Pub Date : 2025-03-02DOI: 10.1016/j.molstruc.2025.141919
Mehdi Ghanbarlou , Somaye Karimian , Fatemeh Doraghi , Armin Dadgar , İlbilge Merve Şenol , Bagher Larijani , Maryam Mohammadi-Khanaposhtani , Aydın Aktaş , Nastaran Sadeghian , Parham Taslimi , Mina Ebrahimi-Rad , Mohammad Mahdavi , İlhami Gülçin
Type-2 diabetes mellitus (T2DM) can be managed by targeting carbohydrate hydrolases such as α-glucosidase and α-amylase. In this regard, a new 4-phenylthiazol-benzamide-1,2,3-triazole-N-phenylacetamide scaffold was designed via molecular hybridization (MH), and 15 derivatives (9a-o) were synthesized by changing the substituents on the phenyl ring of the N-phenylacetamide moiety. These compounds were evaluated as potent α-glucosidase and α-amylase inhibitors. The in vitro results indicated that the half maximal inhibitory concentration (IC50) of compounds 9a-o ranged from 10.71 to 42.35 nM against α-glucosidase and 49.17–81.94 nM against α-amylase while the IC50 values of the positive control acarbose against α-glucosidase and α-amylase were 62.03 and 105.44 nM, respectively. The most potent compound against both digestive enzymes was compound 9g with two methyl groups on positions 2 and 3 of the phenyl ring of the N-phenylacetamide moiety. Compound 9g was 5.79 and 2.14 times more potent than acarbose against α-glucosidase and α-amylase, respectively. The docking study showed that all the synthesized compounds (9a-o) attached to the active sites of α-glucosidase and α-amylase with lower binding energies in comparison to acarbose. Furthermore, according to the dynamics simulation, compound 9g established a stable complex with the active site of α-glucosidase.
{"title":"4-Phenylthiazol-1,2,3-triazole derivatives as new potential α-glucosidase and α-amylase inhibitors","authors":"Mehdi Ghanbarlou , Somaye Karimian , Fatemeh Doraghi , Armin Dadgar , İlbilge Merve Şenol , Bagher Larijani , Maryam Mohammadi-Khanaposhtani , Aydın Aktaş , Nastaran Sadeghian , Parham Taslimi , Mina Ebrahimi-Rad , Mohammad Mahdavi , İlhami Gülçin","doi":"10.1016/j.molstruc.2025.141919","DOIUrl":"10.1016/j.molstruc.2025.141919","url":null,"abstract":"<div><div>Type-2 diabetes mellitus (T2DM) can be managed by targeting carbohydrate hydrolases such as α-glucosidase and α-amylase. In this regard, a new 4-phenylthiazol-benzamide-1,2,3-triazole-N-phenylacetamide scaffold was designed via molecular hybridization (MH), and 15 derivatives (<strong>9a-o</strong>) were synthesized by changing the substituents on the phenyl ring of the N-phenylacetamide moiety. These compounds were evaluated as potent α-glucosidase and α-amylase inhibitors. The in vitro results indicated that the half maximal inhibitory concentration (IC<sub>50</sub>) of compounds <strong>9a-o</strong> ranged from 10.71 to 42.35 nM against α-glucosidase and 49.17–81.94 nM against α-amylase while the IC<sub>50</sub> values of the positive control acarbose against α-glucosidase and α-amylase were 62.03 and 105.44 nM, respectively. The most potent compound against both digestive enzymes was compound <strong>9g</strong> with two methyl groups on positions 2 and 3 of the phenyl ring of the N-phenylacetamide moiety. Compound <strong>9g</strong> was 5.79 and 2.14 times more potent than acarbose against α-glucosidase and α-amylase, respectively. The docking study showed that all the synthesized compounds (<strong>9a-o</strong>) attached to the active sites of α-glucosidase and α-amylase with lower binding energies in comparison to acarbose. Furthermore, according to the dynamics simulation, compound <strong>9g</strong> established a stable complex with the active site of α-glucosidase.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1334 ","pages":"Article 141919"},"PeriodicalIF":4.0,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143551305","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 : 2025-03-02DOI: 10.1016/j.molstruc.2025.141927
Moises Bruno Marinho Rocha , Luiz Everson da Silva , Wanderlei do Amaral , Cícero Deschamps , Ricardo Andrade Rebelo , Iêda Maria Begnini , Adriana Daniel Boyen , Maria Kueirislene Amâncio Ferreira , Francisco Rogenio da Silva Mendes , Emmanuel Silva Marinho , Marcia Machado Marinho , Emanuel Paula Magalhães , Ramon Róseo Paula Pessoa Bezerra de Menezes , Antônio César Honorato Barreto , Alejandro Pedro Ayala , Alexandre Magno Rodrigues Teixeira , Jane Eire Silva Alencar de Menezes , Hélcio Silva dos Santos
The drugs that treat anxiety disorder have variable efficacy and associated side effects. This study evaluated the anxiolytic and anticonvulsant potential of natural product 2-methoxy-carvacrol isolated from Rhabdocaulon lavanduloides, its respective mechanism of action in adult zebrafish (ZFa), in addition to an in silico. Each animal (n=6/group) was treated intraperitoneally (i.p.; 20 µL) with the natural product (4, 20 and 40 mg/Kg) and with the vehicle (DMSO 3 %; 20 µL), being submitted to the tests of locomotor activity and 96 h acute toxicity. The study showed that 2-methoxy-carvacrol was not toxic in the assessment of locomotion behavior of adult zebrafish at all doses evaluated. The two highest doses displayed anxiolytic effect, and when examining the mechanism of action, it was found that this effect is neuromodulated by the GABAergic pathway. Furthermore, the sample was able to reverse the convulsive behavior of the animals in the early stage of analysis (Stage I). Molecular docking simulations indicate that 2-methoxy-carvacrol has a distinct affinity from that of the co-crystallized inhibitor, suggesting allosteric activity. Furthermore, its interactions with the GABAAR receptor are like those of DZP, highlighting potential anxiolytic effects. The pharmacokinetic test showed that PAMPA suggests high cellular permeability for potential intestinal absorption.
