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Background: Plasmonic core-shell nanostructures with embedded internal markers used as Raman probes have attracted great attention in surface-enhanced Raman scattering (SERS) immunoassay for cancer biomarkers due to their excellent uniform enhancement. However, current core-shell nanostructures typically exhibit a spherical shape and are coated with a gold shell, resulting in constrained local field enhancement., Results: In this work, we prepared a core-shell AuNR@BDT@Ag structure by depositing silver on the surface of Raman reporter-modified gold nanorods (AuNR). With cysteamine-driven specific deposition of Ag atoms, the internal standard nanoprobes with an ortho-tetrahedral morphology were obtained. Owing to its tetrahedral morphology and the effective plasmon coupling at the Ag-Au interface, this internal standard Raman probe exhibited excellent Raman enhancement. Also, with embedded Raman reporter, the probes of Au nanorod in Ag tetrahedron avoided the desorption of Raman reporter and competitive adsorption of interfering molecule, which greatly improved the stability and reproducibility of SERS signal and addressed the drawbacks of low reproducibility existing in SERS immunoassay. The feasibility of the AuNR@BDT@Ag probe was demonstrated by the sensitive detection of the liver cancer biomarker alpha-fetoprotein (AFP) in Eppendorf (EP) tubes and microfluidic chips. The results in EP tubes revealed a linear range of 1 fg/mL-1 ng/mL and a detection limit of 0.631 fg/mL. When the detection was performed in microfluidic chips, the linear range was 10 pg/mL to 0.1 μg/mL, with a limit detection of 8.29 pg/mL., Significance: The performance of AFP detection in EP tubes and microfluidic chips demonstrates that the tetrahedral core-shell AuNR@BDT@Ag nanostructures used as internal standard Raman probes have the potential to detect biomarkers in blood samples for cancer screening., Competing Interests: Declaration of competing interest 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., (Copyright © 2025 Elsevier B.V. All rights reserved.)

This study characterizes the steroidal saponin diosgenin by theoretical and experimental spectroscopic techniques. Theoretical simulations were performed using the DFT/B3LYP/6-311++G(d,p) basis set to simulate spectroscopic, structural and other properties. Optimized geometries from simulations and experiments showed strong agreement, with R 2 value of 0.99846 for bond lengths and 0.88092 for bond angles. Vibrational spectra revealed distinctive peaks for the methyl, methylene, and methine groups in diosgenin. Solvent-solute interactions on the Frontier Molecular Orbitals (FMO), Molecular Electrostatic Potential (MEP) surfaces, and electronic spectra were analyzed, revealing insights into diosgenin's behavior in different environments. The FMO energy gap shows that polar solvents like acetone, ethanol, and water have wider band gaps (6.22-6.23 eV) than non-polar solvents like benzene, chloroform, and toluene (6.17-6.20 eV), indicating stronger interactions with polar groups, enhanced stability, and reduced reactivity. NBO analysis shows substantial stabilization energy (14.71 kJ/mol) when electrons from oxygen's (O 1 ) lone pair are donated to the anti-bonding orbital of O 2 C 15 through the transition of LP (2) → σ*. The carbon (C 15 ) situated between oxygen (O 1 ) and (O 2 ) exhibits increased electronegativity (-1.65605 e), confirming the electronegativity of the oxygen atoms. Hirshfeld surfaces shows that the crystal structure is mainly influenced by H…H (90.7 %) interaction. Topological analyses revealed molecular interactions and chemical bonding within diosgenin, highlighting its diverse chemical functionalities. Furthermore, molecular docking and ADME predictions underscores diosgenin's potential biological activity against human hexokinase (-8.09 kcal/mol) and phosphofructokinase (-8.35 kcal/mol), suggesting its efficacy as an antitumor drug., Competing Interests: Declaration of competing interest 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., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Accurate detection of multiple pathogens in the early stages of infection is critical for guiding treatment and saving patients' lives, but current methods are still challenged by low sensitivity, poor robustness and long turnaround times. Here, we report a CRISPR/dCas9-based hotspot self-assembling surface-enhanced Raman scattering (SERS) biosensor (called dCasSERS) and its integration with a smartphone to address these challenges. In this design, bacterial DNA was pre-amplified by loop-mediated isothermal amplification (LAMP), and the repeat sequences of the amplicons were recognized by CRISPR/dCas9, providing abundant sites for the assembly of gold nanoparticles (AuNPs) and forming numerous hotspots for SERS analysis. Using AuNPs labeled with different Raman molecules as reporters, the presence of Staphylococcus aureus (S. aureus), Pseudomonas aeruginosa (P. aeruginosa) and Escherichia coli O157:H7 (E. coli O157:H7) could be dexterously converted into distinguishable SERS signals. CRISPR/dCas9-based amplicon-specific recognition and SERS hotspot self-assembly improved the specificity and sensitivity, enabling the biosensor to simultaneously detect three target pathogens down to 1 CFU/mL without any cross-reactivity. By introducing a rapid extraction procedure and a smartphone-integrated handheld Raman spectrometer, rapid on-site analysis of multiple pathogens could be achieved in less than 50 min. The accuracy and robustness of the biosensor were demonstrated by 500 real urine specimens. This study displays a new paradigm for CRISPR/Cas-based self-assembly of SERS hotspots and provides insight into the future development of pathogen screening tools., Competing Interests: Declaration of competing interest 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., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Background: The foodborne pathogens, e.g., Salmonella typhimurium (S. typ) and Staphylococcus aureus (S. aureus), pose a serious threat to human health. Accurate identification, rapid detection and efficient inactivation are crucial in the early diagnosis and treatment of S. typ and S. aureus. To date, however, the majority of studies have only concentrated on the construction of single-function biological platform for detection or inactivation of S. typ and S. aureus. Therefore, it is imperative to develop a multifunctional surface-enhanced Raman scattering (SERS) biosensor that can effectively sterilize S. typ and S. aureus while simultaneously achieving sensitive detection and selective identification., Results: Herein, we designed and constructed a multifunctional SERS biosensor based on sandwich structure of "capture probe/bacteria/signal probe" in order to simultaneously identify, detect and kill S. typ and S. aureus. Aptamer-modified ZnO/Ag was used as a capture probe to accurately identify and capture the target bacteria in complex environments. Au@Ag-4-MPBA-Aptamer was employed as signal probe to provide the corresponding bacterial SERS "fingerprint" information. The SERS enhancement mechanism of the sandwich-structure ZnO/Ag-Au@Ag SERS substrate was discussed. The sandwich-type SERS biosensor exhibited the strong localized surface plasmon resonance (LSPR) effect and the detection limit for S. typ and S. aureus was as low as 10 cfu/mL. Furthermore, the sandwich-type SERS biosensor offered excellent photothermal conversion efficiency (54.32 %), enabling photothermal killing of target bacteria when exposed to laser irradiation., Significance and Novelty: A dual enhancement strategy based on a sandwich structure was proposed to maximize the sensitivity of SERS signals using synergistic action of electromagnetic enhancement and chemical enhancement. SERS enhancement factor (EF) was as high as 4.67 × 10 5 . In addition, the sandwich-type SERS biosensor not only exhibited negligible cytotoxicity, but also was proved to be a promising tool for photothermally inactivate of S. typ and S. aureus in food samples., Competing Interests: Declaration of competing interest 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., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Aging is a multifactorial process that significantly impairs organismal function. Yeast is one of the model organisms used in aging research. Our understanding of the impact of the cell wall on aging remains elusive. Yeast cell wall is a complex and dynamic structure that plays a crucial role in the growth, survival, and aging of Saccharomyces cerevisiae. In this study, we demonstrated for the first time that the deletion of genes involved in cell wall biogenesis leads to significant impact on aging. In this study, we analysed five deletion mutants: crh2Δ, cwp1Δ, flo11Δ, gas1Δ and hsp12Δ. We showed a correlation between Raman spectroscopy signatures assigned to proteins, nucleic acids and RNA and replicative aging. Using Raman spectroscopy, we also revealed that a lack GAS1 gene results in significant changes in the biochemical composition of the cells that may increase sensitivity to environmental stressors. Our data unequivocally indicate that employing yeast as a model in aging research is appropriate, as long as the factors under analysis are not implicated in cell wall biogenesis., Competing Interests: Declarations. Competing interests: The authors declare no competing interests., (© 2025. The Author(s), under exclusive licence to Springer Nature B.V.)

