Nanoplastics (NPs) have emerged as ubiquitous environmental contaminants, raising increasing concerns over their ecological impacts and potential risks to human health. However, accurate quantification of NPs in aquatic environments remain analytically challenging due to the lack of effective enrichment techniques capable of operating at trace concentrations. Herein, we developed a robust, rapid, and organic-free flocculation-based preconcentration strategy for NP quantification in water samples. Utilizing polymerized ferrous sulfate (PFS) as an flocculant, diverse NPs, including polystyrene (PS), poly(methyl methacrylate) (PMMA), poly(vinyl chloride) (PVC), polypropylene (PP), and poly(ethylene terephthalate) (PET), were efficiently coprecipitated with ferrihydrite (FeOOH) and subsequently isolated by centrifugation. The enriched NPs were analyzed by pyrolysis gas chromatography/mass spectrometry (Py-GC/MS), achieving high recoveries (≥92.8%) and low detection limits (0.01-0.02 μg/L). Field application revealed PS NP concentrations ranging from 0.11 to 0.36 μg/L, while recovery experiments in representative natural waters yielded consistent results (81.3-97.3%), confirming the method's accuracy and matrix tolerance. Compared with conventional extraction approaches (e.g., cloud point extraction), this protocol avoids the introduction of organic additives that may interfere with pyrolysis, thereby improving analytical sensitivity and reducing background complexity. Overall, the proposed method provides a reliable and practical platform for monitoring NP pollution in diverse aquatic systems.
The pervasive occurrence of organic contaminants in food and environmental samples poses serious threats to public health and ecological security, highlighting the urgent need for rapid, on-site detection methods. In recent years, the integration of ambient ionization with miniature mass spectrometry (MS) has emerged as a powerful analytical strategy. Ambient ionization enables direct desorption and ionization of analytes from complex matrices under atmospheric pressure with minimal pretreatment, while miniature MS offers portability, rapid response, and high sensitivity—together making on-site analysis feasible. This review systematically outlines recent advances in this integration, with an emphasis on the core components of miniature mass spectrometers and interface designs. Representative ambient ionization techniques—such as desorption electrospray ionization, low-temperature plasma, paper spray ionization, extraction nanoelectrospray ionization, and thermal desorption–electrospray ionization—are described alongside their coupling strategies with miniature MS. Furthermore, the review highlights applications in food safety and environmental monitoring, demonstrating the capability of this technology for rapid, on-site, and multi-analyte detection. Finally, current challenges and future research directions are discussed, underscoring the potential of this integrated approach to enhance real-time contamination monitoring and support decision-making in public health and environmental protection.
Taraxacum kok-saghyz Rodin, a perennial herbaceous plant of the genus Taraxacum (Asteraceae), has widely distributed in Europe, the Americas, and northwestern and northeastern China. However, the specific bioactive compounds responsible for its pharmacological effects remain uncharacterized, necessitating experimental validation to establish a theoretical foundation. This study systematically characterized the chemical constituents of Taraxacum kok-saghyz Rodin, a medicinal plant of the dandelion genus, using ultra-high-performance liquid chromatography coupled with quadrupole/Orbitrap high-resolution mass spectrometry (UHPLC-Q/Orbitrap HRMS). The sample pretreatment process involved optimizing solvent selection. One gram of dried rubber dandelion root or leaf powder was mixed with methanol and subjected to ultrasonic/microwave-assisted extraction (microwave power of 450 W, ultrasonic power of 550 W, temperature of 50 ℃, and extraction time of 30 min), followed by chromatographic separation on an ACQUITY UHPLC BEH C18 column (150 