{"title":"A phenolic ether 2-methoxy-carvacrol isolated from Rhabdocaulon lavanduloides (Benth) Epling. (Lamiaceae): New crystal structure, Hirshfeld surface, quantum chemical calculation, anxiolytic and anticonvulsant potential in zebrafish, and molecular docking of GABAA receptor","authors":"Moises Bruno Marinho Rocha , Luiz Everson da Silva , Wanderlei do Amaral , Cícero Deschamps , Ricardo Andrade Rebelo , Iêda Maria Begnini , Adriana Daniel Boyen , Maria Kueirislene Amâncio Ferreira , Francisco Rogenio da Silva Mendes , Emmanuel Silva Marinho , Marcia Machado Marinho , Emanuel Paula Magalhães , Ramon Róseo Paula Pessoa Bezerra de Menezes , Antônio César Honorato Barreto , Alejandro Pedro Ayala , Alexandre Magno Rodrigues Teixeira , Jane Eire Silva Alencar de Menezes , Hélcio Silva dos Santos","doi":"10.1016/j.molstruc.2025.141927","DOIUrl":"10.1016/j.molstruc.2025.141927","url":null,"abstract":"<div><div>The drugs that treat anxiety disorder have variable efficacy and associated side effects. This study evaluated the anxiolytic and anticonvulsant potential of natural product 2-methoxy-carvacrol isolated from <em>Rhabdocaulon lavanduloides</em>, its respective mechanism of action in adult zebrafish (ZFa), in addition to an <em>in silico</em>. Each animal (n=6/group) was treated intraperitoneally (<em>i.p</em>.; 20 µL) with the natural product (4, 20 and 40 mg/Kg) and with the vehicle (DMSO 3 %; 20 µL), being submitted to the tests of locomotor activity and 96 h acute toxicity. The study showed that 2-methoxy-carvacrol was not toxic in the assessment of locomotion behavior of adult zebrafish at all doses evaluated. The two highest doses displayed anxiolytic effect, and when examining the mechanism of action, it was found that this effect is neuromodulated by the GABAergic pathway. Furthermore, the sample was able to reverse the convulsive behavior of the animals in the early stage of analysis (Stage I). Molecular docking simulations indicate that 2-methoxy-carvacrol has a distinct affinity from that of the co-crystallized inhibitor, suggesting allosteric activity. Furthermore, its interactions with the GABAAR receptor are like those of DZP, highlighting potential anxiolytic effects. The pharmacokinetic test showed that PAMPA suggests high cellular permeability for potential intestinal absorption.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 141927"},"PeriodicalIF":4.0,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143577941","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}
Non-enzymatic glycation of human serum albumin (HSA) is implicated in diabetes mellitus, its complications, and neurodegenerative diseases. This complex process yields diverse products across various stages, yet traditional assays lack the capability to characterize early and intermediate glycation phases effectively. Infrared spectroscopy, encompassing near-infrared (NIR) and mid-infrared (MIR) regions, offers insights into molecular vibrations and has gained traction in studying protein-molecule interactions. Our study employed NIR and MIR spectroscopy to monitor the glycation of HSA induced by 50 mM glucose over five weeks, establishing quantitative models for glycated HSA. NIR analysis revealed that HSA produced the highest amount of fructosamine at 3 weeks, while five characteristic peaks 4768 cm−1, 5644 cm−1, 5982 cm−1, 7012 cm−1, 7143 cm−1 were found. Meanwhile, MIR spectroscopy further revealed the peaks 675 cm−1, 1517 cm−1, 1685 cm−1, 1792 cm−1, and 1840 cm−1, which reflected the degree of glycation of HSA. A robust quantitative model, integrating NIR and MIR data, demonstrated high predictive accuracy (R²c = 0.9994, R²p = 0.9524, RMSEP = 1.59 mmol/L) and reliability (RPD = 3.35). This research not only elucidates HSA glycation levels but also pioneers a novel quantification methodology for glycated HSA.