A multifunctional surface-enhanced Raman scattering substrate Fe 3 O 4 @AgNPs@MIL-101 was prepared. Rapid SERS detection of pesticide residues was realized by direct pre-enrichment and separation on the peel surface. MIL-101 has an ortho-octahedral framework and large pore size, which endowed Fe 3 O 4 @AgNPs@MIL-101 with the ability to rapidly adsorb and separate positively charged targets. The introduction of tannic acid realized the in situ growth of AgNPs on the backbone, to modulate the electromagnetic enhancement. Pesticide molecules were adsorbed onto the surface of AgNPs mediated by central S atoms, accompanied by the interaction between pesticide molecules and AgNPs, the corresponding SERS signals of different pesticides were observed. Together with the introduction of magnetic coating Fe 3 O 4 , the molecules were enriched in the hotspot and separated to further enhance the SERS performance. Magnet instead of centrifugation was used to simultaneously perform surface extraction and sample separation for a noninvasive, rapid, immediate, and portable assay. The method was accomplished in measurement of thiram and thiabendazole on apple and tangerine epidermis, and the limits of detection (LODs) were 20 ng/cm 2 and 4 μg/cm 2 , respectively. The recovery was reasonable, and it showed that the procedure is valuable for the rapid and nondestructive surface analysis of residual chemicals., (© 2025 John Wiley & Sons Ltd.)

The disease progression and treatment options of leukemia between different subtypes vary considerably, emphasizing the importance of phenotyping. However, early typing of leukemia remains challenging due to the lack of highly sensitive and specific analytical tools. Herein, we propose a SERS-based platform for the classification of acute lymphoblastic T-cell leukemia (T-ALL) and chronic myeloid leukemia (CML) through the combination of machine learning and microfluidic chips. The ordered arrays in microfluidic channels reshape the microscopic flow field and contacting interfaces, facilitating the uniform and efficient capture of tumor cells. To enable phenotypic analysis, spectrally orthogonal SERS aptamer nanoprobes were applied, providing composite spectral signatures of individual cells in accordance with surface protein expression. Further, machine learning algorithms were employed to analyze the SERS signatures automatically, resulting in an accuracy of 98.6 % for 73 clinical blood samples. The results demonstrate that this platform holds promising potential for clinical leukemia diagnosis and precision medicine., Competing Interests: Declaration of competing interest 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., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Based on inconsistencies observed in literature regarding microplastic levels released by takeaway plastic containers, this study investigates the release from takeaway containers composed of polypropylene (PP), polystyrene (PS), and polyethylene terephthalate (PET). To simulate real-world conditions, experiments were conducted using Milli-Q water at room temperature, 100 °C, and at pH 4.5. Containers were subjected to 20-min exposure with agitation, and microplastics were quantified via optical microscopy, with micro-Raman spectroscopy to confirm the particle polymeric nature. The results indicate that PET and PS containers released microplastic in varying quantities: 9 and 1 at room temperature, 7 and 3 in acidified water, and 17 and 30 at 100 °C, respectively. The particle sizes ranged between 13 and 32 μm. Notably, no microplastics were detected from PP containers under any tested conditions. This study underscores the significant release of microplastics from PET and PS containers, particularly at elevated temperatures, suggesting that PP may represent a safer alternative., Competing Interests: Declaration of competing interest 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., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Solid-state reaction method is employed to prepare K 2 Ba 3 (P 2 O 7 ) 2 :VO 2+ nanopowder and studied by using powder x-ray diffraction (XRD), scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS), Fourier transform infrared (FT-IR) spectroscopy, Raman spectroscopy, optical absorption spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and photoluminescence (PL) spectroscopy. XRD studies revealed VO 2+ ion doped K 2 Ba 3 (P 2 O 7 ) 2 nanopowder have 21 nm crystallite size, orthorhombic phase, and Pmn2 1 space group. From Williamson-Hall analysis, crystallite size is found as 24 nm. SEM morphology recorded the presence of irregular-sized and round-shaped agglomerates. FT-IR and Raman spectra reveal characteristic bands of phosphate groups. Three characteristic peaks are observed at 848, 695, and 452 nm in optical absorption spectrum. Also, crystal and tetragonal field parameters are calculated as Dq = 1439, Ds = -2789, and Dt = 3422 cm -1 . In addition, bandgap energy is found as 3.97 eV. Optical and EPR analyses led to understand the incorporation of vanadyl ions into host lattice. Spin Hamiltonian parameters are evaluated. Basing PL spectrum, Commission Internationale de l'Éclairage's (CIE) chromaticity coordinates are calculated, which are present in reddish-orange region with good color correlated temperature (CCT) and color rendering index (CRI) values facilitating the use in lighting applications and LEDs., (© 2025 John Wiley & Sons Ltd.)

Background Information: The primary objectives of this study were to characterize 3,5-dibromosalicylaldehyde (3,5-DBSA) and, investigate its antiproliferative, antimetastatic, cytotoxic, and immunoregulatory properties. NMR, Raman, UV, and FT-IR spectroscopies were used to characterize 3,5-DBSA. Potential conformations of 3,5-DBSA were evaluated using Spartan's MMFF method. Geometry optimization calculations using Gaussian software calculated conformation energy values., Results: Subsequently, Raman, FT-IR, UV (ethanol) and NMR (DMSO) parameters were calculated. The experimental spectrum was compared to theoretical spectroscopic data. The present investigation investigated 3,5-DBSA's anticancer properties; therefore, docking was done once the stable structure had been identified., Conclusion: Identifying stable structure is crucial to molecular docking studies. In order to identify the mechanism by which 3,5-DBSA binds to PI3K as a therapeutic target, molecular docking was utilized. This work is the first to show that 3,5-DBSA is cytotoxic, anticlonogenic, antimetastatic, and immunomodulatory in glioblastoma cell line U87MG compared to healthy fibroblast L929 cells. Cytotoxicity and anti-clonogenicity studies investigated 3,5-DBSA's antiproliferative activities, whereas wound healing assays assessed cell migration. The immunomodulatory effects of 3,5-DBSA in glioblastoma were assessed by measuring Netrin-1 and IL-6 protein levels. According to our findings, 3,5-DBSA may treat glioblastoma., Significance: This work analyzes 3,5-DBSA's conformational search, characterization, molecular docking, and structural and anticancer properties., (© 2025 Société Française des Microscopies and Société de Biologie Cellulaire de France. Published by John Wiley & Sons Ltd.)

Bone metastases related to breast and prostate cancer present with multiple challenges and skeletal related events like fragility fractures impair the quality of life of the patients significantly. To determine local alterations in bone material quality with bone metastasis, we subjected murine tibial specimens, generated after intratibial injections of either RM1 prostate cancer cells or EO771 breast cancer cells into male and female mice respectively, to high-resolution imaging modalities. Small and wide-angle X-ray scattering showed unaltered mineral characteristics in the more osteosclerotic prostate cancer model, while the quantification of calcium weight percentage via backscattered electron microscopy determined minor differences along the perilacunar bone matrix. Further analyses of mineral and collagen characteristics were performed using Raman spectroscopy and focused ion beam electron microscopy. Our study indicates that alterations in nanochannel properties occur due to the presence of bone seeking tumor cells with more prevalent nanopores in the perilacunar matrix., Competing Interests: Declaration of competing interest 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., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Alzheimer's disease (AD) is a public health concern, for which an early diagnosis is essential. Biomass-derived carbon fibres with surface-decorated silver nanoparticles (Ag@CFs) have been utilized as surface enhanced raman spectroscopy (SERS) sensor platform for the detection of the amyloid beta Aβ (25-35) for the pre-diagnosis of Alzheimer's disease. Structural and morphological characterizations confirmed the distribution of plasmonic silver nanoparticles over the surface of carbon fibres. The SERS sensor performance of Ag@CFs was evaluated using rhodamine 6G, which showed an enhancement of the order of 10 6 which proved the effectiveness of the developed SERS sensor towards trace level detection of analyte. A range of amyloid beta concentrations, from 100uM to 10pM, have been analyzed as a proof-of concept for this study, showcasing the efficacy of the Ag@CFs based SERS sensor to detect trace level concentrations of amyloid beta, even as low as 10 pM. This investigation is a promising development in the field of AD diagnostics since it may turn out to be a non-invasive, economical and early diagnostic tool., (© 2024 Wiley‐VCH GmbH.)

