In this work, a simple and modified method for immobilizing Pd(0) NPs on the surface of dual functionalized magnetic Fe3O4 microspheres with chitosan-agarose (CS-Agar) has been used. The high area surface showed a dispersion of the minuscule Pd NPs. The key role of the CS-Agar hydrogel is to reduce Pd ions via a green pathway, stabilizing them via capping in the process. In order to determine the morphological aspects of the synthesized material, it was subjected to a variety of physicochemical techniques, including FE-SEM (Field Emission Scanning Electron Microscopy) and TEM (Transmission Electron Microscopy). The new material was studied catalytically as a reusable heterogeneous nanocatalyst that is effective in phosphine-free production of a variety of stilbene derivatives using the Sonogashira coupling method. Excellent results were obtained in every reaction, with the exception of chloroarenes and sterically hindered substrates. Without seeing a discernible decline in activity, the catalyst was reused seven times in a row.
{"title":"Application of supported palladium nanoparticles over chitosan-agarose encapsulated Fe3O4 microspheres as efficient catalyst in the Sonogashira cross-coupling reactions","authors":"Ali Kakanejadifard , Parisa Safarimehr , Bikash Karmakar , Mozhgan Pirhayati , Hojat Veisi","doi":"10.1016/j.jorganchem.2025.123553","DOIUrl":"10.1016/j.jorganchem.2025.123553","url":null,"abstract":"<div><div>In this work, a simple and modified method for immobilizing Pd(0) NPs on the surface of dual functionalized magnetic Fe<sub>3</sub>O<sub>4</sub> microspheres with chitosan-agarose (CS-Agar) has been used. The high area surface showed a dispersion of the minuscule Pd NPs. The key role of the CS-Agar hydrogel is to reduce Pd ions via a green pathway, stabilizing them via capping in the process. In order to determine the morphological aspects of the synthesized material, it was subjected to a variety of physicochemical techniques, including FE-SEM (Field Emission Scanning Electron Microscopy) and TEM (Transmission Electron Microscopy). The new material was studied catalytically as a reusable heterogeneous nanocatalyst that is effective in phosphine-free production of a variety of stilbene derivatives using the Sonogashira coupling method. Excellent results were obtained in every reaction, with the exception of chloroarenes and sterically hindered substrates. Without seeing a discernible decline in activity, the catalyst was reused seven times in a row.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1029 ","pages":"Article 123553"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143268005","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-01DOI: 10.1016/j.jorganchem.2024.123484
Maryam Mirza-Aghayan , Amir Sepehr Moieni
Reduction of unsaturated compounds using a standard method in laboratories as well as in industry to achieve valuable compounds is very important. The catalytic activity of various types of palladium (Pd) catalysts in the presence of organosilane for the reduction of unsaturated compounds has been proven over the years. As the main goal of the review, we present a comprehensive overview of the application of Pd catalysts in the presence of organosilane compounds for the reduction of organic building blocks such as thio esters, organic halides, acid chlorides, carboxylic acids, olefins, alkynes, ethers, α,β-unsaturated compounds, carbonyl compounds, alcohols, nitroaromatic derivatives, and imine compounds. We present the recent reports on the reduction of unsaturated compounds using the Pd catalyst/silane system. We briefly discuss the general mechanistic roles played by palladium and organosilane in the reduction reactions.
