Pub Date : 2024-11-08DOI: 10.1016/j.molstruc.2024.140619
Mohamad AbdulKarim Hameed, Mohamad J. Al-Jeboori
This research outlines the efficient one-pot calcium chloride-catalysed synthesis of three novel Mannich bases: M1, M2 and M3. M1 and M2 resulted from the condensing of benzaldehyde with m-nitroaniline and m-bromoaniline, respectively, in conjunction with cyclopentanone. However, M3 was obtained through the reaction of p-methoxybenzaldehyde, m-bromoaniline and cyclopentanone. The isolated compounds were thoroughly characterised using elemental analysis and various analytical and spectroscopic techniques, including the determination of their melting points, electrospray mass spectrometry (ESMS), Fourier transform infrared (FTIR), electronic spectroscopy (UV–Vis), and nuclear magnetic resonance (NMR) spectroscopy (1H- and 13C NMR). Thermal stability (TGA and DTA analysis) of the three Mannich compounds was also examined. The newly synthesised Mannich bases exhibit remarkable potential as metal ion complexing agents and as fundamental building blocks for forming small organic molecules, particularly bioactive molecules and novel ligands for coordination chemistry. In addition to their structural significance, the biological efficacy of these compounds was assessed, revealing their excellent antimicrobial properties toward bacterial and fungal species. These activities suggest their potential use in combating microbial infections. Theoretical DFT simulations employing the B3LYP functional at the 6-311++G(d,p) level provided a thorough analysis of the stability of compounds, electrical properties, and geometry. Additionally, molecular docking studies of the Mannich compounds with two protein targets, 5IQ9 and 5VBU (both relevant for drug discovery) were performed. These studies revealed that the three Mannich compounds exhibit similar binding energies and effective interaction with both the 5IQ9 and 5VBU proteins, suggesting the potential of these Mannich compounds as dual inhibitors targeting both proteins.
{"title":"Synthesis, spectral characterisation, DFT calculations, biological evaluation and molecular docking analysis of new Mannich compounds derived from cyclopentanone","authors":"Mohamad AbdulKarim Hameed, Mohamad J. Al-Jeboori","doi":"10.1016/j.molstruc.2024.140619","DOIUrl":"10.1016/j.molstruc.2024.140619","url":null,"abstract":"<div><div>This research outlines the efficient one-pot calcium chloride-catalysed synthesis of three novel Mannich bases: M1, M2 and M3. M1 and M2 resulted from the condensing of benzaldehyde with <em>m</em>-nitroaniline and <em>m</em>-bromoaniline, respectively, in conjunction with cyclopentanone. However, M3 was obtained through the reaction of <em>p</em>-methoxybenzaldehyde, <em>m</em>-bromoaniline and cyclopentanone. The isolated compounds were thoroughly characterised using elemental analysis and various analytical and spectroscopic techniques, including the determination of their melting points, electrospray mass spectrometry (ESMS), Fourier transform infrared (FTIR), electronic spectroscopy (UV–Vis), and nuclear magnetic resonance (NMR) spectroscopy (<sup>1</sup>H- and <sup>13</sup>C NMR). Thermal stability (TGA and DTA analysis) of the three Mannich compounds was also examined. The newly synthesised Mannich bases exhibit remarkable potential as metal ion complexing agents and as fundamental building blocks for forming small organic molecules, particularly bioactive molecules and novel ligands for coordination chemistry. In addition to their structural significance, the biological efficacy of these compounds was assessed, revealing their excellent antimicrobial properties toward bacterial and fungal species. These activities suggest their potential use in combating microbial infections. Theoretical DFT simulations employing the B3LYP functional at the 6-311++G(d,p) level provided a thorough analysis of the stability of compounds, electrical properties, and geometry. Additionally, molecular docking studies of the Mannich compounds with two protein targets, 5IQ9 and 5VBU (both relevant for drug discovery) were performed. These studies revealed that the three Mannich compounds exhibit similar binding energies and effective interaction with both the 5IQ9 and 5VBU proteins, suggesting the potential of these Mannich compounds as dual inhibitors targeting both proteins.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140619"},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142659579","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 : 2024-11-08DOI: 10.1016/j.molstruc.2024.140692
Yi-Dan Qiao , Meng-Meng Zhai , Qin-Ying Jin , Yin-Hang Chai , Ya-Pan Wu , Ying Zhao , Lu-Fang Ma
By utilizing an aromatic π-conjugated organic ligand as a linker, we successfully synthesized two new coordination complexes, namely, a three-dimensional framework (3D) [Co(DCPA)(DMA)(H2O)] (Co-MOF-1) and a one-dimensional chain (1D) [Co(DCPA)(H2O)4]·4H2O (Co-MOF-2) (DCPA = 9, 10-di (p-carboxyphenyl) anthracene). Both complexes were determined by single crystal X-ray diffraction analysis, Thermogravimetric analysis, PXRD, XPS, UV–vis and IR spectrum, etc. Interestingly, the reversibly single-crystal-to-single-crystal (SC-SC) structural transformation between the 3D framework and 1D chain structures could be achieved successfully by controlling the stimulation of external temperature and solvent. Besides, a series of fluorescence sensing experiments were carried out for Co-MOF-1, demonstrating excellent selective and sensitive “turn-on” towards Al3+, Cr3+, Amoxicillin (AMX), and 4,5-Imidazoledicarbonitrile (DCI), especially Al3+ and AMX. Moreover, the detection mechanism was also further investigated. In addition, the magnetic studies indicated that Co-MOF-1 and Co-MOF-2 have weak antiferromagnetic interaction. The current research elucidates different structural variations exhibited by cobalt-containing compounds in extended framework architectures and properties.
