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The local valence orbital structure of solid glycine, diglycine, and triglycine is studied using soft X-ray emission spectroscopy (XES), resonant inelastic soft X-ray scattering (RIXS) maps, and spectra calculations based on density-functional theory. Using a building block approach, the contributions of the different functional groups of the peptides are separated. Cuts through the RIXS maps furthermore allow monitoring selective excitations of the amino and peptide functional units, leading to a modification of the currently established assignment of spectral contributions. The results thus paint a new-and-improved picture of the peptide bond, enhance the understanding of larger molecules with peptide bonds, and simplify the investigation of such molecules in aqueous environment. [ABSTRACT FROM AUTHOR]

The occupied and unoccupied electronic structure of imidazole (C3N2H4) and imidazolium (C3N2H5+) in aqueous solutions is studied by X-ray emission spectroscopy (XES) and resonant inelastic soft X-ray scattering (RIXS). Both systems show distinct RIXS fingerprints with strong resonant effects. A comparison with calculated X-ray emission spectra of isolated imidazole and imidazolium suggests only a small influence of hydrogen bonding in the aqueous solution on the electronic structure of imidazole and imidazolium, and allows the attribution of specific spectral features to the non-equivalent nitrogen and carbon atoms in the molecules. In the case of nitrogen, this can also be achieved by site-selective resonant excitation. Furthermore, we find spectator shifts and symmetry selectivity in the RIXS spectra, as well as indications for rapid proton dynamics on the femtosecond timescale of the RIXS process, and derive the HOMO–LUMO gaps for the two molecules in aqueous solution. [ABSTRACT FROM AUTHOR]

The development of low-cost, earth-abundant, and high-efficiency catalysts for electrocatalytic water splitting is central to developing sustainable and clean energy. The abundant reserves of nickel sulfides are promising noble metal-free materials for the hydrogen evolution reaction (HER). In this work, a highly active cauliflower-like S-doped nickel microsphere film directly grown on a copper wire (CW) substrate (labeled as NiSx/CW) was facilely prepared via a one-step electrodeposition approach in a choline chloride/ethylene glycol (ethaline)-based deep eutectic solvent. Doping of S is found to induce an interesting structural transition from nanosheets to porous cauliflower-like microspheres, electronic structure changes at the surface, and a significant improvement in the HER catalytic performance. The as-prepared NiS0.25/CW with a Ni/S atomic ratio of 1 : 0.25 exhibits the best performance, showing a negligible onset potential (−18 mV) with a low overpotential (−54 mV at 10 mA cm−2) and small Tafel slope (54 mV dec−1) in 1.0 M KOH solution. Additionally, the NiS0.25/CW catalyst displays good durability and affords long-term electrolysis without activity degradation for 60 h. This study offers a facile synthesis route for in situ growth of the active phases on current collectors to fabricate self-supported noble-metal free HER catalysts and deep insights into the relationships among the S-doping, catalyst microstructure, and catalytic properties. [ABSTRACT FROM AUTHOR]

MnWO4 nano photocatalysts with plate shapes and in high yields are in situ synthesized on the surface of a porous TiO2 film by the conventional plasma electrolytic oxidation (PEO) method combined with a subsequent ambient annealing process. Transmission electron microscopy (TEM) analysis shows that the MnWO4 nano photocatalysts are single crystals free of structural defects and scanning electron microscopy (SEM) observation on the cross-section reveals that these MnWO4 nano photocatalysts are in situ grown on the porous TiO2 film surface with strong adhesion. The morphology and dimension size can be selectively tailored through controlling the reaction time, showing the simplicity and versatility of the proposed method. In addition, the photodegradation of methylene blue (MB) solution using the MnWO4/TiO2 photocatalysts demonstrated the superior photocatalytic performance with high efficiency and excellent photostability. A high photodegradation rate of MB solution of over 90% in 60 min has been achieved and a superior cyclic capability is also obtained. The superior photocatalytic performance of MnWO4/TiO2 photocatalysts can be mainly attributed to the good crystallinity, all-surface covering and strong mechanical properties of the MnWO4 nanostructures with TiO2 film. The prevailing advantage of the PEO method in combination with the ambient annealing process will open up more opportunity for the rational synthesis of a wide range of oxide photocatalysts ranging from tungstate to titanate, molybdate and vanadate for promising catalytic applications in diverse fields. [ABSTRACT FROM AUTHOR]

To probe the influence of hydrogen bonding on the electronic structure of ammonia, gas phase and aqueous NH3 have been investigated using soft X-ray absorption (XAS), resonant inelastic soft X-ray scattering (RIXS), and electronic structure calculations including dynamical effects. Strong spectral differences in the XAS scans as well as in the RIXS spectra between gas phase and aqueous NH3 are attributed to orbital mixing with the water orbitals, dipole–dipole interactions, differences in vibronic coupling, and nuclear dynamics on the time-scale of the RIXS process. All of these effects are consequences of hydrogen bonding and the impact of the associated orbitals, demonstrating the power of XAS and RIXS as unique tools to study hydrogen bonding in liquids. [ABSTRACT FROM AUTHOR]