{"title":"Recent progress in palladium-catalyzed reduction with organosilanes","authors":"Maryam Mirza-Aghayan , Amir Sepehr Moieni","doi":"10.1016/j.jorganchem.2024.123484","DOIUrl":"10.1016/j.jorganchem.2024.123484","url":null,"abstract":"<div><div>Reduction of unsaturated compounds using a standard method in laboratories as well as in industry to achieve valuable compounds is very important. The catalytic activity of various types of palladium (Pd) catalysts in the presence of organosilane for the reduction of unsaturated compounds has been proven over the years. As the main goal of the review, we present a comprehensive overview of the application of Pd catalysts in the presence of organosilane compounds for the reduction of organic building blocks such as thio esters, organic halides, acid chlorides, carboxylic acids, olefins, alkynes, ethers, α,β-unsaturated compounds, carbonyl compounds, alcohols, nitroaromatic derivatives, and imine compounds. We present the recent reports on the reduction of unsaturated compounds using the Pd catalyst/silane system. We briefly discuss the general mechanistic roles played by palladium and organosilane in the reduction reactions.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123484"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143139468","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The current study focuses on the eco-friendly, bio-synthesis and of silver nanoparticles (AgNPs), utilizing an aqueous extract of Mikania micrantha. A rigorous analysis was performed to investigate the effects of several operational factors on the synthesis of AgNPs, including the various quantities of leaf extract, temperature, contact duration, and pH solution. The outcomes demonstrated that the optimal circumstances for producing nanoparticles are Mikania micrantha leaf extract dosage (5 % v/v), pH 9, and 80 °C temperature, with a duration of 60 min incubation time. The bio-synthesized AgNPs were examined using UV–Vis, FT-IR, X-ray diffraction (XRD), FE-SEM, EDX, TEM, and SAED studies. The FT-IR study proved that phytochemicals were involved in the AgNPs production process, and its spherical morphologies with the size range of 12.35 - 46.83 nm were apparent in the TEM images. The face-centered cubic structure of AgNPs was validated by the XRD spectrum. The XRD investigations also substantiated the SAED spectrum's indication that the AgNPs were crystalline. AgNPs were identified as an eco-friendly heterogeneous catalyst, demonstrating high catalytic efficiency in the Biginelli reaction under acid-free, mild conditions, achieving excellent yields in 30 s. 1,1-diphenyl- 2-picrylhydrazyl (DPPH) and Ferric reducing antioxidant power (FRAP) assays were used to assess the biological efficiency showing 89.8 % inhibition activity with an average IC50 value of 24.99± 0.19 µg mL-1 and higher reducing power than the positive control, respectively. This confirms that the leaf extract of Mikania micrantha and its biosynthesized nanoparticles also showed promising antioxidant capability.
{"title":"Biosynthesis of Mikania micrantha mediated silver nanoparticles: Its application as a sustainable catalyst for Biginelli reaction and antioxidant capacity","authors":"Manthae C. Phom , Betokali K. Zhimomi , Putusenla Imchen , Phitovili Sumi , Shisak Sharma , Khonzani Yanthan , Shokip Tumtin , Toka Swu , Tovishe Phucho","doi":"10.1016/j.jorganchem.2024.123482","DOIUrl":"10.1016/j.jorganchem.2024.123482","url":null,"abstract":"<div><div>The current study focuses on the eco-friendly, bio-synthesis and of silver nanoparticles (AgNPs), utilizing an aqueous extract of <em>Mikania micrantha</em>. A rigorous analysis was performed to investigate the effects of several operational factors on the synthesis of AgNPs, including the various quantities of leaf extract, temperature, contact duration, and pH solution. The outcomes demonstrated that the optimal circumstances for producing nanoparticles are <em>Mikania micrantha</em> leaf extract dosage (5 % v/v), pH 9, and 80 °C temperature, with a duration of 60 min incubation time. The bio-synthesized AgNPs were examined using UV–Vis, FT-IR, X-ray diffraction (XRD), FE-SEM, EDX, TEM, and SAED studies. The FT-IR study proved that phytochemicals were involved in the AgNPs production process, and its spherical morphologies with the size range of 12.35 - 46.83 nm were apparent in the TEM images. The face-centered cubic structure of AgNPs was validated by the XRD spectrum. The XRD investigations also substantiated the SAED spectrum's indication that the AgNPs were crystalline. AgNPs were identified as an eco-friendly heterogeneous catalyst, demonstrating high catalytic efficiency in the Biginelli reaction under acid-free, mild conditions, achieving excellent yields in 30 s. 1,1-diphenyl- 2-picrylhydrazyl (DPPH) and Ferric reducing antioxidant power (FRAP) assays were used to assess the biological efficiency showing 89.8 % inhibition activity with an average IC<sub>50</sub> value of 24.99± 0.19 µg mL<sup>-1</sup> and higher reducing power than the positive control, respectively. This confirms that the leaf extract of <em>Mikania micrantha</em> and its biosynthesized nanoparticles also showed promising antioxidant capability.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123482"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138862","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-01DOI: 10.1016/j.jorganchem.2024.123468
Anastasiya S. Soldatenko , Alexander I. Albanov , Alexander A. Korlyukov , Alexander D. Volodin , Nataliya F. Lazareva
The interaction of fenamic acid with Me2SiCl2, MePhSiCl2, Me(ClCH2)SiCl2 and Ph2SiCl2 led to the formation of previously unknown polyfunctional six-membered Si-containing heterocycles. Their structure was characterized by NMR, IR and X-ray crystallography. Monitoring this reaction by NMR method showed that in the first step unknown (chlorodiorganyl)silyl esters of fenamic acid are formed. The formation of hydroxy(methyl)phenylsilyl 2-anilinobenzoate as an intermediate of the hydrolysis of 2-methyl-1,2-diphenyl-1,2-dihydro-4H-3,1,2-benzoxazasilin-4-one was detected by NMR spectroscopy.