Microplastics intrigue kidney toxicity such as mitochondrial dysfunction and inflammation promotion. However, as an organ relying heavily on fatty acid oxidation, how microplastics influence kidney lipidomes remain unclear. Hence, we performed Raman spectra and multidimensional mass spectrometry-based shotgun lipidomics to decode kidney lipidomics landscape under polypropylene microplastics exposure. Kidney functions and cellular redox homeostasis were remarkably disturbed as revealed by levels of biochemical renal function markers, malonaldehyde, hydrogen peroxide and antioxidants. Ultrastructure alterations including the foot process fusion implied the kidney injury associated with lipidomic changes. Raman spectra successfully further confirmed the cellular change of reactive oxygen species and lipid disorders. Lipidomics showed that polypropylene microplastics caused abnormal lipidome and irregular exchange by remodeling triglycerides and phospholipids. Genes involved in lipid metabolism such as Fads1 and Elovl5 exhibited highly diversified expression profiles responding to polypropylene microplastics stress and possessed significant correlations with ROS indicators. These results explained ultrastructure alterations and aggravation of kidney injuries. Our work revealed polypropylene microplastics inducing lipidomic detriment in mouse kidney by Raman spectra and lipidomics firstly, elucidating the significances of lipidomic remodeling coupled with ROS stress in the kidney damages. The findings provided reliable evidence on the health risks of polypropylene microplastics in kidney., Competing Interests: Declaration of competing interest 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., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Microbes have been increasing their potential against newly developed drugs and antibiotics daily. The increased microbial drug resistance is still a challenging societal inconvenience. 2D nanomaterials, such as graphene, fascinate researchers with their unique physical and chemical properties and have a major role in current science and technology. Nowadays, researchers have been replacing graphene with its analogous 2D material, borophene, which is a single layer of boron with a honeycomb plane. Boron nanosheets which are theoretically investigated, have been synthesized by various top-down and bottom-up approaches. Our study focuses on synthesizing boron-based material from the precursor MgB 2 which possesses a honeycomb boron structure with sandwiched Mg atoms. The Mg atoms have been selectively removed using the chelating agents at alkaline pH. The synthesized boron nanosheets have been characterized by FT-IR, Raman, XRD, FESEM, EDS, and TGA. The formation of B-H-B, B-B and B-O bond is confirmed by FT-IR and Raman spectra. It is also evident from XPS spectra which possess B1s spectra at 193 eV. The efficient chelation and exfoliation is confirmed by EDS and FESEM analysis which shows the presence of boron and trace amount of Mg with bark like projections. Though there are several studies on antibacterial activity of compounds, generally the studies are with laboratory cultures of bacterial strains. Clinical studies offer more valid results and are very sparse in literature. The use of clinical strains in the present study is one of the novelty. It has also been analyzed for its anti-bacterial activity against clinical strains of B. subtilis, S. aureus, E. coli, and K. pneumonia. Boron nanosheets possess an enhanced zone of inhibition (8 mm, 11 mm) against clinical strains of B. subtilis where the micro dilution studies show MIC and MBC values as 125 μg and 62.5 μg. The in vivo toxicity studies carried out using Brine Shrimp Lethality Assay reveal higher LC50 values of boron nanosheets (>1 mg/ml), which in turn portrays its non-toxic nature. Thus, the synthesized boron nanosheets are toxic to multidrug-resistant B. subtilis where it is non-toxic to mammalian cells. Thus, the study could advance the applications of borophene in biomedical applications., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The outbreak of COVID-19 coronavirus disease around the end of 2019 was a pandemic. The virus has been mutated and so many strains like Alpha, Beta, and Omicron are present in different parts of the world. Hence, timely detection technique is important to overcome the diagnostic challenges. Considering the need for this pandemic situation, we used a spectroscopy test methodology to distinguish different strains of Covid-19 by computing the infrared & Raman frequencies and the optical absorption data. Optimization of spike protein of Alpha, and Omicron mutations showed the high value of dipole moment (4.44, and 4.36) Debye, and polarizability [Alpha (233.62), Omicron (228.65)] indicating more bioactivity of Alpha and Omicron instead of Beta. Molecular electrostatic potential map exhibits the presence of electrophilic and nucleophilic region suggesting charge transfer of spikes to accept/donate electrons and hence the system increased reactiveness. UV-Vis absorption analysis also shows electronic transitions (σ to π∗ and π to π∗) due to that protein probe mechanism of Alpha and Omicron becomes increasingly become unsaturated thus confirming its easy binding ability to the target human protein as compared to binding affinity of Beta spike protein., Competing Interests: Declaration of competing interest ƴ 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., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Breast augmentations, commonly performed for aesthetic or medical reasons, often use silicone (polydimethylsiloxane [PDMS]) implants. Some patients develop complications like capsular contracture, where scar tissue forms around the implant. Previously, we used stimulated Raman scattering (SRS) microscopy to detect and quantify silicone in stained capsule tissue, finding a correlation between silicone amount and contracture severity. However, we suspected silicone loss during histological preparation, which includes multiple steps like formalin fixation and paraffin embedding. In this study, we assessed silicone loss by comparing adjacent tissue samples from the same capsule: one prepared conventionally and the other snap-frozen. SRS microscopy revealed that snap-frozen samples had roughly five times more silicone, indicating significant silicone loss during conventional preparation. Thus, measuring silicone in histologically prepared samples likely underestimates PDMS content., (© 2024 The Author(s). Journal of Biophotonics published by Wiley‐VCH GmbH.)

Objective: The anti-caries effects of titanium tetrafluoride (TiF4) are well-documented, but its low pH challenges clinical application. This study evaluated PEG-citrate dendrimer as a carrier to enhance TiF4 stability and efficacy., Methods: PEG-citrate dendrimer and TiF4-dendrimer gel were synthesized, and their structures confirmed using Fourier Transform Infrared Spectroscopy (FTIR), Hydrogen Nuclear Magnetic Resonance (1H NMR), and Liquid Chromatography-Mass Spectrometry (LC-MS). Thirty-six intact human teeth were prepared, randomly divided into three groups (n = 12) and subjected to pH cycling with the following treatments: titanium tetrafluoride (T), dendrimer (D), and dendrimer with TiF4 (TD). Vickers microhardness and Raman spectroscopy evaluated dentin demineralization. EDS analysis measured titanium and fluoride penetration into dentin in T and TD groups and mineral content (calcium and phosphorus) in all groups., Results: The T group showed the highest microhardness loss (p < 0.001), followed by D and TD groups. EDS analysis revealed no significant difference in titanium and fluoride content between the surface and subsurface in TD (p = 0.344), while T had more titanium on the surface (p < 0.001). TD had higher subsurface calcium content compared to T (p = 0.008). Raman spectroscopy revealed significant changes in phosphate-to-amide and carbonate-to-amide ratios before and after pH cycling in all groups (p < 0.001), with no statistical differences among the groups., Conclusion: Using dendrimer as a carrier for TiF4 increased pH and enhanced TiF44 ability to limit dentin demineralization and microhardness loss., Clinical Relevance: The application of the newly-developed TiF4-dendrimer gel might be an effective approach to prevent/ limit dentin demineralization and dentin caries., Competing Interests: Declaration of Competing Interest The authors have no conflicts of interest to declare., (Copyright © 2024. Published by Elsevier Inc.)

Objective: Cartilage pathologic calcification is a hallmark of osteoarthritis (OA). Here, we aimed to describe a new ex vivo human model to study the progression of cartilage calcification., Method: Cartilage explants (n = 11), as well as primary chondrocytes (n = 3), were obtained from OA patients undergoing knee replacement. Explants and chondrocytes were cultured in control (NT) or calcification (CM) medium (supplemented with ascorbic acid and β-glycerophosphate). Calcification was evaluated by micro-CT scan at day 0 and 21 in explants, and by Alizarin red staining in chondrocyte monolayers. Raman spectrometry allowed characterization of the crystal type. Interleukin-6 (IL-6) secretion in explant and cell supernatants was measured by ELISA. Finally, matrix degradation was evaluated by Safranin-O staining of explant sections and by glycosaminoglycans (GAG) released in supernatants., Results: Micro-CT scan showed calcifications in all explants at baseline (day 0), which in the CM group increased significantly in number and size after 21 days compared with the NT group. Raman spectrometry revealed that crystals were exclusively basic calcium phosphate crystals (carbonated hydroxyapatite) both in NT and CM. IL-6 secretion was significantly increased in calcifying conditions. Finally, CM significantly increased cartilage catabolism as assessed by decreased Safranin-O staining of tissue explants and increased GAG release in supernatants. CM effects (enhanced calcification, IL-6 secretion and proteoglycans turn-over) were recapitulated in vitro in OA chondrocytes., Conclusions: We have described a new ex vivo human model of cartilage calcification that can summarize the triad of events seen during osteoarthritis progression, i.e. calcification, inflammation and cartilage degradation. This model will allow the identification of new anti-calcification compounds., (© The Author(s) 2024. Published by Oxford University Press on behalf of the British Society for Rheumatology.)