{"title":"Solvent-induced SC-SC transformation between 3D and 1D Co-MOFs: Fluorescence sensing and magnetic properties","authors":"Yi-Dan Qiao , Meng-Meng Zhai , Qin-Ying Jin , Yin-Hang Chai , Ya-Pan Wu , Ying Zhao , Lu-Fang Ma","doi":"10.1016/j.molstruc.2024.140692","DOIUrl":"10.1016/j.molstruc.2024.140692","url":null,"abstract":"<div><div>By utilizing an aromatic π-conjugated organic ligand as a linker, we successfully synthesized two new coordination complexes, namely, a three-dimensional framework (3D) [Co(DCPA)(DMA)(H<sub>2</sub>O)] (<strong>Co-MOF-1</strong>) and a one-dimensional chain (1D) [Co(DCPA)(H<sub>2</sub>O)<sub>4</sub>]·4H<sub>2</sub>O (<strong>Co-MOF-2</strong>) (DCPA = 9, 10-di (p-carboxyphenyl) anthracene). Both complexes were determined by single crystal X-ray diffraction analysis, Thermogravimetric analysis, PXRD, XPS, UV–vis and IR spectrum, etc. Interestingly, the reversibly single-crystal-to-single-crystal (SC-SC) structural transformation between the 3D framework and 1D chain structures could be achieved successfully by controlling the stimulation of external temperature and solvent. Besides, a series of fluorescence sensing experiments were carried out for <strong>Co-MOF-1</strong>, demonstrating excellent selective and sensitive “turn-on” towards Al<sup>3+</sup>, Cr<sup>3+</sup>, Amoxicillin (AMX), and 4,5-Imidazoledicarbonitrile (DCI), especially Al<sup>3+</sup> and AMX. Moreover, the detection mechanism was also further investigated. In addition, the magnetic studies indicated that <strong>Co-MOF-1</strong> and <strong>Co-MOF-2</strong> have weak antiferromagnetic interaction. The current research elucidates different structural variations exhibited by cobalt-containing compounds in extended framework architectures and properties.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140692"},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142659668","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}
In this study, we present a comprehensive exploration of sixteen novel 2-amino-4-aryl-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitriles synthesized through a streamlined multicomponent microwave method. These chromene derivatives, obtained in remarkable yields (92–94 %), exhibit a fascinating array of stereochemical complexities. The influence of electron-withdrawing groups was subtly evident in chemical shifts, underscoring the nuanced interplay between structure and substituent effects. Infrared spectroscopy confirmed characteristic NH₂ functionalities across the series, with notable deviations in compounds featuring electron-withdrawing groups. Compounds studied by single crystal X-Ray diffraction, were all in the monoclinic crystal system, with interesting molecular disorder in select diastereomers. Intermolecular hydrogen bonding networks formed between the amino functional group and the chromenone O atom or a solvent O atom, lead to motifs similar to the previously reported motifs by our group including an extra N—Hb…O3-interaction involving the amino and the methoxy substituent in compound 3c. Hirshfeld surface analysis further showed the contributions of key intermolecular contacts, while energy calculations highlighted the dominant role of electrostatics in motif stabilization. This work not only enriches the structural landscape of chromene derivatives but also opens avenues for future investigations into their potential applications in material science and beyond.