mm×2.1 mm,1.7 µm) at 40 ℃, with an injection volume of 3 μL per run. The mobile phase consisted of water containing 0.1% formic acid and 2.5 mmol/L ammonium formate (A) and acetonitrile (B) at a flow rate of 0.3 mL/min. Electrospray ionization (ESI) was employed for ionization. Full scan/data-dependent tandem mass spectrometry (MS/MS) scan (Full MS/dd-MS2) acquisition mode ensured comprehensive coverage of precursor and fragment ions, with a scan range of m/z 80-1 200. Full scan resolution was set at 60 000, while dd-MS2 scan resolution reached 15 000. The raw data were processed using Xcalibur 4.1 software for chromatographic peak alignment and extraction. Accurate mass information for precursor and fragment ions was meticulously compared with three databases of the Orbitrap Traditional Chinese Medicine Library (OTCML), a self-curated database, and the Global Natural Products Social Molecular Networking online platform. A total of 94 compounds were identified, encompassing 4 flavonoids, 5 alkaloids, 11 terpenoids, 8 phenolics, 6 amino acids, 13 phenylpropanoids, 10 organic acids, 4 nucleotides, and 33 other types of compounds. To ensure the accuracy of compound identification, reference standards (chlorogenic acid, caffeic acid, p-coumaric acid, 7-hydroxycoumarin, and ferulic acid) were subjected to mass spectrometric characterization, effectively eliminating false-positive interferences. This study revealed that amino acids and phenylpropanoids exhibit higher mass spectrometric responses, whereas alkaloids show weaker responses. By analyzing the fragmentation pathways of representative compounds, the structural characteristics were elucidated, providing a scientific basis for deciphering the pharmacodynamic material foundation of non-latex components in Taraxacum kok-saghyz Rodin. This study also offers data support for exploring the high-value utilization of non-rubber components in Taraxacum kok-saghyz Rodin. Taraxacum kok-saghyz Rodin exhibits a complex matrix composition and a diverse array of natural constituents. Future research prospects should integrate nuclear magnetic resonance (NMR) spectroscopy with artificial intelligence (AI)-driven pattern recognition methodologies to enhance data accuracy and improve the comprehensiveness of phytochemical characterization.
Ambient ionization mass spectrometry (AIMS) enables direct analysis of samples under open-air conditions with little or no pretreatment. Among AIMS techniques, plasma-based ionization has attracted particular attention because atmospheric-pressure plasmas can generate reagent ions, metastable species, radicals, photons, and gas streams that support rapid desorption and ionization of solid, liquid, gaseous, and heterogeneous surface samples. Representative sources include direct analysis in real time (DART), desorption atmospheric-pressure chemical ionization (DAPCI), flowing atmospheric-pressure afterglow (FAPA), plasma-assisted desorption/ionization (PADI), dielectric barrier discharge ionization (DBDI), and low-temperature plasma (LTP). This review critically examines plasma-based AIMS from the perspectives of discharge mechanism, ionization pathway, source architecture, and analytical performance. Rather than simply listing individual applications, we compare how different plasma-generation strategies influence reagent-ion chemistry, thermal effects, fragmentation, matrix tolerance, quantitative capability, and suitability for field deployment. Applications in environmental analysis, forensic analysis, explosive detection, pharmaceutical screening, food safety, biological analysis, and materials characterization are discussed with attention to both analytical value and remaining limitations. Plasma-based AIMS has strong potential for high-throughput screening and on-site testing, but routine implementation requires improved mechanistic understanding, source standardization, quantitative robustness, matrix-effect control, and integration with portable MS and validated data-analysis workflows. Future development should move beyond stand-alone application demonstrations toward fit-for-purpose, reproducible, and validated analytical platforms.