{"title":"New Si-containing heterocycles on the base of fenamic acid","authors":"Anastasiya S. Soldatenko , Alexander I. Albanov , Alexander A. Korlyukov , Alexander D. Volodin , Nataliya F. Lazareva","doi":"10.1016/j.jorganchem.2024.123468","DOIUrl":"10.1016/j.jorganchem.2024.123468","url":null,"abstract":"<div><div>The interaction of fenamic acid with Me<sub>2</sub>SiCl<sub>2</sub>, MePhSiCl<sub>2</sub>, Me(ClCH<sub>2</sub>)SiCl<sub>2</sub> and Ph<sub>2</sub>SiCl<sub>2</sub> led to the formation of previously unknown polyfunctional six-membered Si-containing heterocycles. Their structure was characterized by NMR, IR and X-ray crystallography. Monitoring this reaction by NMR method showed that in the first step unknown (chlorodiorganyl)silyl esters of fenamic acid are formed. The formation of hydroxy(methyl)phenylsilyl 2-anilinobenzoate as an intermediate of the hydrolysis of 2-methyl-1,2-diphenyl-1,2-dihydro-4H-3,1,2-benzoxazasilin-4-one was detected by NMR spectroscopy.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123468"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138869","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The Cp* rhodium-catalyzed dehydrogenative coupling of 1,4-bis(pivaroylamino)benzene with diarylacetylenes smoothly proceeds to form tetraarylpyrrolo[2,3-f]indole derivatives as double annulated products. The annulation procedure has also been found to be applicable to the construction of a pyrano[3,4-f]indol-5(1H)-one framework.
{"title":"Construction of multiply arylated fused heterocycles through rhodium-catalyzed double annulation of acylamido arenes with alkynes","authors":"Mikishiro Hayashi, Yoshinosuke Usuki, Tetsuya Satoh","doi":"10.1016/j.jorganchem.2025.123550","DOIUrl":"10.1016/j.jorganchem.2025.123550","url":null,"abstract":"<div><div>The Cp* rhodium-catalyzed dehydrogenative coupling of 1,4-bis(pivaroylamino)benzene with diarylacetylenes smoothly proceeds to form tetraarylpyrrolo[2,3-<em>f</em>]indole derivatives as double annulated products. The annulation procedure has also been found to be applicable to the construction of a pyrano[3,4-<em>f</em>]indol-5(1<em>H</em>)-one framework.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1028 ","pages":"Article 123550"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143322438","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this study, an efficient heterogeneous palladium was developed by moifying the MIL-125-NH2 metal-organic framework bromoacetyl bromide and tetraethylenepentamine ligands. The resulting modified framework was then used as a platform for immobilizing Pd nanoparticles (NPs) to generate the Pd@MIL-125-NH-Ac-TEPA nanocomposite. FT-IR, FESEM, EDS, TEM, CHN, TGA, XRD, and ICP-OES were used to identify the structure of the nanocomposite. The characterization findings approve the formation of well-dispersed Pd nanoparticles with a size distribution of 9 to 23 nm. The Pd@MIL-125-NH-Ac-TEPA nanocomposite with 2.97 % loading of Pd exhibited high efficiency in the Suzuki-Miyaura coupling reaction of arylboronic acids with various aryl and heteroaryl halides (chlorides, bromides, and iodides) containing electron-donor and electron-acceptor substituents. The coupling products were obtained in water/ethanol mixture (1:1) as solvent at 60 °C for 30 min in 70–99 % yields. The nanocatalyst can be recovered easily and reused for at least five consecutive runs without losing its activity significantly. The palladium leaching of the reused nanocatalyst was less than 1 %. The results revealed that the introduced nanocatalyst has the potential for other organic transformations.