在本研究中，我们全面探讨了通过精简的多组分微波法合成的十六种新型 2-氨基-4-芳基-5-氧代-5,6,7,8-四氢-4H-色烯-3-甲腈。这些色烯衍生物的收率极高（92-94%），并呈现出一系列迷人的立体化学复杂性。在化学位移中，抽电子基团的影响非常明显，突出了结构和取代基效应之间微妙的相互作用。红外光谱证实了整个系列的 NH₂官能团特征，而具有抽电子基团的化合物则出现了明显的偏差。用单晶 X 射线衍射法研究的化合物均为单斜晶系，在部分非对映异构体中存在有趣的分子无序现象。氨基官能团与色烯酮 O 原子或溶剂 O 原子之间形成的分子间氢键网络，导致了与我们课题组之前报告的基团相似的基团，包括化合物 3c 中涉及氨基和甲氧基取代基的额外 N-Hb...O3 相互作用。Hirshfeld 表面分析进一步显示了关键分子间接触的贡献，而能量计算则强调了静电在图案稳定中的主导作用。这项工作不仅丰富了色烯衍生物的结构，而且为今后研究它们在材料科学及其他领域的潜在应用开辟了途径。
{"title":"Structural studies of racemic and diastereomeric 2-amino-3-carbonitrile-based chromene derivatives","authors":"Precious Ntombizonke Ngubane , Tshephiso Papo , Sizwe Zamisa , Bernard Omondi","doi":"10.1016/j.molstruc.2024.140567","DOIUrl":"10.1016/j.molstruc.2024.140567","url":null,"abstract":"<div><div>In this study, we present a comprehensive exploration of sixteen novel 2-amino-4-aryl-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitriles synthesized through a streamlined multicomponent microwave method. These chromene derivatives, obtained in remarkable yields (92–94 %), exhibit a fascinating array of stereochemical complexities. The influence of electron-withdrawing groups was subtly evident in chemical shifts, underscoring the nuanced interplay between structure and substituent effects. Infrared spectroscopy confirmed characteristic NH₂ functionalities across the series, with notable deviations in compounds featuring electron-withdrawing groups. Compounds studied by single crystal X-Ray diffraction, were all in the monoclinic crystal system, with interesting molecular disorder in select diastereomers. Intermolecular hydrogen bonding networks formed between the amino functional group and the chromenone O atom or a solvent O atom, lead to motifs similar to the previously reported motifs by our group including an extra N—H<sub>b</sub>…O<sub>3-</sub>interaction involving the amino and the methoxy substituent in compound <strong>3c</strong>. Hirshfeld surface analysis further showed the contributions of key intermolecular contacts, while energy calculations highlighted the dominant role of electrostatics in motif stabilization. This work not only enriches the structural landscape of chromene derivatives but also opens avenues for future investigations into their potential applications in material science and beyond.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140567"},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142659556","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 : 2024-11-08DOI: 10.1016/j.molstruc.2024.140624
Amna Siddique , Muhammad Nadeem Arshad , Mohammed M. Rahman , Mohammad Asad , Khalid A. Alzahrani , Aftab Aslam Parwaz Khan , Tahir Ali Sheikh
Environmental pollution spurred by dint of noxious chemicals and heavy metals has popped up as a pressing threat for present day community. In this study, we synthesized the N,N'-(ethane 1,2-diyl)bis(4-acetylbenzene-1-sulfonamide) (EDBABS) and N,N'-(cyclohexane-1,2-diyl)bis(4-acetylbenzenesulfonamide) (CDBABS) as bidentate chelating agents with the intention to detect the heavy metal cations in water systems. Conventional spectroscopic techniques such as UV–Vis spectroscopy, Fourier transform-infra red (FT-IR) spectroscopy, 1H-NMR and 13C-NMR in addition to single crystal X-ray diffraction studies were performed to expound structural characterization data of these newly synthesized non-reported bidentate chelating agents. After Characterization, a novel electrochemical current – potential (I-V) approach based on their modified GCEs was applied to detect the toxic cations in water systems. For this purpose, Keithley electrometer was employed as a constant voltage source. On the trail of fabricating an efficient as well as selective electrochemical sensor, for the detection of heavy metal cations in phosphate buffer system of pH = 7.0, EDBABS and CDBABS coupled with nafion as adhesive conducting binder were coated separately onto the Glassy Carbon Electrodes (GCEs). It was delineated that newly designed EDBABS/Nafion/GCE induced a high current response for Ba2+ cations in the presence of other interfering heavy metal cations (Y3+, Sn2+, Sb3+, Mn2+, Hg2+, Cr3+, As3+ and Ag+) than CDBABS/Nafion/GCE and found to be selective and sensitive towards Ba2+ cations, predominantly contributing towards environmental pollution. In order to optimize this newly designed EDBABS/Nafion/GCE as selective electrochemical Ba2+ cationic sensor, different analytical parameters such as sensitivity, limit of detection (LOD) at S/N of 3, limit of quantification (LOQ), and linear dynamic range (LDR) turned out to be satisfactory towards Ba2+ cations. The calibration curve emerged to be linear with a broad concentration range of Ba2+cations from 0.1 nM to 0.01 M and sensitivity was estimated as 3.481 × 10−3µAµM−1cm−2 in addition to (r2) as 0.9834, limit of detection (LOD) as 0.027 nM (at S/N = 3) and limit of quantification (LOQ) as 0.091 nM. Within the realm of extensive environmental protection and public health care field, this work inducts a reliable and effective way for the fabrication of sensitive as well as selective cationic electrochemical sensors based on chelating agents which can be launched as an advanced approach for quick probing of heavy metal cations in water systems, reliably and effectively.