Traditional Chinese medicine(TCM),both a longstanding medical practice in Asia and an increasingly utilized supplement or alternative medicine in Western countries,has become a focal point within the life sciences in recent years.TCM formulations represent a cornerstone of treatment,with their chemical composition serving as the fundamental basis for their pharmacological effects.However,the intricate nature of chemical composition,low abundance of various constituents,and presence of numerous isomeric compounds,alongside interactions among different medicinal substances,render the effective separation and identification of the components in TCM herbs challenging by using traditional analytical methods.In this study,an analytical method of ultra-high-performance liquid chromatography-quadrupole/Orbitrap high-resolution mass spectrometry(UHPLC-Q/Orbitrap HRMS)was developed for identifying the chemical components in the traditional Chinese medicine formula of Jiuwei decoction.The sample pretreatment method involved ultrasonic/microwave-assisted extraction,ensuring comprehensive extraction of the active components in Jiuwei decoction.Parameters of this extraction included a microwave power at 300 W,ultrasonic power at 340 W,temperature at 45 ℃,and an extraction duration of 30 min.Subsequent to extraction,chromatographic separation was achieved using a Waters ACQUITY UPLC BEH C1 8 column(150 mm×2.1 mm,1.7 μm)at 30 ℃,with an injection volume of 2 μL per run.The mobile phase consisted of water with 0.1%formic acid(A)and acetonitrile(B)at a flow rate of 0.3 mL/min.Before entering the quadrupole/Orbitrap high-resolution mass spectrometer for detection,samples underwent ionization under both positive and negative ion modes.Data acquisition was then conducted in full MS scan/data-dependent MS/MS scan(Full MS/dd-MS2)acquisition mode.Following data collection,chromatographic peak alignment and extraction were performed using the Xcalibur 4.1 software.Accurate mass information of precursor ions and fragment ions was meticulously compared with various databases,including the Orbitrap Traditional Chinese Medicine Library(OTCML),as well as other online databases such as TCMSP,ChemSpider,PubChem,PubMed,and Web of Science,in addition to a self-curated database for identification purposes.A total of 144 compounds are successfully identified,encompassing 24 flavonoids,30 alkaloids,12 terpenes,23 phenylpropanoids,26 phenols,10 amino acids,7 organic acids,5 steroids,and 7 other types of compounds.Among these compounds,alkaloids such as sinomenine,phellodendrine,magnoflorine,isocorydine,and corydinematrine exhibit notably high contents and mass spectrometric responses,whereas flavonoids and saponins display comparatively lower MS responses.The herbal sources of these compounds were identified,and the fragmentation patterns of representative compounds were thoroughly analyzed.This study provides a precise identification of the chemical constituents in Jiuwei decoction,thus furnishing a robust scientific foundation for further exploration into its pharmacological effects and mechanisms of action.Moreover,this study serves as an invaluable reference for the analysis of the chemical composition of TCM formulations.Nonetheless,it is crucial to acknowledge the inherent limitations and scopes of various analytical methods and instruments.Therefore,in the pursuit of analyzing active components in TCMs,it is advisable to delve deeper into separation and identification through the utilization of diverse techniques such as nuclear magnetic resonance spectroscopy,ultraviolet/infrared spectroscopy,and capillary electrophoresis-mass spectrometry.
Ensuring consistent quality across batches and developing a quality standard for sauce-aroma baijiu (SAB, a Chinese spirit with a complex aroma) is challenging, as conventional methods lack objectivity and efficiency. In this study, a rapid, objective approach combining soft ionization by a chemical reaction with transfer-quadrupole Orbitrap high-resolution mass spectrometry (SICRIT-Q Orbitrap HRMS) was developed for SAB quality grading. This optimized ultrasonic nebulization system with a 3D-printed structure enabled fingerprint data collection in 1 min. Based on multivariate analysis, 18 key compounds were identified for grade differentiation in baijiu. Furthermore, environmental assessments with Green Analytical Procedure Index (GAPI, low environmental impact), Analytical Greenness Calculator (AGREE, score 0.75), and Blue Applicability Grade Index (BAGI, score 75.0) confirmed the eco-friendliness. Compared with conventional gas chromatography-mass spectrometry (GC-MS), this method reduced solvent use by 50% and energy consumption by 30%. This SICRIT-HRMS method could be a greener, faster alternative for baijiu quality assessment.
Ambient ionization mass spectrometry (AIMS) allows rapid analysis of targets, while its overall selectivity is somewhat limited due to the lack of chromatographic separation. Recently, magnetic blade spray (MBS) has enhanced AIMS by incorporating immunomagnetic beads instead of the traditional coated blade spray (CBS) coating, thereby improving selectivity and sensitivity by targeted analyte detection and reducing background interference. In this study, an aptamer-functionalized and nucleic acid dye (GelRed)-loaded MS probe (AGMP) was developed and employed with MBS-based miniature mass spectrometer. Specifically, AGMP was assembled using aptamer-functionalized magnetic nanoparticles loaded with GelRed as mass tags for highly sensitive analysis of endoglin (CD105). For the preparation of AGMP, the CD105 binding aptamer of End-A2 was first selected through three rounds of capillary electrophoresis (CE)-SELEX with an optimal affinity of 62.3 pM. After optimizing the critical parameters that affected adsorption, desorption, and ionization efficiency, this method displayed satisfactory sensitivity with detection and quantitation limits of 0.2 and 1 ng/mL, respectively, as well as reliable recoveries of 90.1-106.8 % with relative standard deviations of 1.6-5.4 %. Besides, the method effectively mitigated the matrix effects with a slope deviation of 10.03 %, and exhibited good selectivity and environmental friendliness. Furthermore, this AGMP-based MBS strategy was successfully applied for CD105 detection in serum samples, demonstrating its potential for sensitive and on-site biomolecule analysis in complex matrices.
