfactants expands the accessible material constructs relevant for biomedical engineering, water purification, energy storage, electromagnetic electronics, catalysis, and so on.Cyclobutanols undergo an oxidative ring expansion with Co(acac)2 and triplet oxygen to give 1,2-dioxanols. The formation of an alkoxy radical drives the regioselective cleavage of the ring on the more substituted side before insertion of molecular oxygen. The reaction is particularly effective on secondary cyclobutanols but works also on certain tertiary alcohols. Further substitution with neutral nucleophiles under catalytic Lewis acid conditions led to original 1,2-dioxanes with a preferred 3,6-cis-configuration.Volatile organic compounds strongly contribute to both the positive and negative sensory attributes of virgin olive oil, and more and more studies have been published in recent years focusing on several aspects regarding these molecules. This Review is aimed at giving an overview on the state of the art about the virgin olive oil volatile compounds. Particular emphasis was given to the composition of the volatile fraction, the analytical issues and approaches for analysis, the sensory characteristics and interaction with phenolic compounds, and the approaches for supporting the Panel Test in virgin olive oil classification and in authentication of the botanical and geographic origin based on volatile compounds. A pair of detailed tables with a total of approximately 700 volatiles identified or tentatively identified to date and tables dealing with analytical procedures, sensory characteristics of volatiles, and specific chemometric approaches for quality assessment are also provided.Although van der Waals-layered transition metal dichalcogenides from transient absorption spectroscopy have successfully demonstrated an ideal carrier multiplication (CM) performance with an onset of nearly 2Eg, interpretation of the CM effect from the optical approach remains unresolved owing to the complexity of many-body electron-hole pairs. We demonstrate the escalated photocurrent with excitation photon energy by fabricating the dual-gate p-n junction of a MoTe2 film on a transparent substrate. Electrons and holes were efficiently extracted by eliminating the Schottky barriers in the metal contact and minimizing multiple reflections. The photocurrent was elevated proportionately to the excitation photon energy. The boosted quantum efficiency confirms the multiple electron-hole pair generation of >2Eg, consistent with CM results from an optical approach, pushing the solar cell efficiency beyond the Shockley-Queisser limit.Small extracellular vesicles (sEVs) are increasingly recognized as noninvasive diagnostic markers for many diseases. Hence, it is highly desirable to isolate sEVs rapidly for downstream molecular analyses. However, conventional methods for sEV isolation (such as ultracentrifugation and immune-based isolation) are time-consuming and expensive and require large sample volumes. Herein, we developed artificial magnetic colloid antibodies (MCAs) via surface imprinting technology for rapid isolation and analysis of sEVs. This approach enabled the rapid, purification-free, and low-cost isolation of sEVs based on size and shape recognition. The MCAs presented a higher capture yield in 20 min with more than 3-fold enrichment of sEVs compared with the ultracentrifugation method in 4 h. Moreover, the MCAs also proposed a reusability benefiting from the high stability of the organosilica recognition layer. By combining with volumetric bar-chart chip technology, this work provides a sensitive, rapid, and easy-to-use sEV detection platform for point-of-care (POC) diagnostics.Herein, we report a strategy for the total synthesis of a structurally unique fungal glycolipid fusaroside. The first total synthesis of the proposed structure involved construction of the complex, branched lipid chain having a variety of alkenes with E stereochemistry and attachment of the masked α,β-unsaturated β-keto acid at the O-4 position of trehalose as key steps. We propose a revision in the structure of fusaroside, particularly the position of olefins in the lipid chain.Surface tension of chemically complex aqueous droplets is significant to atmospheric aerosol particle dynamics and fate. Isotherm-based predictive surface tension models are available which consider one layer of solute molecules sorbed at the liquid-vapor interface. However, the concentration depth profile (CDP) of solute molecules near the surface is continuous, making the single monolayer assumption inappropriate. Here, this work extends the isotherm framework by dividing the surface region into multiple layers to capture the continuity of the spatial distribution of solute molecules for binary solutions. Partition functions are established based on the displacement of water molecules by solute molecules. The number of displaced water molecules and energy of solute molecules at the surface and in the bulk are key model parameters relating surface tension and solute activity. Number densities of surface molecules from molecular dynamic (MD) simulations available in the literature are applied to determine model parameters. Finally, the model is extended to predict surface tension for mixture solutions, considering both independent and dependent adsorptions of different solute species to the liquid-vapor interface. The proposed model works well for both electrolyte and nonelectrolyte solutions and their mixtures from pure solvent to pure solute.We study the structural and electronic properties of beryllium (Be) and magnesium (Mg) clusters for sizes 2-20 using a two-step approach. In the first step, a global search of the stable and low-lying metastable isomer structures is carried