{"title":"Preparation and characterization of Pd immobilized on the MIL-125-NH2 as an efficient recyclable metal-organic framework in the Suzuki–Miyaura reaction","authors":"Zeynab Sadati, Heshmatollah Alinezhad, Mahmood Tajbakhsh","doi":"10.1016/j.jorganchem.2024.123466","DOIUrl":"10.1016/j.jorganchem.2024.123466","url":null,"abstract":"<div><div>In this study, an efficient heterogeneous palladium was developed by moifying the MIL-125-NH<sub>2</sub> metal-organic framework bromoacetyl bromide and tetraethylenepentamine ligands. The resulting modified framework was then used as a platform for immobilizing Pd nanoparticles (NPs) to generate the Pd@MIL-125-NH-Ac-TEPA nanocomposite. FT-IR, FESEM, EDS, TEM, CHN, TGA, XRD, and ICP-OES were used to identify the structure of the nanocomposite. The characterization findings approve the formation of well-dispersed Pd nanoparticles with a size distribution of 9 to 23 nm. The Pd@MIL-125-NH-Ac-TEPA nanocomposite with 2.97 % loading of Pd exhibited high efficiency in the Suzuki-Miyaura coupling reaction of arylboronic acids with various aryl and heteroaryl halides (chlorides, bromides, and iodides) containing electron-donor and electron-acceptor substituents. The coupling products were obtained in water/ethanol mixture (1:1) as solvent at 60 °C for 30 min in 70–99 % yields. The nanocatalyst can be recovered easily and reused for at least five consecutive runs without losing its activity significantly. The palladium leaching of the reused nanocatalyst was less than 1 %. The results revealed that the introduced nanocatalyst has the potential for other organic transformations.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123466"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138866","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
An azomethine-functionalized triazole-coupled organosilane was successfully synthesized using a Cu(I)-catalyzed click chemistry reaction. The resulting silane was thoroughly characterized through 1H and 13C NMR spectroscopy, FT-IR spectroscopy, and mass spectrometry. UV–visible spectroscopy revealed the silane's exceptional selectivity for detecting Sulphur 80 % WDG fungicide, with no interference from other fungicides. Titration studies determined a detection limit of 1.3 × 10–5 M and an association constant of 8.8 × 103 M-1. The binding stoichiometry between the silane and Sulphur 80 % WDG was confirmed to be 1:1 using Job's plot analysis. Theoretical studies further demonstrated that silane possesses drug-like properties and exhibits non-toxic behaviour. Additionally, the organosilane showed potential to mitigate the harmful effects of Fusarium vanettenii on plants, with docking studies indicating strong ligand-protein interaction characterized by a binding energy of -6.68 kcal/mol and an inhibition constant (Ki) of 12.62 µM.
{"title":"Triazole allied organosilane: Synthesis, photophysical study to detect sulphur 80 % WDG fungicide and molecular docking","authors":"Gurjaspreet Singh , Samiksha Sharma , Manickam Selvaraj , Sumesh Khurana , Jigmat Stanzin , Devina Sharma , Mithun , Vikas","doi":"10.1016/j.jorganchem.2024.123474","DOIUrl":"10.1016/j.jorganchem.2024.123474","url":null,"abstract":"<div><div>An azomethine-functionalized triazole-coupled organosilane was successfully synthesized using a Cu(I)-catalyzed click chemistry reaction. The resulting silane was thoroughly characterized through <sup>1</sup>H and <sup>13</sup>C NMR spectroscopy, FT-IR spectroscopy, and mass spectrometry. UV–visible spectroscopy revealed the silane's exceptional selectivity for detecting Sulphur 80 % WDG fungicide, with no interference from other fungicides. Titration studies determined a detection limit of 1.3 × 10<sup>–5</sup> M and an association constant of 8.8 × 10<sup>3</sup> M<sup>-1</sup>. The binding stoichiometry between the silane and Sulphur 80 % WDG was confirmed to be 1:1 using Job's plot analysis. Theoretical studies further demonstrated that silane possesses drug-like properties and exhibits non-toxic behaviour. Additionally, the organosilane showed potential to mitigate the harmful effects of <em>Fusarium vanettenii</em> on plants, with docking studies indicating strong ligand-protein interaction characterized by a binding energy of -6.68 kcal/mol and an inhibition constant (Ki) of 12.62 µM.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123474"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138868","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-01DOI: 10.1016/j.jorganchem.2024.123448
Yunus Penlik , Oguzhan Avcıata , Semih Gorduk
In this study, tetra-substituted metal-free and In(III)Cl phthalocyanine compounds containing 2-(5‑chloro-2-benzotriazolyl)-6-tertbutyl-p-cresol (Tinuvin-326) group were synthesized and their photophysicochemical properties were investigated for the first time. This study was performed in three steps. In the first step, a new 2-(5‑chloro-2-benzotriazolyl)-6-tertbutyl-p-cresoldicyanobenzene (4TpC) structure was synthesized and this compound was characterized by various methods. In the second step, peripherally tetra-substituted metal-free (4TpCH2Pc) and In(III) (4TpC-InPc) phthalocyanine compounds were synthesized using 4TpC compound and these compounds were characterized using different instrumental methods. In the last step, the aggregation, photophysical and photochemical properties of 4TpCH2Pc and 4TpC-InPc compounds were investigated and their suitability as photosensitizers for PDT studies was determined. After photochemical studies, singlet oxygen quantum yields were calculated in DMF (0.18 for 4TpCH2Pc and 0.68 for 4TpC-InPc) and DMSO (0.21 for 4TpCH2Pc and 0.72 for 4TpC-InPc) solvents. From these results, it is concluded that the synthesized phthalocyanine compounds are suitable compounds as photosensitizers in PDT studies.