{"title":"Study of glycated human serum albumin in non-enzymatic glycation process based on MIR/NIR spectroscopy","authors":"Bing Zhao , Hui Zhang , Xiuping Liu , Qin Dong , Hengchang Zang","doi":"10.1016/j.molstruc.2025.141928","DOIUrl":"10.1016/j.molstruc.2025.141928","url":null,"abstract":"<div><div>Non-enzymatic glycation of human serum albumin (HSA) is implicated in diabetes mellitus, its complications, and neurodegenerative diseases. This complex process yields diverse products across various stages, yet traditional assays lack the capability to characterize early and intermediate glycation phases effectively. Infrared spectroscopy, encompassing near-infrared (NIR) and mid-infrared (MIR) regions, offers insights into molecular vibrations and has gained traction in studying protein-molecule interactions. Our study employed NIR and MIR spectroscopy to monitor the glycation of HSA induced by 50 mM glucose over five weeks, establishing quantitative models for glycated HSA. NIR analysis revealed that HSA produced the highest amount of fructosamine at 3 weeks, while five characteristic peaks 4768 cm<sup>−1</sup>, 5644 cm<sup>−1</sup>, 5982 cm<sup>−1</sup>, 7012 cm<sup>−1</sup>, 7143 cm<sup>−1</sup> were found. Meanwhile, MIR spectroscopy further revealed the peaks 675 cm<sup>−1</sup>, 1517 cm<sup>−1</sup>, 1685 cm<sup>−1</sup>, 1792 cm<sup>−1</sup>, and 1840 cm<sup>−1</sup>, which reflected the degree of glycation of HSA. A robust quantitative model, integrating NIR and MIR data, demonstrated high predictive accuracy (<em>R²c</em> = 0.9994, <em>R²p</em> = 0.9524, RMSEP = 1.59 mmol/L) and reliability (RPD = 3.35). This research not only elucidates HSA glycation levels but also pioneers a novel quantification methodology for glycated HSA.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 141928"},"PeriodicalIF":4.0,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561723","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 : 2025-03-02DOI: 10.1016/j.molstruc.2025.141933
Haibing Han, Lin Li, Jinjian Liu
In this work, two metal-viologen complexes, formulated as [Zn2(AQ)2(BTEC)(H2O)8](H2BTEC)·6H2O (1) and {[Cu(AQ)(HBTEC)(H2O)]·(H4BTEC)0.5}n (2), have been designed and prepared in the reaction of the mono-substituted viologen ligand 1-amyl-4,4′-bipyridinium bromide (AQBr), 1,2,4,5-benzenetetracarboxylic acid (H4BTEC) and different metal ions. Single-crystal structure analysis reveals that compound 1 has a discrete structure and compound 2 has a layered structure. In general, incorporating the viologen ligand into the framework will result in expected photochromic behavior. However, only compound 1 exhibits obvious photochromic behavior, compound 2 is non-photochromic. In addition, compound 1 also exhibits photo-modulated luminescence properties in the solid state and can be deposited on the filter paper, showing potential applications as an inkless printing material.
{"title":"Structure and photochromic properties of two metal-viologen complexes derived from 1-amyl-4,4′-bipyridinium ligand","authors":"Haibing Han, Lin Li, Jinjian Liu","doi":"10.1016/j.molstruc.2025.141933","DOIUrl":"10.1016/j.molstruc.2025.141933","url":null,"abstract":"<div><div>In this work, two metal-viologen complexes, formulated as [Zn<sub>2</sub>(AQ)<sub>2</sub>(BTEC)(H<sub>2</sub>O)<sub>8</sub>](H<sub>2</sub>BTEC)·6H<sub>2</sub>O (<strong>1</strong>) and {[Cu(AQ)(HBTEC)(H<sub>2</sub>O)]·(H<sub>4</sub>BTEC)<sub>0.5</sub>}<sub>n</sub> (<strong>2</strong>), have been designed and prepared in the reaction of the mono-substituted viologen ligand 1-amyl-4,4′-bipyridinium bromide (AQBr), 1,2,4,5-benzenetetracarboxylic acid (H<sub>4</sub>BTEC) and different metal ions. Single-crystal structure analysis reveals that compound <strong>1</strong> has a discrete structure and compound <strong>2</strong> has a layered structure. In general, incorporating the viologen ligand into the framework will result in expected photochromic behavior. However, only compound <strong>1</strong> exhibits obvious photochromic behavior, compound <strong>2</strong> is non-photochromic. In addition, compound <strong>1</strong> also exhibits photo-modulated luminescence properties in the solid state and can be deposited on the filter paper, showing potential applications as an inkless printing material.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1334 ","pages":"Article 141933"},"PeriodicalIF":4.0,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143551189","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 : 2025-03-01DOI: 10.1016/j.molstruc.2025.141916
R. Idouhli , M. Oubaaqa , M. Lasri , M. Loughzail , B. EL Ibrahimi , S. Zekri , M. Khadiri , A. Baouid , A. Abouelfida