out on the basis of first-principles potential energy surfaces at the level of the generalized gradient approximation (GGA) of density functional theory (DFT). In the second step, vertical ionization potentials (VIPs) and energy gaps between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are determined using the G0W0 methods for up to the fourth-lowest-energy isomers. Novel globally lowest-energy isomer structures are identified for Be14, Mg14, and Mg16 clusters. The van der Waals interactions are found to have a stronger influence on Mg clusters than on Be clusters. A second-difference analysis for both the binding energies and HOMO-LUMO gaps reveals a close relationship between the structural stability and chemical hardness for both types of clusters.This work aims to synthesize a core-shell material of CeO2@SiO2 based on rice husk as a novel hybridized adsorbent for antibiotic removal. The phase structures of CeO2@SiO2 and CeO2 nanoparticles that were fabricated by a simple procedure were examined by X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), and Fourier transform infrared (FT-IR) spectroscopy, while their interfacial characterizations were performed by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), the Brunauer-Emmett-Teller (BET) method, and ζ-potential measurements. The removal efficiency of the antibiotic amoxicillin (AMX) using CeO2@SiO2 nanoparticles was much greater than that using SiO2 and CeO2 materials in solutions of different pH values. The optimum conditions for AMX removal using CeO2@SiO2 including contact time and adsorbent dosage were 120 min and 5 mg/mL, respectively. The maximum AMX removal using CeO2@SiO2 reached 100% and the adsorption capacity was 12.5 mg/g. Adsorption isotherms of AMX onto CeO2@SiO2 were fitted by Langmuir, Freundlich, and two-step adsorption models, while the adsorption kinetics of AMX achieved a better fit by the pseudo-second-order model than the pseudo-first-order model. The electrostatic and nonelectrostatic interactions between the zwitterionic form of AMX and the positively charged CeO2@SiO2 surface were controlled by adsorption. The effects of different organics such as humic acid, ionic surfactants, and pharmaceutical substances on AMX removal using CeO2@SiO2 were also thoroughly investigated. The high AMX removal efficiencies of about 75% after four regenerations and about 70% from an actual water sample demonstrate that CeO2@SiO2-based rice husk is a hybrid nanomaterial for antibiotic removal from water environments.We have developed a metal-free, mild, and green synthetic route toward benzothieno[3,2-b]benzofurans by the annulation of 3-nitrobenzothiophene with phenols. The reaction was found to be general with a range of substituted phenols. In addition, we could extend the methodology for the synthesis of pentacenes and could demonstrate the synthesis in gram-scale. Moreover, we extended the strategy for the synthesis of benzothieno[2,3-b]benzofurans by starting from 2-nitrobenzothiophenes.A new and general Sc(OTf)3-catalyzed C-C bond-forming reaction of 3-(2-methoxyethoxy)-endoperoxy ketals with silyl ketene acetals, silyl enol ethers, allyltrimethylsilane, and trimethylsilyl cyanide has been developed via the reactive peroxycarbenium ions, affording a wide range of complicated 3,3,6,6-tetrasubstituted 1,2-dioxenes bearing adjacent quaternary carbons and 3-acetyl/allyl/cyano functional groups in good yields at room temperature. Notably, the resultant 1,2-dioxenes are structurally stable, which can be facially transformed into another important 1,2-dioxane endoperoxide under conventional hydrogenation conditions without deconstructing the weak O-O bond.Rh(III)-catalyzed redox-neutral C-H olefination of aryldiazenecarboxylates has been realized using arylate esters as the olefinating reagents. This reaction proceeds under mild and redox-neutral conditions, resulting in integration of C-H activation and transfer hydrogenation. The chemoselectivity complements that of previously reported rhodium-catalyzed coupling of the same substrates.Borylated aza-arenes are of great importance in the area of organic synthesis. A radical borylative cyclization of isocyanoarenes with N-heterocyclic carbene borane (NHC-BH3) under metal-free conditions was developed. The reaction allows the efficient assembly of several types of borylated aza-arenes (phenanthridines, benzothiazoles, etc.), which are difficult to access using alternative methods. Mild reaction conditions, a good functional-group tolerance, and generally good efficiencies were observed. The utility of these products is demonstrated, and the mechanism is discussed.Fluorinated malonic acid half thioesters (F-MAHTs) were used as thioester enolate equivalents in organocatalyzed addition reactions to isatins. The products from a range of different N-protected and nonprotected isatins were obtained under mild reaction conditions in high yields and enantioselectivities. The unique reactivity of the thioester moiety enabled diverse derivatization and allowed for the straightforward access to a fluorinated analogue of the anticancer agent (S)-YK-4-279, a therapeutically active compound against Ewing's sarcoma.Surface functionalization of mesoporous silica nanoparticles is important for their applications but fairly challenging using benzene-bridged organosilane as the precursor through the postsynthesis approach. Herein, we report an acid-catalysis approach for the postmodification of benzene-bridged organosilica onto the surface of large-pore mesoporous silica nanoparticles. By using HCl (∼1 M) as the acid catalyst in a tetrahydrofuran solvent, the self-assembly of the bridged organosilica precursor is avoided, while surface modification of mesoporous silica nanoparticles