{"title":"Preparation of tetra-substituted In(III)Cl and metal-free phthalocyanines containing benzotriazole groups and investigation photophysicochemical properties","authors":"Yunus Penlik , Oguzhan Avcıata , Semih Gorduk","doi":"10.1016/j.jorganchem.2024.123448","DOIUrl":"10.1016/j.jorganchem.2024.123448","url":null,"abstract":"<div><div>In this study, tetra-substituted metal-free and In(III)Cl phthalocyanine compounds containing 2-(5‑chloro-2-benzotriazolyl)-6-tertbutyl-p-cresol (Tinuvin-326) group were synthesized and their photophysicochemical properties were investigated for the first time. This study was performed in three steps. In the first step, a new 2-(5‑chloro-2-benzotriazolyl)-6-tertbutyl-p-cresoldicyanobenzene (4TpC) structure was synthesized and this compound was characterized by various methods. In the second step, peripherally tetra-substituted metal-free (4TpC<img>H<sub>2</sub>Pc) and In(III) (4TpC-InPc) phthalocyanine compounds were synthesized using 4TpC compound and these compounds were characterized using different instrumental methods. In the last step, the aggregation, photophysical and photochemical properties of 4TpC<img>H<sub>2</sub>Pc and 4TpC-InPc compounds were investigated and their suitability as photosensitizers for PDT studies was determined. After photochemical studies, singlet oxygen quantum yields were calculated in DMF (0.18 for 4TpC<img>H<sub>2</sub>Pc and 0.68 for 4TpC-InPc) and DMSO (0.21 for 4TpC<img>H<sub>2</sub>Pc and 0.72 for 4TpC-InPc) solvents. From these results, it is concluded that the synthesized phthalocyanine compounds are suitable compounds as photosensitizers in PDT studies.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123448"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138870","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Electrochemical sensors are emerging as promising tools for point-of-care diagnostic medical devices, benefiting from advancements in nanomaterials. These nanomaterials enable the development of smaller, more sensitive, and selective sensors while reducing fabrication and maintenance costs. This work presents a comprehensive theoretical investigation of the potential application of pristine, Ga- and Al-doped Zn12O12 nanoclusters for detecting methadone, a critical analyte in various medical and law enforcement applications. Employing density functional theory (DFT) calculations at the B3LYP-D level with the 6–311 G (d, p) basis set, we have elucidated the interactions between these nanoclusters and methadone. The results reveal that methadone exhibits intense adsorption energies of -41.02, -39.79, and -59.77 kcal/mol on the pristine Zn12O12, GaZn11O12, and AlZn11O12 nanoclusters, respectively, in their most stable configurations. The doped nanoclusters, GaZn11O12 and AlZn11O12, displayed significant gap energies (Eg) changes upon methadone adsorption, indicating enhanced sensitivity towards this analyte. The UV–Vis spectroscopic analysis showed that methadone adsorption on the GaZn11O12 and AlZn11O12 nanoclusters led to distinct spectral shifts and oscillator strength variations compared to the Zn12O12 nanocluster. The transition theory calculations highlighted the GaZn11O12 nanocluster's short recovery time of 0.44 s, a crucial attribute for practical applications. Solvent effect studies demonstrated the stability of the methadone/GaZn11O12 complex in water and revealed its heightened polarization, as evidenced by the increased dipole moment. These findings suggest that the GaZn11O12 nanocluster is a promising candidate for detecting methadone in gas and liquid phases, with favorable attributes such as high sensitivity, rapid reversibility, and stability in gas and aqueous environments. Thus, this nanocluster can be used in sensor devices.