{"title":"Synthesis, crystal structure and exploration of N,N'-(ethane-1,2-diyl)bis(4-acetylbenzenesulfonamide) (EDBABS) fabricated glassy carbon electrode as highly sensitive barium (Ba2+) sensor: An electrochemical approach","authors":"Amna Siddique , Muhammad Nadeem Arshad , Mohammed M. Rahman , Mohammad Asad , Khalid A. Alzahrani , Aftab Aslam Parwaz Khan , Tahir Ali Sheikh","doi":"10.1016/j.molstruc.2024.140624","DOIUrl":"10.1016/j.molstruc.2024.140624","url":null,"abstract":"<div><div>Environmental pollution spurred by dint of noxious chemicals and heavy metals has popped up as a pressing threat for present day community. In this study, we synthesized the <em>N,N'</em>-(ethane 1,2-diyl)bis(4-acetylbenzene-1-sulfonamide) (<strong>EDBABS</strong>) and <em>N,N'</em>-(cyclohexane-1,2-diyl)bis(4-acetylbenzenesulfonamide) (<strong>CDBABS</strong>) as bidentate chelating agents with the intention to detect the heavy metal cations in water systems. Conventional spectroscopic techniques such as UV–Vis spectroscopy, Fourier transform-infra red (FT-IR) spectroscopy, <sup>1</sup>H-NMR and <sup>13</sup>C-NMR in addition to single crystal X-ray diffraction studies were performed to expound structural characterization data of these newly synthesized non-reported bidentate chelating agents. After Characterization, a novel electrochemical current – potential (<em>I-V</em>) approach based on their modified GCEs was applied to detect the toxic cations in water systems. For this purpose, Keithley electrometer was employed as a constant voltage source. On the trail of fabricating an efficient as well as selective electrochemical sensor, for the detection of heavy metal cations in phosphate buffer system of pH = 7.0, EDBABS and CDBABS coupled with nafion as adhesive conducting binder were coated separately onto the Glassy Carbon Electrodes (GCEs). It was delineated that newly designed EDBABS/Nafion/GCE induced a high current response for Ba<sup>2+</sup> cations in the presence of other interfering heavy metal cations (Y<sup>3+</sup>, Sn<sup>2+</sup>, Sb<sup>3+</sup>, Mn<sup>2+</sup>, Hg<sup>2+</sup>, Cr<sup>3+</sup>, As<sup>3+</sup> and Ag<sup>+</sup>) than CDBABS/Nafion/GCE and found to be selective and sensitive towards Ba<sup>2+</sup> cations, predominantly contributing towards environmental pollution. In order to optimize this newly designed EDBABS/Nafion/GCE as selective electrochemical Ba<sup>2+</sup> cationic sensor, different analytical parameters such as sensitivity, limit of detection (LOD) at S/N of 3, limit of quantification (LOQ), and linear dynamic range (LDR) turned out to be satisfactory towards Ba<sup>2+</sup> cations. The calibration curve emerged to be linear with a broad concentration range of Ba<sup>2+</sup>cations from 0.1 nM to 0.01 M and sensitivity was estimated as 3.481 × 10<sup>−3</sup>µAµM<sup>−1</sup>cm<sup>−2</sup> in addition to (<em>r</em><sup><em>2</em></sup>) as 0.9834, limit of detection (LOD) as 0.027 nM (at S/<em>N</em> = 3) and limit of quantification (LOQ) as 0.091 nM. Within the realm of extensive environmental protection and public health care field, this work inducts a reliable and effective way for the fabrication of sensitive as well as selective cationic electrochemical sensors based on chelating agents which can be launched as an advanced approach for quick probing of heavy metal cations in water systems, reliably and effectively.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1323 ","pages":"Article 140624"},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142651777","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}
Cancer has emerged as a significant global health concern due to its high mortality rate and the threat it poses to human life. Consequently, there has been a significant focus in synthetic and medicinal chemistry on the creation, advancement, and production of powerful new anticancer compounds. This research aimed to assess the in vitro cytotoxic activity of synthesized pyrazolo[1,5-c]quinazoline-triazole conjugates against various cancer cell lines. First, several pyrazolo[1,5-c]quinazoline-triazole conjugates were synthesized. These synthesized compounds were then tested for their in vitro cytotoxic activity against the human breast cancer cell line (MCF-7) and the human lung carcinoma epithelial cell line (A549). All synthesized compounds displayed IC50 values <8 µM for both cell lines, suggesting substantial anticancer capabilities for these conjugates. Notably, the 6C4 structure exhibited superior efficacy in suppressing the growth of the MCF-7 cell line compared to Doxorubicin, a widely recognized commercial drug used as a positive control in our investigation. Furthermore, the majority of our active compounds demonstrated a low in silico toxicity risk profile, comparable to that of Doxorubicin, Gefitinib, and Lapatinib.