is promoted with controllable organic contents and retained large pore sizes. This strategy can also be applied to the postmodification of organosilica with end benzene groups. The strategy developed in this study is expected to be applied for the postmodification of other organosilica precursors with various functions.The budding deuteriodifluoromethyl group (CF2D) is a potentially significant functional group in medicinal chemistry. Herein, we investigated t-BuOK-catalyzed H/D exchange reaction of difluoromethylarenes in DMSO-d6 solution. The method provides excellent deuterium incorporation at the difluoromethyl group. Meanwhile, the effect of a trace amount of D2O in DMSO-d6 solution on the deuteration reaction was also investigated.Herein is a report on the molecular exchange occurring between multilateral symbiosis partners-a tit-for-tat exchange that led to the characterization of two new metabolites, conocandin B (fungal-derived) and dentigerumycin F (bacterial-derived). The structures were determined by NMR, mass spectrometry, genomic analysis, and chemical derivatizations. Conocandin B exhibits antimicrobial activity against both the bacterial symbionts of fungus-growing ant and human pathogenic strains by selectively inhibiting FabH, thus disrupting fatty acid biosynthesis.The potential of 2-(3,4-dihydroxybenzoyl)-2,4,6-trihydroxy-3(2H)-benzofuranone (BZF), a quercetin oxidation metabolite, and that of a BZF-rich onion peel aqueous extract (OAE) to protect Caco-2 monolayers against the oxidative stress (OS) and an increased permeability (IP) induced by five nonsteroidal anti-inflammatory drugs (NSAIDs) (indomethacin, diclofenac, piroxicam, ibuprofen, and metamizole) were investigated. Under identical OS conditions, the NSAIDs substantially differed in their ability to induce an IP and/or NF-kB activation. The OAE (100 nM BZF) protected in identical magnitude (84-86%) against OS but in a highly dissimilar manner against the IP (18-73%). While all NSAIDs activated NF-kB, the OAE prevented only that induced by indomethacin. Results reveal that the IP has no direct relationship with the OS and that with the exception of indomethacin, the prevention of NSAIDs-induced OS and/or NF-kB activation plays no fundamental role in the IP-protecting effect of OAE. These results warrant the in vivo evaluation of OAE against indomethacin-induced loss of intestinal barrier function.Chemokines and chemokine receptors play an important role in the initiation and progression of atherosclerosis by mediating the trafficking of inflammatory cells. Chemokine receptor 5 (CCR5) has major implications in promoting the development of plaques to advanced stage and related vulnerability. CCR5 antagonist has demonstrated the effective inhibition of atherosclerotic progression in mice, making it a potential biomarker for atherosclerosis management. To accurately determine CCR5 in vivo, we synthesized CCR5 targeted Comb nanoparticles through a modular design and construction strategy with control over the physiochemical properties and functionalization of CCR5 targeting peptide d-Ala-peptide T-amide (DAPTA-Comb). In vivo pharmacokinetic evaluation through 64Cu radiolabeling showed extended blood circulation of 64Cu-DAPTA-Combs conjugated with 10%, 25%, and 40% DAPTA. The different organ distribution profiles of the three nanoparticles demonstrated the effect of DAPTA on not only physicochemical properties but also targeting efficiency. In vivo positron emission tomography/computed tomography (PET/CT) imaging in an apolipoprotein E knockout mouse atherosclerosis model (ApoE-/-) showed that the three 64Cu-DAPTA-Combs could sensitively and specifically detect CCR5 along the progression of atherosclerotic lesions. In an ApoE-encoding adenoviral vector (AAV) induced plaque regression ApoE-/- mouse model, decreased monocyte recruitment, CD68+ macrophages, CCR5 expression, and plaque size were all associated with reduced PET signals, which not only further confirmed the targeting efficiency of 64Cu-DAPTA-Combs but also highlighted the potential of these targeted nanoparticles for atherosclerosis imaging. Moreover, the up-regulation of CCR5 and colocalization with CD68+ macrophages in the necrotic core of ex vivo human plaque specimens warrant further investigation for atherosclerosis prognosis.At present, environmentally friendly biobased flexible films are of particular interest as next-generation fireproof packaging and sensor materials. To reduce the moisture uptake and fire risks induced by hygroscopic and flammable biobased films, we report a simple and green approach to develop a hydrophobic, flame-retardant composite film with synergetic benefit from soy protein isolate (SPI), sisal cellulose microcrystals (MSF-g-COOH), graphene nanosheets (GN), and citric acid (CA). Compared with SPI/MSF-g-COOH composite films, the as-prepared SPI/MSF-g-COOH/CA/GN composite films have significantly improved water resistance and can maintain excellent physical structure and good electrical conductivity in an ethanol flame. This work opens a pathway for the development of novel fire-retardant fire alarm biosensors.In addition to its vital significance in combustion and atmospheric chemistry, the reaction between H' and HO2 on the ground triplet state represents a prototype with multiple product channels, including H2 + O2, OH + OH, O + H2O, and H + H'O2. In this work, a full-dimensional accurate potential energy surface (PES) for the title reaction was developed to provide reliable descriptions for all dynamically relevant regions. Using this PES, we adopted the quasi-classical trajectory approach to study the corresponding reaction dynamics, including the reactivity of each product channel and the associated product branching ratio, the