Pub Date : 2026-01-02DOI: 10.1016/j.saa.2025.127418
Jiayi Ying , Zimeng Luo , Qiaoan Zhang , Huyan Chen , Wei Wang , Qianqian Wang , Min Jiang , Lei-Hong Xiang , Jing Luan , Wen-Qi Meng
Tyrosinase (TYR) and hydrogen sulfide (H₂S) are two notable biomarkers implicated in melanocyte physiology and melanoma progression. However, no fluorescent probe has been developed for their simultaneous detection in biological systems. Here, we present a dual-locked fluorescein-based probe TyNitro-1 capable of concurrently sensing TYR and H₂S, which incorporates a 3-hydroxyphenyl group for TYR recognition and a nitro moiety for H₂S recognition. Upon dual-analyte activation, the probe displays an obvious fluorescence enhancement at 517 nm. It offers an efficient response (≤120 min for TYR; ≤60 min for H₂S), excellent selectivity, and low detection limits (1.41 U/mL−1 for TYR and 0.28 μM for H2S). In human primary melanocytes, TyNitro-1 reliably monitored changes of TYR and H₂S. While in human melanoma tissues, cryosections incubated with TyNitro-1 exhibited tumor-selective fluorescence that correlated strongly with SOX10 and HMB45 immunostaining. Collectively, this work establishes TyNitro-1 as a proof-of-concept dual-locked fluorescent probe, providing new opportunities to investigate the role of TYR and H₂S in melanocyte biology and highlighting its potential for melanoma diagnosis and intraoperative margin assessment.
{"title":"A dual-locked fluorescent probe for imaging of human primary melanocytes and melanoma tissues via tyrosinase and hydrogen sulfide activation","authors":"Jiayi Ying , Zimeng Luo , Qiaoan Zhang , Huyan Chen , Wei Wang , Qianqian Wang , Min Jiang , Lei-Hong Xiang , Jing Luan , Wen-Qi Meng","doi":"10.1016/j.saa.2025.127418","DOIUrl":"10.1016/j.saa.2025.127418","url":null,"abstract":"<div><div>Tyrosinase (TYR) and hydrogen sulfide (H₂S) are two notable biomarkers implicated in melanocyte physiology and melanoma progression. However, no fluorescent probe has been developed for their simultaneous detection in biological systems. Here, we present a dual-locked fluorescein-based probe TyNitro-1 capable of concurrently sensing TYR and H₂S, which incorporates a 3-hydroxyphenyl group for TYR recognition and a nitro moiety for H₂S recognition. Upon dual-analyte activation, the probe displays an obvious fluorescence enhancement at 517 nm. It offers an efficient response (≤120 min for TYR; ≤60 min for H₂S), excellent selectivity, and low detection limits (1.41 U/mL<sup>−1</sup> for TYR and 0.28 μM for H<sub>2</sub>S). In human primary melanocytes, TyNitro-1 reliably monitored changes of TYR and H₂S. While in human melanoma tissues, cryosections incubated with TyNitro-1 exhibited tumor-selective fluorescence that correlated strongly with SOX10 and HMB45 immunostaining. Collectively, this work establishes TyNitro-1 as a proof-of-concept dual-locked fluorescent probe, providing new opportunities to investigate the role of TYR and H₂S in melanocyte biology and highlighting its potential for melanoma diagnosis and intraoperative margin assessment.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127418"},"PeriodicalIF":4.6,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145919239","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-02DOI: 10.1016/j.saa.2025.127427
Alexandre Augusto Muniz Garcia , Nicole Sayuri Miranda Okayama , Eduardo Sérgio de Souza , Cássia Alessandra Marquezin
The interaction between the nitrogenous base thymine (Thy) and the amino acid tryptophan (Trp) plays a role in DNA–protein cross-linking and has been associated with the inhibition of urothelial carcinogenesis. In this work, we investigate these molecules through their fluorescence emission and electronic absorption properties in the presence of bioinspired membrane models, such as ionic surfactant micelles and neutral liposomes. Photophysical parameters, such as single-photon cross section, fluorescence quantum yield, and molar absorption coefficient, were determined for Thy in different solvents. The low partitioning of the target molecules into highly hydrophobic environments, such as the micelle core, was overcome by changing the medium pH, thereby exploiting the protonation/deprotonation states of Trp and Thy. Under these conditions, the molecules were electrostatically attracted to the micelle surfaces. The optical absorption spectrum of Thy is highly dependent on the medium pH, whereas for Trp, the greatest pH sensitivity lies in its fluorescent emission. The results demonstrate that Trp and Thy interact with micelle surfaces when their charges are opposite to those of the micelle. Steady-state anisotropy of Trp, combined with the spectral position of its emission, enabled accurate monitoring of the critical micelle concentration (CMC) of sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) micelles. In contrast, in the presence of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DMPC) liposomes, neither Trp nor Thy caused changes in the bilayer phase behavior, as monitored by the fluorescence anisotropy of two distinct probes inserted into different bilayer environments.