The inhibitory effect of diazepine derivatives as corrosion inhibitors of mild steel (MS) in 1 M HCl, namely sulfate of 2,4-dimethyl-3H-benzo[b][1,4]diazepine-1-ium (TML1) and sulfate of 2,4, 8-trimethyl-3H-benzo[b][1,4]diazepine-1-ium (TML2) was studied by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curves (PDP) at different concentrations (10−3 to 5.10−5 M). The optimal concentration of 10−3 M was investigated for its inhibitory efficacy at diverse temperatures (293–323 K). The analysis of Tafel plots and EIS diagrams indicated that the compounds exhibited a notable adsorption behavior, which suggests that they may serve as an effective inhibitor for the control of MS rust in acidic solutions. In accordance with the Langmuir isotherm, the adsorption of inhibitors onto the MS surface occurred. The impact of the methyl groups and the influence of cross conjugation on the electron-providing and electron-accepting capabilities of the nitrogen heteroatoms (N) and π-electrons in MS oxidization has been analyzed and discussed. This may be achieved through calculations based on DFT (Density Functional Theory) at the RB3LYP [6–311 G(D,P)] level. Scanning electron microscopy (SEM) and Raman spectroscopy demonstrated the formation of an inhibitive barrier on the MS surface, which was built on the adsorbed inhibiting molecules. Moreover, quantum-based computational chemistry has been employed to investigate the relationship between the corrosion-inhibiting efficacy and adsorption strength of the inhibitors, with a particular focus on the influence of their molecular structure.
{"title":"Mild steel corrosion inhibition performance of novel diazepine derivatives: Electrochemical and morphological soundings paired with quantum chemical calculations","authors":"R. Idouhli , M. Oubaaqa , M. Lasri , M. Loughzail , B. EL Ibrahimi , S. Zekri , M. Khadiri , A. Baouid , A. Abouelfida","doi":"10.1016/j.molstruc.2025.141916","DOIUrl":"10.1016/j.molstruc.2025.141916","url":null,"abstract":"<div><div>The inhibitory effect of diazepine derivatives as corrosion inhibitors of mild steel (MS) in 1 M HCl, namely sulfate of 2,4-dimethyl-3H-benzo[b][1,4]diazepine-1-ium (TML1) and sulfate of 2,4, 8-trimethyl-3H-benzo[b][1,4]diazepine-1-ium (TML2) was studied by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curves (PDP) at different concentrations (10<sup>−3</sup> to 5.10<sup>−5</sup> M). The optimal concentration of 10<sup>−3</sup> M was investigated for its inhibitory efficacy at diverse temperatures (293–323 K). The analysis of Tafel plots and EIS diagrams indicated that the compounds exhibited a notable adsorption behavior, which suggests that they may serve as an effective inhibitor for the control of MS rust in acidic solutions. In accordance with the Langmuir isotherm, the adsorption of inhibitors onto the MS surface occurred. The impact of the methyl groups and the influence of cross conjugation on the electron-providing and electron-accepting capabilities of the nitrogen heteroatoms (N) and π-electrons in MS oxidization has been analyzed and discussed. This may be achieved through calculations based on DFT (Density Functional Theory) at the RB3LYP [6–311 G(D,P)] level. Scanning electron microscopy (SEM) and Raman spectroscopy demonstrated the formation of an inhibitive barrier on the MS surface, which was built on the adsorbed inhibiting molecules. Moreover, quantum-based computational chemistry has been employed to investigate the relationship between the corrosion-inhibiting efficacy and adsorption strength of the inhibitors, with a particular focus on the influence of their molecular structure.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1334 ","pages":"Article 141916"},"PeriodicalIF":4.0,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143551304","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 : 2025-03-01DOI: 10.1016/j.molstruc.2025.141892
Ali Muhammad Ashfaq , Qiuyue Zhang , Yizhou Wang , Yanping Ma , Qifeng Xing , Min Sun , Tongling Liang , Wen-Hua Sun
The unsymmetrical bis(imino)acenaphthene derivatives modified by ortho-chloro and para-flouro groups, 1-[2-{(C6H5)2CH}-6-Cl-4-FC6H2N]-2-(ArN)C2C10H6 (Ar = 2,6-Me2C6H3L1, 2,6-Et2C6H3L2, 2,6-iPr2C6H3L3, 2,4,6-Me3C6H2L4, 2,6-Et2-4-MeC6H2L5, 2-{(C6H5)2CH}-6-Cl-4-FC6H2L6), as well as their nickel complexes, LNiBr2 and LNiCl2 (Ni1-Ni12), have been synthesized in high yields and fully characterized by the NMR, FT-IR and elemental analysis. Moreover, the molecular structures of Ni1 and Ni11 are confirmed by the single-crystal X-ray diffraction revealing the distorted tetrahedral geometry of Ni1 and the distorted octahedral geometry of Ni11 with dimer configuration. Upon activation with AlEt2Cl and MMAO, all nickel complexes exhibit high activities in ethylene polymerization up to the range of 107 g of PE (mol of Ni)−1 h−1 at an optimal temperature of 60 °C producing moderately branched polyethylene (31–96 branches / 1000 C) with medium molecular weight (Mw: 0.35–3.06 × 105 g mol−1) and narrow molecular weight distribution (PDI: 1.62 - 2.62). In comparison the polymerization solvent with toluene, hexane, as a potentially industrial application, significantly improve the catalytic performance regarding their activities and molecular weights of resulting polyethylenes. In addition, excellent tensile performance (σb up to 25.3 MPa, εb up to 1635 %) and good elastic recovery characteristics (up to 69 %) are significant features of the obtained thermoplastic polyethylene elastomer.