In this paper, a simple small molecule (L) based on 4-(diethylamino)-2-hydroxy-benzaldehyde and carbohydrazide has been synthesized and characterized. Moreover, under ultrasonic conditions, a host–guest system with β-cyclodextrin and L was obtained. According to the hybridization process, the host–guest system showed excellent water solubility. The investigation of the fluorescence spectra revealed that the host–guest system exhibited a characteristic fluorescence behavior toward Al3+ in a pure water environment. Upon addition of Al3+, the host–guest system showed a strong blue fluorescence, which resulted from the fluorophore of L after the coordination of β-CD–L and Al3+ with a high binding constant (k = 3.1626 × 1011 M−1). In addition, SEM images demonstrated that the host–guest system expressed good crystallization behavior. Fluorescence microscope images of onion epidermal cells with β-CD–L–Al3+ proved that the water-soluble host–guest system possessed a high ability for cell permeability. [ABSTRACT FROM AUTHOR]

Since the performance of the micro-thermophotovoltaic (TPV) system is significantly limited by the mismatch between the radiation spectrum and the photovoltaic (PV) bandgap, for the first time, a wideband and angle-insensitive metamaterial filter was developed and optimized to address this issue. The developed filter was placed between the reactor and the PV cell and it was able to effectively transmit the valuable photons for power generation and reflect the worthless energy, thus offering great potential to improve the performance of the micro-TPV system. In particular, the filter is applicable for the entire near infrared wavelength range and exhibits extraordinary transmission. For the working wavelength applied in this paper, the obtained peak transmission coefficient from experiments is up to 88.3%. Furthermore, the efficiency of the micro-TPV system is also predicted to be enhanced more than twice with the metamaterial filter applied. Both the experimental and theoretical results show that the incorporation of the metamaterial filter with low bandgap PV cells can be a promising approach to improve the efficiency of the existing micro-TPV system. [ABSTRACT FROM AUTHOR]

A series of 2,6-bis(p-dialkylaminostyryl)-9,10-distyrylanthracene (FCn) cruciforms with N-alkyl chains of different lengths have been synthesized, and their aggregation-enhanced fluorescence and piezochromic luminescence (PFC) behaviours are investigated. These 9,10-distyrylanthracene-containing cruciforms exhibit relatively low fluorescence quantum yields (Φ) in THF solution (Φ≈ 10%) and moderate aggregation-enhanced emission in aqueous media (Φ≈ 25%), but strong and chain length-dependent solid-state fluorescence emission. Grinding and pressing experiments indicate that they are all effective PFC materials in terms of mechanical stress-induced spectral shifts (ΔλPFC = 23–54 nm), moreover, the longer alkyl-containing FCn shows a larger ΔλPFC. Powder X-ray diffraction and differential scanning calorimetry measurements reveal that the transformation between the crystalline and amorphous states upon external stimuli is responsible for the reversible PFC behaviour. It is found that increasing the N-alkyl length could effectively decrease the cold-crystallization temperature of the ground states to render the PFC states with a tunable heat-recovering temperature, and ground FC10 and FC12 solids can recover spontaneously to their original states at room temperature. [ABSTRACT FROM AUTHOR]

Magnetic-fluorescent microbeads have been widely used in the multiplex detection of biological molecules. The traditional method relies on flow cytometry to decode and analyze the microbeads. Alternative strategies that employ immobilized microbeads on a plane and involve fluorescence imaging to analyze the microbeads have been proposed. Among these strategies, an integrated chip that controls magnetic field contribution using nickel powder pillars and captured microbeads has attracted great attention. Despite its unique advantages such as low manufacturing costs, reusability and high capture efficiency, existing research had been limited by the inability to precisely capture a single microbead, and the overlapping of microbeads has made multiplex immunoassays based on this strategy impossible. In this work, low-density microbeads were prepared in a microfluidic chip using IBOMA as the main monomer. The low density of the microbeads made the preparation of an aqueous suspension easier. An integration of nickel patterns, magnets and channels was carried out and demonstrated the capacity of capturing single microbeads precisely. Fluorescence coding further empowered this method with the ability of multiplex immunoassay, which was verified using three types of IgG, and a calibration curve for the detection of anti-human IgG was established using a sandwich immunoassay. These results show the promising potential of this strategy for biomedical detection.

Intelligent luminescent materials for rewritable and programmable information display have long been expected to be used to address potential environmental concerns stemming from the extensive use of disposable displays. However, most reported luminescence-colour changeable examples are chemically responsive and not well programmed to sequentially deliver different information within a single system. Additionally, they may suffer from residual chemical accumulation caused by the repeated addition of chemical inks and usually have poor rewritability. Herein, we draw inspiration from the bioelectricity-triggered information display mechanism of chameleon skin to report a robust electrothermally powered polymer gel actuator consisting of one soft conductive graphene/PDMS film and one humidity-responsive fluorescence-colour changeable CD-functionalized polymer (PAHCDs) gel layer. Owing to the good electrocaloric effect of the bottom graphene film and excellent hygroscopicity of the top PAHCDs gel layer, the as-designed actuator could be facilely controlled to exhibit reversible and synergistic 3D-shape/fluorescence-colour changeable behaviours in response to alternating electricity and humidity stimuli. On this basis, robust rewritable information display systems are fabricated, which enable not only on-demand delivery of written information, but also facile rewriting of lots of different information by the synergization of electroheat/humidity-triggered local 3D-deformation and fluorescence-colour changes. This work opens new avenues of research into rewritable information display and potentially inspires the future development of intelligent luminescent materials.