{"title":"Synthesis and in vitro cytotoxic evaluation of pyrazolo[1,5-c]quinazoline-triazole conjugates","authors":"Mohammad Reza Talebian , Samad Nejad Ebrahimi , Sajjad Azizi , Ayoob Bazgir","doi":"10.1016/j.molstruc.2024.140625","DOIUrl":"10.1016/j.molstruc.2024.140625","url":null,"abstract":"<div><div>Cancer has emerged as a significant global health concern due to its high mortality rate and the threat it poses to human life. Consequently, there has been a significant focus in synthetic and medicinal chemistry on the creation, advancement, and production of powerful new anticancer compounds. This research aimed to assess the in vitro cytotoxic activity of synthesized pyrazolo[1,5-c]quinazoline-triazole conjugates against various cancer cell lines. First, several pyrazolo[1,5-c]quinazoline-triazole conjugates were synthesized. These synthesized compounds were then tested for their in vitro cytotoxic activity against the human breast cancer cell line (MCF-7) and the human lung carcinoma epithelial cell line (A549). All synthesized compounds displayed IC<sub>50</sub> values <8 µM for both cell lines, suggesting substantial anticancer capabilities for these conjugates. Notably, the 6C4 structure exhibited superior efficacy in suppressing the growth of the MCF-7 cell line compared to Doxorubicin, a widely recognized commercial drug used as a positive control in our investigation. Furthermore, the majority of our active compounds demonstrated a low in silico toxicity risk profile, comparable to that of Doxorubicin, Gefitinib, and Lapatinib.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140625"},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142659661","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}
Curcumin (Cur), a natural phenolic compound, exhibits promising therapeutic properties including anti-cancer and anti-inflammatory effects. However, its limited bioavailability hinders its efficacy when administered alone. To address this challenge, this study explores the use of cellulose nano crystals (CNCs) derived from cinnamon stick via acid hydrolysis as carriers for Cur. The CNCs were thoroughly characterized, and Cur was successfully bound to them. Structural and morphological analyses of the CNCs-Cur complex were investigated applying Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). Interaction studies between hemoglobin and the CNCs-Cur complex were carried out using various fluorescence spectroscopic techniques. Fluorescence spectroscopy revealed hemoglobin fluorescence quenching by the CNCs-Cur complex, with Stern-Volmer constants determined at different temperatures indicating static mechanism for the quenching. Synchronous fluorescence spectroscopy provided insights into the molecular micro-environment surrounding chromophores, and the distance between the CNCs-Cur complex and hemoglobin fluorophores was calculated using Forster's non-radioactive energy transfer theory (FRET), yielding a distance of <7 nm. Circular dichroism (CD) analysis indicated structural changes in hemoglobin upon the interaction with CNCs-Cur, while oxygenation techniques were employed to investigate oxygen binding, release, and transfer in hemoglobin. This comprehensive investigation sheds light on the potential of CNCs as effective carriers for curcumin, offering valuable insights into their interaction with biological molecules.