{"title":"Thermostable polyhalogen-substituted α-diimine nickel precatalysts towards high performance polyethylene elastomer","authors":"Ali Muhammad Ashfaq , Qiuyue Zhang , Yizhou Wang , Yanping Ma , Qifeng Xing , Min Sun , Tongling Liang , Wen-Hua Sun","doi":"10.1016/j.molstruc.2025.141892","DOIUrl":"10.1016/j.molstruc.2025.141892","url":null,"abstract":"<div><div>The unsymmetrical bis(imino)acenaphthene derivatives modified by ortho-chloro and para-flouro groups, 1-[2-{(C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>CH}-6-Cl-4-FC<sub>6</sub>H<sub>2</sub>N]-2-(ArN)C<sub>2</sub>C<sub>10</sub>H<sub>6</sub> (Ar = 2,6-Me<sub>2</sub>C<sub>6</sub>H<sub>3</sub> <strong>L1</strong>, 2,6-Et<sub>2</sub>C<sub>6</sub>H<sub>3</sub> <strong>L2</strong>, 2,6-<em><sup>i</sup></em>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub> <strong>L3</strong>, 2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub> <strong>L4</strong>, 2,6-Et<sub>2</sub>-4-MeC<sub>6</sub>H<sub>2</sub> <strong>L5</strong>, 2-{(C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>CH}-6-Cl-4-FC<sub>6</sub>H<sub>2</sub> <strong>L6</strong>), as well as their nickel complexes, LNiBr<sub>2</sub> and LNiCl<sub>2</sub> (<strong>Ni1</strong>-<strong>Ni12</strong>), have been synthesized in high yields and fully characterized by the NMR, FT-IR and elemental analysis. Moreover, the molecular structures of <strong>Ni1</strong> and <strong>Ni11</strong> are confirmed by the single-crystal X-ray diffraction revealing the distorted tetrahedral geometry of <strong>Ni1</strong> and the distorted octahedral geometry of <strong>Ni11</strong> with dimer configuration. Upon activation with AlEt<sub>2</sub>Cl and MMAO, all nickel complexes exhibit high activities in ethylene polymerization up to the range of 10<sup>7</sup> g of PE (mol of Ni)<sup>−1</sup> h<sup>−1</sup> at an optimal temperature of 60 °C producing moderately branched polyethylene (31–96 branches / 1000 C) with medium molecular weight (Mw: 0.35–3.06 × 10<sup>5</sup> g mol<sup>−1</sup>) and narrow molecular weight distribution (PDI: 1.62 - 2.62). In comparison the polymerization solvent with toluene, hexane, as a potentially industrial application, significantly improve the catalytic performance regarding their activities and molecular weights of resulting polyethylenes. In addition, excellent tensile performance (σ<sub>b</sub> up to 25.3 MPa, ε<sub>b</sub> up to 1635 %) and good elastic recovery characteristics (up to 69 %) are significant features of the obtained thermoplastic polyethylene elastomer.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1334 ","pages":"Article 141892"},"PeriodicalIF":4.0,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143551187","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 : 2025-03-01DOI: 10.1016/j.molstruc.2025.141917
Riya Gaur, Priti Boora Doon
The orange light emanating Samarium complexes are synthesized, by using β-keto carboxylic acid (L) as the prime ligand and four auxiliary ligands: bathophenanthroline, 2,2′-bipyridyl, 1,10-phenanthroline and 4,4′-dimethyl-2,2′-bipyridyl. Elemental analysis is used to assess the elemental content of prepared compounds, Whereas the bonding evidence between metal and the primary and secondary sensitizers is ascertained by examining the FT-IR, NMR and UV-visible spectra. The luminescent parameters such as excitation, emission and decay time are determined by stimulating the complexes at λmax=353 nm. The bright orange emitting hue of the complex is attributable to the intense peak at 566nm, 602nm and 650nm due to the transition from 4G5/2 to 6H5/2, 6H7/2 and 6H9/2 respectively. Synthesized complexes show exceptional thermal stability which demonstrates their potential applications in military radars and solar devices. The crystalline nature of the synthesized complex is examined via XRD analysis which indicate that the particles lie in the nano range. The optoelectronic characteristics like refractive index and optical band gap also reflect the applicability of these complexes in photonic devices and wide-gap semiconductors. Furthermore, the colorimetric properties like CIE 1931 color coordinates, Correlated color temperature (CCT value ˂ 3000 K) and Exquisite color purity show conformance with the warm reddish-orange light coordinates provided by "The National Television System Committee and also validate their use as marvelous emitters in electroluminescent, display, OLEDs (organic light emitting diodes) and laser materials.
