As with runoff, chum salmon appeared insensitive to TWP leachate at concentrations lethal to coho. Our results confirm that environmentally relevant TWP exposures cause acute mortalities of a keystone aquatic species.The reactivities of [Mn(13-TMC)(OOH)]2+ (1) and [Mn(13-TMC)(O2)]+ (2) in the sulfoxidation of thioanisole have been compared using density functional theory methods. The orientation of the 13-TMC ligand and substrate and non-redox metal ion effects have been considered to improve the oxidation efficiency of 1 and 2. In 1, the syn- and anti-orientation of the 13-TMC ligand do not change the coordination of the Mn ion. In contrast, the orientation of the 13-TMC ligand regulates the geometry of 2, wherein the syn-13-TMC ligand exhibits the MnIII-peroxo (2hs and 2ls) species, while the anti-13-TMC shows the MnII-superoxo (2’hs and 2’ls) species. However, the MnII-superoxo species are found to be less stable than the MnIII-peroxo complexes by around +26.6 kcal/mol. The ground state geometries of 1 and 2 with the syn-13-TMC ligand are found to be more stable in the high- (S = 2) spin states (1hs and 2hs) than the low- (S = 1) spin complexes (1ls and 2ls), by +15.6 and +25.5 kcal/mol, respectively. The computed mechreases the ΔG‡ of 2hs by 58.7%, which is in fact lower than the ΔG‡ of 1hs by +2.0 kcal/mol. Hence, in the presence of Y3+, the reactivity of 2hs is comparable with 1hs in the sulfoxidation of thioanisole.Biological functions are related to long-time protein dynamics (rare events) that are induced over microseconds. Such protein dynamics can be investigated using molecular dynamics (MD) simulations. However, the detection of rare events remains challenging using conventional MD (cMD) since the accessible timescales of cMD are shorter than those of the biological functions. Recently, the parallel cascade selection MD (PaCS-MD) has been proposed to detect such rare events, wherein transition paths are generated between a given reactant and product. As an extension, the nontargeted PaCS-MD (nt-PaCS-MD) has been proposed to predict the transition paths without requiring reference to any product. Thus, as a further extension, we herein propose independent nt-PaCS-MD, namely, Ino-PaCS-MD, wherein multiple walkers are launched from a set of different starting configurations. Each walker repeats a cycle of restarting short-time MD simulations from configurations with high potentials for making transitions to neighboring metastable states. To further enhance the sampling ability, Ino-PaCS-MD temporarily stops the conformational search and periodically resets the starting configurations so that they are uniformly distributed in a conformational subspace, thereby preventing a given protein from being trapped in one of the metastable states. As a demonstration, Ino-PaCS-MD successfully detects rare events of a maltose-binding protein as open-close transitions with a nanosecond-order simulation time, although a microsecond-order cMD simulation failed to detect these rare events, showing the high sampling efficiency of Ino-PaCS-MD.Integrating characteristics of materials through constructing artificial superlattices (SLs) has raised extensive attention in multifunctional materials. Here, we report the synthesis of BiFeO3/BiMnO3 SLs with considerable ferroelectric polarizations and tunable magnetic moments. The polarization of BiFeO3/BiMnO3 SLs presents a decent value of 12 μC/cm2, even as the dimensionality of BiFeO3 layers per period is reduced to about five-unit cells when keeping the BiMnO3 layers same. Moreover, it is found that the tunable magnetic moments of SLs are linked intimately to the dimensionality of BiFeO3 layers. Our simulations demonstrate that the superexchange interaction of Fe-O-Mn tends to be antiferromagnetic (AFM) with a lower magnetic domain formation energy rather than ferromagnetic (FM). Therefore, as the dimensionality of BiFeO3 per period is reduced, the AFM superexchange interaction between BiFeO3 and BiMnO3 in the SLs becomes weak, promoting a robust magnetization. This interlayer modulation effect in SLs presents an alluring way to accurately control the multiple order parameters in a multiferroic oxide system.Targeting peptides are a promising tool for early diagnosis and therapy of cancer. Overexpression of urokinase plasminogen activator receptor (uPAR) leads to the progression of tumors including prostate, colorectal, ovarian, and breast cancers. To improve the diagnosis and imaging efficiency, herein we report a stable nanocomplex comprising methoxy-PEG-hydrazide (mPEG-H-M)-modified gold nanoparticles (AuNPs) conjugated to uPAR (urokinase plasminogen activator receptor)-targeting peptides GFD (growth factor domain-G) and SMB (somatomedian B-S) for efficient imaging of uPAR-overexpressing cancer cells. Fluorescently labeled targeting peptides were covalently linked to mPEG-H coated AuNPs, characterized, and analyzed by UV-vis spectroscopy, diffraction light scattering (DLS), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and fluorescence spectroscopy. In vitro evaluation was assessed with a fluorescence-activated cell sorter (FACS), cell adhesion, and fluorescence microscopy. The peptide-functionalized nanocomplex showed a higher uptake of AuNPs@MGS in comparison with AuNPs@G or AuNPs@S alone in uPAR-overexpressing cells and exhibits no toxicity when analyzed with MTT assay. Our results demonstrated that the developed nanocomplex can be used as a platform for imaging and diagnosis of metastatic tumors.Room temperature phosphorescence (RTP) as a fascinating phenomenon shows great potential toward multiple applications. Howbeit, it is challengeable to improve the phosphorescence efficiency of carbon dots (CDs) owing