{"title":"Spectral properties of thymine and its interaction with tryptophan and bioinspired membranes","authors":"Alexandre Augusto Muniz Garcia , Nicole Sayuri Miranda Okayama , Eduardo Sérgio de Souza , Cássia Alessandra Marquezin","doi":"10.1016/j.saa.2025.127427","DOIUrl":"10.1016/j.saa.2025.127427","url":null,"abstract":"<div><div>The interaction between the nitrogenous base thymine (Thy) and the amino acid tryptophan (Trp) plays a role in DNA–protein cross-linking and has been associated with the inhibition of urothelial carcinogenesis. In this work, we investigate these molecules through their fluorescence emission and electronic absorption properties in the presence of bioinspired membrane models, such as ionic surfactant micelles and neutral liposomes. Photophysical parameters, such as single-photon cross section, fluorescence quantum yield, and molar absorption coefficient, were determined for Thy in different solvents. The low partitioning of the target molecules into highly hydrophobic environments, such as the micelle core, was overcome by changing the medium pH, thereby exploiting the protonation/deprotonation states of Trp and Thy. Under these conditions, the molecules were electrostatically attracted to the micelle surfaces. The optical absorption spectrum of Thy is highly dependent on the medium pH, whereas for Trp, the greatest pH sensitivity lies in its fluorescent emission. The results demonstrate that Trp and Thy interact with micelle surfaces when their charges are opposite to those of the micelle. Steady-state anisotropy of Trp, combined with the spectral position of its emission, enabled accurate monitoring of the critical micelle concentration (CMC) of sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) micelles. In contrast, in the presence of 1,2-dipalmitoyl-<em>sn</em>-glycero-3-phosphocholine (DMPC) liposomes, neither Trp nor Thy caused changes in the bilayer phase behavior, as monitored by the fluorescence anisotropy of two distinct probes inserted into different bilayer environments.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127427"},"PeriodicalIF":4.6,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145919433","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Due to increasing prevalence of obesity new safe and non-invasive therapies are sought to cope with the epidemic. Transcranial direct current stimulation (tDCS) is a neurostimulation technique that targets both the cortical and deeper brain structures. Both experimental studies and clinical research suggest the effectiveness of tDCS in suppressing appetite and reducing body mass. Therefore, to boost current knowledge on possible biochemical mechanisms underlying biological action of tDCS we determined the effects of tDCS on structural changes of lipids and proteins in key organs in obese rodents. For this purpose, Fourier transform infrared spectroscopy (FTIR) involving microscopic or horizontal attenuated total reflectance (HATR) sampling modes was applied. In order to complement the intergroup comparisons, principal component analysis (PCA) and receiver operator characteristics (ROC) analysis were utilized. Our study revealed that eight days of daily anodal tDCS (atDCS) induced immediate alterations in hepatic metabolism, but not in white adipose tissue (WAT). Furthermore, atDCS led to a significant reduction in lipid content in the renal medulla and renal pelvis. No substantial or interpretable changes were observed in cardiac and skeletal muscle tissues. These findings indicate that, based on the observed effects in these specific organs, atDCS may be a promising approach for restoring biomolecular parameters, particularly in the liver and kidney, and thus serves as a potential therapeutic method for addressing obesity-related conditions.
