Pub Date : 2026-08-01Epub Date: 2026-01-19DOI: 10.1016/j.bioelechem.2026.109229
Hou-Yun Yang , Xiang Geng , Zhi-Dao Quan , Li Yu , Xian-Huai Huang , Wei-Hua Li , Tong-Zhan Xue , Yang Mu
Azo dyes, containing one or more azo bonds (–N=N–), are widely used but pose environmental and health risks due to their toxicity and resistance to degradation. Bioelectrochemical systems (BESs) offer a potential approach for their reductive degradation, yet the role of molecular structure in degradation remains unclear. In this study, nine representative azo dyes were examined to access how substituent type and position affect degradation kinetics and electron transfer under controlled cathodic potentials in BESs. Electron-withdrawing substituents (e.g., –SO3−, –NO2) and o−/m- substitution enhanced azo bond cleavage, while p-substitution or steric hindered degradation. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) revealed that higher reduction currents and lower charge-transfer resistance correlated with faster degradation. Quantitative structure-activity relationship (QSAR) analysis identified that the –N=N– group and other molecular features such as atom count, are key determinants of azo dyes removal. Experimental and theoretical calculations showed that molecular structure regulates the electron transfer efficiency from electrode to dye by affecting the electron density and steric hindrance of the azo bond, thereby determining degradation kinetics. This study deepened the influence of the molecular structure on azo dyes bioelectrochemical removal, and provided optimized guidance for the treatment of wastewater containing azo dyes by BESs.
{"title":"Molecular structure-dependent bioelectrochemical decolorization of azo dyes","authors":"Hou-Yun Yang , Xiang Geng , Zhi-Dao Quan , Li Yu , Xian-Huai Huang , Wei-Hua Li , Tong-Zhan Xue , Yang Mu","doi":"10.1016/j.bioelechem.2026.109229","DOIUrl":"10.1016/j.bioelechem.2026.109229","url":null,"abstract":"<div><div>Azo dyes, containing one or more azo bonds (–N=N–), are widely used but pose environmental and health risks due to their toxicity and resistance to degradation. Bioelectrochemical systems (BESs) offer a potential approach for their reductive degradation, yet the role of molecular structure in degradation remains unclear. In this study, nine representative azo dyes were examined to access how substituent type and position affect degradation kinetics and electron transfer under controlled cathodic potentials in BESs. Electron-withdrawing substituents (e.g., –SO<sub>3</sub><sup>−</sup>, –NO<sub>2</sub>) and o−/m- substitution enhanced azo bond cleavage, while p-substitution or steric hindered degradation. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) revealed that higher reduction currents and lower charge-transfer resistance correlated with faster degradation. Quantitative structure-activity relationship (QSAR) analysis identified that the –N=N– group and other molecular features such as atom count, are key determinants of azo dyes removal. Experimental and theoretical calculations showed that molecular structure regulates the electron transfer efficiency from electrode to dye by affecting the electron density and steric hindrance of the azo bond, thereby determining degradation kinetics. This study deepened the influence of the molecular structure on azo dyes bioelectrochemical removal, and provided optimized guidance for the treatment of wastewater containing azo dyes by BESs.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"170 ","pages":"Article 109229"},"PeriodicalIF":4.5,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023969","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 : 2026-08-01Epub Date: 2026-02-07DOI: 10.1016/j.bioelechem.2026.109245
Chengyi Lu , Minjie Yang , Peiwu Chen , Hongyi Zhang , Shi Tang , Ling Zha , Ying Huang , Dong Sun , Ruizhuo Ouyang , Yuqin Jiang , Yuqing Miao , Baolin Liu
Cancer early detection demands highly sensitive, cost-effective, and reliable sensing platforms. Herein, we report the synthesis of lanthanum bismuth oxide nanosheets (LaBi3O6 NSs) via a simple sol–gel method and their innovative application in constructing a label-free electrochemical immunosensor for the detection of carcinoembryonic antigen (CEA). The LaBi3O6 NSs serve as an excellent matrix offering a large specific surface area, high conductivity, and rich active sites, significantly enhancing electron transfer and biomolecular immobilization. The fabricated immunosensor demonstrates outstanding analytical performance: a wide linear range from 0.1 to 1000 ng mL−1, an ultra-low detection limit of 56.2 pg mL−1, and high selectivity against common interferents. It also exhibits remarkable reproducibility (RSD < 5%) and stability (retaining 90% activity after 15 days). Practical applicability was confirmed through successful CEA detection in human serum samples, with recovery rates of 98.8–101.2% and excellent agreement with standard methods. This work not only presents a novel bismuth-based nanomaterial for biosensing but also provides a robust, eco-friendly, and highly efficient strategy for clinical cancer biomarker detection. The proposed platform holds great promise for point-of-care diagnostics and opens new avenues for the development of next-generation electrochemical immunosensors.