Host-defense peptides (HDPs) and their analogs hold significant potential for combating multidrug-resistant (MDR) bacterial infections. However, their clinical use has been hindered by susceptibility to proteases, high production costs, and cytotoxicity towards mammalian cells. Synthetic polymers with diverse topologies and compositions, designed to mimic HDPs, show promise for treating bacterial infections. In this study, we explored the antibacterial activity and biocompatibility of synthetic amphiphilic linear (LPs) and cyclic terpolymers (CPs) containing hydrophobic groups 2-ethylhexyl (E) and 2-phenylethyl (P) at 20% and 30% content. LPs were synthesized via RAFT polymerization and then cyclized into CPs through a hetero-Diels-Alder click reaction. The bioactivity of these terpolymers was correlated with their topology (LPs vs. CPs) and hydrophobic composition. LPs demonstrated superior antibacterial efficacy compared to CPs against four Gram-negative bacterial strains, with terpolymers containing (P) outperforming those with (E). Increasing the hydrophobicity from 20% to 30% in the terpolymers increased toxicity to both bacterial and mammalian cells. Notably, our terpolymers inhibited the MDR Gram-negative bacterial strain PA37 more effectively than gentamicin and ciprofloxacin. Furthermore, our terpolymers were able to disrupt cell membranes and rapidly eliminate Gram-negative bacteria (99.99% within 15 minutes). Interestingly, CPs exhibited higher hemocompatibility and biocompatibility with mammalian macrophage cells compared to LPs, showcasing a better safety profile (CPs > LPs). These findings underscore the importance of tailoring polymer architectures and optimizing the hydrophilic/hydrophobic balance to address challenges related to toxicity and selectivity in developing antimicrobial polymers., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The hybridization state in solids often defines the critical chemical and physical properties of a compound. However, it is difficult to spectroscopically detect and evaluate hybridization beyond just general fingerprint signatures. Here, the valence-band hybridization of metal d-derived bands (short: "metal d bands") in selected metal sulphides is studied with a combined spectroscopic and theoretical approach to derive deeper insights into the fundamental nature of such compounds. The valence bands of the studied sulphides are comprised of hybrid bands derived from the metal d, S 3s, and S 3p states. Employing S K and L 2,3 X-ray emission spectroscopy and spectra calculations based on density functional theory, the degree of hybridization ( i.e. , the covalency) of these bands can be directly probed as a function of their relative energies. We find that the relative intensity of the "metal d band" features in the spectra scales with the inverse square of the energy separation to the respective sulfur-derived bands, which can be analytically derived from a simple two-orbital model. This study demonstrates that soft X-ray emission spectroscopy is a powerful tool to study valence state hybridization, in particular in combination with hard X-ray emission spectroscopy, promising a broad impact in many research fields.

Pseudouridine (Ψ) is one of the most abundant RNA modifications, playing crucial roles in various biological processes. Identifying Ψ sites is vital for understanding their functions. In this study, we proposed a novel method for identifying Ψ sites with an improved signal-to-noise ratio. This method, called RNA exonuclease-assisted identification of pseudouridine sites (RIPS), combines specific CMC-labeling of Ψ sites with an exonuclease-assisted digestion strategy for the detection of Ψ sites. Utilizing exonuclease XRN1 to digest RNA strands not labeled by CMC, RIPS significantly reduces the background signal from unlabeled strands and enhances the positive signal of Ψ sites labeled by CMC, which terminates exonuclease digestion. As a result, we can enrich Ψ sites and identify them at single-base resolution. Considering the unique functions of single-stranded RNA (ssRNA), we employed RIPS to distinguish Ψ sites in single-stranded and double-stranded regions of RNA. Our results indicated that CMC could specifically label Ψ sites in ssRNA under natural conditions, enabling RIPS to selectively identify Ψ sites in ssRNA, which may facilitate the study on the functions of Ψ sites., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The distribution, composition, and risk assessment of 8 EDCs in the surface water of 14 national aquatic germplasm resource reserves (freshwater) were investigated during dry and wet seasons. Bisphenol A (BPA), nonylphenol (NP), and octylphenol (OP) were the main contributors of the 8 EDCs. The concentrations of phenolic pollutants in surface water during the dry season were higher than those in the wet season. However, no significant seasonal differences were found among the steroid hormones. According to the evaluation of estrogenic activity (EEQ > 1.0), E2 and EE2 were the main contributors to estrogenic activity. EDC mixtures posed a higher risk to crustaceans and fish (RQ > 1.0) and a moderate to high risk to algae (RQ > 0.1). Fish were the most sensitive aquatic organisms. In the study areas, EE2, E1, BPA, NP, and E2 had a higher risk than the other three compounds and should be controlled as a priority.