{"title":"Preparation of cellulose nano crystals from cinnamon stick, curcumin delivery and interaction with human hemoglobin protein: A novel view of the oxygenation hemoglobin","authors":"Hanieh Golestan , Setayesh Gharebaghi , Samaneh Tavana , Kiana Vahdat-Farimani , Zahra Modaresi , Jamshidkhan Chamani","doi":"10.1016/j.molstruc.2024.140626","DOIUrl":"10.1016/j.molstruc.2024.140626","url":null,"abstract":"<div><div>Curcumin (Cur), a natural phenolic compound, exhibits promising therapeutic properties including anti-cancer and anti-inflammatory effects. However, its limited bioavailability hinders its efficacy when administered alone. To address this challenge, this study explores the use of cellulose nano crystals (CNCs) derived from cinnamon stick via acid hydrolysis as carriers for Cur. The CNCs were thoroughly characterized, and Cur was successfully bound to them. Structural and morphological analyses of the CNCs-Cur complex were investigated applying Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). Interaction studies between hemoglobin and the CNCs-Cur complex were carried out using various fluorescence spectroscopic techniques. Fluorescence spectroscopy revealed hemoglobin fluorescence quenching by the CNCs-Cur complex, with Stern-Volmer constants determined at different temperatures indicating static mechanism for the quenching. Synchronous fluorescence spectroscopy provided insights into the molecular micro-environment surrounding chromophores, and the distance between the CNCs-Cur complex and hemoglobin fluorophores was calculated using Forster's non-radioactive energy transfer theory (FRET), yielding a distance of <7 nm. Circular dichroism (CD) analysis indicated structural changes in hemoglobin upon the interaction with CNCs-Cur, while oxygenation techniques were employed to investigate oxygen binding, release, and transfer in hemoglobin. This comprehensive investigation sheds light on the potential of CNCs as effective carriers for curcumin, offering valuable insights into their interaction with biological molecules.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140626"},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142659742","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 : 2024-11-08DOI: 10.1016/j.molstruc.2024.140672
Khawla Boudebbous , Mehdi Boutebdja , Paul J. Bernard , Lhassane Ismaili , Thierry Roisnel , Anthony Robert , Dominique Harakat , Mahdi Hamdi , Houssem Boulebd
A new green methodology has been developed for the synthesis of a series of substituted 5-arylidene-2,4-thiazolidinediones (ATZDs) 3a-q through Knoevenagel condensation, using barium hydroxide as an efficient heterogeneous catalyst. All compounds were characterized by ¹H NMR, ¹³C NMR, and HRMS spectroscopy. Additionally, seven compounds were analyzed by X-ray diffraction (XRD). Furthermore, some selected TZD derivatives were screened for their antioxidant activity using oxygen radical absorbance capacity (ORAC) assays. The results showed that five compounds exhibited excellent antioxidant properties, with ORAC values ranging from 4.73 TE to 6.31 TE, surpassing the reference antioxidants ferulic acid (3.70 TE) and melatonin (2.45 TE). Computational investigations based on the DFT method revealed that these compounds exert their antioxidant activity primarily through the HAT mechanism, preferentially from the OH bond rather than the NH bond. This study highlights the advantages of this methodology, providing products of high purity, with good yields and short reaction times, and proposes 5-arylidene-thiazolidine-2,4‑dione derivatives as promising antioxidants.
以氢氧化钡为高效异相催化剂，通过克诺文纳格尔缩合法合成了一系列取代的 5-芳基-2,4-噻唑烷二酮（ATZDs）3a-q。所有化合物都通过 ¹H NMR、¹³C NMR 和 HRMS 光谱进行了表征。此外，还通过 X 射线衍射 (XRD) 分析了七种化合物。此外，研究人员还利用氧自由基吸收能力（ORAC）测定法筛选了一些选定的 TZD 衍生物的抗氧化活性。结果表明，五种化合物表现出优异的抗氧化性，其 ORAC 值从 4.73 TE 到 6.31 TE 不等，超过了参考抗氧化剂阿魏酸（3.70 TE）和褪黑素（2.45 TE）。基于 DFT 方法的计算研究表明，这些化合物主要通过 HAT 机理发挥抗氧化活性，而且更倾向于通过 OH 键而不是 NH 键发挥抗氧化活性。这项研究凸显了这种方法的优势，它能提供纯度高、产率高和反应时间短的产品，并提出 5-芳基噻唑烷-2,4-二酮衍生物是一种很有前景的抗氧化剂。
{"title":"Synthesis, crystal structures, DFT calculations, and oxygen radical absorbance capacity of 5-arylidene-thiazolidine-2,4‑dione derivatives","authors":"Khawla Boudebbous , Mehdi Boutebdja , Paul J. Bernard , Lhassane Ismaili , Thierry Roisnel , Anthony Robert , Dominique Harakat , Mahdi Hamdi , Houssem Boulebd","doi":"10.1016/j.molstruc.2024.140672","DOIUrl":"10.1016/j.molstruc.2024.140672","url":null,"abstract":"<div><div>A new green methodology has been developed for the synthesis of a series of substituted 5-arylidene-2,4-thiazolidinediones (ATZDs) <strong>3a-q</strong> through Knoevenagel condensation, using barium hydroxide as an efficient heterogeneous catalyst. All compounds were characterized by ¹H NMR, ¹³C NMR, and HRMS spectroscopy. Additionally, seven compounds were analyzed by X-ray