Objectives: To investigate volumetric changes, in vivo biocompatibility, and systemic migration from eight commercial endodontic sealer materials in paste/paste, powder/liquid, and pre-mixed forms., Materials and Methods: The sealers AH Plus Bioceramic, AH Plus Jet, BioRoot RCS, MTApex, Bio-C Sealer, Bio-C Sealer Ion+, EndoSequence BC Sealer and NeoSEALER Flo were studied. After characterisation by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), Raman spectroscopy and X-ray diffractometry (XRD), tubes were implanted in Wistar rats' alveolar bone and subcutaneous tissues. Micro-CT evaluated volumetric changes pre/post 30 days of implantation. Histological and immunohistochemistry analyses assessed biocompatibility. Kidney samples underwent spectrometry (ICP-MS) for tantalum, tungsten and zirconium. Statistical analysis determined normality and significance (udp < 0.05)., Results: Characterisation revealed calcium, silicon, and radiopacifiers in the materials. Volumetric changes showed greater alteration in subcutaneous tissues than alveolar bone; BioRoot RCS and MTApex (powder/liquid) were most stable. Histological analysis indicated intense inflammation for AH Plus Jet, moderate for others; IL-10 was marked positively for all materials. AH Plus Jet had an 18-fold higher tungsten and a 37-fold higher zirconium mass fraction in kidneys versus controls, while tantalum showed lower accumulation patterns., Conclusion: Root canal filling materials' responses varied by implantation site and form, demonstrating acceptable biocompatibility. Tantalum and zirconium oxide radiopacifiers appear systemically safe; tungsten-based radiopacifiers are unsuitable due to metal accumulation risks., Clinical Relevance: This study highlights the need for further in vivo studies on endodontic sealers' chemical, biological, and physical behaviors and their systemic migration., Competing Interests: Declarations. Ethical approval: This study was approved by the institutional ethics committee animal research of the Piracicaba Dental School (code CEUA 5888-1/2021 and 5889-1/2021). Consent to participate: This study did not involve humans. Competing interests: The authors declare no competing interests., (© 2025. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Rapid and accurate analysis of trace targets in complex samples remains an enormous challenge. Herein, the calix[ x ]arene-based magnetic cross-linked polymer decorating AgNPs, abbreviated Fe 3 O 4 -CXA-DAB@AgNPs nanosponge, was developed for fast surface-enhanced Raman scattering (SERS) analysis in complex samples. The Fe 3 O 4 -CXA-DAB@AgNPs nanosponge surface was constructed by high-density CXA units with special cavity size and structure, which could selectively recognize and enrich targets to the sensing surface by the host-guest effect and molecule interactions. The Fe 3 O 4 -C4A-DAB@AgNPs showed significant SERS enhancement to choline chloride (ChCl) and succinylcholine chloride (SCC) with an enhancement factor (EF) of 2.9 × 10 7 and 6.3 × 10 6 , respectively. The Fe 3 O 4 -C6A-DAB@AgNPs exhibited high SERS activity to thiabendazole with an EF of 7.6 × 10 6 . Introducing recognition-enrichment-separation with SERS sensing, the nanosponge could achieve rapid enrichment sensing of targets within 6-8 min. Also, the Fe 3 O 4 -CXA-DAB@AgNPs nanosponge exhibited good stability for rapid detection with relative standard deviations less than 6.3% for intra-batch ( n = 25) and 6.8% for inter-batch ( n = 15). Benefiting from these merits, the Fe 3 O 4 -C4A-DAB@AgNPs was employed for fast SERS analysis of ChCl and SCC in real samples. The limits of detection were 0.62 μg/L for ChCl and 2.0 μg/L for SCC. ChCl was found in feed sample with recoveries of 85.3-108%, and SCC was found in serum samples with recoveries of 85.7-111%. The methods provided a significant reference for the selective analysis of targets by regulating the calix[ x ]arenes cavity size to satisfy different molecules and rapid quantification strategy by integrating sample pretreatment technology with sensing detection all-in-one.

Early prediction of the neoadjuvant therapy efficacy for HER2-positive breast cancer is crucial for personalizing treatment and enhancing patient outcomes. Exosomes, which play a role in tumor development and treatment response, are emerging as potential biomarkers for cancer diagnosis and efficacy prediction. Despite their promise, current exosome detection and isolation methods are cumbersome and time-consuming and often yield limited purity and quantity. In this study, we employed Raman spectroscopy to analyze the molecular changes in exosomes from the sera of HER2-positive breast cancer patients before and after two cycles of neoadjuvant therapy. Utilizing machine learning techniques (PCA, LDA, and SVM), we developed a predictive model with an AUC value exceeding 0.89. Additionally, we introduced an innovative HER2-positive exosome capture and detection system, termed Magnetic beads@HER2-Exos@HER2-SERS detection nanoprobes (HER2-MEDN). This system enabled us to efficiently extract and analyze HER2-positive exosomes, refining our predictive model to achieve an accuracy greater than 0.94. Our study has demonstrated the potential of the HER2-MEDN system in accurately predicting early treatment response, offering novel insights and methodologies for assessing the efficacy of neoadjuvant therapy in HER2-positive breast cancer.

The fabrication of high-performance microbial fuel cells requires the evaluation of the activity of electrochemically active bacteria. However, this is challenging because of the time-consuming nature of biofilm formation and the invasive nature of labeling. To address this issue, we developed a fast, label-free, single-cell Raman spectroscopic method. This method involves investigating the "pure" linear Stark effect of endogenous CO in the silent region of biological samples, which allows for probing the intrinsic electric field in the outer-membrane cytochromes of live bacterial cells. We found that reduced outer-membrane cytochromes can generate an additional intrinsic electric field equivalent to an applied potential of +0.29 V. We also found that the higher the electrical activity of the cell, the larger the generated electric field. This was also reflected in the output current of the constructed microbial fuel cells. Raman spectroscopy was employed to facilitate the assessment of electrochemical activity at the single-cell level in highly-diluted bacterial samples. After analysis, inactive bacteria were ablated by laser heating, and 20 active cells were cultured for further testing. The rapid and high-throughput probing of the intrinsic electric field offers a promising platform for high-efficiency screening of electrochemically active bacterial cells for bioenergetic and photosynthetic research., (© 2024 Wiley-VCH GmbH.)

We fabricated flexible, three-dimensional (3D) ordered silicon nanowire (SiNW) arrays decorated with high-density silver nanoparticles (AgNPs) for the sensitive and reproducible detection of pesticide residues. These sensors demonstrated a detection limit of 10 -9 M for methyl parathion (MPT) on curved surfaces.

To evaluate the effect of sulfinate salt on the bond performance of a two-step self-etch adhesive to an intracoronally bleached pulpal dentin surface. Intracoronally bleached bovine teeth were treated with or without sulfinate salt (sulfinate agent (SA): Clearfil DC activator) before 2-SEA (Clearfil SE Bond 2) application, while unbleached teeth served as the control (n = 5 teeth). Microtensile bond strength (µTBS) using the bonded surface area of 1 mm 2 at the crosshead speed of 1 mm/min measurements after 24 h storage and thermocycles (TC), degree of conversion (DC) analyses by Raman spectroscopy (n = 3 teeth), ultrastructure of resin-dentin interface (n = 3 teeth), and intracoronally bleached pulp chamber dentin surface (n = 3 teeth) observations by scanning electron microscopy (SEM) were subsequently performed. Data were analyzed using the one-way ANOVA, Tukey's post-hoc, and paired t-test. SA significantly increased the initial µTBS to bleached pulp chamber dentin surfaces (from 34.7 ± 4.5 to 50.6 ± 5.2 MPa, p < 0.001) and maintained post-TC bond durability (49.5 ± 8.8, p = 0.58). The application of SA also significantly increased DC on bleached pulp chamber dentin (p < 0.001). Interestingly, the highest DC was found in the SA group. SEM analyses revealed no obvious alteration in surface morphology; however, numerous and longer resin tags were observed at the resin-dentin interface in the bleached group, regardless of SA application. SA could improve bond performance together and enhance the polymerization of 2-SEA to intracoronally bleached pulp chamber dentin., Competing Interests: Declarations. Competing interests: The authors declare no competing interests., (© 2025. The Author(s).)