As a kind of anode material with high theoretical sodium storage capacity for sodium-ion batteries (SIBs), MoS 2 has been widely studied. However, its low conductivity and large volume change hamper its application in SIBs. Herein, MoS 2 microspheres were first synthesized through the sulfidation of molybdenyl acetylacetonate via a solvothermal method and then successfully covered with a few layers of MXene nanosheets using the electrostatic assembly method. The ratio of MoS 2 to MXene was also investigated. The obtained MXene@MoS 2 composite has a large specific surface area due to its porous and non-stacked structure, which benefits the enhancement of ion and electron diffusion kinetics in SIBs. Therefore, the MXene@MoS 2 composite has a specific capacity of 257.8 mA h g -1 after 1000 cycles at a current density of 1 A g -1 with a capacity retention of 95.7% and excellent rate performance (220.8 mA h g -1 at 5 A g -1 ).

In this paper, we propose a multiband adjustable metamaterial absorption device based on a Dirac semimetal (BDS) AlCuFe and a thermally controlled phase-change material VO 2 . The absorption device has an axially symmetric structure, resulting in polarization-independent characteristics, and when VO 2 is in a high-temperature metal state, ultra-high absorption rates and sensitives at frequencies of M 1 = 2.89 THz, M 2 = 7.53 THz, M 3 = 7.97 THz, and M 4 = 9.02 THz are achieved. Using a parameter inversion method, we calculated the impedance of the absorber, proving that it achieves impedance matching and produces perfect absorption in the resonance region. Additionally, we changed the physical and chemical parameters of the absorption device, demonstrating the device's excellent tunability and manufacturing tolerance. Furthermore, by lowering the temperature of VO 2 to that of a low dielectric state, additional resonant peaks with ultra-high absorption rates at frequencies M 5 = 5.62 THz, M 6 = 7.16 THz, M 7 = 7.64 THz, and M 8 = 8.80 THz were obtained, broadening the absorption band of the device. Lastly, we investigated the detection sensitivity of the device by changing the external refractive index, resulting in a maximum sensitivity of 2229 GHz RIU -1 . To sum up, the absorption device has great application potential in the fields of communication, sensing, temperature detection and photoelectric instruments.

The lack of blue-emissive materials with high efficiency and excellent color purity commonly represents a pivotal obstacle in the development of organic light-emitting diodes (OLEDs). In this work, two blue to near-ultraviolet (NUV) donor-π-acceptor (D-π-A) emitters based on a fluorene π-bridge, 9-PCZCFTZ and 3-PCZCFTZ, are thus designed and synthesized, and non-doped devices derived from these two materials exhibit electroluminescence (EL) emission peaks at 404 nm and 417 nm, respectively. Interestingly, due to the specific stacking, a phenomenon appears in both materials in which the mobility of the electron is much higher than that of the hole, prompting us to use host doping to increase the hole mobilities, which ultimately leads to excellent OLED performances. As a result, the maximum external quantum efficiency (EQE max ) values of 9-PCZCFTZ and 3-PCZCFTZ in the doped devices reach as high as 14.5% and 10.8% respectively. Notably, both OLEDs show high blue purity very close to the BT.2020 standard., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Bacterial keratitis is a common form of inflammation caused by the bacterial invasion of the corneal stroma after trauma. In extreme cases, it can lead to severe visual impairment or even blindness; therefore, timely medical intervention is imperative. Unfortunately, widespread misuse of antibiotics has led to the development of drug resistance. In recent years, organ-on-chips that integrate multiple cell co-cultures have extensive applications in fundamental research and drug screening. In this study, immortalized human corneal epithelial cells and primary human corneal fibroblasts were co-cultured on a porous polydimethylsiloxane membrane to create a cornea-on-a-chip model. The developed multilayer epithelium closely mimicked clinical conditions, demonstrating high structural resemblance and repeatability. By introducing a consistently defective epithelium and bacterial infection using the space-occupying method, we successfully established an in vitro model of bacterial keratitis using S . aureus . We validate this model by evaluating the efficacy of antibiotics, such as levofloxacin, tobramycin, and chloramphenicol, through simultaneously observing the reactions of bacteria and the two cell types to these antibiotics. Our study has revealed the barrier function of epithelium of the model and differentiated efficacy of three drugs in terms of bactericidal activity, reducing cellular apoptosis, and mitigating scar formation. Altogether, the cornea on chip enables the assessment of ocular antibiotics, distinguishing the impact on corneal cells and structural integrity. This study introduced a biomimetic in vitro disease model to evaluate drug efficacy and provided significant insights into the extensive effects of antibiotics on diverse cell populations within the cornea.

