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The nanomaterial has been well characterized by different spectroscopic and microscopic studies. The obtained nanoparticles also exhibit substantial pH-responsive behaviors in aqueous medium and show better susceptibility as compared to the free organic indicator. Thus, this report explores detailed studies on the IL-based indicator in sensing the acidity/basicity of various media.The nanostructure in water solutions of three organic ionic liquids relevant for biological applications has been studied by molecular dynamics simulations based on empirical force fields. The three compounds consisted of two different triethylammonium salts, known to affect the fibrillation kinetics of Aβ peptides, and a phosphonium dication, which has been shown to possess a marked bactericidal activity. The structure of solutions spanning a wide concentration range (from 25 to 75 wt%) has been analysed by computing several combinations of partial structure factors, measuring the fluctuation of the ion and water distribution in space. At moderate salt concentration, the results reflect the formation in water of salt-rich domains of nanometric size. find more With salt concentration increasing beyond 50 wt%, the system enters the so-called water-in-salt regime, in which the aggregation properties of water become relevant, giving origin to water-rich domains in the nearly uniform salt environment. The persistence over a wide concentration range of nearly integer (∼6; ∼4) water-ion coordination numbers suggests the formation of stoichiometric liquid ionic hydrates.Obesity is a chronic and recurrent disease with potential risks. Traditional weight-loss methods (like exercises, surgeries, oral drugs, etc.) have shown different side effects. In this experiment, the microneedle (MN) patch was selected as the drug carrier of the weight-loss drug Rosiglitazone (Rosi). Besides, melanin was added to enhance the photo-thermal effect and accelerate the release of drugs to the target fat region under near-infrared (NIR) light. Afterwards, with exterior cold stimulation, the significant and accurate effect of body slimming could be achieved. This combination of soluble MN patches and variable temperatures provides an attractive nonsurgical method for future accurate body slimming management.A palladium-catalyzed redox-neutral allylic alkylation of indoles with cyclopropyl acetylenes has been disclosed. Various 1,3-diene indolenine framework bearing a quaternary stereocenter at the C3 position were synthesized straightforwardly in good to excellent yields with high regio- and stereoselectivities. The reaction could be further expanded to the dearomatization of naphthols to synthesize functionalized cyclohexadienones with 1,3-diene motifs. The reaction exhibited high atom economy and good functional group tolerance.Electron scattering on liquid samples has been enabled recently by the development of ultrathin liquid sheet technologies. The data treatment of liquid-phase electron scattering has been mostly reliant on methodologies developed for gas electron diffraction, in which theoretical inputs and empirical fittings are often needed to account for the atomic form factor and remove the inelastic scattering background. In this work, we present an alternative data treatment method that is able to retrieve the radial distribution of all the charged particle pairs without the need of either theoretical inputs or empirical fittings. The merits of this new method are illustrated through the retrieval of real-space molecular structure from experimental electron scattering patterns of liquid water, carbon tetrachloride, chloroform, and dichloromethane.Cancer cells are generally immersed in an oxidative stress environment with a high intracellular reduction level. Thus, nanocarriers with sequential responsiveness to oxidative and reductive species, matching the traits of high oxidation in the tumor tissue microenvironment and high reduction potential inside cancer cells, are highly desired for specific cancer therapy. Herein, we report a supramolecular nanomedicine comprised of a reduction-responsive nanoparticle (NP) core whose surface was modified by an oxidation-responsive polyethylene glycol (PEG) derivative via strong host-guest interactions. In this delicate design, the PEGylation of NPs not only reduced their immunogenicity and extended systemic circulation, but also enabled oxidation-responsive de-PEGylation in the tumor tissues and subsequent intracellular payload release in response to glutathione (GSH) inside tumor cells. As a proof of concept, this supramolecular nanomedicine exhibited specific chemotherapeutic effects against cancer in vitro and in vivo with a decent safety profile.Photosensitizers with high energy, long lasting charge-transfer states are important components in systems designed for solar energy conversion by multistep electron transfer. Here, we show that in a push-pull type, μ-oxo-bridged porphyrin heterodimer composed of octaethylporphyrinatoaluminum(iii) and octaethylporphyrinatophosphorus(v), the strong excitonic coupling between the porphyrins and the different electron withdrawing abilities of Al(iii) and P(v) promote the formation of a high energy CT state. Using, an array of optical and magnetic resonance spectroscopic methods along with theoretical calculations, we demonstrate photodynamics of the heterodimer that involves the initial formation of a singlet CT which relaxes to a triplet CT state with a lifetime of ∼130 ps. The high-energy triplet CT state (3CT = 1.68 eV) lasts for nearly 105 μs prior to relaxing to the ground state.Tumor microenvironment responsive and self-monitored multimodal synergistic theranostic strategies can significantly improve therapeutic efficacy by overcoming biological barriers. Herein, we report a type of smart fluorescent hyaluronic acid nanogel that can respond to the reducing microenvironment and activate tumor targeting with light-traceable monitoring in cancer therapy. First, the derivative of hyaluronic acid (HA) with a vinyl group and cystamine bisacrylamide were used to synthesize bioreducible HA