diffraction (XRD). Furthermore, some selected TZD derivatives were screened for their antioxidant activity using oxygen radical absorbance capacity (ORAC) assays. The results showed that five compounds exhibited excellent antioxidant properties, with ORAC values ranging from 4.73 TE to 6.31 TE, surpassing the reference antioxidants ferulic acid (3.70 TE) and melatonin (2.45 TE). Computational investigations based on the DFT method revealed that these compounds exert their antioxidant activity primarily through the HAT mechanism, preferentially from the OH bond rather than the NH bond. This study highlights the advantages of this methodology, providing products of high purity, with good yields and short reaction times, and proposes 5-arylidene-thiazolidine-2,4‑dione derivatives as promising antioxidants.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1323 ","pages":"Article 140672"},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142651781","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 : 2024-11-08DOI: 10.1016/j.molstruc.2024.140630
Manjunath R , Preethi G Anantharaju , Subbarao V Madhunapantulas , Santosh L Gaonkar
A novel series of eight compounds, 2-butyl-4-chloroimidazole-derived 1,3,4-oxadiazoles, were designed and synthesized conveniently over four steps in good yield. The synthesized 1,3,4-oxadiazoles were confirmed via various analytical techniques, such as FTIR, 1H NMR, 13C NMR, and mass spectrometry. The ACE enzyme inhibitory potential of the synthesized compounds was evaluated, with compounds 5b and 5c showing IC50 values of 81.29 ± 0.70 and 51.01± 1.58 µM, respectively. Additionally, the synthesized compounds were screened for anticancer activity against the MDA-MB-231 and Caco-2 cell lines, and an antitubercular evaluation against the M. tuberculosis H37RV strain was also carried out. In silico studies, such as molecular docking to determine orientation and binding interactions, ADME prediction to determine Lipinski's rule, and molecular dynamics simulations to evaluate ligand‒protein stability were also conducted.
{"title":"Design, synthesis, and biological evaluation of 2-butyl-4-chloroimidazole-derived 1,3,4-oxadiazoles: ACE inhibition, anticancer, and antitubercular activities","authors":"Manjunath R , Preethi G Anantharaju , Subbarao V Madhunapantulas , Santosh L Gaonkar","doi":"10.1016/j.molstruc.2024.140630","DOIUrl":"10.1016/j.molstruc.2024.140630","url":null,"abstract":"<div><div>A novel series of eight compounds<strong>,</strong> 2-butyl-4-chloroimidazole-derived 1,3,4-oxadiazoles, were designed and synthesized conveniently over four steps in good yield. The synthesized 1,3,4-oxadiazoles were confirmed via various analytical techniques, such as FTIR, <sup>1</sup>H NMR, <sup>13</sup>C NMR, and mass spectrometry. The ACE enzyme inhibitory potential of the synthesized compounds was evaluated, with compounds <strong>5b</strong> and <strong>5c</strong> showing IC<sub>50</sub> values of 81.29 ± 0.70 and 51.01± 1.58 µM, respectively. Additionally, the synthesized compounds were screened for anticancer activity against the MDA-MB-231 and Caco-2 cell lines, and an antitubercular evaluation against the <em>M. tuberculosis</em> H37RV strain was also carried out. In silico studies, such as molecular docking to determine orientation and binding interactions, ADME prediction to determine Lipinski's rule, and molecular dynamics simulations to evaluate ligand‒protein stability were also conducted.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140630"},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142659608","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 : 2024-11-08DOI: 10.1016/j.molstruc.2024.140631
Quan V. Vo , Bich-Tram Truong-Le , Nguyen Thi Hoa , Adam Mechler
Methyl orange (MO) is extensively used in the food, textile, leather, and paper industries. As with many industrial chemicals, while primary environmental effects are documented, the secondary effects from its natural degradation have not been fully established. This study employs quantum chemical calculations to investigate the reaction of MO with HO• radicals that is a typical breakdown pathway in aqueous environments. It was found that the HO• + MO reaction in water can occur via either hydrogen transfer, single electron transfer, or radical adduct formation mechanisms, resulting in a variety of metastable intermediates and products. The calculated total rate constant (ktotal = 2.43×1010M−1s−1 at 298 K, pH = 9.2) is in good agreement with the experimental rate constant (kExp = (2.0 ± 0.3) ×1010M−1s−1at 298 K, pH = 9.2), thus confirming the accuracy of the calculation method. MO can degrade in natural water within the broad time range of 3.28 hrs to 56.6 years. The breakdown of methyl orange by HO• radicals is more effective at high temperatures and basic pH levels.