{"title":"Identification of molecular changes in organs of obese rats following transcranial direct current stimulation (tDCS) – studies by FTIR microspectroscopy and chemometrics","authors":"Kaja Piana , Agata Ziomber-Lisiak , Magdalena Szczerbowska-Boruchowska","doi":"10.1016/j.saa.2025.127428","DOIUrl":"10.1016/j.saa.2025.127428","url":null,"abstract":"<div><div>Due to increasing prevalence of obesity new safe and non-invasive therapies are sought to cope with the epidemic. Transcranial direct current stimulation (tDCS) is a neurostimulation technique that targets both the cortical and deeper brain structures. Both experimental studies and clinical research suggest the effectiveness of tDCS in suppressing appetite and reducing body mass. Therefore, to boost current knowledge on possible biochemical mechanisms underlying biological action of tDCS we determined the effects of tDCS on structural changes of lipids and proteins in key organs in obese rodents. For this purpose, Fourier transform infrared spectroscopy (FTIR) involving microscopic or horizontal attenuated total reflectance (HATR) sampling modes was applied. In order to complement the intergroup comparisons, principal component analysis (PCA) and receiver operator characteristics (ROC) analysis were utilized. Our study revealed that eight days of daily anodal tDCS (atDCS) induced immediate alterations in hepatic metabolism, but not in white adipose tissue (WAT). Furthermore, atDCS led to a significant reduction in lipid content in the renal medulla and renal pelvis. No substantial or interpretable changes were observed in cardiac and skeletal muscle tissues. These findings indicate that, based on the observed effects in these specific organs, atDCS may be a promising approach for restoring biomolecular parameters, particularly in the liver and kidney, and thus serves as a potential therapeutic method for addressing obesity-related conditions.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127428"},"PeriodicalIF":4.6,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145936793","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01DOI: 10.1016/j.saa.2025.127424
Kun Yu , Chunxv Han , Qi Su , Wenxuan Hu , Fan Wang , Yuqing Wang , Lei Hu , Hui Wang
Mitochondria are central to the maintenance of cellular energy homeostasis and functional integrity, with alterations in their microenvironmental parameters being closely linked to the pathogenesis of various diseases. In particular, abnormal fluctuations in viscosity and polarity can disrupt cellular homeostasis, thereby promoting inflammation, tumorigenesis, and metabolic disorders. To overcome the limitations of existing fluorescent probes such as operational complexity and short emission wavelengths, we designed a mitochondria-targeted fluorescent probe AK based on a D-π-A molecular architecture. In this design, phenothiazine acts as the electron-donating core, a thiophene group enhances electron-donating capacity, and a positively charged indole derivative functions as the electron acceptor. The resulting probe exhibited red emission and responded dually to both viscosity and polarity. Photophysical characterization revealed that AK displayed significantly enhanced fluorescence under high-viscosity or low-polarity conditions, with a favorable linear response within specific ranges. Biological evaluation further confirmed that AK has low cytotoxicity, enables wash-free imaging, and targets mitochondria independently of membrane potential, allowing efficient imaging even at ultralow concentrations (5 nM). Moreover, AK sensitively monitored viscosity changes in both cellular and living systems, distinguished cancer cells from normal cells, and achieved precise in vivo tumor imaging. Additionally, AK enabled dynamic tracking of viscosity and polarity changes during processes such as ferroptosis and starvation, and facilitated multi-scale imaging of drug-induced liver injury across cellular, tissue and organ imaging.