Although zinc oxide nanoparticles (ZnO NPs) with distinct physicochemical properties have attracted great attention, the application of ZnO NPs is still limited due to their potential biotoxicity. In this work, ZnO- Polygonatum sibiricum (PS) NPs are synthesized to overcome this challenge. The ZnO NPs stably combine with PS according to microstructural observation, particle size distribution, zeta potential results and Fourier transform infrared spectroscopy analysis. The cytotoxicity of ZnO NPs is alleviated by combining them with PS as a consequence of the diminished generation of reactive oxygen species and reinforced superoxide dismutase activity. Furthermore, the respiratory index and histopathologic results of mice exposed to NPs manifest that the pulmonary dysfunction caused by ZnO NPs is avoided in the ZnO-PS NPs group. This study provides the foundations for the amelioration and universal utilization of ZnO NPs and emphasizes the potential of ZnO-PS NPs in biomedical applications., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (This journal is © The Royal Society of Chemistry.)

Complex plasmas consist of ionized gas and charged solid microparticles, representing the plasma state of soft matter. We apply machine learning methods to investigate a melting transition in a two-dimensional complex plasma. A convolutional neural network is constructed and trained with the numerical simulation. The hexatic phase is successfully identified and the evolution of topological defects is studied during melting transition in both simulations and experiments.

In recent years, Alzheimer disease (AD) as a neurodegenerative disorder has been increasing annually with the aging of the global population, therefore, development of novel anti-AD drugs is imperative. Studies have proven that glycogen synthase kinase-3β (GSK-3β) is a pivotal factor in the development of AD. Therefore, GSK-3β inhibitors would provide powerful means to treat the disorders, such as AD. To in-depth study the structure-activity relationship of a series of oxadiazole derivatives as multifunctional anti-Alzheimer agents, computational three dimensional quantitative structure-activity relationship (3D-QSAR) studies, molecular docking and molecular dynamics were conducted. The comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) methods were conducted to build up the 3D-QSAR models, and exhibited significant results ( R cv 2 = 0.692, R pred 2 = 0.6885/CoMFA, R cv 2 = 0.696, R pred 2 = 0.6887/CoMSIA). The accuracy of the 3D-QSAR models was validated by external validation and applicability domain analysis. The derived contour maps provided structural information for designing novel compounds to improve the inhibitory activities. Additionally, molecular docking and molecular dynamics were also employed to investigate the bonding interactions and stability of this series of inhibitors in the active site of GSK-3β, and the results revealed that the importance of residues Ile62, Asn64 Val70, Tyr128, Val129 and Leu182 for ligand binding to the receptor GSK-3β. All the results would be of great help for the discovery of new GSK-3β agents that can solve the problem of AD., Competing Interests: The authors declare that there are no conflicts of interest., (This journal is © The Royal Society of Chemistry.)

Delayed fluorescence (DF) is a unique emitting phenomenon of great interest for important applications in organic optoelectronics. In general, DF requires well-separated frontier orbitals, inherently corresponding to charge transfer (CT)-type emitters. However, facilitating intrinsic DF for local excited (LE)-type conjugated emitters remains very challenging. Aiming to overcome this obstacle, we demonstrate a new molecular design strategy with a DF-inactive B,N-multiple resonance (MR) emitter as a model system. Without the necessity of doping with heavy atoms, we synthesized a co-facial dimer in which an excimer-like state (S exc ) was expected to facilitate efficient reverse intersystem crossing (RISC, T 1 → S exc ) and intrinsic DF. Benefiting from greatly enhanced SOC and reduced Δ E ST , the proof-of-concept emitter Np-2CzB exhibited k RISC up to 6.5 × 10 5 s -1 and intrinsic DF with >35% contribution ( Φ DF / Φ F ) in dilute solution. Further investigation indicated that S exc state formation relies on an optimized co-facial distance ( d = ∼4.7 Å), strong inter-chromophore interaction ( J coul > 450 cm -1 ) and a rigid structure ( Γ S 1 →S 0 < 350 cm -1 ). Although our strategy was demonstrated with a B,N-MR emitter, it can be applicable to many LE-type conjugated emitters without intrinsic DF. By triggering potential DF emission, many classic emitters might play a more important role in optoelectronics., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

Covering: 1987 to 2023Naturally existing glycoproteins through post-translational protein glycosylation are highly heterogeneous, which not only impedes the structure-function studies, but also hinders the development of their potential medical usage. Chemical synthesis represents one of the most powerful tools to provide the structurally well-defined glycoforms. Being the key step of glycoprotein synthesis, glycosylation usually takes place at serine, threonine, and asparagine residues, leading to the predominant formation of the O - and N -glycans, respectively. However, other amino acid residues containing oxygen, nitrogen, sulfur, and nucleophilic carbon atoms have also been found to be glycosylated. These diverse glycoprotein linkages, occurring from microorganisms to plants and animals, play also pivotal biological roles, such as in cell-cell recognition and communication. The availability of these homogenous rare glycopeptides and glycoproteins can help decipher the glyco-code for developing therapeutic agents. This review highlights the chemical approaches for assembly of the functional glycopeptides and glycoproteins bearing these "rare" carbohydrate-amino acid linkages between saccharide and canonical amino acid residues and their derivatives.