{"title":"Engineered LaBi₃O₆ nanosheet interface enabling robust and ultrasensitive detection of carcinoembryonic antigen","authors":"Chengyi Lu , Minjie Yang , Peiwu Chen , Hongyi Zhang , Shi Tang , Ling Zha , Ying Huang , Dong Sun , Ruizhuo Ouyang , Yuqin Jiang , Yuqing Miao , Baolin Liu","doi":"10.1016/j.bioelechem.2026.109245","DOIUrl":"10.1016/j.bioelechem.2026.109245","url":null,"abstract":"<div><div>Cancer early detection demands highly sensitive, cost-effective, and reliable sensing platforms. Herein, we report the synthesis of lanthanum bismuth oxide nanosheets (LaBi<sub>3</sub>O<sub>6</sub> NSs) via a simple sol–gel method and their innovative application in constructing a label-free electrochemical immunosensor for the detection of carcinoembryonic antigen (CEA). The LaBi<sub>3</sub>O<sub>6</sub> NSs serve as an excellent matrix offering a large specific surface area, high conductivity, and rich active sites, significantly enhancing electron transfer and biomolecular immobilization. The fabricated immunosensor demonstrates outstanding analytical performance: a wide linear range from 0.1 to 1000 ng mL<sup>−1</sup>, an ultra-low detection limit of 56.2 pg mL<sup>−1</sup>, and high selectivity against common interferents. It also exhibits remarkable reproducibility (RSD < 5%) and stability (retaining 90% activity after 15 days). Practical applicability was confirmed through successful CEA detection in human serum samples, with recovery rates of 98.8–101.2% and excellent agreement with standard methods. This work not only presents a novel bismuth-based nanomaterial for biosensing but also provides a robust, eco-friendly, and highly efficient strategy for clinical cancer biomarker detection. The proposed platform holds great promise for point-of-care diagnostics and opens new avenues for the development of next-generation electrochemical immunosensors.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"170 ","pages":"Article 109245"},"PeriodicalIF":4.5,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146170110","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 : 2026-08-01Epub Date: 2026-02-01DOI: 10.1016/j.bioelechem.2026.109244
Yuchen Tang , Hongbo Su , Chunxiao Chen , Kaida Liu , Xing Li
In current clinical practice, Tumor Treating Fields (TTFields) are delivered through insulated ceramic electrode arrays via capacitive coupling, which limits the efficiency of electric field energy transfer. In this study, we propose a new TTFields delivery mode based on conductive electrodes, termed conductive TTFields (Ce-TTFields), to enhance energy delivery efficiency. Electromagnetic-field and lumped-circuit analysis was conducted to understand the underlying mechanisms of TTFields delivery and proposed the novel Ce-TTFields concept. We designed and fabricated a Ce-TTFields culture dish and conducted electromagnetic simulations, in vitro electric-field measurements, and U-87 glioma cell proliferation assays to validate this novel concept. Simulation and test experimental results demonstrate that Ce-TTFields produce stronger electric field intensities in the cell culture and the simulated human brain model compared with conventional insulated electrodes under the same driving voltage. U-87 glioma cell proliferation assays consistently confirmed that the U-87 glioma inhibition efficiency is enhanced by Ce-TTFields, indicating significantly improved energy-delivery efficiency. These findings suggest that Ce-TTFields may help optimize TTFields treatment protocols and offer a promising direction for developing more efficient, lightweight, and cost-effective TTFields therapeutic systems.