product energy distributions, product angular distributions, and associated microscopic mechanisms. For representing distributions of the product energies, such as product translational energy as well as product rotational and vibrational energies, both the traditional histogram and the kernel density estimation (KDE) methods were used and compared. It seems that the features of the resulting distributions in this work are very similar to each other among different methods. The KDE method is suggested for statistics, particularly for those populations with small oscillations in the histogram plot.Rare earth ion-doped oxyfluoride glasses in the system 50SiO2-(50 - x)PbO-xPbF2-mLa2O3-nEr2O3 were prepared by the melt-quenching method. PbF2 and LaF3 were selectively crystallized by subsequent heat treatment in these glasses. The promotion and suppression effects of La3+ ions on the crystallization of PbF2 were observed in this selective crystallization. We used advanced solid-state nuclear magnetic resonance (NMR) and X-ray diffraction techniques to probe the structural evolution in the atomic level during these crystallizations. Based on the in-depth structure study, it can be inferred that both the different effects arise from the stronger ability of La3+ ions in attracting F- ions than that of Pb2+ ions. Intensive upconversion visible luminescence was observed in these glasses. The NMR and the upconversion luminescence results imply that most Er3+ ions are dissolved in the LaF3 crystal rather than in the PbF2 crystal and the glass phases even when the content of the LaF3 crystal is as small as less than 1 mol %. The results show that the past expectation that rare earth ions are homogenously incorporated into bivalent metal fluoride crystals might not be right and prove the validity of the strategy that multiple rare earth ions are codoped to increase the upconversion luminescent efficiency.State-of-the-art electrochemical and optical sensors present distinct advantages and disadvantages when used individually. Combining both methodologies offers interesting synergies and makes it possible to exploit strengths and circumvent possible problems of the individual methods. We report a dynamic sensing concept for buffer capacity by applying water electrolysis to modulate the pH microenvironment in front of an optical pH sensor placed in a flow cell. Using this combinatory approach in a nonequilibrium readout mode allowed us to assess the concentration of different buffer species in relatively short time (1 min per measurement). Theoretical simulations of the system were performed to validate the presented method. Additionally, the dynamic measurement approach enabled in situ determination of the apparent pKa of MOPS (3-(N-morpholino)propanesulfonic acid) buffer at ambient conditions. The dynamic and combinatory approach presented here holds large potential also for other pH-active analytes.The extent to which climate change and other factors will influence building energy use and population exposures to indoor pollutants is not well understood. Here, we develop and apply nationally representative residential energy and indoor pollutant model sets to estimate energy use, indoor pollutant concentrations, and associated chronic health outcomes across the U.S. residential building stock in the mid-21st century. The models incorporate expected changes in meteorological and ambient air quality conditions associated with IPCC RCP 8.5 and assumptions for changes in housing characteristics and population movements while keeping other less predictable factors constant. Site and source energy consumption for residential space-conditioning are predicted to decrease by ∼37-43 and ∼20-31%, respectively, in the 2050s compared to those in a 2010s reference scenario. Population-average indoor concentrations of pollutants of ambient origin are expected to decrease, except for O3. Holding indoor emission factors constant, indoor concentrations of pollutants with intermittent indoor sources are expected to decrease by 30% (NO2); indoor concentrations of pollutants with persistent indoor sources (e.g., volatile organic compounds (VOCs)) are predicted to increase by ∼15-45%. We estimate negligible changes in disability-adjusted life-years (DALYs) lost associated with residential indoor pollutant exposures, well within uncertainty, although the attribution among pollutants is predicted to vary.Nucleic acids typically form a double helix structure through Watson-Crick base-pairing. In contrast, non-Watson-Crick base pairs can form other three-dimensional structures. Although it is well-known that Watson-Crick base pairs may be more unstable than non-Watson-Crick base pairs under some conditions, the importance of non-Watson-Crick base pairs has not been widely examined. Hoogsteen base pairs, the non-Watson-Crick base pairs, contain important hydrogen-bond patterns that form the helices of nucleic acids, such as in Watson-Crick base pairs, and can form non-double helix structures such as triplexes and quadruplexes. In recent years, non-double helix structures have been discovered in cells and were reported to considerably influence gene expression. The complex behavior of these nucleic acids in cells is gradually being revealed, but the underlying mechanisms remain almost unknown.Quantitatively analyzing the structural stability of nucleic acids is important for understanding their behavior. A nucleihe stability of nucleic acid structures. We developed new methods for predicting the stability of double and non-double helices in various molecular environments by mimicking intracellular environments. Furthermore, the physicochemical approach used for analyzing gene expression regulated by non-double helix structures is