This study investigates the characterization, mechanisms of action, structure-activity relationships, and in vivo antihypertensive effects of ACE inhibitory peptides derived from sufu hydrolysate following simulated gastrointestinal digestion. Sufu was enzymatically digested using pepsin, trypsin, and chymotrypsin to mimic gastrointestinal conditions, followed by ultrafiltration to fractionate the peptides based on molecular weight. The fraction under 1 kDa exhibited the highest ACE inhibitory activity. LC-MS/MS analysis identified 119 peptide fragments, with bioinformatics screening highlighting 41 peptides with potential ACE inhibitory properties. Among these, two peptides, AWR and LLR, were selected and synthesized for in vitro validation, displaying IC 50 values of 98.04 ± 2.56 μM and 94.01 ± 5.07 μM, respectively. Stability tests showed that both peptides maintained their ACE inhibitory activity across various temperatures and pH levels. Molecular docking and Highest Occupied Molecular Orbital analysis indicated strong binding interactions between these peptides and ACE, with the second-position tryptophan in AWR and the N-terminal leucine in LLR identified as key bioactive sites. These findings were further supported by molecular dynamics simulations, which confirmed the stability of the peptide-ACE complexes. In vivo studies using spontaneously hypertensive rats demonstrated significant reductions in both systolic and diastolic blood pressure, indicating that AWR and LLR have strong antihypertensive potential. This study illustrates that ultrafiltration, combined with LC-MS/MS and bioinformatics analysis, is an effective approach for the rapid screening of ACE inhibitory peptides. These results not only enhance our understanding of sufu-derived peptides but also offer promising implications for hypertension management.

It is well known that obtaining efficient carbamazepine degradation materials or rapid carbamazepine-removal methods is still a challenge in the field of environmental remediation. Hence, the present study aimed to concurrently address these issues by combining a self-driven, heterostructured and low-cost biomass-templated urchin-like Janus micromotor catalyst for highly efficient carbamazepine degradation. The catalyst could autonomously move in a circle-like motion pattern via O 2 bubbles generated from the Mn 3 O 4 -catalyzed decomposition of H 2 O 2 with a velocity of 223.5 ± 7.0 μm s -1 in 1% H 2 O 2 . Benefiting from the well-structured heterojunction at the interface of C 3 N 4 and Mn 3 O 4 , carbamazepine (CBZ) was degraded by 61% in 100 min under sunlight irradiation. In addition, density functional theory calculation results proved that the formation of the heterojunction structure promoted the generation of photo-generated carriers. Thus, the presented method provides a promising pathway for the rational construction and preparation of movable catalysts for the efficient removal of organic pollutants from wastewater., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The nanoscale ampification of light-matter interactions exhibits profound potential in multiple scientific fields, such as physics, chemistry, surface science, materials science, and nanophotonics. Nonetheless, achieving robust optical mode coupling within cavities faces significant hurdles due to modal dispersion and weak optical field confinement. In this theoretical investigation, we demonstrate the viability of strong coupling between the anapole mode of a slotted silicon nanodisk and the plasmonic modes of an Ag nanodisk dimer at visible light frequencies. By introducing anapole modes, we successfully confine light to subwavelength volumes, suppressing radiative losses and achieving a remarkable Rabi splitting of 468 meV. This substantial coupling is facilitated by the large spatial overlap of intense optical fields. Capitalizing on this strong mode coupling, we generate novel hybrid energy states with significant electromagnetic field enhancement. Our study serves as a valuable blueprint for designing platforms based on strong anapole mode coupling at visible frequencies and paves the way for deeper explorations into nanoscale light-matter interactions.

Biological weapons, primarily dispersed as aerosols, can spread not only to the targeted area but also to adjacent regions following the movement of air driven by wind. Thus, there is a growing demand for toxin analysis because biological weapons are among the most influential and destructive. Specifically, such a technique should be hand-held, rapid, and easy to use because current methods require more time and well-trained personnel. Our study demonstrates the use of a novel lateral flow immunoassay, which has a confined structure like a double barbell in the detection area (so called c-LFA) for toxin detection such as staphylococcal enterotoxin B (SEB), ricinus communis (Ricin), and botulinum neurotoxin type A (BoNT-A). Additionally, we have explored the integration of machine learning (ML), specifically, a toxin chip boosting (TOCBoost) hybrid algorithm for improved sensitivity and specificity. Consequently, the ML powered c-LFA concurrently categorized three biological toxin types with an average accuracy as high as 95.5%. To our knowledge, the sensor proposed in this study is the first attempt to utilize ML for the assessment of toxins. The advent of the c-LFA orchestrated a paradigm shift by furnishing a versatile and robust platform for the rapid, on-site detection of various toxins, including SEB, Ricin, and BoNT-A. Our platform enables accessible and on-site toxin monitoring for non-experts and can potentially be applied to biosecurity.