to their short lifetime. Herein, we proposed a facile, rapid, and gram-scale strategy to synthesize the cross-linked carbon dots (named N-CDs) with both bright blue fluorescence and green RTP emissions. To be specific, the polymer of polyethylenimine (PEI) served as the cross-linking agent and carbon source, during which process phosphoric acid accelerated the formation of the compact carbon core within 30 s. Subsequently, the cross-linked carbon dots with the rigid network formed a small singlet-triplet energy splitting (ΔEST) of 0.490 eV, thus exhibiting a long RTP lifetime of 429.880 ms while coated on the filter paper through the hydrogen bonds. Taking advantage of the double luminescence, we successfully achieved the dual-channel detection of promethazine by N-CDs. The fluorescence of N-CDs was obviously quenched by promethazine through the electron-transfer process, displaying the linear range from 0.4 to 8 mM. Significantly, the electron transfer (ET) from carbon dots to promethazine boosted their phosphorescence efficiency and prolonged the lifetime to 565.190 ms, and the enhanced phosphorescence facilitated the sensitive recognition of promethazine with the concentration range of 1-3000 μM. Meanwhile, the possible autofluorescence interference from biological samples could be avoided through this RTP assaying mode, providing the more accurate results. Also, their RTP and fluorescence endowed the current N-CDs with the ability of dual-signal painting and imaging. This strategy may broaden the new approaches to produce the long-lifetime and high-efficiency RTP material toward the sensing purpose.A thermally reversible nanogel is used in capillary electrophoresis to create discrete regions for a galactosyltransferase reaction and separation. The β1-4 galactosyltransferase enzyme, donor, and co-factor were patterned in the capillary. The substrate was driven through these zones and converted to galactosylated products, which were separated and identified. Using this capillary electrophoresis method, the degree of glycosylation was discernible for a pentasaccharide and for biantennary N-glycans. With the ability to distinguish between reaction products for which either one or two galactose residues were transferred, the capillary nanogel electrophoresis system was used to determine the Michaelis-Menten value, KM. For the β1-4 galactosyltransferase, the KM value obtained for a pentasaccharide substrate was 1.23 ± 0.08 mM. Once KM was established, the enzyme/substrate ratio was evaluated to add a single galactose residue or to fully galactosylate a biantennary N-glycan. Additionally, capillary nanogel electrophoresis was adapted to transfer galactose residues to protein. The applicability of the method for real-time online modification of whole protein was demonstrated with the Herceptin glycoprotein. Complete retardation by Erythrina cristagalli lectin after enzymatic modification confirmed the addition of galactose residues to the Herceptin. This demonstrated the potential of the method to be used for online modification of other glycoproteins.Rewritable paper has greatly promoted the sustainable development of society. However, the hydrophilicity/lipophilicity of the poly(3,4-ethylenedioxythiophene) (PEDOT) film limits its application as the rewritable paper. Herein, we constructed a repeatable writing/erasing pattern on a PEDOT film (rewritable PEDOT paper) by combining wettability control, water-induced dedoping, and an electrochemical redox reaction. The treatment with a medium-polarity/high-volatility solvent (MP/HVS) adjusted the wettability of the PEDOT film (water contact angle increased from 6.5° to 146.2°), contributing to the formation of a hydrophobic writable substrate. The treatment with a high-polarity solvent (HPS) induced the dedoping of anions in the PEDOT chain, resulting in the film’s color changed from blue to purple and serving as a writing process. The intrinsic electrochemical redox (elimination of color change by doping/dedoping of lithium ions in the PEDOT chain) of the PEDOT film enabled the erasing process. This writing/erasing process can be repeated at least 10 times. The patterned PEDOT film maintained excellent stability to standing diverse solvents (low-polarity solvent (LPS) and MP/HVS), high temperatures (350 °C), and irradiation of different light wavelengths (wavelengths of 365, 380, 460, 520, and 645 nm). Additionally, the conductivity of the PEDOT film was quantitatively measured (impedance LPS, increased 8.84%; MP/HVS, decreased 6.67%; and HPS, increased 27.97%) by fabricating a micropatterned PEDOT electrode. This work will provide a method for the fabrication of PEDOT-based optoelectronic functional materials.The γ radiolysis behavior of polydimethylsiloxane (PDMS) in the radiation-thermal environments (dose rate, 0.2 Gy/s) is studied to pinpoint the basic knowledge of the temperature (20-70 °C) effects. The non-monotonous temperature effects on the formation of gas products, paramagnetic species in silica, and cross-linking density are proposed to correlate with the complex chemical reaction mechanisms. Besides, molecular dynamics simulation and theoretical calculation are first performed simultaneously based on the radical chemistry and intricate material composition, making it easier to comprehend and further harness the radiolysis mechanisms and structure deterioration of PDMS. The γ radiation-induced primary gas products and dominant cross-linking phenomena are reproduced by the molecular dynamics simulations with a reactive force field, and the reaction mechanisms and physicochemical interactions among PDMS chains, gas products, reactive radicals, and silica fillers are thoroughly studied at the atomic scale.