Peroxynitrite (ONOO−) plays a pivotal role in environmental pollution and ecosystem health, necessitating its detection for assessing ecological impacts and risks. Surface-enhanced Raman scattering (SERS) offers high sensitivity but is often limited by narrow Raman cross sections of analytes. Specialized molecules can aid SERS detection, but are complex to design and may cause nonspecific reactions in biological systems. Therefore, developing new SERS strategies is crucial for simpler, more accurate ONOO− detection. Herein, the shape instability of Ag nanomaterials in the hotspots, due to oxidation and dissolution of Ag atoms at the edges and corners, is investigated, and the detection of ONOO− is performed by SERS probes. ONOO− reacts first with the (111) facet, especially at the edges and corners. Consequently, the SERS signal of the adsorbed probe, Rhodamine 6G in hotspots can be used to monitor edge and corner dissolution that positively related to the ONOO− concentration. As a result, ONOO− concentration from 0.1 to 25 μM was detected, achieving a coefficient of determination of R2 = 0.9896. The method exhibits good reproducibility (RSD < 3.25
Developing ambient ionization methods for direct mass spectrometry (MS) analysis is crucial for achieving sample-to-answer capabilities, especially for rapid analysis and monitoring in specific scenarios. Herein, a compact device is presented that utilizes mesh-collision microtube plasma (MC-μTP) ionization for direct online MS analysis. This device features a self-aspirating design that enables the direct analysis of various sample types. It includes an energy-efficient μTP generator with a single microneedle electrode and a high-efficiency molecule-ion reactor. The reactor integrates a screen mesh that disrupts and disperses the plasma plume, optimizing the mixing and contact probability between reactant ions and analyte molecules to enhance the ionization efficiency. For the data analysis, Venn diagrams were employed to facilitate the differential analysis of components in red wines from various regions. Furthermore, the release patterns of volatile organic compounds (VOCs) from leather products in a simulated high-temperature enclosed space were investigated through online monitoring. The integration of MC-μTP with a miniature mass spectrometer enabled the detection of eight distinct VOCs in leather products, showcasing promising potential for future on-site VOC monitoring within vehicle interiors.
As an emerging class of extended crystalline organic materials, covalent organic framework (COF)-based aggregation-induced emission luminogen (AIE-gen) exhibited encouraging emissive properties. In this work, 4’,4’’,4‴,4‴’-(1,1,2,2-Ethenetetrayl)tetra(4-biphenylcarbaldehyde) (ETBC) as AIEgen was used to prepare AIE-COF (ET-COF-COOH) luminescent nanoprobe. ETBC and 1,3,5-Tris(4-aminophenyl)benzene (TAPB) had an extended π electronic system that allowed electron delocalization and overlapping transport. Because AIEgen-ETBC served as the luminescence center of ET-COF-COOH, the ET-COF-COOH possessed an ideal anodic electrochemiluminescence (ECL) performance. Moreover, due to the surface plasmonic coupling (SPC) effect of the CuS@Ag square-cavity array, the ECL signal of ET-COF-COOH was amplified as 2.8 times. The AIE-COF/CuS@Ag SCH array-based SPC-ECL sensor was used to detect miRNA-124-3p with a wide range of 1 fM-10 nM and LOD of 0.49 fM. Furthermore, the proposed biosensor can effectively distinguish between tumor tissue and adjacent tissue and offer significant potential for advancing glioma diagnosis.