{"title":"Improving the efficiency of tumor treating fields delivery in tumor cell proliferation inhibition through conductive electrodes","authors":"Yuchen Tang , Hongbo Su , Chunxiao Chen , Kaida Liu , Xing Li","doi":"10.1016/j.bioelechem.2026.109244","DOIUrl":"10.1016/j.bioelechem.2026.109244","url":null,"abstract":"<div><div>In current clinical practice, Tumor Treating Fields (TTFields) are delivered through insulated ceramic electrode arrays via capacitive coupling, which limits the efficiency of electric field energy transfer. In this study, we propose a new TTFields delivery mode based on conductive electrodes, termed conductive TTFields (Ce-TTFields), to enhance energy delivery efficiency. Electromagnetic-field and lumped-circuit analysis was conducted to understand the underlying mechanisms of TTFields delivery and proposed the novel Ce-TTFields concept. We designed and fabricated a Ce-TTFields culture dish and conducted electromagnetic simulations, in vitro electric-field measurements, and U-87 glioma cell proliferation assays to validate this novel concept. Simulation and test experimental results demonstrate that Ce-TTFields produce stronger electric field intensities in the cell culture and the simulated human brain model compared with conventional insulated electrodes under the same driving voltage. U-87 glioma cell proliferation assays consistently confirmed that the U-87 glioma inhibition efficiency is enhanced by Ce-TTFields, indicating significantly improved energy-delivery efficiency. These findings suggest that Ce-TTFields may help optimize TTFields treatment protocols and offer a promising direction for developing more efficient, lightweight, and cost-effective TTFields therapeutic systems.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"170 ","pages":"Article 109244"},"PeriodicalIF":4.5,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146117344","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 : 2026-08-01Epub Date: 2026-02-02DOI: 10.1016/j.bioelechem.2026.109240
Lata Pasupulety , Mohamed I. Zaki , Lakshmi A.N.
A stable nanofluid containing ZnO nanoparticles (ZnO NPs) and a plant-based surfactant, soapnut, was synthesized and its composite nature established by thermogravimetry, Fourier-transform infrared spectroscopy, scanning electron microscopy, and energy dispersive X-ray (EDX) analyses. Its effectiveness as a microbially induced corrosion (MIC) inhibitor was investigated. Gravimetric and electrochemical techniques-potentiodynamic polarisation and electrochemical impedance spectroscopy, revealed a reduction in corrosion rates (from 31.63 to 1.17 mils/year), achieving an inhibition efficiency of up to 97% at a low nanofluid concentration of 4 vol%. Both the components- ZnO NPs and the soapnut extract (SN) exhibited pronounced bactericidal activity, leading to effective suppression of biofilm formation, as confirmed by biofilm inhibition assays (78%) and confocal laser scanning microscopy imaging. The amphiphilic nature of SN, together with the high surface availability of ZnO NPs, enhanced inhibitor adsorption on the metal surface which was supported by adsorption studies and surface analyses- field-emission scanning electron microscopy coupled with EDX. In the synthesized composite, SN acting as a ligand, prevented aggregation of ZnO NPs and thereby improved surface coverage and stability. Overall, the synergistic interaction between SN and ZnO NPs produced an environmentally benign nanofluid with strong potential for mitigating MIC in petrochemical pipeline systems.
{"title":"Biofilm inhibition and microbial corrosion protection of carbon steel by a green surfactant based novel ZnO nanofluid","authors":"Lata Pasupulety , Mohamed I. Zaki , Lakshmi A.N.","doi":"10.1016/j.bioelechem.2026.109240","DOIUrl":"10.1016/j.bioelechem.2026.109240","url":null,"abstract":"<div><div>A stable nanofluid containing ZnO nanoparticles (ZnO NPs) and a plant-based surfactant, soapnut, was synthesized and its composite nature established by thermogravimetry, Fourier-transform infrared spectroscopy, scanning electron microscopy, and energy dispersive X-ray (EDX) analyses. Its effectiveness as a microbially induced corrosion (MIC) inhibitor was investigated. Gravimetric and electrochemical techniques-potentiodynamic polarisation and electrochemical impedance spectroscopy, revealed a reduction in corrosion rates (from 31.63 to 1.17 mils/year), achieving an inhibition efficiency of up to 97% at a low nanofluid concentration of 4 vol%. Both the components- ZnO NPs and the soapnut extract (SN) exhibited pronounced bactericidal activity, leading to effective suppression of biofilm formation, as confirmed by biofilm inhibition assays (78%) and confocal laser scanning microscopy imaging. The amphiphilic nature of SN, together with the high surface availability of ZnO NPs, enhanced inhibitor adsorption on the metal surface which was supported by adsorption studies and surface analyses- field-emission scanning electron microscopy coupled with EDX. In the synthesized composite, SN acting as a ligand, prevented aggregation of ZnO NPs and thereby improved surface coverage and stability. Overall, the synergistic interaction between SN and ZnO NPs produced an environmentally benign nanofluid with strong potential for mitigating MIC in petrochemical pipeline systems.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"170 ","pages":"Article 109240"},"PeriodicalIF":4.5,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146136969","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 : 2026-08-01Epub Date: 2026-01-14DOI: 10.1016/j.bioelechem.2026.109225