{"title":"An ultralow-concentration, red-emissive dual-responsive fluorescent probe for real-time mitochondrial viscosity/polarity imaging","authors":"Kun Yu , Chunxv Han , Qi Su , Wenxuan Hu , Fan Wang , Yuqing Wang , Lei Hu , Hui Wang","doi":"10.1016/j.saa.2025.127424","DOIUrl":"10.1016/j.saa.2025.127424","url":null,"abstract":"<div><div>Mitochondria are central to the maintenance of cellular energy homeostasis and functional integrity, with alterations in their microenvironmental parameters being closely linked to the pathogenesis of various diseases. In particular, abnormal fluctuations in viscosity and polarity can disrupt cellular homeostasis, thereby promoting inflammation, tumorigenesis, and metabolic disorders. To overcome the limitations of existing fluorescent probes such as operational complexity and short emission wavelengths, we designed a mitochondria-targeted fluorescent probe <strong>AK</strong> based on a D-π-A molecular architecture. In this design, phenothiazine acts as the electron-donating core, a thiophene group enhances electron-donating capacity, and a positively charged indole derivative functions as the electron acceptor. The resulting probe exhibited red emission and responded dually to both viscosity and polarity. Photophysical characterization revealed that <strong>AK</strong> displayed significantly enhanced fluorescence under high-viscosity or low-polarity conditions, with a favorable linear response within specific ranges. Biological evaluation further confirmed that <strong>AK</strong> has low cytotoxicity, enables wash-free imaging, and targets mitochondria independently of membrane potential, allowing efficient imaging even at ultralow concentrations (5 nM). Moreover, <strong>AK</strong> sensitively monitored viscosity changes in both cellular and living systems, distinguished cancer cells from normal cells, and achieved precise in vivo tumor imaging. Additionally, <strong>AK</strong> enabled dynamic tracking of viscosity and polarity changes during processes such as ferroptosis and starvation, and facilitated multi-scale imaging of drug-induced liver injury across cellular, tissue and organ imaging.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127424"},"PeriodicalIF":4.6,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145883237","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01DOI: 10.1016/j.saa.2025.127421
Havva Nur Tatlı , Bakr Aldoori , Semahat Küçükkolbaşı , Serkan Erdemir
Acrylamide (AA) is a toxic and potentially carcinogenic compound formed in carbohydrate-rich foods subjected to high-temperature processes such as frying, baking, and roasting. Its adverse health effects, including neurotoxicity and carcinogenicity, have raised serious concerns regarding food safety. In this study, we developed a novel fluorescent sensor based on a manganese metal–organic framework (Mn-MOF) incorporating 2-(2-hydroxyphenyl)benzothiazole (HBT) for the rapid and sensitive detection of AA in food and water samples. The Schiff base 3-((3-(benzo[d]thiazol-2yl)-5-bromo-2-hydroxybenzylidene)amino)-5-(1-hydroxyvinyl)benzoicacid (HBTN) precursor was synthesized via a condensation reaction and subsequently used to fabricate Mn-MOF-HBT through a solvothermal method. The structure of the Mn-MOF-HBT fluorescent probe was characterized by FTIR, SEM, EDS/X, and TGA analyses. The sensor exhibited a fluorescence “turn-off” response upon exposure to AA, with a low detection limit of 1.08 × 10−9 M and a rapid response time of 10 s in Britton–Robinson buffer (0.04 M, pH 8.0) at λem = 468 nm. Selectivity studies confirmed negligible interference from various metal ions, drug molecules, and biological substances. The method was further validated using real samples, including water and fried potato extracts, showing satisfactory recovery and %RSD values. Owing to its high sensitivity, rapid response, and operational simplicity, the Mn-MOF-HBT probe demonstrates strong potential for routine monitoring of acrylamide in complex food and environmental matrices, contributing to enhanced public health surveillance and risk assessment.