A range of novel simple gold(III) compounds has been synthesized in their monocrystalline form, including two previously unknown chloro-complexes of Au 3+ with 2-cyanopyridine or 3-cyanopyridine, respectively. Our investigations have revealed the intricate nature of the reaction between 2-cyanopyridine and tetrachloroauric acid, yielding at least three distinct products. The main product, obtained in high yield, is a salt featuring a tetrachloroauric anion and a pyridinium cation stabilized by a hydrogen bond to a further 2-cyanopyridine molecule. Moreover, we observed the in-situ formation of a 2-cyanopyridine-AuCl 3 complex, which undergoes hydrolysis of the nitrile bond to yield a picolinamide-Au(III) complex. The complexes were characterized by IR and Raman spectroscopies, NMR spectroscopy, and single-crystal XRD studies. Additional computational studies were conducted to explain unusual spectral features, the observed disparities in the complexation reactions of the three isomeric cyanopyridine ligands and the distinct reactivity of the complex with 2-cyanopyridine. Based on these studies, we propose a mechanism for the catalyzed hydrolysis of the nitrile bond within the Au(III) complex. Finally, we assessed the antimicrobial efficacy of the synthesized gold(III) complexes against a spectrum of bacteria and fungi., Competing Interests: Declaration of competing interest 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., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Microplastic contamination has emerged as a global environmental concern, while the limitation of single-technique identification methods in complex biological matrices calls for multi-analytical approaches for accurate microplastic detection. This study pioneers a dual-method approach, combining Raman spectroscopy and pyrolysis gas chromatography-mass spectrometry (Py-GC/MS), to investigate microplastics in human amniotic fluid. In total, samples from 48 pregnant women were collected and analyzed under stringent quality control measures, then Raman spectroscopy and Py-GC/MS were employed for comprehensive polymer identification and verification. Our analysis revealed 6 distinct microplastic polymer types in 39 subjects, with an average particle size of 3.05 ± 1.05 µm, polytetrafluoroethylene (PTFE, 31.25 %), polystyrene (PS, 20.83 %), and acrylonitrile-butadiene-styrene (ABS, 14.58 %) being the most prevalent. Py-GC/MS analysis corroborated the Raman spectroscopy findings, identifying pyrolytic markers such as fluoroethylene for PTFE and styrene for PS. However, no significant associations were found between microplastic exposure and immediate adverse pregnancy outcomes. This study, for the first time, utilizes a dual-method approach combining Raman spectroscopy and Py-GC/MS to conclusively demonstrate the presence of diverse microplastics in human amniotic fluid, which underscores the need for larger-scale, longitudinal investigations to elucidate the potential long-term health implications of microplastic exposure., Competing Interests: Declaration of Competing Interest 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., (Copyright © 2024 Elsevier B.V. All rights reserved.)

High-sensitivity and repeatable detection of hydrophobic molecules through the surface-enhanced Raman scattering (SERS) technique is a tough challenge because of their weak adsorption and non-uniform distribution on SERS substrates. In this research, we present a simple self-assembly protocol for monolayer SERS mediated by 6-deoxy-6-thio-β-cyclodextrin (β-CD-SH). This protocol allows for the rapid assembly of a compact silver nanoparticle (Ag NP) monolayer at the oil/water interface within 40 s, while entrapping analyte molecules within hotspots. The proposed method shows general applicability for detecting hydrophobic molecules, exemplified as Nile blue, Nile red, fluconazole, carbendazim, benz[a]anthracene, and bisphenol A. The detection limits range from 10 -6 to 10 -9 M, and the relative standard deviations (RSDs) of signal intensity are less than 10%. Moreover, this method was used to investigate the release behaviors of a hydrophobic pollutant (Nile blue) adsorbed on the nanoplastic surface in the water environment. The results suggest that elevated temperatures, increased salinities, and the coexistence of fulvic acid promote the release of Nile blue. This simple and fast protocol overcomes the difficulties related to hotspot accessibility and detection repeatability for hydrophobic analytes, holding out extensive application prospects in environmental monitoring and chemical analysis.

Fibroblast activation protein (FAP) is an important antigen in the tumor microenvironment, which plays a crucial role in promoting extracellular matrix remodeling and tumor cell metastasis. A circulating form of soluble FAP has also been identified in the serum, becoming a biomarker for pan-cancer diagnosis and prognosis. However, the current peptide substrate-based enzymatic activity detection or antibody-dependent detection methods have been hindered by insufficient selectivity and complex operations, so it is valuable to develop effective nucleic acid aptamers as FAP affinity ligands. In order to deeply explore the biomimetic recognition technology, this study proposed an elaborate aptamer screening strategy for targeting the protein characteristic structure. Taking the glycosylation of the FAP protein as a target, four FAP-specific aptamers with high performance were successfully generated. Further, using the champion aptamer as a recognition tool and combining it with ultrasensitive detection technology-surface enhanced Raman scattering (SERS), a novel dual aptamer-based sandwich sensor was constructed for the rapid determination of FAP. Due to the dual-specific recognition of the orthogonal aptamer pair, the sandwich method obviously improved the selectivity to FAP protein, with a maximum cross-reactivity of less than 8% and a quantitation limit of 100 pg/mL. It was conveniently applied in high-sensitive and high-selective detection of serum FAP in cancer patient samples. Therefore, the research of this study not only opens new access for the selection of antiglycan aptamers but also boosts the application of the FAP aptamer as a recognition tool in cancer diagnostics.

Plastic pollution, particularly from microplastics (MPs) and nanoplastics (NPs), has become a critical environmental and health concern due to their widespread distribution, persistence, and potential toxicity. MPs and NPs originate from primary sources, such as cosmetic microspheres or synthetic fibers, and secondary fragmentation of larger plastics through environmental degradation. These particles, typically less than 5 mm, are found globally, from deep seabeds to human tissues, and are known to adsorb and release harmful pollutants, exacerbating ecological and health risks. Effective detection and quantification of MPs and NPs are essential for understanding and mitigating their impacts. Current analytical methods include physical and chemical techniques. Physical methods, such as optical and electron microscopy, provide morphological details but often lack specificity and are time-intensive. Chemical analyses, such as Fourier transform infrared (FTIR) and Raman spectroscopy, offer molecular specificity but face challenges with smaller particle sizes and complex matrices. Thermal analytical methods, including pyrolysis gas chromatography-mass spectrometry (Py-GC-MS), provide compositional insights but are destructive and limited in morphological analysis. Emerging (bio)sensing technologies show promise in addressing these challenges. Electrochemical biosensors offer cost-effective, portable, and sensitive platforms, leveraging principles such as voltammetry and impedance to detect MPs and their adsorbed pollutants. Plasmonic techniques, including surface plasmon resonance (SPR) and surface-enhanced Raman spectroscopy (SERS), provide high sensitivity and specificity through nanostructure-enhanced detection. Fluorescent biosensors utilizing microbial or enzymatic elements enable the real-time monitoring of plastic degradation products, such as terephthalic acid from polyethylene terephthalate (PET). Advancements in these innovative approaches pave the way for more accurate, scalable, and environmentally compatible detection solutions, contributing to improved monitoring and remediation strategies. This review highlights the potential of biosensors as advanced analytical methods, including a section on prospects that address the challenges that could lead to significant advancements in environmental monitoring, highlighting the necessity of testing the new sensing developments under real conditions (composition/matrix of the samples), which are often overlooked, as well as the study of peptides as a novel recognition element in microplastic sensing.