useful for not only determining how gene expression is controlled by cellular environments but also for developing new technologies to chemically regulate gene expression by targeting non-double helix structures. We discuss the roles of Watson-Crick and Hoogsteen base pairs in cells based on our results and why both types of base pairing are required for life. Finally, a new concept in nucleic acid science beyond that of Watson and Crick base pairing is introduced.The present work elaborates the high-energy-density, stable, and flexible supercapacitor devices (full-cell configuration with asymmetric setup) based on a two-dimensional tungsten oxide/selenium (2D WO3/Se) nanocomposite. For this, the 2D WO3/Se nanocomposite synthesized by a hydrothermal method followed by air annealing was coated on a flexible carbon cloth current collector and combined separately with both 0.1 M H2SO4 and 1-butyl-3-methyl imidazolium tetrafluoroborate room temperature ionic liquid (BmimBF4 RTIL) as electrolyte. Different physicochemical characterization techniques, viz., transmission electron microscopy, scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, are utilized for phase confirmation and morphology identification of the obtained samples. The electrochemical analysis was used to evaluate charge storage mechanism. The half-cell configuration (three electrode system) in 0.1 M H2SO4 shows a specific capacitance of 564 F g-1 at 6 A g-1 current density, whereas with ionic liquid as electrolyte, a higher specific capacitance of 1650 F g-1 was obtained at a higher current of 40 mA and working potential of 4 V. Importantly, the asymmetric flexible supercapacitor device with PVA-H2SO4 electrolyte shows a working voltage of 1.7 V. A specific capacitance of 858 mF g-1 is obtained for the asymmetric electrode system with an energy density of 47 mWh kg-1 and a power density of 345 mW kg-1 at a current density of 0.2 A g-1.Radicals of flavin adenine dinucleotide (FAD), as well as tyrosine and tryptophan, are widely involved as key reactive intermediates during electron-transfer (ET) reactions in flavoproteins. Due to the high reactivity of these species and their corresponding short lifetime, characterization of these intermediates in functional processes of flavoproteins is usually challenging but can be achieved by ultrafast spectroscopic studies of light-activatable flavoproteins. In ferredoxin-NADP+ oxidoreductase from Bacillus subtilis (BsFNR), fluorescence of the FAD cofactor that very closely interacts with a neighboring tyrosine residue (Tyr50) is strongly quenched. Here we study short-lived photoproducts of this enzyme and its variants, with Tyr50 replaced by tryptophan or glycine. Using time-resolved fluorescence and absorption spectroscopies, we show that, upon the excitation of WT BsFNR, ultrafast ET from Tyr50 to the excited FAD cofactor occurs in ∼260 fs, an order of magnitude faster than the decay by charge recombination, facilitating the characterization of the reaction intermediates in the charge-separated state with respect to other recently studied systems. These studies are corroborated by experiments on the Y50W mutant protein, which yield photoproducts qualitatively similar to those observed in other tryptophan-bearing flavoproteins. By combining the experimental results with molecular dynamics simulations and quantum mechanics calculations, we investigate in detail the effects of protein environment and relaxations on the spectral properties of those radical intermediates and demonstrate that the spectral features of radical anionic FAD are highly sensitive to its environment, and in particular to the dynamics and nature of the counterions formed in the photoproducts. Altogether, comprehensive characterizations are provided for important radical intermediates that are generally involved in functional processes of flavoproteins.The multifunctional protein p53 is the central molecular sensor of cellular stresses. The canonical function of p53 is to transcriptionally activate target genes in response to, for example, DNA damage that may trigger apoptosis. Recently, p53 was also found to play a role in the regulation of necrosis, another type of cell death featured by the mitochondrial permeability transition (mPT). In this process, p53 directly interacts with the mPT regulator cyclophilin D, the detailed mechanism of which however remains poorly understood. Here, we report a comprehensive computational investigation of the p53-cyclophilin D interaction using molecular dynamics simulations and associated analyses. We have identified the specific cyclophilin D binding site on p53 that is located at proline 151 in the DNA binding domain. As a peptidyl-prolyl isomerase, cyclophilin D binds p53 and catalyzes the cis-trans isomerization of the peptide bond preceding proline 151. We have also characterized the effect of such an isomerization and found that the p53 domain in the cis state is overall more rigid than the trans state except for the local region around proline 151. Dynamical changes upon isomerization occur in both local and distal regions, indicating an allosteric effect elicited by the isomerization. We present potential allosteric communication pathways between proline 151 and distal sites, including the DNA binding surface. Our work provides, for the first time, a model for how cyclophilin D binds p53 and regulates its activity by switching the configuration of a specific site.Selective separation of phenanthrene (PHE) from aromatic isomer mixtures is a big challenge in industry. In this work, a light-responsive water-soluble azobenzene-based macrocycle 1 is synthesized and an aqueous solution of E,E-1 is employed to separate PHE from anthracene via a solid-liquid extraction method under