The Royal Society of Chemistry最新文献

Metal-free donor-acceptor photocatalysts enable efficient O-ATRP under visible light, allowing for precise control over polymer molecular weight with low dispersity. These photocatalysts achieve sufficient reductive potential to drive the reaction in their charge-transfer (CT) excited state. The reported efficient photocatalytic O-ATRP has significant potential in scalable polymer synthesis and photolithography.

Viscosity is a crucial indicator of the flow state of proteins, lipids, and polysaccharides in the cell microenvironment and plays a vital role in maintaining normal cellular activities. Abnormal viscosity in any part of the cell constituents can lead to various diseases in the organism. For instance, abnormal mitochondrial viscosity can lead to diseases, such as diabetes and Parkinson's disease. Therefore, real-time monitoring of changes in mitochondrial viscosity in both pathological and physiological environments is relevant. This study describes a water-soluble xylan-based near-infrared fluorescence probe that can detect changes in cellular viscosity. The designed mitochondria-targeting near-infrared fluorophores were introduced into modified xylan to form a viscosity-sensing fluorescent probe (NI-XylV). The fluorescence intensity of NI-XylV at 590 and 670 nm gradually increases with an increase in viscosity caused by environmental changes, enabling the sensitive detection of viscosity changes in mitochondria within living cells. NI-XylV exhibits good photostability, biocompatibility, excellent mitochondrial targeting, and broad application prospects as a bio-based fluorescence probe.

To enhance the electrochemical stability and kinetics of V₂O₅, 3,4-ethylenedioxythiophene (EDOT) was in situ polymerized within V₂O₅ interlayers, rendering PEDOT@V₂O₅ with enlarged layer spacing, increased stability in organic electrolyte, and superior electrochemical kinetics (bleaching/coloration times 10.9/9.1 s) and cyclability (98.5% ΔT and 85.6% capacity retention after 1000 cycles) in a PEDOT@V₂O₅‖Zn electrochromic device.

The fast and reliable detection, segmentation and visualization of latent fingerprints are the main tasks in forensics. Currently, conventional fingerprints are searched for, recorded and subsequently analyzed via traditional destructive physical and chemical methods. For firmly defined crime objects and undefined crime scenes, the forensic process is very time-consuming and can take several hours for a single fingerprint. In this context, a laser-based measurement technique that records complete latent fingerprints under fifteen seconds in a non-destructive manner was developed that digitizes the fingerprint for postprocessing steps. The optical system is based on confocal measurements in the mid-infrared wavelength range (2 μm-4 μm) to analyze specific chemical substances at crime scenes. The resulting chemical segmentation allows molecule-dependent analysis of latent and visually invisible fingerprints, providing clear conclusions about the perpetrator or the course of the crime. In this study, the application of the developed measurement system (MIR scanner) to capture fingerprints in a molecule-dependent manner within few seconds is demonstrated, compared with reference methods such as FTIR (Fourier transform infrared spectroscopy) imaging, and extended to real crime objects.

A new series of aminodiols, aminotetraols and 1,2,3-triazoles based on allo-gibberic acid were synthesized in a stereoselective manner, starting from commercially available gibberellic acid. allo-Gibberic acid, prepared from gibberellic acid according to a literature method, was applied to SeO₂/t-BuOOH-mediated allylic oxidation, yielding the triol, which is a key intermediate. After protecting the 1,4-diol functionality as acetonide, epoxidation was performed using either m-CPBA or t-BuOOH/VO(acac)₂ to produce the epoxy alcohol. Then, the oxirane ring was opened with either primary amines to provide aminodiols or sodium azide to afford azido diols. The latter was subjected to the CuAAC reaction to obtain dihydroxy 1,2,3-triazoles. HCl-mediated acetonide deprotection of the prepared derivatives furnished aminotetraols and tetrahydroxy 1,2,3-triazoles. The antiproliferative effects of the prepared compounds were studied by the in vitro MTT method against a panel of human cancer cell lines (HeLa, SiHa, A2780, MCF-7 and MDA-MB-231) and fibroblasts, and the structure–activity relationships for the prepared compounds were explored.

Direct magnetic writing of ferromagnetic nanoscale elements provides an alternative pathway for potential application in data storage or spintronic devices. Magnetic patterning due to local chemical disordering of Fe₆₀Al₄₀ thin films results in adjacent nanoscale regions that possess two different phases, viz. a low-magnetization and high-coercive chemically ordered phase (non-irradiated ferromagnetic area, NIFM) and a high-magnetization and low-coercive chemically disordered phase (irradiated ferromagnetic area, IMF). Depending on the volume of NIFM and IFM phases, different interaction mechanisms were revealed. It was shown that the modulated films of the coexisting magnetic phases do not lead to exchange coupling in most cases. Evidence for exchange-spring behaviour, however, was found. Moreover, both magneto-structural phases at low temperatures show spin-glass-like properties. Understanding the influence of chemical ordering on magnetic properties is crucial for the advancement of the functionalities of spintronic devices and for the development of alloys with controllable magnetic properties.