Graphite oxidation to graphene oxide (GO) is carried out using methods developed by Brodie (GO-B) and Hummers (GO-H). However, a comparison of the antibacterial properties based on the physicochemical properties has not been performed. Therefore, this paper outlines a comparative analysis of GO-H and GO-B on antibacterial efficacy against Gram-positive and Gram-negative bacterial cultures and biofilms in an aqueous environment and discusses which of the properties of these GO nanomaterials have the most significant impact on the antibacterial activity of these materials. Synthesis of GO with Brodie's and modified Hummers' methods was followed by an evaluation of their structural, morphological, and physicochemical properties by Raman, FTIR, UV-vis spectroscopy, and X-ray diffraction (XRD). The GO-B surface appeared more oxidized than that of GO-H, which could be crucial for interactions with bacteria. According to our results, GO-B demonstrated notably superior anti-biofilm efficacy. Despite its higher production cost, GO-B exhibits more excellent capabilities in combating bacterial biofilms than GO-H.

Background: Treatment of deep carious lesions poses significant challenges in dentistry, as complete lesion removal risks compromising pulp vitality, while selective removal often reduces the longevity of restorations. Herein, we propose a minimally invasive approach using High-Intensity Focused Ultrasound (HIFU) for microscale removal of carious dentine. Concurrently, HIFU's antimicrobial effects against associated cariogenic biofilms and the corresponding thermal and biological impacts on surrounding tissues were investigated., Methods: A total of 238 sound human molars were utilized, with 203 samples of artificial carious-simulated dentine (ACSD) prepared for HIFU exposure. HIFU (250 kHz) was applied at 20 W for varying durations (60, 120, and 180 s). The acoustic waves were administered via a collimated cone coupled to the dentine surface using ultrasonic gel., Results: Advanced characterization techniques including scanning electron microscopy (n = 5/group), Raman spectroscopy, atomic force microscopy, and nano-indentation (n = 5/group), demonstrated HIFU's effectiveness in removing demineralized collagen-fibrils. This was reflected in the increased mineral content, nano-hardness, and reduced elastic-modulus of ACSD lesions. Micro-CT (n = 6/group) confirmed the increase in mineral density post-HIFU exposure. Confocal microscopy of Rhodamine-B stained ACSD (n = 5/group) quantified the depth of dentine microscale removal post-HIFU exposure in a time-dependent manner. HIFU's potent anti-biofilm effect (n = 9/group) against Streptococcus mutans biofilms was evidenced by microscopic characterizations and significant reductions in metabolic-activity and colony-forming units. Furthermore, HIFU promoted the proliferation of dental pulp stem cells (n = 3/group) while maintaining the associated temperature-rise within the physiological tolerance., Conclusion: HIFU's potential as an innovative, minimally invasive, non-ionizing tool for dentine carious lesion micromanipulation was demonstrated through the interaction between focused acoustic waves and dentine, warranting further studies for future clinical translation in restorative and/or preventive dentistry., Competing Interests: Declarations. Ethical approval: Ethical approval was obtained from the University of Western Australia Human Research Ethics Committee (grant# RE 2019/RA/4/20/5863). Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

Nucleic acid aptamers are single-stranded oligonucleotides that are selected through exponential enrichment (SELEX) technology from synthetic DNA/RNA libraries. These aptamers can specifically recognize and bind to target molecules, serving as specific recognition elements. Surface-enhanced Raman scattering (SERS) spectroscopy is an ultra-sensitive, non-destructive analytical technique that can rapidly acquire the "fingerprint information" of the measured molecules. It has been widely applied in qualitative and trace analysis across various fields, including food safety, environmental monitoring, and biomedical applications. Small molecules, such as toxins, antibiotics, and pesticides, have significant biological effects and are harmful to both human health and the environment. In this paper, we mainly introduced the application and the research progress of SERS detection with aptamers (aptamer-based SERS techniques) in the field of small-molecule detection, particularly in the analysis of pesticide (animal) residues, antibiotics, and toxins. And the progress and prospect of combining the two methods in detection were reviewed.

Raman Optical Activity combined with Circularly Polarized Luminescence (ROA-CPL) was used in the spectral recognition of glutathione peptide (GSH) and its model post-translational modifications (PTMs). We demonstrate the potential of ROA spectroscopy and CPL probes (EuCl 3 , Na 3 [Eu(DPA) 3 ], NaEuEDTA) in the study of unmodified peptide, i.e. GSH, and its derivatives, i.e. glutathione oxidized (GSSG), S-acetylglutathione (GSAc) and S-nitrosoglutathione (GSNO). ROA spectral features of GSH, GSSG, and GSAc were determined along with thier changes upon the different pH conditions. Apart from the ROA, induced CPL signals of Eu(III) probes also proved to be sensitive to the structural modifications of GSH-based model PTMs, enabling their spectral recognition, especially by the NaEuEDTA probe., Competing Interests: Declaration of competing interest 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., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Real-time monitoring of mRNA in living cells is crucial for understanding dynamic biological processes. Traditional methods such as northern blotting, PCR, and sequencing require cell lysis and do not allow for continuous observation. Fluorescence-based techniques have advanced this field, but they are limited by photobleaching, which hinders long-term monitoring. In this study, we designed a dual-probe system combining fluorescence and surface-enhanced Raman scattering (SERS) signals to monitor mRNA in living cells. Our system uses silica nanoparticles (SiNPs) with DNA sequences which are hybridized with fluorescent DNA sequences and DNA-modified gold nanoparticles (AuNPs) to detect heat shock protein 70A mRNA, which can be induced by photothermal damage from laser exposure. Following nanoparticle uptake and induction of heat shock, we observed a time-dependent decrease in fluorescence intensity and increase in SERS intensity, indicating successful mRNA monitoring in living cells. These findings suggest that our dual-probe system with SiNPs and AuNPs is a promising nanotechnological platform for sensitive, long-term monitoring of gene expression in living cells, offering significant potential for future biological and medical research.

Exosomes have emerged as a promising noninvasive biomarker for early cancer diagnosis due to their ability to carry specific bioinformation related to cancer cells. However, accurate detection of trace amount of cancer-derived exosomes in complex blood remains a significant challenge. Herein, an ultra-highly sensitive SERS sensor, powered by the branched hybridization chain reaction (bHCR) and tetrahedral DNA-based trivalent aptamer (triApt-TDN), has been proposed for precise detection of cancer-derived exosomes. Taking gastric cancer SGC-7901 cells-derived exosomes as a test model, the triApt-TDNs were constructed by conjugating aptamers specific to mucin 1 (MUC1) protein with tetrahedral DNAs and subsequently immobilized on the surface of silver nanorods (AgNRs) arrays to create SERS-active sensing chips capable of specifically capturing exosomes overexpressing MUC1 proteins. The bHCR was further initiated by the trigger aptamers (tgApts) bound to exosomes, and as a result the SERS tags were assembled into AuNP network structures with abundant SERS hotspots. By optimizing the sensing conditions, the SERS sensor showed good performance in ultra-highly sensitive detection of target exosomes within 60 min detection time, with a broad response ranging of 1.44 to 1.44 × 10 4 particles·μL -1 and an ultralow limit of detection capable of detecting a single exosome in 2 μL sample. Furthermore, the SERS sensor exhibited good uniformity, repeatability and specificity, and capability to distinguish between gastric cancer (GC) patients and healthy controls (HC) through the detection of exosomes in clinical human serums, indicating its promising clinical potential for early diagnosis of gastric cancer., Competing Interests: Declaration of competing interest 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., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Cytochrome c oxidase (CcO) is the terminal enzyme in the electron transfer chain in mitochondria. It catalyzes the four-electron reduction of O 2 to H 2 O and harnesses the redox energy to drive unidirectional proton translocation against a proton electrochemical gradient. A great deal of research has been conducted to comprehend the molecular properties of CcO. However, the mechanism by which the oxygen reduction reaction is coupled to proton translocation remains poorly understood. Here, we review the chemical properties of a variety of key oxygen intermediates of bovine CcO (bCcO) revealed by time-resolved resonance Raman spectroscopy and the structural features of the enzyme uncovered by serial femtosecond crystallography, an innovative technique that allows structural determination at room temperature without radiation damage. The implications of these data on the proton translocation mechanism are discussed., Competing Interests: Declaration of competing interest 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., (Copyright © 2024 Elsevier Inc. All rights reserved.)