{"title":"Photometric study and spectral characterization of samarium-tris-β-carboxylate complexes with heterocyclic auxiliary moieties","authors":"Riya Gaur, Priti Boora Doon","doi":"10.1016/j.molstruc.2025.141917","DOIUrl":"10.1016/j.molstruc.2025.141917","url":null,"abstract":"<div><div>The orange light emanating Samarium complexes are synthesized, by using β-keto carboxylic acid (L) as the prime ligand and four auxiliary ligands: bathophenanthroline, 2,2′-bipyridyl, 1,10-phenanthroline and 4,4′-dimethyl-2,2′-bipyridyl. Elemental analysis is used to assess the elemental content of prepared compounds, Whereas the bonding evidence between metal and the primary and secondary sensitizers is ascertained by examining the FT-IR, NMR and UV-visible spectra. The luminescent parameters such as excitation, emission and decay time are determined by stimulating the complexes at λ<sub>max</sub>=353 nm. The bright orange emitting hue of the complex is attributable to the intense peak at 566nm, 602nm and 650nm due to the transition from <sup>4</sup><em>G</em><sub>5/2</sub> to <sup>6</sup><em>H</em><sub>5/2</sub>, <sup>6</sup><em>H</em><sub>7/2</sub> and <sup>6</sup><em>H</em><sub>9/2</sub> respectively. Synthesized complexes show exceptional thermal stability which demonstrates their potential applications in military radars and solar devices. The crystalline nature of the synthesized complex is examined via XRD analysis which indicate that the particles lie in the nano range. The optoelectronic characteristics like refractive index and optical band gap also reflect the applicability of these complexes in photonic devices and wide-gap semiconductors. Furthermore, the colorimetric properties like CIE 1931 color coordinates, Correlated color temperature (CCT value ˂ 3000 K) and Exquisite color purity show conformance with the warm reddish-orange light coordinates provided by \"The National Television System Committee and also validate their use as marvelous emitters in electroluminescent, display, OLEDs (organic light emitting diodes) and laser materials.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 141917"},"PeriodicalIF":4.0,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143578024","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 four new hydrazone Schiff bases have been synthesized in absolute ethanol at the reflux of 78 °C. These hydrazones are named as: (E)-1-(2,4-dinitrophenyl)-2-(2-ethoxy benzylidene) hydrazine(2-EDNPH) (L1), (E)-1-(2,4-dinitrophenyl)-2-(4-ethoxy benzylidene) hydrazine(4-EDNPH) (L2), (E)-3-chloro-2-((2-(2,4-dinitrophenyl) hydrazinylidene) methyl) phenol(3-Cl-2-OH-DNPH) (L3) and (E)-1-(2,4-dinitrophenyl)-2-(thiophen-3-ylmethylene) hydrazine (3-Thiophene Carbaldehyde-DNPH) (L4). Spectroscopic and physicochemical techniques were employed to validate these compound's structure, including 1H NMR, 13C NMR spectra, UV–Vis, IR, and melting point. A solubility test is also carried out on all the Schiff bases, indicating that all four ligands are soluble in THF and DMF. The thermal breakdown behavior of all ligands is being examined by thermogravimetric analysis (TGA/DTG) at a heating rate of 10 °C min−1 under a nitrogen environment. The crystalline structure of L1 was also investigated in an XtaLAB AFC12 (RINC): Kappa single diffractometer, which included unit cell computation and data collecting. The radioactive photon was created with MoKα (λ = 0.7107Å). In addition, density functional theory (DFT) is utilized to compute the optimized molecular structures, stability, reactivity, and numerous chemical characteristics of the synthesized ligands. The in-silico prediction of ADME features revealed that synthesized compounds gain notable drug-like characteristics. Also, molecular docking was enforced to predict the inhibitory action of the β-ketoacyl acyl carrier (KAS1) protein of E. Coli (PDB Id: 6TZF) on the examined hydrazones. Finally, all ligands were to assess the anti-bacterial properties against gram-positive (B. subtilis and MRSA) and gram-negative (P. mirabilis and E. coli) infections; only L1 and L2 showed activity against these pathogens.