2-Pyrones are valuable structural motifs in organic chemistry, found in numerous natural products and pharmaceuticals. The synthesis of these heterocycles has been significantly advanced by the application of N-Heterocyclic Carbene (NHC) catalysis. This review examines the recent advancements in NHC-catalyzed synthesis of 2-pyrones, highlighting key methodologies, mechanisms, and synthetic applications. NHC catalysis has revolutionized the synthesis of 2-pyrones, providing efficient, selective, and versatile methods for constructing these valuable heterocycles., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Biomineralization is a natural process in which organisms regulate the growth of inorganic minerals to form biominerals with unique layered structures, such as bones and teeth, primarily composed of calcium and phosphorus. Tooth decay significantly impacts our daily lives, and the key to tooth regeneration lies in restoring teeth through biomimetic approaches, utilizing mineralization strategies or materials that mimic natural processes. This review delves into the types, properties, and transformations of calcium and phosphorus minerals, followed by an exploration of the mechanisms behind physiological and pathological mineralization in living organisms. It summarizes the mechanisms and commonalities of biomineralization and discusses the advancements in dental biomineralization research, guided by insights into calcium and phosphorus mineral biomineralization. This review concludes by addressing the current challenges and future directions in the field of dental biomimetic mineralization.

Multifunctional flexible electronics integrated with superhydrophobicity and flexible sensing can greatly promote broader applications. However, the hierarchical roughness morphology of superhydrophobic surfaces is vulnerable to complex mechanical deformations of stretchable sensors leading to degradation of hydrophobic properties, so constructing robust superhydrophobic stretchable sensors remains challenging. Herein, we propose a facile strategy to fabricate superhydrophobic stretchable sensors based on self-assembled carbon nanotube (CNT) films at the air-water interface. The customizable functions of superhydrophobic stretchable sensors can be achieved by controlling the combination of the CNT film and polydimethylsiloxane (PDMS) through a simple and efficient interfacial transferring strategy. Even under large mechanical deformations, the developed sensors can present excellent robustness and superhydrophobicity with a water contact angle of 150.9° at 80% strain. As a proof-of-concept, this work demonstrates their potential application in self-sensing drag-reduction shipping, which is expected to realize greener, more sustainable and safer aquatic transportation., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Nicotinamide and its derivatives, recognized as crucial drug intermediates, have been a focal point of extensive chemical modifications and rigorous pharmacological studies. Herein, a series of novel nicotinamide derivatives, nicotinimidamides, were synthesized via a tandem CuAAC/ring-cleavage/cyclization/oxidation four-component reaction procedure from O -acetyl oximes, terminal ynones, sulfonyl azides, and NH 4 OAc. This strategy is significantly more efficient than previously reported, and the cytotoxicity of the nicotinimidamides is also tested. This project not only exhibits a sustainable and eco-friendly domino methodology for the creation of nicotinimidamides but also presents a promising candidate for liver cancer treatment., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The self-assembled structure has a significant impact on the performance of ion conductors. We prepared a new type of electrolyte with self-assembled structures from an azobenzene-based liquid crystalline (LC) monomer and its corresponding polymer. By doping different amounts of monomers and lithium salt LiTFSI, the self-assembled nanostructure of the electrolyte was changed from lamellae to double gyroid. The ionic conductivity of the azobenzene-based electrolytes with the double gyroid structure was 1.64 × 10 -4 S cm -1 , higher than most PEO-based polymer electrolytes. The azobenzene-based system provides a new strategy to design solid electrolytes with self-assembled structures that may be potentially used in solid-state lithium-ion batteries.

Aims : Epidemiological studies that use dietary biomarkers to investigate the association between whole grain intake and the risk of obesity are sparse. We assessed the association between urinary alkylresorcinol metabolites including 3-(3,5-dihydroxyphenyl)-1-propanoic acid (DHPPA) and 3,5-dihydroxybenzoic acid (DHBA), biomarkers of whole grain wheat and rye intake, and body fat measures. Methods : We measured urinary excretion of DHPPA and DHBA, body weight, height, and circumferences of the waist and hip at the baseline and again after 1-year in a representative sample of 306 community-dwelling adults in Huoshan, China. We also measured liver fat accumulation [indicated by the controlled attenuation parameter (CAP)] and other body composition after 1 year. Multivariate-adjusted linear models and linear mixed-effects models were used to analyze single measurement and repeated measurements, respectively. Results : Each 1 μg g -1 creatinine increase in urinary DHPPA levels was associated with 0.21%, 0.23%, 3.64%, and 4.80% decrease in body weight, body mass index (BMI), body fat mass (BFM) and visceral fat level (VFL), respectively (all P < 0.05). Higher DHBA levels were inversely associated with CAP (percentage difference per 1 μg g -1 creatinine increment: -1.98%, P < 0.05). Higher total urinary alkylresorcinol metabolite (DHPPA + DHBA) levels were associated with lower body weight, BMI, BFM, VFL, and CAP, with the percentage differences per 1 μg g -1 creatinine increment of -0.27%, -0.27%, -3.79%, -5.12%, and -2.24%, respectively (all P < 0.05). Conclusions : Our findings suggest that the intake of whole grain wheat and rye, reflected by urinary DHPPA and DHBA, is favorably associated with liver fat and other fat measures.