This study explores the integration of Raman spectroscopy (RS) with machine learning for the early detection and subtyping of breast cancer using blood plasma samples. We performed detailed spectral analyses, identifying significant spectral patterns associated with cancer biomarkers. Our findings demonstrate the potential for classifying the four major subtypes of breast cancer at stage Ia with an average sensitivity and specificity of 90% and 95%, respectively, and a cross-validated macro-averaged area under the curve (AUC) of 0.98. This research highlights efforts to integrate vibrational spectroscopy with machine learning, enhancing cancer diagnostics through a non-invasive, personalised approach for early detection and monitoring disease progression. This study is the first of its kind to utilise RS and machine learning to classify the four major breast cancer subtypes at stage Ia., (© 2024 The Author(s). Journal of Biophotonics published by Wiley‐VCH GmbH.)

Demineralization of the chemically treated pig shoulder bone in hydrochloric, hydrofluoric, and acetic acid was monitored by ATR-FTIR, Raman, and LIBS spectroscopies and SEM-EDX technique. SEM-EDX analysis showed reduced calcium and phosphorus content after the treatment with acids and erosion of the overall morphology of the bone compared to the sample kept in water. Alterations in bone structure during the 14-day-long immersion in acid solutions indicated significant chemical changes in the obtained spectra. Fourier deconvolution applied in the amide I (1700-1600 cm -1 ), phosphate (900-1200 cm -1 ), and carbonate (500-650 cm -1 ) region indicated the presence of different components in the bone sample, depending on the environment and acid concentration, providing information about the composition. Parameters such as mineral-to-matrix ratio, crystallinity index, and carbonate-to-phosphate ratio were calculated and compared using ATR-FTIR and Raman data. These parameters were also correlated with calcium ionic-to-atomic and phosphorous-to-carbon line intensities obtained from LIBS spectra. Calcium and phosphorus atomic contents obtained by SEM-EDX analysis were in agreement with LIBS data. The results suggested that an increase in acid concentration has primarily affected the phosphate band's intensity and structure, as the phosphate content was more susceptible to demineralization. Hydrochloric acid was proven to be a more powerful demineralization agent than hydrofluoric and acetic acids. The results of this study could be further applied to the investigation of the bone remains at the crime scene, especially when their removal is attempted by immersion in acid solutions., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Dusan Dimic reports financial support was provided by Ministry of Science, Technological Development and Innovation of the Republic of Serbia. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Optimization of the manufacturing process based on scientific evidence is essential for quality control of active pharmaceutical ingredients. Real-time monitoring can ensure the production of stable quality crystals in the crystallization process. Raman spectroscopy is an attractive tool for pharmaceutical quality evaluation and process analytical technology because of its ability to analyze samples non-destructively and rapidly. In this study, we attempted to monitor the crystal polymorphs of carbamazepine (CBZ I and CBZ III) during the dissolution and crystallization processes using low-frequency Raman spectroscopy, which can reflect differences in lattice vibrations originating from polymorphs in the scattering peaks. Furthermore, using multivariate analysis of the obtained spectra, we attempted to develop a model that enables the quantification of each polymorph. A partial least squares was performed to build the prediction model. The prediction model was built using a set of 33 calibration samples, and an external set of 12 validation samples was used to evaluate the model. The model presents a good prediction capacity. The quantitative results for the solid amount of carbamazepine in suspension calculated using the model during the dissolution and crystallization process showed results that correlated very well with the particle view results. It is suggested that low-frequency Raman spectroscopy can be used as a useful process analytical technology tool.

Objective: To evaluate the impact of sterilization methods on the structural integrity and antimicrobial properties of graphene nanocoating on titanium (GN)., Methods: GN was transferred to titanium using wet (WT) or dry transfer (DT) techniques and sterilized using an autoclave (AC), glutaraldehyde (GA), or ethylene oxide (EtO). The GN structure was characterized using Raman spectroscopy before and after sterilization. Additional specimens were characterized by Raman after AC and water jetting. Biofilm formation was assessed before and after AC using colony-forming units (CFU), biofilm biomass, and SEM (uncoated titanium was the control). Three independent samples were used for structural characterization and biofilm quantification. Statistical analyses were conducted using one-way analysis of variance (ANOVA) and Tukey's test (α = 0.05)., Results: WT and DT demonstrated high structural stability after sterilization and water jetting, with negligible coating quality or coverage loss. GN exhibited lower biofilm formation even after AC sterilization, as shown by the reduction in CFU counts, biofilm biomass, and SEM images compared to the control., Significance: GN demonstrated high resistance to the stresses imposed by all sterilization methods tested, maintaining its structural integrity, resistance to water-jet cleaning, and antibiofilm potential. The findings suggest that standard industrial practices can effectively sterilize highly resilient GN on titanium implants and possibly other biomaterials., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Microplastics are a new type of pollutants that have attracted attention recently. However, there is limited research on the uptake of environmental microplastics by plants. In this study, scanning electron microscopy (SEM), micro-Raman spectroscopy, and Raman mapping were employed to identify and detect label-free micron-sized polystyrene (PS) microplastics accumulated in the roots and stems of maize (Zea mays L.) seedlings. The results demonstrated that the Raman spectra of PS microplastics were predominantly concentrated in the xylem and ducts of seedlings, confirming the transfer behavior of microplastics in the plants. The Raman spectra of PS microplastics in seedlings exhibited distinctive peaks at 621, 1002, 1030, and 1604 cm -1 , and the matching scores of these spectra with the standard PS Raman spectrum ranged from 40.61 % to 86.93 %. Additionally, the Raman mapping facilitated the precise identification and visualization of microplastics within the roots and stems of seedlings. The smallest size of the detected PS microplastics was ∼2 μm. This study provides new insights into the use of Raman spectroscopy for the detection of microplastics in plants., Competing Interests: Declaration of competing interest 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., (Copyright © 2024. Published by Elsevier B.V.)

Surface-enhanced Raman spectroscopy (SERS) was utilized to measure low-level fentanyl concentrations mixed in common cutting agents, cocaine, 3,4-methylenedioxymethamphetamine (MDMA), methamphetamine, and caffeine. Mixtures were prepared with a fentanyl concentration range of 0-339 μM. Data was initially analyzed by plotting the area of a diagnostic peak (1026 cm -1 ) against concentration to generate a calibration model. This method was successful with fentanyl/MDMA samples (LOD 0.04 μM) but not for the other mixtures. A chemometric approach was then employed. The data was evaluated using principal component analysis (PCA), partial least squares (PLS1) regression, and linear discriminant analysis (LDA). The LDA model was used to classify samples into one of three designated concentration ranges, low = 0-0.4 mM, medium = 0.4-14 mM, or high >14 mM, with fentanyl concentrations correctly classified with greater than 85% accuracy. This model was then validated using a series of "blind" fentanyl mixtures and these unknown samples were assigned to the correct concentration range with an accuracy >95%. The PLS1 model failed to provide accurate quantitative assignments for the samples but did provide an accurate prediction for the presence or absence of fentanyl. The combination of the two models enabled accurate quantitative assignment of fentanyl in binary mixtures. This work establishes a proof of concept, indicating a larger sample size could generate a more accurate model. It demonstrates that samples, containing variable, low concentrations of fentanyl, can be accurately quantified, using SERS., (© 2024 American Academy of Forensic Sciences.)

Immunotherapy represents a promising therapeutic strategy for cancer treatment, but its clinical applications are currently hindered by insufficient therapeutic potency, nonspecific delivery, and adverse side effects. Herein, a novel near-infrared II (NIR-II) photo-triggered plasmonic hyperthermia immunomodulator (RP@IR-pcNS@HA nanoparticles (NPs)) for anticancer treatment of both primary and distant cancers is reported. This immunomodulator comprises an IR-1061 dye-encoded NIR-II porous cubic AuAg nanoshell (pcNS) loaded with a Toll-like receptor 7 agonist - R837 in phase change materials (PCMs), further modified with hyaluronic acid (HA). In response to NIR-II photoirradiation, the RP@IR-pcNS@HA NPs controllably deliver and release R837 to tumor sites, subsequently perform plasmonic hyperthermia therapy for direct ablation of primary tumors, and elicit robust anticancer immune responses. It is demonstrated that upon NIR-II irradiation, such a plasmonic hyperthermia immunomodulator combined with anti-programmed death 1 antibody (αPD-1) completely eradicates both primary and distant cancers. In addition, this combination treatment successfully elicits robust immune memory responses for effective suppression of recurrence and distant metastasis of cancer. With the excellent NIR-II surface-enhanced Raman scattering (SERS) detection ability, the RP@IR-pcNS@HA NPs combined with αPD-1 represent an efficient way to develop high-performance theranostic agents for SERS-guided combination cancer photoimmunotherapy., (© 2024 Wiley‐VCH GmbH.)