To address the health risks posed by microplastics (MPs), this work developed a poly-L-cysteine (poly-L-cys)-based electrochemiluminescence (ECL) sensor for detecting MPs in water environments. The porous structure of poly-L-cys film can regulate the generation of copper nanoclusters (Cu NCs) in the pores, effectively limiting the migration and aggregation of nanopaticles. In addition, poly-L-cys film also acted as co-reactant promoters, promoting electron transfer and effectively enhancing ECL signal of Cu NCs. Therefore, Cu NCs in the poly-L-cys porous membrane has been used as luminescent probes. Furthermore, the poly-L-cys/Cu NC-based ECL sensor was constructed with the protein corona induced aggregation effect (PCIAE) to determine the concentration of MP. Due to the strong binding affinity of PCIAE, MP can adsorb strongly to biomolecule surfaces as a protein crown. So, the modified BSA on the poly-L-cys film was removed by MP, resulting in the ECL signal enhancement. The PCIAE-ECL sensor has been successfully applied to measure MP in lakes with excellent recovery rates (90.7-106.0%). The PCIAE-ECL sensor provided a new analytical method for detecting MPs in water environments.
Rapid and accurate methods for tracing and identifying the origin of lamb are crucial for ensuring food authenticity and quality. This study developed a precise traceability method to determine the origin of lamb by integrating rapid evaporative ionization mass spectrometry (REIMS) with multivariate statistical analysis. Lamb samples from Xilin Gol, Ordos, and Hulun Buir ranches were identified by REIMS fingerprinting within 1 min. The discrimination model based on lipid molecular features achieved the highest recognition accuracy of 99.14% compared to models based on small-molecule metabolites (91.59%), fatty acids (98.52%), and full-spectrum molecules (98.49%). Furthermore, differential analyses were conducted to assess lamb meat from different origins and feeding methods (grazing versus feedlot) using REIMS fingerprints. Lamb products from the Xilin Gol ranch exhibited significantly lower glycerophosphate (PA) content compared to lambs from other regions, while grazing resulted in significantly lower PA content in lamb meat compared to those fed in feedlots. Additionally, meat from grazed lambs had significantly higher unsaturated fatty acid content, providing molecular evidence for its superior nutritional quality and distinct flavor profile compared to the lambs from feedlot systems. REIMS is a promising tool for rapid discrimination of lamb meat from different origins and feeding systems with high accuracy, offering valuable technical support for lamb origin traceability and quality assessment.
Phthalate esters, particularly di(2-ethylhexyl) phthalate (DEHP), are widely used plasticizers found in various consumer products, posing significant environmental and health risks due to their endocrine-disrupting effects. In this study, a novel enzyme-free intra-capacitive biofuel cell self-powered sensor (ICBFC-SPS) was developed. The ICBFC-SPS integrated a ternary heterostructure-based capacitive anode and a cathode with a sensing interface into a single-chamber electrolytic cell. The ternary heterostructure based on Ti3C2Tx MXene with ultra-small Au NPs and polypyrrole (PPy) NPs was prepared to provide the efficient glucose oxidation and robust electron production. Furthermore, the charge storage capacity was significantly enhanced through a synergistic combination of the double-layer capacitor mechanism of Ti3C2Tx and the pseudocapacitive behavior of PPy. Additionally, the intercalation of PPy NPs expanded the interlayer spacing, promoting electrolyte ion diffusion and charge transfer. The ICBFC-SPS demonstrated exceptional sensitivity with a linear detection range from 0.05 to 100000 ng/L and a detection limit of 9.51 pg/L for the sensitive and selective detection of DEHP in complex environmental and biological samples. The ICBFC-SPS addresses the limitations of traditional methods by providing a self-powered, highly sensitive, and portable platform for rapid, on-site DEHP detection. This work underscores the potential of self-powered sensors as transformative tools for real-time environmental monitoring and public health protection.