Christian Meinert Bache , Michael E.J. López Mujica , Stepan Shipovskov , Andrew Ewing , Elena E. Ferapontova
Specific electroanalysis of neurotransmitters in the brain, bloodstream, cerebrospinal fluid (CSF), or at the cellular level critically depends on the availability of miniaturized electrodes for aptasensing. Yet, with electrode miniaturization, sensitivity of analysis and limits of detection (LOD) can be compromised. Here, we adapted the RNA-aptamer-based macroelectrode assay for dopamine to the microelectrode format, by using gold-plated carbon fiber microelectrodes (CFE), modified via thiol chemistry with cysteamine and an RNA aptamer, for specific dopamine detection. The sensitivity of analysis with gold-plated cylindrical microelectrodes improved 90-fold, to 9.75 μA μM−1 cm−2 (at +0.100 V) vs. 108 nA μM−1 cm−2 (at optimal +0.185 V) shown with gold disk macroelectrodes, with LOD being 60 and 100 nM, in PBS and in artificial CSF, respectively. Yet, epinephrine interfered at 0.1 V. At 0.05 V, the sensitivity dropped to 4.62 μA μM−1 cm−2 but the RNA-aptamer/cysteamine-modified CFEs demonstrated excellent selectivity for dopamine over epinephrine, norepinephrine, L-DOPA, DOPAC, and uric and ascorbic acids. These findings suggest a straightforward strategy for constructing biospecific aptamer-based microelectrodes. However, in matrices more complex than CSF, such as serum, dopamine oxidation was inhibited. Therefore, effective monitoring of dopamine levels in blood using aptamer microelectrodes will likely require the use of protective membranes.
{"title":"RNA aptamer-modified gold-plated carbon fiber microelectrodes for selective dopamine sensing","authors":"Christian Meinert Bache , Michael E.J. López Mujica , Stepan Shipovskov , Andrew Ewing , Elena E. Ferapontova","doi":"10.1016/j.bioelechem.2026.109225","DOIUrl":"10.1016/j.bioelechem.2026.109225","url":null,"abstract":"<div><div>Specific electroanalysis of neurotransmitters in the brain, bloodstream, cerebrospinal fluid (CSF), or at the cellular level critically depends on the availability of miniaturized electrodes for aptasensing. Yet, with electrode miniaturization, sensitivity of analysis and limits of detection (LOD) can be compromised. Here, we adapted the RNA-aptamer-based macroelectrode assay for dopamine to the microelectrode format, by using gold-plated carbon fiber microelectrodes (CFE), modified via thiol chemistry with cysteamine and an RNA aptamer, for specific dopamine detection. The sensitivity of analysis with gold-plated cylindrical microelectrodes improved 90-fold, to 9.75 μA μM<sup>−1</sup> cm<sup>−2</sup> (at +0.100 V) vs. 108 nA μM<sup>−1</sup> cm<sup>−2</sup> (at optimal +0.185 V) shown with gold disk macroelectrodes, with LOD being 60 and 100 nM, in PBS and in artificial CSF, respectively. Yet, epinephrine interfered at 0.1 V. At 0.05 V, the sensitivity dropped to 4.62 μA μM<sup>−1</sup> cm<sup>−2</sup> but the RNA-aptamer/cysteamine-modified CFEs demonstrated excellent selectivity for dopamine over epinephrine, norepinephrine, L-DOPA, DOPAC, and uric and ascorbic acids. These findings suggest a straightforward strategy for constructing biospecific aptamer-based microelectrodes. However, in matrices more complex than CSF, such as serum, dopamine oxidation was inhibited. Therefore, effective monitoring of dopamine levels in blood using aptamer microelectrodes will likely require the use of protective membranes.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"170 ","pages":"Article 109225"},"PeriodicalIF":4.5,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146008106","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 : 2026-07-15Epub Date: 2026-03-11DOI: 10.1016/j.ccr.2026.217739
Luca Demonti , Hana Tabikh , Noel Nebra
Organofluorine compounds, mainly those containing F itself or trifluoromethyls (−CF3) in arenes, are ubiquitous in pharma/agrochemical industries and material science, making them essential to the well-being of mankind. The metal-mediated aryl−Rf bond formations (Rf = F, CF3) are commonly hampered by multiple factors (low nucleophilicity of the F− anion, strong M−CF3 bonds, difficult transmetallation, moisture sensitivity, etc.). Accordingly, the finding of synthetic schemes to build aryl−Rf bonds constitutes a major challenge in modern coordination/organometallic chemistry. This review seeks to critically summarize the most appealing approaches to aryl−F/CF3 couplings taking place from structurally characterized MIVRf species (M = Ni, Pd, Pt; Rf = F, CF3).
The concept of inverted ligand field (ILF) often displayed by some of the ‘formally’ MIVRf species compiled herein, together with spectroscopic and reactivity insights supporting the ILF electronic structure picture, is also introduced and briefly discussed.