Hydrogel strain sensors have received increasing attention due to their potential applications in human-machine interfaces and flexible electronics. However, they usually suffer from both mechanical and electrical hysteresis and poor water retention, which limit their practical applications. To address this challenge, a poly(acrylic acid- co -acrylamide) hydrogel crosslinked by silica nanoparticles is fabricated via photo polymerization and salting-out of hydrophilic ions for the strain sensor. The resulting hydrogel strain sensor possessed low electrical hysteresis (1.6%), low mechanical hysteresis (<7%), high cycle stability (>10 000 cycles), high durability, water retention and anti-freezing ability. Moreover, this strain sensor can be used as a wearable sensor for real-time control of robotic hands and hand gesture recognition. Finally, a sign language translation system has been demonstrated with the aid of machine learning, achieving recognition rates of over 98% for 15 different sign languages. This work offers a promising prospect for human-machine interfaces, smart wearable devices, and the Internet of Things.

Magnetic refrigeration based on the magnetocaloric effect is gaining interest in orthogonal or hexagonal rare-earth manganite. However, a more comprehensive understanding of the underlying mechanism is still required. We grew a high-quality single crystal of Dy 0.5 Ho 0.5 MnO 3 using the optical floating zone method, since the parent crystals DyMnO 3 and HoMnO 3 have orthogonal and hexagonal structures, respectively. The magnetic and magnetocaloric properties and refrigeration mechanisms are thoroughly investigated. Doping modifies the magnetism according to the results obtained from the investigation of magnetic and dielectric properties and heat capacity. The spin reorientation transition shifts towards low temperature in comparison to HoMnO 3 . Near the Néel temperature of rare-earth sublattices (5 K), the highest changes in negative magnetic entropy under 0-70 kOe are 18 J kg -1 K -1 and 13 J kg -1 K -1 along the a - and c -axes, respectively. The low-temperature metamagnetic phase transition caused by the alterations in the magnetic symmetry of Ho 3+ contributes to an increased magnetocaloric effect in comparison to the parent crystals, rendering it a promising choice for magnetic refrigeration applications. Dy 0.5 Ho 0.5 MnO 3 exhibits a clear magnetocrystalline anisotropy with enhanced refrigeration capacity and negative magnetic entropy change along the a -axis. The adiabatic temperature change of Dy 0.5 Ho 0.5 MnO 3 is 8.5 K, larger than that of HoMnO 3 , rendering it a promising choice for low-temperature magnetic refrigeration applications.

The exploitation of shape-stabilized phase change materials with high thermal conductivity and energy storage capacity is an effective strategy for improving energy efficiency. In this work, sunflower stem carbon/polyethylene glycol (SS-PEG) and sunflower receptacle carbon/polyethylene glycol (SR-PEG) shape-stabilized phase change materials, utilizing sunflower stem and receptacle biomass carbon with high specific surface area and pore volume obtained by carbonization as frameworks and polyethylene glycol as an energy storage material, were prepared by the vacuum impregnation method. The ability to load polyethylene glycol into the pore structure of carbon materials in different sunflower parts was mainly investigated, and the micro-morphology, compositional structure and thermal properties were characterized and analyzed using SEM, IR spectroscopy, XRD, DSC and TG techniques. The results showed that the carbonized sunflower stems maintained the sieve pore structure, and the carbonized sunflower receptacle was a macroporous structure containing a large number of three-dimensional interconnections. At the same time, the interaction between polyethylene glycol and each carbon material occurred through physisorption. The melting enthalpies of SS-PEG and SR-PEG shape-stabilized phase change materials were 153.4 J g -1 and 171.5 J g -1 , respectively, and the loading rates reached 81.9% and 91.5%, with initial thermal decomposition temperatures ( T 5% ) of 344 °C and 368 °C., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Foodborne pathogens including Salmonella typhimurium ( S. typhimurium ) are responsible for over 600 million global incidences of illness annually, posing a significant threat to public health. Inductively coupled plasma mass spectrometry (ICP-MS), coupled with element labeling strategies, has emerged as a promising platform for multivariate and accurate pathogen detection. However, achieving high specificity and sensitivity remains a critical challenge. Herein, we synthesize clustered magnetic nanoparticles (MNPs) and popcorn-shaped gold nanoparticles (AuNPs) to conjugate capture and report DNA probes for S. typhimurium , respectively. These engineered nanoparticles facilitate the identification of S. typhimurium DNA through a sandwich hybridization technique. ICP-MS quantification of Au within the sandwich-structure complexes allows for precise S. typhimurium detection. The unique morphology of the AuNPs and MNPs increases the available sites for probe attachment, enhancing the efficiency of S. typhimurium DNA capture, broadening the detection range to 10 1 -10 10 copies mL -1 , and achieving a low detection limit of 1 copy mL -1 , and the overall assay time is 70 min. The high specificity of this method is verified by anti-interference assays against ten other pathogens. The recovery was 96.8-102.8% for detecting S. typhimurium DNA in biological samples. As these specially designed nanoparticles may facilitate the attachment of various proteins and nucleic acid probes, they may become an effective platform for detecting multiple pathogens.