Current industrial separation and sorting technologies struggle to efficiently identify and classify a large part of Waste of Electric and Electronic Equipment (WEEE) plastics due to their high content of certain additives. In this study, Raman spectroscopy in combination with machine learning methods was assessed to develop classification models that could improve the identification and separation of Polystyrene (PS), Acrylonitrile Butadiene Styrene (ABS), Polycarbonate (PC) and the blend PC/ABS contained in WEEE streams, including black plastics, to increase their recycling rate, and to enhance plastics circularity. Raman spectral analysis was carried out with two lasers of different excitation wavelengths (785 nm and 1064 nm) and varying setting parameters (laser power, integration time, focus distance) with the aim at reducing the fluorescence. Raman spectral data were used to train and test Discriminant Analysis (DA) and Support Vector Machine (SVM) algorithms in an iterative procedure to assess their performance in identifying and classifying real WEEE plastics. Analysis settings were optimized considering industry requirements, such as process productivity (classification rate, short measuring time for fast identification) and product quality (purity of the sorted polymers). Classification models were trained, in a first approach, only on the target WEEE plastics; and in a second approach, on all polymers expected in the WEEE stream, leading to a realistic overview of the potential scalability of the advanced sorting methods and their limitations. The best classification models, based on DA of Raman spectral data obtained with the 1064 nm laser at 500 mW and 1.0 s, led to classify PS and ABS with a purity up to 80 %., Competing Interests: Declaration of competing interest 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., (Copyright © 2025 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Cerium pollution in waterbodies by improper industrial waste disposal is a major concern due to its detrimental impacts on the environment. Therefore, treatment of cerium-contaminated water is inevitable. Hence, this study is focused on the remediation of cerium pollution using phosphoric acid-activated biochar (PPMB) as an adsorbent, synthesized upon pyrolytic activation of palmyra palm male flower-based pristine biochar (PMFB) with H 3 PO 4 at 500 °C. The physico-chemical surface properties of PMFB and PPMB were evaluated through various microscopic and spectroscopic analyses. The key parameters such as biochar dosage, pH, temperature, contact time and initial cerium concentration were optimized as 0.5 g/L, 5.0, 303 K, 180 min and 50 mg/L respectively via batch adsorption. Pseudo-second order kinetic and Toth isotherm are the best-fitted models. The thermodynamic parameters including ΔG ◦ (-30.4707 ± 0.7618 kJ/mol at 303 K), ΔH ◦ (16.1499 ± 0.78 kJ/mol), and ΔS ◦ (153.617 ± 3.8404 J/mol/K) conveying that cerium adsorption onto PPMB was spontaneous, endothermic, and highly disordered at PPMB-bulk adsorption medium interface. Precipitation, electrostatic attraction, and surface complexation are predicted to be the predominant mechanisms for the chosen PPMB-cerium adsorption system. Moreover, cerium phytotoxicity on Vigna radiata explains the real-time applicability and feasibility of cerium adsorption using PPMB. Thus, the key findings of this study specified that the higher adsorption capacity of PPMB (141.3484 ± 6.9856 mg/g) contributed by the incorporated phosphate groups, predominant mesoporosity, SSA BET of 230.559 m 2 /g and anionic surface at a wider pH range (pH>3.08) make PPMB as efficient, economically feasible and environmentally friendly adsorbent for cerium adsorption in aqueous system., Competing Interests: Declaration of competing interest 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., (Copyright © 2024 Elsevier Inc. All rights reserved.)

We aim to evaluate the feasibility of Raman spectroscopy for parathyroid gland (PG) identification during thyroidectomy. Using a novel side-viewing handheld Raman probe, a total of 324 Raman spectra of four tissue types (i.e., thyroid, lymph node, PG, and lipid) commonly encountered during thyroidectomy were rapidly (< 3 s) acquired from 80 tissue sites (thyroid [n = 10], lymph node [n = 10], PG [n = 40], lipid [n = 20]) of 10 euthanized Wistar rats. Two partial least-squares (PLS)-discriminant analysis (DA) detection models were developed, differentiating the lipid and nonlipid (i.e., thyroid, lymph node, and PG) tissues with an accuracy of 100%, and PG, lymph node, and thyroid could be detected with an accuracy of 98.4%, 93.9%, and 95.4% respectively. This work demonstrates the feasibility of Raman spectroscopy technique for PG identification and protection during thyroidectomy at the molecular level., (© 2024 Wiley‐VCH GmbH.)

Chiral Au@Pt nanoparticles (NPs) with optically plasmonic and catalytic active surfaces were sustainably prepared to serve as label-free surface enhanced Raman scattering (SERS) platform to distinguish D- and L-enantiomers of alanine and tartaric acid. Surface morphologies were characterized by high-angle annular dark-field imaging-scanning transmission electron microscopy (HADDF-STEM) and selected area energy diffraction (SAED) patterns. The amounts of Pt on chiral Au NPs were estimated by the inductively coupled plasma-optical emission spectrometer (ICP-OES) and X-ray diffraction (XRD). The versatile applications including the environmental hazardous species monitoring and the fundamental enantiomeric differentiation are demonstrated for the novelty of prepared materials. Au@Pt NPs were used as a unique platform of H 2 O 2 and Hg 2+ concentrations using UV-Vis absorption and surface enhanced Raman scattering (SERS). The chiral Au@Pt NP platform may provide an efficient approach to achieve chiral nanocatalysis for numerous chemical reactions., Competing Interests: Declaration of competing interest 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., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Humans exposed to altitude hypoxia experience dysfunctions of the urinary system. As a non-invasive, easily manageable and informative biological sample, urine represents a relevant matrix for detecting clinical impairments of urinary system, as well as alterations of other systems and extracellular vesicles (EVs) biology during high-altitude expeditions. Nevertheless, gaps exist in the comprehensive assessment of dysfunction, molecular burden and EVs biology due to high-altitude acute exposure. This study aimed to find a biophysical and biochemical signature of urinary EVs for hypoxia-induced changes in urinary function, putatively accompanied by an oxinflammatory burden. Urine samples of 15 participants were sampled at low and high-altitude during an Alpine project (7 women and 8 men, aged 24-to-63 years and with BMI 17.93-to-30.76 kg/m 2 ) and analysed for: creatinin and albumin, lipid peroxidation, IL6, NO derivatives; atomic force microscopy and Raman spectroscopy were carried out after urinary EVs were isolated through sucrose-gradient ultracentrifugation. Albumin-to-creatinin ratio increased at high altitude, as did IL6 and 8-isoprostane. AFM showed a globular and flattened shape of EVs, although several samples were characterized by a lot of contaminants and EVs lost their prototypal spherical shape; EVs comprehensively maintained their morphology at high altitude. Raman spectroscopy revealed some typical phospholipidic-like pattern, often masked by contaminants of spectra that most often refer to high-altitude samples. Collectively, short-term exposure to altitude hypoxia increased renal concentrating ability, produced non-pathological impairment or renal function, and triggered an oxyinflammatory burden with heterogeneous response of NO system. The combination of AFM and Raman spectroscopy revealed that EVs collected at high altitude more likely are fused together and incorporated into a sediment matrix, and contain contaminants peaks that make the purification process less efficient. The combination of analytical procedures as in the present study offers novel possibilities to detect the biological and clinical effects of high altitude on renal system., Competing Interests: Declaration of competing interest 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., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Aims: To analyze the protective properties of fluor dental varnishes in teeth subjected to radiotherapy., Methods and Results: Eighty teeth were irradiated with a single dose of 60 Gy. Samples were randomized, and the following groups were made: negative control (n = 16); irradiation control (n = 16); irradiation + Duraphat (n = 16); irradiation + Mi Varnish (n = 16); and irradiation + Rivastar (n = 16). Energy dispersive x-ray (EDX) analysis and Raman spectrometry were performed to analyze the elemental composition and enamel's chemical structure. The Mi Varnish group presented a lower value (p < .05) in the Ca/F ratio than the other groups. Duraphat group presents differences (p < .05) in the ratio 1070 cm 1 -960 cm -1 compared to all the other groups., Conclusion: Based on these in vitro results, the different varnishes used showed a similar preventive effect on the lesions produced by radiotherapy, with none standing out over the others., (© 2024 The Author(s). Special Care in Dentistry published by Special Care Dentistry Association and Wiley Periodicals LLC.)