{"title":"Arene fluorination and trifluoromethylation enabled by tetravalent group 10 metals ('formally' NiIV, PdIV, PtIV)","authors":"Luca Demonti , Hana Tabikh , Noel Nebra","doi":"10.1016/j.ccr.2026.217739","DOIUrl":"10.1016/j.ccr.2026.217739","url":null,"abstract":"<div><div>Organofluorine compounds, mainly those containing F itself or trifluoromethyls (−CF<sub>3</sub>) in arenes, are ubiquitous in pharma/agrochemical industries and material science, making them essential to the well-being of mankind. The metal-mediated aryl−R<sub>f</sub> bond formations (R<sub>f</sub> = F, CF<sub>3</sub>) are commonly hampered by multiple factors (low nucleophilicity of the F<sup>−</sup> anion, strong M−CF<sub>3</sub> bonds, difficult transmetallation, moisture sensitivity, etc.). Accordingly, the finding of synthetic schemes to build aryl−R<sub>f</sub> bonds constitutes a major challenge in modern coordination/organometallic chemistry. This review seeks to critically summarize the most appealing approaches to aryl−F/CF<sub>3</sub> couplings taking place from structurally characterized M<sup>IV</sup>R<sub>f</sub> species (M = Ni, Pd, Pt; R<sub>f</sub> = F, CF<sub>3</sub>).</div><div>The concept of inverted ligand field (ILF) often displayed by some of the <em>‘formally’</em> M<sup>IV</sup>R<sub>f</sub> species compiled herein, together with spectroscopic and reactivity insights supporting the ILF electronic structure picture, is also introduced and briefly discussed.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"559 ","pages":"Article 217739"},"PeriodicalIF":23.5,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-07-15Epub Date: 2026-03-11DOI: 10.1016/j.ccr.2026.217821
Daiane N. Maronde , José E. Rodríguez-Borges , Leandro M.O. Lourenço
Cationic porphyrins (Por) and phthalocyanine (Pc) derivatives are photoactive compounds with strong absorption in the UV–Vis region, making them promising candidates for photodynamic therapy (PDT) against cancer cells. Due to less solubility properties of some compounds in aqueous environments, structural modifications are often required to enhance their amphiphilicity and bioavailability. Introducing positively charged groups, such as e.g., pyridinium or ammonium moieties, into the macrocyclic framework significantly improves water solubility and cellular uptake, optimizing their potential for the PDT approach. This review focuses on the recent advancements in the design and application of cationic Por and Pc dyes for PDT of cancer diseases. Several parameters of the different PDT studies with versatile molecules are analyzed and compared across different structural modifications, light absorption properties (Soret and Q bands), singlet oxygen quantum yield (Ф∆), fluorescence quantum yield (ФF), (photo)stability, and attending to the half-maximal inhibitory concentration (IC50). Additionally, the impact of metal insertion and the nature, number, and position of cationic substituents, peripheral or axial, are discussed in relation to their photodynamic performance. Emphasis is placed on structure activity relationships, the selective accumulation in tumor cells, subcellular localization, and phototoxicity under different light irradiation conditions. This review is distinguished by a critical and comparative assessment of the literature, addressing relevant gaps in previous studies, particularly the insufficient and non-systematic determination of key photophysical parameters. Notwithstanding this standpoint, this review underscores the central role of rational molecular design and structure–activity relationships, contributing significantly to the development of efficient and selective cationic photosensitizers and to the advancement of PDT as a minimally invasive and targeted therapeutic strategy.