Green analytical chemistry (GAC), as a manifestation of sustainable development in the analytical field, has become widely recognized and is actively promoted by analysts. The twelve principles of GAC serve as guiding standards for the development of green analytical methods. Mass spectrometry (MS) is a fundamental tool in modern analytical chemistry, and its miniaturized variants have gained significant attention in green chemistry due to their unique advantages. Ambient ionization, a novel technique designed to overcome the limitations of traditional ionization methods, reduces or eliminates the need for sample pretreatment, greatly simplifying the front-end processes in MS analysis. The combination of ambient ionization and miniature MS has become one of the most promising areas of green analysis due to its complementary benefits in reducing solvent use, energy consumption, and the need for sample preparation. This review highlights the green aspects of ambient ionization and miniature MS, emphasizing the enhanced sustainability achieved when the two techniques are used together. Applications of this combination in various fields are also discussed, underscoring their growing importance in GAC.
This study was to investigate the in vitro antimicrobial activity of fish protein hydrolysate (FPH) against Vibrio harveyi, V. anguillarum, and V. scophthalmi, as well as the nonspecific immunity, intestinal microbiota, and disease resistance to V. harveyi in turbot. FPH was prepared from Pollock. The antibacterial activity of FPH was measured by the agar well diffusion, turbidometric assay, and plate count. The feeding trial was performed to study the effect of FPH on the resistance against V. harveyi in turbot after feeding three diets containing a high level of fish meal (FM), a high level of soybean meal (SM), and 100 g/kg FPH. Agar well diffusion showed the clearest inhibition zone of FPH was observed against V. harveyi, followed by V. scophthalmi. The bacterial growth curve and plate count showed a slight antibacterial effect of FPH against V. anguillarum. Results of the feeding trial showed that FPH enhanced antioxidant and immune responses before V. harveyi challenge as modulating immunoglobulin M (IgM), catalase (CAT), and myeloperoxidase (MPO) activities in serum, as well as the number of goblet cells in the intestine. Meanwhile, the expression of some pro‐inflammatory cytokines (interleukin‐1β [il-1β], il-6, and il-8) was downregulated in the FPH group after the V. harveyi challenge. Survival probability in the FPH group increased after challenging to V. harveyi based on the Kaplan–Meier analysis. Results of intestinal microbiota showed the relative abundance of Vibrio in the SM group was the highest, followed by the FPH and control groups. Similarly, the relative abundance of distal intestinal V. harveyi was significantly reduced in the FPH group by analyzing the vhhp2 gene. In conclusion, the present FPH against Vibrio strains was species‐specific, with stronger antibacterial activity to V. harveyi. Dietary FPH enhanced the nonspecific immunity and antibacterial activity of turbot, increasing the resistance to V. harveyi.
A rapid and efficient method of soldering iron cauterization coupled with rapid evaporative ionization mass spectrometry (SIC-REIMS) was developed for fast acquisition of mass spectrometric data from textile samples. This approach utilized a heated electric soldering iron to directly cauterize the sample surface, generating smoke plumes that were simultaneously analyzed by a REIMS system. The method required no sample pretreatment, making it straightforward and time-efficient, with each data acquisition cycle completed within just 4-5 s. The performance of SIC-REIMS was optimized by adjusting key operational parameters, the cone voltage was set to 50 V, the heating bias voltage to 60 V, the auxiliary solvent flow rate to 200 μL/min, and the soldering iron temperature to 450 ℃. These optimized conditions ensured stable and reproducible mass spectrometric signals, which met reproducibility standards for MS analysis. Mass spectrometric data were collected from 39 authenticated textile samples spanning seven fiber categories by SIC-REIMS, including cotton, silk, wool, polyester, polyamide, spandex, and acrylic. The resulting dataset, comprising 359 mass spectra and 4 500 variables (m/z values), was processed with the LiveID software to develop a principal component analysis-linear discriminant analysis (PCA-LDA) model for classifying textile fiber compositions. The PCA-LDA model undergoing five-fold cross-validation achieves a misclassification rate of 2.23%. It exhibits exceptional classification performance for various fiber types, accuracy, precision, recall, and F1 scores exceed 99% for cotton, silk, polyester, and polyamide. For wool, these metrics are not less than 90%, and for spandex and acrylic, they are over 75%. This accuracy makes the method suited for rapid and reliable identification of textile fiber, addressing the needs of rapid quality assessments. Feature importance analysis of the PCA-LDA model combined with Progenesis QI screening identifies 29 characteristic fragment ions specific to the seven fiber categories, including seven ions from cotton, four from silk, three from wool, eight from polyester, five from polyamide, and one each from spandex and acrylic. These characteristic ions provide critical chemical markers for further understanding and classification of textile fibers. The trained PCA-LDA model was subsequently applied to analyze 20 textile samples obtained from the market or online. Using LiveID's offline recognition mode, the predicted results aligned with both the claimed fiber compositions and manual identification results. Overall, the SIC-REIMS method offers a rapid, accurate, and technically advanced solution for textile authentication and quality evaluation, serving as a valuable reference for the authentication and quality control of clothing and textile products.