based nanogels via copolymerization in aqueous medium. Then, multifunctional mHA-gold cluster (mHA-GC) hybrid nanogels were successfully prepared by the in situ reduction of gold salt in the HA nanogels. The HA matrix turns the nanogels into a capsule for effective drug loading with excellent colloidal stability. Interestingly, the reducing tumor microenvironment dramatically enhanced the fluorescence signal of gold clusters in the hybrid nanogels. The highly selective cancer cell uptake and efficient intratumoral accumulation of the hybrid nanogels were demonstrated by fluorescence tracking of these nanogels. Responsive disassembly of the hybrid nanogels and drug release were triggered by excess glutathione presence in cancer cells. Moreover, in vivo and in vitro tumor suppression assays revealed that the doxorubicin-loaded hybrid nanogels exhibited significantly superior tumor cell inhibition abilities compared to free DOX. Overall, the mHA-GC hybrid nanogels emerge as a promising theranostic nanoplatform for the targeted delivery and controlled release of antitumor drugs with light-traceable monitoring in cancer treatment.The emergence of nanofluidics in the last few decades has led to the development of various applications such as water desalination, ultrafiltration, osmotic energy conversion, etc. In particular, understanding water molecule transport in nanotubes is of importance for designing novel ultrafiltration and filtering devices. In this paper, we use an electric field to form a nanoscale water bridge as an artificial water channel to connect two separate disjoint nanotubes by molecular dynamics simulations. link2 The extended length of the water bridge under different electric field strengths could adjust the diffusion process of the water molecules crossing the two disjoint nanotubes and the diffusion coefficients could be remarkably enhanced up to 4 times larger than the value in bulk water. By analyzing the structure of the water bridge, it is found that the diffusion enhancement originates from the strengthened interactions and the increase of hydrogen bonds between the water molecules due to the restrained reorientation from the external electric field. Our result provides a promising insight for realizing an efficient mass transport between various disjoint nanochannels.Paramagnetic colloidal spheres assemble to colloidal bipeds of various length in an external magnetic field. When the bipeds reside above a magnetic pattern and we modulate the direction of the external magnetic field, the rods perform topologically distinct classes of protected motion above the pattern. The topological protection allows each class to be robust against small continuous deformations of the driving loop of the external field. We observe motion of the rod from a passive central sliding and rolling motion for short bipeds toward a walking motion with both ends of the rod alternately touching down on the pattern for long bipeds. The change of character of the motion occurs in form of discrete topological transitions. The topological protection makes walking a form of motion robust against the breaking of the non symmorphic symmetry. In patterns with non symmorphic symmetry walking is reversible. In symmorphic patterns lacking a glide plane the walking can be irreversible or reversible involving or not involving ratchet jumps. Using different gauges allows us to unravel the active and passive aspects of the topological walks.An approach to quantitatively analyze the factors contributing to the activation of aggregation-induced emission (AIE) of a molecule is proposed using molecular simulations. A cyanostilbene derivative, 1-cyano-1,2-bis-(4'-methylbiphenyl)ethylene (CN-MBE), has two isomers, E and Z forms. The E-form of CN-MBE exhibits AIE, and is non-emissive in dilute solutions but becomes highly emissive in aggregated states. The Z-form is non-emissive, even in the solid state, that is, the E-form of CN-MBE is AIE-active, while its Z-form is AIE-inactive. In this study, the free energy profiles of the AIE processes of the E and Z forms of CN-MBE are investigated using the free energy perturbation method at the quantum mechanics/molecular mechanics level. The free energy profiles reveal significant differences in the extent to which steric hindrance from surrounding molecules restricts the intramolecular motions of the E and Z forms in the aggregated states. link3 The structural features of the E and Z forms are characterized based on the conformational changes in the excited state relaxation process to reach the conical intersections and the free volume space around the molecules in the aggregated states. This study determines the contributing factors that cause the AIE activity of the molecule by identifying characteristic differences in the free energy profiles of the AIE processes of the AIE-active E-form of CN-MBE and the inactive Z-form. The approach used in this study can be applied to the rational design of highly efficient AIE luminogens utilizing computer modeling.Next generation lithium ion batteries are envisaged as those which feature an all solid-state architecture. This will enable the higher energy density storage required to meet the demands of modern society, especially for the growing electric vehicle market. Solid state batteries have, however, proved troublesome to implement commercially due to the lack of a suitable solid-state electrolyte, which needs to be highly conductive, have a low interfacial resistance and a suitably wide electrochemical stability window. Garnet materials are potential contenders for these batteries, demonstrating many of the desired properties, although there remain challenges to overcome. Here we report a facile synthesis of Li7La3Hf2O12 and Ga/AlxLi7-3xLa3Hf2O12 garnets, with the synthesis of Ga0.2Li6.4La3Hf2O12 requiring only dissolution of precursors in water and heating to 700 °C. Ga0.2Li6.4La3Hf2O12 was shown to display a high room temperature conductivity (0.373 mS cm-1 at 28 °C). Moreover, in Li|garnet|Li cells, we observed a comparable critical current density compared to Ga0.
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