{"title":"Advances of light-activated cationic porphyrins and phthalocyanines for cancer photodynamic therapy","authors":"Daiane N. Maronde , José E. Rodríguez-Borges , Leandro M.O. Lourenço","doi":"10.1016/j.ccr.2026.217821","DOIUrl":"10.1016/j.ccr.2026.217821","url":null,"abstract":"<div><div>Cationic porphyrins (Por) and phthalocyanine (Pc) derivatives are photoactive compounds with strong absorption in the UV–Vis region, making them promising candidates for photodynamic therapy (PDT) against cancer cells. Due to less solubility properties of some compounds in aqueous environments, structural modifications are often required to enhance their amphiphilicity and bioavailability. Introducing positively charged groups, such as <em>e.g.</em>, pyridinium or ammonium moieties, into the macrocyclic framework significantly improves water solubility and cellular uptake, optimizing their potential for the PDT approach. This review focuses on the recent advancements in the design and application of cationic Por and Pc dyes for PDT of cancer diseases. Several parameters of the different PDT studies with versatile molecules are analyzed and compared across different structural modifications, light absorption properties (Soret and Q bands), singlet oxygen quantum yield (Ф<sub>∆</sub>), fluorescence quantum yield (Ф<sub>F</sub>), (photo)stability, and attending to the half-maximal inhibitory concentration (IC<sub>50</sub>). Additionally, the impact of metal insertion and the nature, number, and position of cationic substituents, peripheral or axial, are discussed in relation to their photodynamic performance. Emphasis is placed on structure activity relationships, the selective accumulation in tumor cells, subcellular localization, and phototoxicity under different light irradiation conditions. This review is distinguished by a critical and comparative assessment of the literature, addressing relevant gaps in previous studies, particularly the insufficient and non-systematic determination of key photophysical parameters. Notwithstanding this standpoint, this review underscores the central role of rational molecular design and structure–activity relationships, contributing significantly to the development of efficient and selective cationic photosensitizers and to the advancement of PDT as a minimally invasive and targeted therapeutic strategy.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"559 ","pages":"Article 217821"},"PeriodicalIF":23.5,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The unique photophysical properties of cyanine dyes—strong NIR absorption, large molar extinction coefficients, and flexible structural tunability—have positioned them as an important class of photosensitizers for photothermal therapy (PTT) and photodynamic therapy (PDT). However, free cyanine dyes suffer from intrinsic limitations, including poor stability, aggregation-caused quenching (ACQ), low ROS generation, and rapid clearance, which severely restrict their biomedical utility.
Recent advances in molecular self-assembly now offer powerful strategies to overcome these obstacles. Through π–π stacking, hydrophobic interaction, electrostatic association, peptide/protein templating, or metal-ion coordination, cyanine dyes can be organized into highly ordered nanostructures—such as J-aggregates, H-aggregates, nanomicelles, and hybrid nanoassemblies—with precisely tunable morphology and optical behavior. These nanoassemblies restrict conformational freedom, stabilize the excited state, suppress ACQ, and markedly enhance ROS yield and photothermal conversion. In particular, J-aggregates enable red-shifted and sharpened absorption bands, improving tissue penetration and energy utilization for deep-tissue phototherapy.
Beyond enhancing PDT/PTT performance, self-assembled cyanine nanostructures integrate naturally into multifunctional platforms capable of tumor targeting, tumor microenvironment (TME)-responsive activation, multimodal imaging, and combination therapy—such as PTT–PDT synergy, chemo-phototherapy, SDT, or immunotherapy. Despite these promising advances, challenges remain, including controlling assembly stability in vivo, achieving batch-to-batch reproducibility, and predicting biological fate in complex physiological environments.
This review summarizes recent progress in cyanine-dye self-assembly, with emphasis on assembly mechanisms, aggregate-state engineering, structure–property relationships, and strategies for improving PDT/PTT efficacy and combination cancer therapy. We further discuss existing limitations and future opportunities for translating assembled cyanine nanotherapeutics into precision oncology. Together, these insights highlight the power of supramolecular engineering in transforming traditional cyanine dyes into robust, versatile, and clinically meaningful phototheranostic nanoplatforms.