The achievement of a superlubric state with vanishing friction and negligible wear has important applications in minimizing energy dissipation and prolonging the service life of moving mechanical systems. However, the search for a superlubricious oil system applicable to industrial fields remains a major challenge. In this work, we demonstrate for the first time that precisely employing polyether modification for silicone oil molecules could induce direct superlubricity and superlow wear for engineering steel tribopairs. Superlubricity originates from the fact that polyether-modified silicone oil (PESO) can effectively employ polyether functional groups to interact with friction surfaces, during which a complex tribochemical reaction process can be induced under the catalytic role of friction, where an organic lubricious film composed mainly of carbon, silicon and oxygen can be induced in situ, which can not only effectively passivate friction surfaces but also enable superlubric sliding by virtue of its easy-to-shear nature. Furthermore, iron oxides and chromium oxides could also be confirmed to be distributed within the tribofilm, which is desirable for increasing the load-bearing capability of the tribofilm and toughness. Thus, a remarkable superlubricity of 0.01 without running-in combined with superlow wear was realized at the same time. The results of this work show high promise in promoting the industrial use of oil superlubricity and revolutionizing the development of mechanical systems.
Native mass spectrometry ( MS) is a powerful and complementary tool and has been widely used for the characterization of proteins and protein complexes. Over the past decades, several mass analyzers have been developed with extended mass range and increased mass resolution for the analysis of higher-order structures of native macromolecular assemblies. In particular, the Orbitrap mass analyzer has attracted considerable interest due to its superior desolvation and resolution capabilities. In this review, the recent progress of native Orbitrap-MS in the characterization of higher-order structures of proteins is summarized. A brief introduction to the evolution of Orbitrap mass analyzer and commonly used ionization techniques in Orbitrap mass spectrometers is presented, including electrospray ionization (ESI), nanoESI, and desorption ESI (DESI). Then, four activation techniques in tandem MS and their applications in native Orbitrap-MS are examined. The applications of native Orbitrap-MS are emphasized according to three main aspects: membrane proteins, protein assemblies, and proteoform profiling. Finally, future perspectives and challenges are explored regarding the instrumentation and research orientations of Orbitrap-MS. This review provides the scientific community with a comprehensive understanding of native Orbitrap-MS for the analysis of large macromolecular assemblies and encourages the promotion of Orbitrap-MS.
Mammalian cytosolic selenoprotein thioredoxin reductase (TXNRD1) is crucial for maintaining the reduced state of cellular thioredoxin 1 (TXN1) and is commonly up-regulated in cancer cells. TXNRD1 has been identified as an effective target in cancer chemotherapy. Discovering novel TXNRD1 inhibitors and elucidating the cellular effects of TXNRD1 inhibition are valuable for developing targeted therapies based on redox regulation strategies. In this study, we demonstrated that butein, a plant-derived small molecule flavonoid, is a novel TXNRD1 inhibitor. We found that butein irreversibly inhibited recombinant TXNRD1 activity in a time-dependent manner. Using TXNRD1 mutant variants and LC-MS, we identified that butein modifies the catalytic cysteine (Cys) residues of TXNRD1. In cellular contexts, butein promoted the accumulation of reactive oxygen species (ROS) and exhibited cytotoxic effects in HeLa cells. Notably, we found that pharmacological inhibition of TXNRD1 by butein overcame the cisplatin resistance of A549 cisplatin-resistant cells, accompanied by increased cellular ROS levels and enhanced expression of p53. Taken together, the results of this study demonstrate that butein is an effective small molecule inhibitor of TXNRD1, highlighting the therapeutic potential of inhibiting TXNRD1 in platinum-resistant cancer cells.