{"title":"A novel Mn-MOF-HBT based fluorescent sensor for selective and sensitive detection of acrylamide in food products","authors":"Havva Nur Tatlı , Bakr Aldoori , Semahat Küçükkolbaşı , Serkan Erdemir","doi":"10.1016/j.saa.2025.127421","DOIUrl":"10.1016/j.saa.2025.127421","url":null,"abstract":"<div><div>Acrylamide (AA) is a toxic and potentially carcinogenic compound formed in carbohydrate-rich foods subjected to high-temperature processes such as frying, baking, and roasting. Its adverse health effects, including neurotoxicity and carcinogenicity, have raised serious concerns regarding food safety. In this study, we developed a novel fluorescent sensor based on a manganese metal–organic framework (Mn-MOF) incorporating 2-(2-hydroxyphenyl)benzothiazole (HBT) for the rapid and sensitive detection of AA in food and water samples. The Schiff base 3-((3-(benzo[<em>d</em>]thiazol-2yl)-5-bromo-2-hydroxybenzylidene)amino)-5-(1-hydroxyvinyl)benzoicacid (HBTN) precursor was synthesized via a condensation reaction and subsequently used to fabricate Mn-MOF-HBT through a solvothermal method. The structure of the Mn-MOF-HBT fluorescent probe was characterized by FTIR, SEM, EDS/X, and TGA analyses. The sensor exhibited a fluorescence “turn-off” response upon exposure to AA, with a low detection limit of 1.08 × 10<sup>−9</sup> M and a rapid response time of 10 s in Britton–Robinson buffer (0.04 M, pH 8.0) at λ<sub>em</sub> = 468 nm. Selectivity studies confirmed negligible interference from various metal ions, drug molecules, and biological substances. The method was further validated using real samples, including water and fried potato extracts, showing satisfactory recovery and %RSD values. Owing to its high sensitivity, rapid response, and operational simplicity, the Mn-MOF-HBT probe demonstrates strong potential for routine monitoring of acrylamide in complex food and environmental matrices, contributing to enhanced public health surveillance and risk assessment.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127421"},"PeriodicalIF":4.6,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145883240","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-31DOI: 10.1016/j.saa.2025.127381
Wei Luo , Wenyoujia Li , Haihua Huang , Zhijian Qu , Yanfang Gao , Weifa Peng , Hailiang Zhang , Guozhu Fan
Diesel, a crucial energy source for transportation and industrial applications. The cetane number (CN) plays a key role in assessing diesel quality and combustion performance. In this study, near-infrared spectroscopy (NIRS) data of diesel were encoded into images using the Markov transition field (MTF). A hybrid CNN-BiLSTM model with multi-head attention was developed to achieve multimodal feature extraction and fusion by simultaneously inputting spectral data and MTF images, enabling accurate CN prediction. For comparison, PLSR, 1D-CNN, and 2D-CNN models were established using feature wavelengths selected by variable combination population analysis (VCPA), SG1-preprocessed full spectra, and MTF images, respectively. Results demonstrated that the CNN-BiLSTM achieved the best performance (Rp2 = 0.9824, RMSEP = 0.3106), whereas the VCPA-PLSR performed the worst (Rp2 = 0.7541, RMSEP = 1.6425). The 1D-CNN outperformed the VCPA-PLSR, and the 2D-CNN further improved upon the 1D-CNN. This study demonstrates that converting NIRS data into images via MTF effectively leverages the potential of CNNs and improves CN prediction performance without feature wavelength extraction, while the introduced BiLSTM channel mitigates the distortion of original data caused by MTF encoding. The approach provides a non-destructive and reliable framework for liquid samples' quality evaluation in industrial applications.
{"title":"Combination of markov transition field and multi-scale feature extraction for cetane number prediction in diesel using near-infrared spectroscopy","authors":"Wei Luo , Wenyoujia Li , Haihua Huang , Zhijian Qu , Yanfang Gao , Weifa Peng , Hailiang Zhang , Guozhu Fan","doi":"10.1016/j.saa.2025.127381","DOIUrl":"10.1016/j.saa.2025.127381","url":null,"abstract":"<div><div>Diesel, a crucial energy source for transportation and industrial applications. The cetane number (CN) plays a key role in assessing diesel quality and combustion performance. In this study, near-infrared spectroscopy (NIRS) data of diesel were encoded into images using the Markov transition field (MTF). A hybrid CNN-BiLSTM model with multi-head attention was developed to achieve multimodal feature extraction and fusion by simultaneously inputting spectral data and MTF images, enabling accurate CN prediction. For comparison, PLSR, 1D-CNN, and 2D-CNN models were established using feature wavelengths selected by variable combination population analysis (VCPA), SG1-preprocessed full spectra, and MTF images, respectively. Results demonstrated that the CNN-BiLSTM achieved the best performance (R<sub>p</sub><sup>2</sup> = 0.9824, RMSEP = 0.3106), whereas the VCPA-PLSR performed the worst (R<sub>p</sub><sup>2</sup> = 0.7541, RMSEP = 1.6425). The 1D-CNN outperformed the VCPA-PLSR, and the 2D-CNN further improved upon the 1D-CNN. This study demonstrates that converting NIRS data into images via MTF effectively leverages the potential of CNNs and improves CN prediction performance without feature wavelength extraction, while the introduced BiLSTM channel mitigates the distortion of original data caused by MTF encoding. The approach provides a non-destructive and reliable framework for liquid samples' quality evaluation in industrial applications.