Sugar mimics are valuable tools in medicinal chemistry, offering the potential to overcome the limitations of carbohydrate inhibitors, such as poor pharmacokinetics and non-selectivity. In our continued efforts to develop heterocyclic galectin-1 inhibitors, we report the synthesis and characterization of thiazole-linked coumarin piperazine hybrids (10a–10i) as Gal-1 inhibitors. The compounds were characterized using ¹H NMR, ¹³C NMR and HRMS. Among the synthesized molecules, four compounds demonstrated significant inhibitory activity, with more than 50% inhibition observed at a concentration of 20 μM in a Gal-1 enzyme assay. Fluorescence spectroscopy was further utilized to elucidate the binding constant for the synthesized compounds. 10g exhibited the highest affinity for Gal-1, with a binding constant (K_a) of 9.8 × 10⁴ M⁻¹. To elucidate the mode of binding, we performed extensive computational analyses with 10g, including 1.2 μs all-atom molecular dynamics simulations coupled with a robust machine learning tool. Our findings indicate that 10g binds to the carbohydrate binding site of Gal-1, with the coumarin moiety playing a key role in binding interactions. Additionally, our study underscores the limitations of relying solely on docking scores for conformational selection and highlights the critical importance of performing multiple MD replicas to gain accurate insights.

The integration of wearable devices, the Internet of Things (IoT), and advanced sensing platforms implies a significant paradigm shift in technological innovations and human interactions. The IoT technology allows continuous monitoring in real time. Thus, Internet of Wearables has made remarkable strides, especially in the field of medical monitoring. IoT-enabled wearable systems assist in early disease detection that facilitates personalized interventions and proactive healthcare management, thereby empowering individuals to take charge of their wellbeing. Until now, physical sensors have been successfully integrated into wearable devices for physical activity monitoring. However, obtaining biochemical information poses challenges in the contexts of fabrication compatibility and shorter operation lifetimes. IoT-based electrochemical wearable sensors allow real-time acquisition of data and interpretation of biomolecular information corresponding to biomarkers, viruses, bacteria and metabolites, extending the diagnostic capabilities beyond physical activity tracking. Thus, critical heath parameters such as glucose levels, blood pressure and cardiac rhythm may be monitored by these devices regardless of location and time. This work presents versatile electrochemical sensing devices across different disciplines, including but not limited to sports, safety and wellbeing by using IoT. It also discusses the detection principles for biomarkers and biofluid monitoring, and their integration into devices and advancements in sensing interfaces.

This study investigated microplastic polyester fibres representative of those shed during laundering as sorbents for metal ions. During sewage distribution and treatment, microplastics are exposed to elevated concentrations of metal ions, typically for several days. Cryogenic milling was used to generate polyethylene terephthalate (PET) fibres. Characterisation using optical microscopy and Raman spectroscopy revealed that milling did not cause significant chemical alteration to the fibres. Milled fibres were subsequently assessed in screening tests for their capacity to retain 12 metal ions-Sb(III), As(III), Cd(II), Cr(VI), Cu(II), Co(II), Pb(II), Hg(II), Mo(VI), Ni(II), V(V) and Zn(II)-at pH 8. All metal ions were sorbed onto PET fibres. The highest distribution coefficient (K_d) was observed for Pb²⁺ (939 mL g^-1), followed by Cd²⁺ (898 mL g^-1), Cu²⁺ (507 mL g^-1), Hg²⁺ (403 mL g^-1), and Zn²⁺ (235 mL g^-1). The extent of sorption is largely explicable by electrostatic interactions between the PET surface (1.95 point of zero net charge) and the predicted metal ion species. The sorption behaviour of Cd²⁺ and Hg²⁺ was examined in more detail since both showed high sorption capacity and are highly toxic. Kinetic experiments revealed that the sorption of both elements was relatively fast, with a steady state reached within six hours. Experimental data from isotherm tests fitted well to the Langmuir sorption model and demonstrated that PET fibres had a much greater sorption capacity for Hg²⁺ (17.3-23.1 μg g^-1) than for Cd²⁺ (4.3-5.3 μg g^-1). Overall, the results indicate that retention of metal ions onto PET fibres originating from laundry is expected during full-scale sewage treatment, which facilitates the subsequent transfer of metals into the terrestrial environment, given that sewage sludge is commonly applied to agricultural land.

M-N₄-C single-atom catalysts (MN₄) have gained attention for their efficient use at the atomic level and adjustable properties in electrocatalytic reactions like the ORR, OER, and HER. Yet, understanding MN₄'s activity origin and enhancing its performance remains challenging. Edge-doped substituents profoundly affect MN₄'s activity, explored in this study by investigating their interaction with MN₄ metal centers in ORR/OER/HER catalysis (Sub@MN₄, Sub = B, N, O, S, CH₃, NO₂, NH₂, OCH₃, SO₄; M = Fe, Co, Ni, Cu). The results show overpotential variations (0 V to 1.82 V) based on Sub and metal centers. S and SO₄ groups optimize FeN₄ for peak ORR activity (overpotential at 0.48 V) and reduce OER overpotentials for NiN₄ (0.48 V and 0.44 V). N significantly reduces FeN₄'s HER overpotential (0.09 V). Correlation analysis highlights the metal center's key role, with ΔG_*H and ΔG_*OOH showing mutual predictability (R² = 0.92). E_g proves a reliable predictor for Sub@CoN₄ (ΔG_*OOH/ΔG_*H, R² = 0.96 and 0.72). Machine learning with the KNN model aids catalyst performance prediction (R² = 0.955 and 0.943 for ΔG_*OOH/ΔG_*H), emphasizing M-O/M-H and the d band center as crucial factors. This study elucidates edge-doped substituents' pivotal role in MN₄ activity modulation, offering insights for electrocatalyst design and optimization.