ambient conditions. After five extraction cycles, the average purity for PHE is about 91.1% and macrocycle 1 can be reused at least five times without obvious reduction of separation performance for PHE. This work not only comprises a new and clean way to separate PHE by taking advantage of a macrocyclic host but also promotes the application of host-guest chemistry.Multiparameter integrated sensors are required for the next generation of flexible wearable electronics. However, mutual interference between detected signals is a technical bottleneck for a flexible tactile sensor to realize pressure-strain monitoring simultaneously and sensitively. Herein, a flexible dual-parameter pressure-strain sensor based on the three-dimensional (3D) tubular graphene sponge (TGS) and spider web-like stretchable electrodes is designed and fabricated. As the pressure-sensitive module, the unique 3D-TGS with an uninterrupted network of tubular graphene and high graphitic degree demonstrates great robust compressibility, supporting compression to ∼20% without shape collapse. The spider web-like stretchable electrodes as the strain-sensitive module are fabricated by a spray-embedded process based on the hierarchical multiscale hybrid nanocomposite of Ag nanowires (NWs) and carbon nanotubes (CNTs) with an optimal mass ratio. By comparing the output signals of spider web-like flexible electrodes, the magnitude and direction of the applied force can be effectively monitored simultaneously. Moreover, the potential applications of the flexible dual-parameter pressure-strain device in human-machine interaction are also explored, showing great promise in artificial intelligence and wearable systems.Most heterogeneous catalytic reactions demand high density and yet spatially separated nanoparticles that are strongly anchored on the oxide surfaces. Such nanoparticles can be deposited or synthesized in situ via nonstoichiometric methods. To date, nanoparticles have been exsolved from perovskite oxide surfaces using nonstoichiometric processes. However, the density of the space-separated nanoparticles on the oxide surfaces is still low. And less attention is paid toward the changes that happen to the host during the nanoparticle exsolution process. In this work, we demonstrated in situ exsolution of ultrafine nanoparticles (∼5 nm) of either Co3O4 or Ca(OH)2 via judicious control of nonstoichiometry in a misfit Ca3Co4O9 (CCO). The nanoparticle density over the CCO surface reached as high as 8500/μm2, which is significantly higher than previously reported values. High-resolution electron microscopy studies reveal the formation mechanism of Co3O4 nanoparticles over CCO, and the formation takes palace via the flysis and thermoelectrics.We investigate hole-selective passivating contacts that consist of an interfacial layer of silicon oxide (SiOx) and a layer of boron-doped SiCx(p). The fabrication process of these contacts involves an annealing step at temperatures above 750 °C which crystallizes the initially amorphous layer and diffuses dopants across the interfacial oxide into the wafer to facilitate charge transport, but it can also disrupt the SiOx layer necessary for wafer-surface passivation. To investigate the transport mechanism of the charge carriers through the selective contact and its changes during the annealing process, we utilize various characterization methods, such as transmission electron microscopy, micro Raman spectroscopy, and conductive atomic force microscopy. Combining the latter with a sequential removal of material, we assemble a tomographic reconstruction of the crystallized layer that reveals the presence of preferential vertical transport channels.In this work, we demonstrate a new approach for interactively assessing hyperspectral data spatial structures for heterogeneity using mass spectrometry imaging. This approach is based on the visualization of the cosine distance as the similarity levels between mass spectra of a chosen region and the rest of the image (sample). The applicability of the method is demonstrated on a set of mass spectrometry images of frontal mouse brain slices. Selection of the reference pixel of the mass spectrometric image and a further view of the corresponding cosine distance map helps to prepare supporting vectors for further analysis, select features, and carry out biological interpretation of different tissues in the mass spectrometry context with or without histological annotation. Visual inspection of the similarity maps reveals the spatial distribution of features in tissue samples, which can serve as the molecular histological annotation of a slide.Metal complexes of 1,2-diamidobenzenes have been long studied because of their intriguing redox properties and electronic structures. We present here a series of such complexes with 1,2-bis(sulfonamido)benzene ligands to probe the utility of these ligands for generating a large zero-field splitting (ZFS, D) in metal complexes that possibly act as single-ion magnets. To this end, we have synthesized a series of homoleptic ate complexes of the form (X)n[Mbis(sulfonamido)benzene2] (n equals 4 minus the oxidation state of the metal), where M (Fe/Co/Ni), X [K+/(K-18-c-6)+/(HNEt3)+, with 18-c-6 = 18-crown ether 6], and the substituents (methyl and tolyl) on the ligand [bmsab = 1,2-bis(methanesulfonamido)benzene; btsab = 1,2-bis(toluenesulfonamido)benzene] were varied to analyze their effect on the ZFS, possible single-ion-magnet properties, and redox behavior of these metal complexes. A combination of X-ray crystallography, (spectro)electrochemistry, superconducting quantum interference device magnetometry, high-nce of ligands that are potentially noninnocent. Our results therefore substantially enhance the scope for this