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127381"},"PeriodicalIF":4.6,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145919593","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The present study investigates the anticancer potential, density functional theory (DFT) calculations and biological target interactions of a novel, hetero-ligated horse-stirrup-shaped thiolato-bridged fac-Mn(CO)3-core-based CO-releasing compound (S-MnC). The S-MnC exhibited selective, broad-spectrum cytotoxicity against ovarian (SKOV-3), breast (MDA-MB-231), pancreatic (PANC-1), and prostate (PC-3) cancer cells. The macromolecular binding potential of S-MnC with DNA and human serum albumin (HSA) was elucidated using spectroscopic and molecular docking studies. The S-MnC interacts with ctDNA through a combination of partial intercalation and groove binding, causing structural changes and exhibiting hydrolytic DNA cleavage, suggesting its potential to induce oxidative DNA damage. Furthermore, DFT calculation confirmed a redox-active MnS core and ligand centred LUMO, supporting the oxidative DNA cleavage and cytotoxic potential of S-MnC. The structural framework of S-MnC contains an ester-functionalized ligand that exhibits a strong binding potential towards human serum albumin (HSA). The flexibility of the ether and ester groups permits the coordinating ligand to embrace different conformations and provides the stability to ligand complexes. The binding process was spontaneous, entropy-driven interactions, indicated by positive ∆H° and ∆S° values and negative ∆G° values. These dynamic binding interactions induced conformational changes in the secondary structure of HSA. Reported results established the structure-activity relationships and biological insights of S-MnC as a potent, selective, Mn-based therapeutic scaffold.
{"title":"Broad-spectrum anticancer properties, DFT calculations and macromolecular binding potential of a novel thiolato-bridged fac-Mn(CO)3-core-based CO-releasing molecule","authors":"Aswathy Anil , Diksha Tripathi , Sriram Shankar , Subhashree Subhasmita Nayak , R. Krishna , Udit Kumar , Bala. Manimaran , Natarajan Sakthivel","doi":"10.1016/j.saa.2025.127406","DOIUrl":"10.1016/j.saa.2025.127406","url":null,"abstract":"<div><div>The present study investigates the anticancer potential, density functional theory (DFT) calculations and biological target interactions of a novel, hetero-ligated horse-stirrup-shaped thiolato-bridged <em>fac</em>-Mn(CO)<sub>3</sub>-core-based CO-releasing compound (<strong>S-MnC</strong>). The <strong>S-MnC</strong> exhibited selective, broad-spectrum cytotoxicity against ovarian (SKOV-3), breast (MDA-MB-231), pancreatic (PANC-1), and prostate (PC-3) cancer cells. The macromolecular binding potential of <strong>S-MnC</strong> with DNA and human serum albumin (HSA) was elucidated using spectroscopic and molecular docking studies. The <strong>S-MnC</strong> interacts with ctDNA through a combination of partial intercalation and groove binding, causing structural changes and exhibiting hydrolytic DNA cleavage, suggesting its potential to induce oxidative DNA damage. Furthermore, DFT calculation confirmed a redox-active Mn<img>S core and ligand centred LUMO, supporting the oxidative DNA cleavage and cytotoxic potential of <strong>S-MnC</strong>. The structural framework of <strong>S-MnC</strong> contains an ester-functionalized ligand that exhibits a strong binding potential towards human serum albumin (HSA). The flexibility of the ether and ester groups permits the coordinating ligand to embrace different conformations and provides the stability to ligand complexes. The binding process was spontaneous, entropy-driven interactions, indicated by positive ∆H° and ∆S° values and negative ∆G° values. These dynamic binding interactions induced conformational changes in the secondary structure of HSA. Reported results established the structure-activity relationships and biological insights of <strong>S-MnC</strong> as a potent, selective, Mn-based therapeutic scaffold.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127406"},"PeriodicalIF":4.6,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145936202","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-31DOI: 10.1016/j.saa.2025.127422
Kai Wang , Wu-Juan Hao , Ren-Min Zhou , You-Zhen Feng , Zhong-Yuan Cheng
Neutrophil elastase (NE) has emerged as a key protease in inflammatory bowel disease pathogenesis, serving as both a diagnostic marker and therapeutic target. This study establishes a comprehensive methodology for monitoring NE activity in inflammatory conditions using a sulfonate-modified hemicyanine-based probe (HDNE). Through systematic evaluation, HDNE demonstrated remarkable aqueous solubility and biocompatibility, with negligible cytotoxicity observed in macrophage cultures. The probe exhibited high sensitivity toward NE with a linear response range up to 2.5 U/L and maintained excellent selectivity against competing biological species. In a dextran sulfate sodium-induced colitis model, HDNE enabled non-invasive visualization of NE activity, revealing distinct spatiotemporal patterns correlating with disease progression. Quantitative analysis confirmed significant signal enhancement in inflammatory regions, achieving maximum contrast at 90 min post-injection. Ex vivo validation further verified the accuracy of in vivo measurements, while histopathological assessment confirmed minimal systemic toxicity. These findings collectively validate HDNE as a reliable tool for investigating NE dynamics in inflammatory environments, providing valuable insights for disease monitoring and therapeutic assessment.