{"title":"Computational investigation of pristine, Al-, and Ga-doped Zn12O12 nanoclusters as detection platforms for methadone in gas and solvent phases","authors":"Farag M.A. Altalbawy , Uday Abdul-Reda Hussein , Iman Samir Alalaq , Irwanjot Kaur , Abhishek Kumar , Mamata Chahar , Suman Saini , Ruaa Sattar , Hadil Hussain Hamza , Marwea Al-hedrewy","doi":"10.1016/j.jorganchem.2024.123469","DOIUrl":"10.1016/j.jorganchem.2024.123469","url":null,"abstract":"<div><div>Electrochemical sensors are emerging as promising tools for point-of-care diagnostic medical devices, benefiting from advancements in nanomaterials. These nanomaterials enable the development of smaller, more sensitive, and selective sensors while reducing fabrication and maintenance costs. This work presents a comprehensive theoretical investigation of the potential application of pristine, Ga- and Al-doped Zn<sub>12</sub>O<sub>12</sub> nanoclusters for detecting methadone, a critical analyte in various medical and law enforcement applications. Employing density functional theory (DFT) calculations at the B3LYP-D level with the 6–311 G (d, p) basis set, we have elucidated the interactions between these nanoclusters and methadone. The results reveal that methadone exhibits intense adsorption energies of -41.02, -39.79, and -59.77 kcal/mol on the pristine Zn<sub>12</sub>O<sub>12</sub>, GaZn<sub>11</sub>O<sub>12,</sub> and AlZn<sub>11</sub>O<sub>12</sub> nanoclusters, respectively, in their most stable configurations. The doped nanoclusters, GaZn<sub>11</sub>O<sub>12</sub> and AlZn<sub>11</sub>O<sub>12</sub>, displayed significant gap energies (E<sub>g</sub>) changes upon methadone adsorption, indicating enhanced sensitivity towards this analyte. The UV–Vis spectroscopic analysis showed that methadone adsorption on the GaZn<sub>11</sub>O<sub>12</sub> and AlZn<sub>11</sub>O<sub>12</sub> nanoclusters led to distinct spectral shifts and oscillator strength variations compared to the Zn<sub>12</sub>O<sub>12</sub> nanocluster. The transition theory calculations highlighted the GaZn<sub>11</sub>O<sub>12</sub> nanocluster's short recovery time of 0.44 s, a crucial attribute for practical applications. Solvent effect studies demonstrated the stability of the methadone/GaZn<sub>11</sub>O<sub>12</sub> complex in water and revealed its heightened polarization, as evidenced by the increased dipole moment. These findings suggest that the GaZn<sub>11</sub>O<sub>12</sub> nanocluster is a promising candidate for detecting methadone in gas and liquid phases, with favorable attributes such as high sensitivity, rapid reversibility, and stability in gas and aqueous environments. Thus, this nanocluster can be used in sensor devices.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123469"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138871","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-01DOI: 10.1016/j.jorganchem.2024.123478
Henrique P. Mota , João M. Anghinoni , Emilly C. Silva , Pâmela Macchion , Sabrina S. Ferreira , Jaqueline F. de Souza , Eder J. Lenardão , André R. Fajardo
Multicomponent reactions (MCRs) provide a greener approach to chemical synthesis, yet their complexity requires efficient catalysts. In this study, we investigate nickel ferrite spinels (NiFe2O4) as heterogeneous catalysts for the aza-Henry MCR to synthesize 2-arylimidazo[1,2-a]pyridines. NiFe2O4 was synthesized via a sol–gel method and calcined at 500, 700, and 1000 °C. Higher calcination temperatures yielded spinels with enhanced purity, crystallinity, and magnetization, improving catalytic performance, particularly for the sample calcined at 1000 °C. Catalytic assays showed that with just 10 mol.% catalyst, the yield of 2-arylimidazo[1,2-a]pyridine reached 93 %, surpassing both homogeneous and heterogeneous alternatives. NiFe2O4 also efficiently catalyzed the synthesis of the gastroprotective drug Zolimidine®, achieving a 65 % yield. Its magnetic properties facilitated easy recovery and reuse over five cycles, maintaining 80 % catalytic efficiency and over 98 % recovery. These results highlight NiFe2O4 spinels as sustainable, recyclable, and highly effective catalysts for MCRs, making them promising candidates for laboratory and industrial applications.
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