class of redox-active ligands.Layering AgNO3 in alcohol onto octavinylsilsesquioxane (OVS) in CHCl3 results in a one-dimensional coordination polymer, Ag4(NO3)4(OVS)·solventsn (SD/Ag4a-d), consisting of unprecedented flat weakly bonded Ag4(NO3)4 alternating with the firmly covalent OVS through AgI-πC═C bonds. The preferential assembling medium for SD/Ag4a is proven to be alcohols, where a 41 silver-OVS adduct is detected by electrospray ionization mass spectrometry. The present outcomes may assist our knowledge of particular interactions for supramolecular architectures of a polynuclear silver system built from OVS containing eight pendent olefin tails.We report a unique dynamic morphology transformation of a Ag+-coordinated supramolecular nanostructure accompanying the conversion of complex structures in aqueous solution. In the presence of AgNO3 (1.0 equiv), the achiral bipyridine-based ligand 1G, possessing hydrazine and glycine moieties, preferentially generated a 1D needle-like structure (nanostructure I) based on the 1GAgNO3 complex (1GAg+ = 11) as a metastable product. Nanostructure I was then transformed into nanostructure II, which was composed of the 1G3Ag2(NO3)2 complex (1GAg+ = 32) as the thermodynamically stable product. This nanostructure exhibited a 1D helical tubular structure with a uniform diameter via a 2D ribbon as an intermediator, which led to the generation of a circular dichroism (CD) signal with right-handed (P-type) helicity. The observed dynamic transformation was attributed to formation of the thermodynamically favored helical 1G3Ag2(NO3)2 complex. In addition, the helical 1G3Ag2(NO3)2 complex acted as an initiator in the transfoorphology transformation process in biological systems.Amorphous coordination polymers and metal-organic frameworks (MOFs) have attracted much attention owing to their various functionalities. Here, we demonstrate the tunable water adsorption behavior of a series of amorphous cyanide-bridged MOFs with different metals (M[Ni(CN)4] MNi; M = Mn, Fe, and Co). All three compounds adsorb up to six water molecules at a certain vapor pressure (Pads) and undergo conversion to crystalline Hofmann-type MOFs, M(H2O)2[Ni(CN)4]·4H2O (MNi-H2O; M = Mn, Fe, and Co). The Pads of MnNi, FeNi, and CoNi for water adsorption is P/P0 = 0.4, 0.6, and 0.9, respectively. Although the amorphous nature of these materials prevented structural elucidation using X-ray crystallography techniques, the local-scale structure around the N-coordinated M2+ centers was analyzed using L2,3-, K-edge X-ray absorption fine structure, and magnetic measurements. Upon hydration, the coordination geometry of these metal centers changed from tetrahedral to octahedral, resulting in significant reorganization of the MOF local structure. On the other hand, Ni[Ni(CN)4] (NiNi) containing square-planar Ni2+ centers did not undergo significant structural transformation and therefore abruptly adsorbed H2O in the low-pressure region. We could thus define how changes in the bond lengths and coordination geometry are related to the adsorption properties of amorphous MOF systems.The ability for biologics to access intracellular targets hinges on the translocation of active, unmodified proteins. This is often achieved using nanoscale formulations, which enter cells through endocytosis. This uptake mechanism often limits the therapeutic potential of the biologics, as the propensity of the nanocarrier to escape the endosome becomes the key determinant. To appropriately evaluate and compare competing delivery systems of disparate compositions, it is therefore critical to assess endosomal escape efficiencies. Unfortunately, quantitative tools to assess endosomal escape are lacking, and standard approaches often lead to an erroneous interpretation of cytosolic localization. In this study we use a split-complementation endosomal escape (SEE) assay to evaluate levels of cytosolic caspase-3 following delivery by polymer nanogels and mesoporous silica nanoparticles. In particular, we use SEE as a means to enable the systematic investigation of the effect of polymer composition, polymer architecture (random vs block), hydrophobicity, and surface functionality. Although polymer structure had little influence on endosomal escape, nanogel functionalization with cationic and pH-sensitive peptides significantly enhanced endosomal escape levels and, further, significantly increased the amount of nanogel per endosome. This work serves as a guide for developing an optimal caspase-3 delivery system, as this caspase-3 variant can be easily substituted for a therapeutic caspase-3 cargo in any system that results in cytosolic accumulation and cargo release. In addition, these data provide a framework that can be readily applied to a wide variety of protein cargos to assess the independent contributions of both uptake and endosomal escape of a wide range of protein delivery vehicles.We investigated chemical vapor-deposited (CVD) two-dimensional (2D) niobium diselenide (NbSe2) material for the resistive switching and synaptic characteristics. Three different atomic switch devices with Ag/HfO2/Pt, Ag/Ti/HfO2/Pt, and Ag/NbSe2/HfO2/Pt were studied as both memory and neuromorphic devices. Both the inserted Ti and NbSe2 buffer layers effectively control the stochastic Ag-ion diffusion, leading to suppressed variation of switching characteristics, which is a critical issue in an atomic switch device. Especially, the device with the 2D NbSe2 buffer layer strikingly enhanced the device reliability in both endurance and retention. In conjunction with scanning transmission electron microscopy (STEM) and energy-dispersive spectrometry (EDS) analysis of the control of the Ag-ion migration, it was understood that filament connection is