{"title":"Sulfonate-functionalized HDNE probe enables detection of neutrophil elastase in colitis mice","authors":"Kai Wang , Wu-Juan Hao , Ren-Min Zhou , You-Zhen Feng , Zhong-Yuan Cheng","doi":"10.1016/j.saa.2025.127422","DOIUrl":"10.1016/j.saa.2025.127422","url":null,"abstract":"<div><div>Neutrophil elastase (NE) has emerged as a key protease in inflammatory bowel disease pathogenesis, serving as both a diagnostic marker and therapeutic target. This study establishes a comprehensive methodology for monitoring NE activity in inflammatory conditions using a sulfonate-modified hemicyanine-based probe (HDNE). Through systematic evaluation, HDNE demonstrated remarkable aqueous solubility and biocompatibility, with negligible cytotoxicity observed in macrophage cultures. The probe exhibited high sensitivity toward NE with a linear response range up to 2.5 U/L and maintained excellent selectivity against competing biological species. In a dextran sulfate sodium-induced colitis model, HDNE enabled non-invasive visualization of NE activity, revealing distinct spatiotemporal patterns correlating with disease progression. Quantitative analysis confirmed significant signal enhancement in inflammatory regions, achieving maximum contrast at 90 min post-injection. Ex vivo validation further verified the accuracy of in vivo measurements, while histopathological assessment confirmed minimal systemic toxicity. These findings collectively validate HDNE as a reliable tool for investigating NE dynamics in inflammatory environments, providing valuable insights for disease monitoring and therapeutic assessment.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127422"},"PeriodicalIF":4.6,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145902114","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Biological sample preparation for nanoscale IR spectroscopy involves fixation, rinsing, and drying steps that can significantly alter biomolecular properties and cellular architecture. Chemical modifications may shift spectral band positions and intensities, compromising interpretation, while structural remodelling can distort morphology and hinder image reconstruction. In this study, we evaluated fixation protocols using paraformaldehyde, glutaraldehyde, ethanol, and osmium tetroxide, combined with different rinsing and dehydration strategies. FT-IR and AFM-IR analyses revealed that paraformaldehyde and glutaraldehyde best preserve protein content and secondary structure, whereas osmium tetroxide is more effective for stabilizing cellular lipids. Nevertheless, the post-fixation steps of rinsing and drying proved equally critical for nanoscale investigations. We found that direct rinsing with water followed by rapid nitrogen drying yields the most faithful preservation of cellular integrity, minimizing structural artefacts and ensuring reliable spectral and AFM imaging data. These findings highlight the need for optimized processing protocols tailored to nanoscale IR studies. By balancing chemical stabilization with minimal physical distortion, the proposed approach improves the accuracy of nanospectroscopic analyses of cellular components.