{"title":"Cyanine Nanoassemblies for synergistic cancer therapy: From aggregate-state modulation to Phototheranostic integration","authors":"Di Zhang , Shuheng Qin , Hai Xu , Hui Bian , Yuan-Yuan Zhao , Xiao Cheng , Jinrong Zheng , Xiaojun Peng , Juyoung Yoon","doi":"10.1016/j.ccr.2026.217783","DOIUrl":"10.1016/j.ccr.2026.217783","url":null,"abstract":"<div><div>The unique photophysical properties of cyanine dyes—strong NIR absorption, large molar extinction coefficients, and flexible structural tunability—have positioned them as an important class of photosensitizers for photothermal therapy (PTT) and photodynamic therapy (PDT). However, free cyanine dyes suffer from intrinsic limitations, including poor stability, aggregation-caused quenching (ACQ), low ROS generation, and rapid clearance, which severely restrict their biomedical utility.</div><div>Recent advances in molecular self-assembly now offer powerful strategies to overcome these obstacles. Through π–π stacking, hydrophobic interaction, electrostatic association, peptide/protein templating, or metal-ion coordination, cyanine dyes can be organized into highly ordered nanostructures—such as J-aggregates, H-aggregates, nanomicelles, and hybrid nanoassemblies—with precisely tunable morphology and optical behavior. These nanoassemblies restrict conformational freedom, stabilize the excited state, suppress ACQ, and markedly enhance ROS yield and photothermal conversion. In particular, J-aggregates enable red-shifted and sharpened absorption bands, improving tissue penetration and energy utilization for deep-tissue phototherapy.</div><div>Beyond enhancing PDT/PTT performance, self-assembled cyanine nanostructures integrate naturally into multifunctional platforms capable of tumor targeting, tumor microenvironment (TME)-responsive activation, multimodal imaging, and combination therapy—such as PTT–PDT synergy, chemo-phototherapy, SDT, or immunotherapy. Despite these promising advances, challenges remain, including controlling assembly stability in vivo, achieving batch-to-batch reproducibility, and predicting biological fate in complex physiological environments.</div><div>This review summarizes recent progress in cyanine-dye self-assembly, with emphasis on assembly mechanisms, aggregate-state engineering, structure–property relationships, and strategies for improving PDT/PTT efficacy and combination cancer therapy. We further discuss existing limitations and future opportunities for translating assembled cyanine nanotherapeutics into precision oncology. Together, these insights highlight the power of supramolecular engineering in transforming traditional cyanine dyes into robust, versatile, and clinically meaningful phototheranostic nanoplatforms.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"559 ","pages":"Article 217783"},"PeriodicalIF":23.5,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-07-15Epub Date: 2026-03-11DOI: 10.1016/j.ccr.2026.217819
Yusu Li , Xinyue Zhao , Jin-ao Duan, Ping Xiao
The growing global antimicrobial resistance crisis and limitations of conventional cancer therapies call for innovative biomedical strategies. Peptide-metal chelates are promising multifunctional biomaterials that leverage peptide-metal ion synergy to overcome traditional therapeutic bottlenecks, with core value in building integrated platforms for programmable targeted delivery, spatiotemporal smart responsiveness and intrinsic theranostic synergy. Research in this field has evolved from basic molecular discovery to systematic rational design and now clinical smart applications. This review presents a novel research and development roadmap for peptide-metal chelates, elaborating their design principles, structure-function mechanisms and latest biomedical advances. It highlights their unique “Trojan horse” strategy for antibacterial resistance and precise tumor targeting via the EPR effect and tumor microenvironmental triggers such as pH and enzymes. It details their applications in intelligent drug delivery, high-efficacy antimicrobial therapy, precision anticancer treatment, and theranostic platforms integrating imaging and therapy. Addressing gaps in existing fragmented summaries, including the lack of systematic design-synthesis-application integration and insufficient basic-clinical translation analysis, the review also notes unresolved challenges in long-term in vivo safety, bioavailability optimization and GMP-compliant large-scale production. Finally, it prospects core directions like AI-assisted rational molecular design, advanced multi-stimuli responsive materials and multimodal theranostic integration, which are expected to accelerate the clinical translation of peptide-metal chelates and offer innovative solutions for drug-resistant infections and refractory cancers.
{"title":"Design mechanisms and biomedical applications of peptide-metal chelates in antimicrobial therapy, tumor theranostics, and integrated diagnosis-treatment systems","authors":"Yusu Li , Xinyue Zhao , Jin-ao Duan, Ping Xiao","doi":"10.1016/j.ccr.2026.217819","DOIUrl":"10.1016/j.ccr.2026.217819","url":null,"abstract":"<div><div>The growing global antimicrobial resistance crisis and limitations of conventional cancer therapies call for innovative biomedical strategies. Peptide-metal chelates are promising multifunctional biomaterials that leverage peptide-metal ion synergy to overcome traditional therapeutic bottlenecks, with core value in building integrated platforms for programmable targeted delivery, spatiotemporal smart responsiveness and intrinsic theranostic synergy. Research in this field has evolved from basic molecular discovery to systematic rational design and now clinical smart applications. This review presents a novel research and development roadmap for peptide-metal chelates, elaborating their design principles, structure-function mechanisms and latest biomedical advances. It highlights their unique “Trojan horse” strategy for antibacterial resistance and precise tumor targeting <em>via</em> the EPR effect and tumor microenvironmental triggers such as pH and enzymes. It details their applications in intelligent drug delivery, high-efficacy antimicrobial therapy, precision anticancer treatment, and theranostic platforms integrating imaging and therapy. Addressing gaps in existing fragmented summaries, including the lack of systematic design-synthesis-application integration and insufficient basic-clinical translation analysis, the review also notes unresolved challenges in long-term <em>in vivo</em> safety, bioavailability optimization and GMP-compliant large-scale production. Finally, it prospects core directions like AI-assisted rational molecular design, advanced multi-stimuli responsive materials and multimodal theranostic integration, which are expected to accelerate the clinical translation of peptide-metal chelates and offer innovative solutions for drug-resistant infections and refractory cancers.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"559 ","pages":"Article 217819"},"PeriodicalIF":23.5,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388423","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-07-15Epub Date: 2026-03-11DOI: 10.1016/j.ccr.2026.217809