interrelated with the SET and RESET processes. Besides resistive behaviors in the memory device, various synapse functions such as spike-rate-dependent plasticity (SRDP), forgetting curve, potentiation, and depression were demonstrated with an atomic switch with the 2D NbSe2 buffer layer. Furthermore, the emulated long-term synaptic property was simulated using the MNIST 28 × 28 pixel database. Using adopting a CVD 2D NbSe2 blocking layer, the stochastic Ag-ion diffusion behavior is well-controlled and therefore stable switching and synapse functions are attained.Hollow multimetallic noble nanoalloys with high surface area/volume ratio, abundant active sites, and relatively effective catalytic activity have attracted considerable research interest. Traditional noble nanoalloys fabricated by hydro-/solvothermal methods usually involve harsh synthetic conditions such as high temperatures and intricate processing. We proposed a simple and mild strategy to synthesize platinum- and palladium-decorated hollow gold-based nanoalloys by the galvanic replacement reaction (GRR) at room temperature using hollow gold nanoparticles as templates and mercury as an intermediate. The hollow gold nanoparticles were essential for increasing the number of surface-active sites of the obtained multimetallic nanoalloys, and the introduction of mercury can eliminate the influence of the electrochemical potential of Pt/Pd with Au in the GRRs, increase alloying degrees, and maintain the nanoalloys that exhibit the hollow nanostructures. The structural characterizations of the hollow nanoalloys were studied by means of high-angle annular dark-field scanning transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. On the basis of the electrochemical catalytic measurements, the platinum-exposed nanoalloys were found to have excellent electrocatalytic activities. Especially in the presence of palladium, owing to the synergistic effect, the quaternary AuHgPdPt hollow nanoalloy displayed a low overpotential of 38 mV at 10 mA cm-2 with a small Tafel slope of 56.23 mV dec-1 for the alkaline hydrogen evolution reaction. In addition, this approach not only expands the application range of the galvanic replacement reaction but also provides new ideas for the preparation of multialloys and even high-entropy alloys at room temperature.Mitophagy has a pivotal protective function in the pathogenesis of neurological disorders. However, the mechanism of its modulation remains elusive, especially in PINK1-mediated mitophagy. Here, we investigated the neuroprotective effects of a walnut-derived peptide, YVLLPSPK, against scopolamine-induced cognitive deficits in mice and explored the underlying PINK1-mediated mitophagy mechanisms in H2O2-treated HT-22 cells. Using the Morris water maze, we showed that YVLLPSPK relieved the cognitive deficiency by alleviating oxidative stress. Mitochondrial morphology was observed in mice hippocampal tissues using transmission electron microscopy (TEM). Both Western blot and immunofluorescence analysis illustrated YVLLPSPK promoted the expression of mitophagy-related proteins and activated the NRF2/KEAP1/HO-1 pathway. Subsequently, an NRF2 inhibitor (ML385) was used to verify the contribution of the YVLLPSPK-regulated NRF2/KEAP1/HO-1 pathway in PINK1-mediated mitophagy in H2O2-treated HT-22 cells. These data suggested that YVLLPSPK improved learning and memory in scopolamine-induced cognitive-impaired mice through a mechanism associated with PINK1-mediated mitophagy via the NRF2/KEAP1/HO-1 pathway.Aliphatic polycarbonates have gained increased attention as biomaterials largely owing to their biocompatibility and tunable degradation. Moreover, the ability to introduce functional handles in the polymer backbone through careful design of cyclic carbonate monomers or copolymerization with other biodegradable polymers has significantly contributed to the interest in exploiting this class of materials for biomedical applications. Such investigations have enabled their utility to be expanded to a wide variety of applications in the biomedical field, from drug delivery to tissue regeneration and the design of vascular grafts. Herein, we review the synthesis, degradation, and studies into biomedical applications of aliphatic polycarbonates obtained by ring-opening polymerization of cyclic carbonate monomers (ring sizes between 6 and 8). While all synthetic methods will be covered, particular emphasis will be given to materials that have been exploited for therapeutic applications in vitro and in vivo.Recently, traditional flame retardant finishing with a single metal compound has been rarely applied owing to its low effectiveness and durability. This study reports metal ion finishing in combination with surface photografting modification (M/P technology) as a novel approach to incorporate an inorganic-organic hybrid structure containing an Fe3+ ion onto the surface of the polyamide (PA) 66 fabric. Specifically, the PA fabric was first surface-modified in the presence of acrylic acid (AA) and N,N'-methylene bisacrylamide (MBAAn) during photografting pretreatment under UV irradiation (step I), then further reacted with the Fe3+ ion in the metal ion finishing (step II). After treatment with M/P technology, the fabric exhibits the required excellent flame retardancy and dripping resistance. Here, flame retardant tests show that the treated PA fabric has the highest limiting oxygen index (LOI) value of 33.4 and no melt dripping during combustion. An interesting inorganic/organic composite thermal barrier consisting of an inorganic iron oxide nanoparticle (NP) outer layer and an organic micro-intumescent inner layer can be observed on the surface of the burnt fabric.
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