{"title":"Toward precision in nanoscale IR spectroscopy: Optimizing biological sample preparation for molecular and morphological integrity","authors":"Karolina Chrabąszcz , Natalia Piergies , Agnieszka Panek, Monika Szczepanek-Dulska, Katarzyna Pogoda","doi":"10.1016/j.saa.2025.127398","DOIUrl":"10.1016/j.saa.2025.127398","url":null,"abstract":"<div><div>Biological sample preparation for nanoscale IR spectroscopy involves fixation, rinsing, and drying steps that can significantly alter biomolecular properties and cellular architecture. Chemical modifications may shift spectral band positions and intensities, compromising interpretation, while structural remodelling can distort morphology and hinder image reconstruction. In this study, we evaluated fixation protocols using paraformaldehyde, glutaraldehyde, ethanol, and osmium tetroxide, combined with different rinsing and dehydration strategies. FT-IR and AFM-IR analyses revealed that paraformaldehyde and glutaraldehyde best preserve protein content and secondary structure, whereas osmium tetroxide is more effective for stabilizing cellular lipids. Nevertheless, the post-fixation steps of rinsing and drying proved equally critical for nanoscale investigations. We found that direct rinsing with water followed by rapid nitrogen drying yields the most faithful preservation of cellular integrity, minimizing structural artefacts and ensuring reliable spectral and AFM imaging data. These findings highlight the need for optimized processing protocols tailored to nanoscale IR studies. By balancing chemical stabilization with minimal physical distortion, the proposed approach improves the accuracy of nanospectroscopic analyses of cellular components.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127398"},"PeriodicalIF":4.6,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145919204","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-30DOI: 10.1016/j.saa.2025.127402
Yan-Zhao Fang , Yan Zhang , Lin-Xin Du , He-Han Huang , Zhi-Jie Mao , Pei Zhang , Shuang Wu , Xiang-Juan Kong , Qiang Xiao
In this study, a new dual-responsive ratiometric fluorescence nanoprobe was rationally designed for heparin (Hep) detection. The negatively charged europium-based coordination polymers (Eu CPs) and positively charged fluorescent polydopamine nanoparticles (FPDA NPs) could assemble via electrostatic interaction, meanwhile, the fluorescence of these both reduced slightly owing to self-quenching (SQ) and inner-filter effect (IFE), respectively. Upon addition of Hep, the Eu CPs emission at 615 nm was markedly quenched due to electron transfer and SQ, while the FPDA NPs emission at 465 nm was enhanced marginally owing to mitigation of the IFE. These opposing signal changes yielded a robust ratiometric readout (I₄₆₅/I₆₁₅) for Hep detection. The probe showed a widely linear response over 0–16 μg/mL with a detection limit as low as 3.58 ng/mL. Furthermore, high sensitivity and accuracy of the probe enabled accurate analysis of Hep in human serum with favorable recoveries, highlighting its potential for biomedical analysis and clinical diagnostics.
{"title":"A dual-responsive ratiometric fluorescence sensor for highly sensitive detection of heparin with Eu CPs and fluorescent polydopamine nanoparticles","authors":"Yan-Zhao Fang , Yan Zhang , Lin-Xin Du , He-Han Huang , Zhi-Jie Mao , Pei Zhang , Shuang Wu , Xiang-Juan Kong , Qiang Xiao","doi":"10.1016/j.saa.2025.127402","DOIUrl":"10.1016/j.saa.2025.127402","url":null,"abstract":"<div><div>In this study, a new dual-responsive ratiometric fluorescence nanoprobe was rationally designed for heparin (Hep) detection. The negatively charged europium-based coordination polymers (Eu CPs) and positively charged fluorescent polydopamine nanoparticles (FPDA NPs) could assemble via electrostatic interaction, meanwhile, the fluorescence of these both reduced slightly owing to self-quenching (SQ) and inner-filter effect (IFE), respectively. Upon addition of Hep, the Eu CPs emission at 615 nm was markedly quenched due to electron transfer and SQ, while the FPDA NPs emission at 465 nm was enhanced marginally owing to mitigation of the IFE. These opposing signal changes yielded a robust ratiometric readout (I₄₆₅/I₆₁₅) for Hep detection. The probe showed a widely linear response over 0–16 μg/mL with a detection limit as low as 3.58 ng/mL. Furthermore, high sensitivity and accuracy of the probe enabled accurate analysis of Hep in human serum with favorable recoveries, highlighting its potential for biomedical analysis and clinical diagnostics.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127402"},"PeriodicalIF":4.6,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145883238","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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