K. Keerthi , E.A. Lohith , Sowjanya Vallem , K. Praveena , Dimpul Konwar , Kasibhatta Sivakumar , Rajenahally V. Jagadeesh , N.V.V. Jyothi , Aristides Bakandritsos , Sada Venkateswarlu , Minyoung Yoon , Radek Zboril
Organic pollutants, including plastics, pharmaceuticals, aromatic compounds, pesticides, and industrial solvents, pose a serious threat to soil quality, aquatic ecosystems, and human health. Single-atom-coordinated MXenes (SAs@MXenes) have emerged as promising platforms for detoxifying organic pollutants because of their tunable surface chemistry, high catalytic activity, and atomic-level precision. Anchoring isolated metal atoms on the MXene surface maximizes atom utilization and modulates the electronic structure, thereby improving charge separation, adsorption affinity, and redox reactivity. However, comprehensive reviews of this emerging class of SAs@MXenes catalysts for organic pollutant detoxification remain limited. This review summarizes diverse synthesis strategies for achieving stable single-atom dispersion, including defect engineering to anchor single atoms at vacancy sites, heteroatom coordination chemistry, axial coordination, the modulation of local electronic structure through ligand control, and UV-mediated synthesis that enables photochemical precision in atom placement. In addition, advanced characterization techniques are used to confirm atomic dispersion, oxidation states, and structural evolution, while electron paramagnetic resonance (EPR) spectroscopy provides insight into the reactive intermediates responsible for detoxification. Furthermore, SAs@MXenes function as both efficient catalysts and a robust adsorbents for the degradation and capture of organic contaminants. Computational approaches, including density functional theory (DFT), machine learning (ML), and molecular dynamics (MD) simulations, are emphasized to elucidate catalytic mechanisms, accelerate catalytic design, and clarify molecular-level interactions. Collectively, these strategies support the rational development of single-atom–coordinated MXenes for sustainable environmental detoxification, and their future perspectives are also presented.
{"title":"Single-atom coordinated MXenes for organic pollutant detoxification: Mechanistic insights, challenges, and future directions","authors":"K. Keerthi , E.A. Lohith , Sowjanya Vallem , K. Praveena , Dimpul Konwar , Kasibhatta Sivakumar , Rajenahally V. Jagadeesh , N.V.V. Jyothi , Aristides Bakandritsos , Sada Venkateswarlu , Minyoung Yoon , Radek Zboril","doi":"10.1016/j.ccr.2026.217809","DOIUrl":"10.1016/j.ccr.2026.217809","url":null,"abstract":"<div><div>Organic pollutants, including plastics, pharmaceuticals, aromatic compounds, pesticides, and industrial solvents, pose a serious threat to soil quality, aquatic ecosystems, and human health. Single-atom-coordinated MXenes (SAs@MXenes) have emerged as promising platforms for detoxifying organic pollutants because of their tunable surface chemistry, high catalytic activity, and atomic-level precision. Anchoring isolated metal atoms on the MXene surface maximizes atom utilization and modulates the electronic structure, thereby improving charge separation, adsorption affinity, and redox reactivity. However, comprehensive reviews of this emerging class of SAs@MXenes catalysts for organic pollutant detoxification remain limited<strong>.</strong> This review summarizes diverse synthesis strategies for achieving stable single-atom dispersion, including defect engineering to anchor single atoms at vacancy sites, heteroatom coordination chemistry, axial coordination, the modulation of local electronic structure through ligand control, and UV-mediated synthesis that enables photochemical precision in atom placement. In addition, advanced characterization techniques are used to confirm atomic dispersion, oxidation states, and structural evolution, while electron paramagnetic resonance (EPR) spectroscopy provides insight into the reactive intermediates responsible for detoxification. Furthermore, SAs@MXenes function as both efficient catalysts and a robust adsorbents for the degradation and capture of organic contaminants. Computational approaches, including density functional theory (DFT), machine learning (ML), and molecular dynamics (MD) simulations, are emphasized to elucidate catalytic mechanisms, accelerate catalytic design, and clarify molecular-level interactions. Collectively, these strategies support the rational development of single-atom–coordinated MXenes for sustainable environmental detoxification, and their future perspectives are also presented.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"559 ","pages":"Article 217809"},"PeriodicalIF":23.5,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388422","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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