{"title":"Comprehensive analysis of hydrazone Schiff bases: Synthesis, structural characterization, DFT studies, molecular docking insights and bioactivity assessment","authors":"Ashish Kumar Tiwari , Vaishnu SK , Mohankumar Narayanan , Mohit Garg , Vishnu Varma Manoharan , Jothi L. Nallasivam , V.M. Biju","doi":"10.1016/j.molstruc.2025.141905","DOIUrl":"10.1016/j.molstruc.2025.141905","url":null,"abstract":"<div><div>The four new hydrazone Schiff bases have been synthesized in absolute ethanol at the reflux of 78 °C. These hydrazones are named as: (E)-1-(2,4-dinitrophenyl)-2-(2-ethoxy benzylidene) hydrazine(<strong>2-EDNPH</strong>) (<strong>L<sub>1</sub></strong>), (E)-1-(2,4-dinitrophenyl)-2-(4-ethoxy benzylidene) hydrazine(<strong>4-EDNPH</strong>) (<strong>L<sub>2</sub></strong>), (E)-3-chloro-2-((2-(2,4-dinitrophenyl) hydrazinylidene) methyl) phenol(<strong>3-Cl-2-OH-DNPH</strong>) (<strong>L<sub>3</sub></strong>) and (E)-1-(2,4-dinitrophenyl)-2-(thiophen-3-ylmethylene) hydrazine (<strong>3-Thiophene Carbaldehyde-DNPH</strong>) (<strong>L<sub>4</sub></strong>). Spectroscopic and physicochemical techniques were employed to validate these compound's structure, including <sup>1</sup>H NMR, <sup>13</sup>C NMR spectra, UV–Vis, IR, and melting point. A solubility test is also carried out on all the Schiff bases, indicating that all four ligands are soluble in THF and DMF. The thermal breakdown behavior of all ligands is being examined by thermogravimetric analysis (TGA/DTG) at a heating rate of 10 °C min<sup>−1</sup> under a nitrogen environment. The crystalline structure of L<sub>1</sub> was also investigated in an <strong>XtaLAB AFC12 (RINC): Kappa single</strong> diffractometer, which included unit cell computation and data collecting. The radioactive photon was created with MoKα (λ = 0.7107Å). In addition, density functional theory (DFT) is utilized to compute the optimized molecular structures, stability, reactivity, and numerous chemical characteristics of the synthesized ligands. The in-silico prediction of ADME features revealed that synthesized compounds gain notable drug-like characteristics. Also, molecular docking was enforced to predict the inhibitory action of the β-ketoacyl acyl carrier (KAS1) protein of E. Coli (PDB Id: <span><span>6TZF</span><svg><path></path></svg></span>) on the examined hydrazones. Finally, all ligands were to assess the anti-bacterial properties against gram-positive (<em>B. subtilis</em> and MRSA) and gram-negative (<em>P. mirabilis and E. coli</em>) infections; only L<sub>1</sub> and L<sub>2</sub> showed activity against these pathogens.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 141905"},"PeriodicalIF":4.0,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143577933","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 : 2025-03-01DOI: 10.1016/j.molstruc.2025.141912
Juan Pablo León-Gómez , Cristian Pinzón-Vanegas , Paola Toledo-Jaldín , Jesús Jara-Cortés , Enrique Camarillo-García , Diego Martínez-Otero , Alfredo R. Vilchis-Nestor , Jesús Valdés-Martínez , Alejandro Dorazco-González
Selective chromogenic sensing and extraction of cyanide (CN−) is a central issue of supramolecular chemistry and analytical sciences that impact biological and environmental chemistry. In this work, we reported a 1D coordination polymer [Co(TPyP)] (TPyP= dianion of 5,10,15,20-tetrapyridylporphyrin) that contains an open coordination site on Co(II) atom that acts as a high-affinity binding point for CN− recognition. This Co(II)-polymer was structurally described by X-ray diffraction and Hirschfeld surfaces. Also, it was thoroughly characterized by several spectroscopic tools and scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS). [Co(TPyP)] was found to be an exceptionally high overall binding constant for CN− (log β= 10.04) with an equilibrium model 1:2 in CH3CN and highly selectivity over common interfering anions including halides and basic oxyanions. Under these conditions, CN− can be sense with a limit of detection of 5.40 μM by UV–Vis and visual change of the solution. On the basis of analytical tools (electrospray ionization mass spectrometry, X-ray single-crystal diffraction, infrared spectroscopy, UV–Vis) and time-dependent density functional theory (TD-DFT) calculations the spectrophotometric change is attributed to the coordination of two CN− ions in the axial positions of the Co(II) atom, with simultaneous formation of anionic complex [Co(TPyP)(CN)2]−2.
[Co(TPyP)] can operate efficiently as an optical selective sensor for CN− in commercial cigarettes in the micromolar concentration range. Additionally, this Co(II)-polymer can capture selectively CN− in solid-liquid extractions. The development of bifunctional molecules able to visually sense CN− ions and extract them from solid crystalline salts has not been explored until now.
{"title":"Bifunctional Co(II)-porphyrin 1D-coordination polymer for selective cyanide sensing in tobacco smoke and efficient solid-liquid extraction","authors":"Juan Pablo León-Gómez , Cristian Pinzón-Vanegas , Paola Toledo-Jaldín , Jesús Jara-Cortés , Enrique Camarillo-García , Diego Martínez-Otero , Alfredo R. Vilchis-Nestor , Jesús Valdés-Martínez , Alejandro Dorazco-González","doi":"10.1016/j.molstruc.2025.141912","DOIUrl":"10.1016/j.molstruc.2025.141912","url":null,"abstract":"<div><div>Selective chromogenic sensing and extraction of cyanide (CN<sup>−</sup>) is a central issue of supramolecular chemistry and analytical sciences that impact biological and environmental chemistry. In this work, we reported a 1D coordination polymer <strong>[Co(TPyP)]</strong> (TPyP= dianion of 5,10,15,20-tetrapyridylporphyrin) that contains an open coordination site on Co(II) atom that acts as a high-affinity binding point for CN<sup>−</sup> recognition. This Co(II)-polymer was structurally described by X-ray diffraction and Hirschfeld surfaces. Also, it was thoroughly characterized by several spectroscopic tools and scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS). <strong>[Co(TPyP)]</strong> was found to be an exceptionally high overall binding constant for CN<sup>−</sup> (log <em>β</em>= 10.04) with an equilibrium model 1:2 in CH<sub>3</sub>CN and highly selectivity over common interfering anions including halides and basic oxyanions. Under these conditions, CN<sup>−</sup> can be sense with a limit of detection of 5.40 μM by UV–Vis and visual change of the solution. On the basis of analytical tools (electrospray ionization mass spectrometry, X-ray single-crystal diffraction, infrared spectroscopy, UV–Vis) and time-dependent density functional theory (TD-DFT) calculations the spectrophotometric change is attributed to the coordination of two CN<sup>−</sup> ions in the axial positions of the Co(II) atom, with simultaneous formation of anionic complex [Co(TPyP)(CN)<sub>2</sub>]<sup>−2</sup>.</div><div><strong>[Co(TPyP)]</strong> can operate efficiently as an optical selective sensor for CN<sup>−</sup> in commercial cigarettes in the micromolar concentration range. Additionally, this Co(II)-polymer can capture selectively CN<sup>−</sup> in solid-liquid extractions. The development of bifunctional molecules able to visually sense CN<sup>−</sup> ions and extract them from solid crystalline salts has not been explored until now.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 141912"},"PeriodicalIF":4.0,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143578047","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-01DOI: 10.1016/j.molstruc.2025.141921
Amitabha Nandi , Rajib Ghosh
Pentacene is the archetypal example of singlet fission material in polyacene family with fastest known singlet fission rate (τSF <100 fs). However, pentacene suffers from fast chemical and photochemical degradation in ambient condition, mainly by oxidation at 6 and 13-positon and hence limits prospects in optoelectronic application. Herein we show phenyl substituted pentacene at 6 and 13 position offers improved photo-stability with preserved SF property. Detailed transient pump-probe spectroscopic investigation on 6,13-diphenylpentacene (DPPn) thin film and nanoaggregates shows efficient singlet exciton fission process occurring in tens of picosecond timescale. In comparison to pentacene, though SF rate in DPPn is observed to slow down about two orders of magnitude due to weaker electronic coupling imposed by two phenyl substitution, triplet yield remains attractively high (∼ 180 %). Remarkably, thermal and photochemical stability of the DPPn thin film (remains stable over several months in ambient condition) is observed to be much superior than pentacene and thus proposed to be more useful for practical application in optoelectronic devices.
{"title":"Singlet exciton fission dynamics in 6,13-diphenylpentacene nanoaggregate and thin film","authors":"Amitabha Nandi , Rajib Ghosh","doi":"10.1016/j.molstruc.2025.141921","DOIUrl":"10.1016/j.molstruc.2025.141921","url":null,"abstract":"<div><div>Pentacene is the archetypal example of singlet fission material in polyacene family with fastest known singlet fission rate (τ<sub>SF</sub> <100 fs). However, pentacene suffers from fast chemical and photochemical degradation in ambient condition, mainly by oxidation at 6 and 13-positon and hence limits prospects in optoelectronic application. Herein we show phenyl substituted pentacene at 6 and 13 position offers improved photo-stability with preserved SF property. Detailed transient pump-probe spectroscopic investigation on 6,13-diphenylpentacene (DPPn) thin film and nanoaggregates shows efficient singlet exciton fission process occurring in tens of picosecond timescale. In comparison to pentacene, though SF rate in DPPn is observed to slow down about two orders of magnitude due to weaker electronic coupling imposed by two phenyl substitution, triplet yield remains attractively high (∼ 180 %). Remarkably, thermal and photochemical stability of the DPPn thin film (remains stable over several months in ambient condition) is observed to be much superior than pentacene and thus proposed to be more useful for practical application in optoelectronic devices.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 141921"},"PeriodicalIF":4.0,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143578023","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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