{"title":"The degradation of methyl orange by OH radicals in aqueous environments: A DFT study on the mechanism, kinetics, temperature and pH effects","authors":"Quan V. Vo , Bich-Tram Truong-Le , Nguyen Thi Hoa , Adam Mechler","doi":"10.1016/j.molstruc.2024.140631","DOIUrl":"10.1016/j.molstruc.2024.140631","url":null,"abstract":"<div><div>Methyl orange (MO) is extensively used in the food, textile, leather, and paper industries. As with many industrial chemicals, while primary environmental effects are documented, the secondary effects from its natural degradation have not been fully established. This study employs quantum chemical calculations to investigate the reaction of MO with HO<sup>•</sup> radicals that is a typical breakdown pathway in aqueous environments. It was found that the HO<sup>•</sup> + MO reaction in water can occur <em>via</em> either hydrogen transfer, single electron transfer, or radical adduct formation mechanisms, resulting in a variety of metastable intermediates and products. The calculated total rate constant (<em>k</em><sub>total</sub> = 2.43×10<sup>10</sup> <em>M</em><sup>−1</sup> <em>s</em><sup>−1</sup> at 298 K, pH = 9.2) is in good agreement with the experimental rate constant (<em>k</em><sub>Exp</sub> = (2.0 ± 0.3) ×10<sup>10</sup> <em>M</em><sup>−1</sup> <em>s</em><sup>−1</sup>at 298 K, pH = 9.2), thus confirming the accuracy of the calculation method. MO can degrade in natural water within the broad time range of 3.28 hrs to 56.6 years. The breakdown of methyl orange by HO<sup>•</sup> radicals is more effective at high temperatures and basic pH levels.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1323 ","pages":"Article 140631"},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142651778","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 : 2024-11-08DOI: 10.1016/j.molstruc.2024.140681
Xiaowen Zhang , Zhouyu Jiang , Mingzhu Yang, Wenhao Su, Zihui Jing, Mingliang Wang
Thiophanate-methyl (TM) and Fludioxonil (FL) are extensively employed fungicides, yet they are hampered by issues of leaching and runoff for TM and limited solubility for FL. To overcome these limitations, we explored the active pharmaceutical ingredient (API)-API cocrystal approach to optimize the solubility of both compounds. In our study, a cocrystal of TM and FL with a stoichiometric ratio of 2:1 was synthesized and characterized using a suite of analytical techniques, including powder X-ray diffraction, single-crystal X-ray diffraction, FT-IR vibrational spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. Quantum chemical calculations were utilized to elucidate the weak interactions within the TM-FL cocrystal. Notably, our solubility studies revealed that the cocrystal reduced TM solubility by 66.58 % and enhanced FL solubility by 48.41 %, which offers a significant reference for the simultaneous change of the solid-state properties of both APIs.
甲基硫菌灵（TM）和氟虫腈（FL）是被广泛使用的杀菌剂，但甲基硫菌灵存在浸出和径流问题，而氟虫腈的溶解度有限。为了克服这些限制，我们探索了活性药物成分（API）-API 共晶方法来优化这两种化合物的溶解度。在我们的研究中，我们合成了化学计量比为 2:1 的 TM 和 FL 共晶，并利用一系列分析技术对其进行了表征，包括粉末 X 射线衍射、单晶 X 射线衍射、傅立叶变换红外振动光谱、差示扫描量热法和热重分析。量子化学计算用于阐明 TM-FL 共晶体内的弱相互作用。值得注意的是，我们的溶解度研究表明，共晶体使 TM 的溶解度降低了 66.58%，FL 的溶解度提高了 48.41%，这为同时改变两种原料药的固态特性提供了重要参考。
{"title":"Dual fungicides cocrystal of thiophanate-methyl and fludioxonil: Theoretical calculation and solubility studies","authors":"Xiaowen Zhang , Zhouyu Jiang , Mingzhu Yang, Wenhao Su, Zihui Jing, Mingliang Wang","doi":"10.1016/j.molstruc.2024.140681","DOIUrl":"10.1016/j.molstruc.2024.140681","url":null,"abstract":"<div><div>Thiophanate-methyl (TM) and Fludioxonil (FL) are extensively employed fungicides, yet they are hampered by issues of leaching and runoff for TM and limited solubility for FL. To overcome these limitations, we explored the active pharmaceutical ingredient (API)-API cocrystal approach to optimize the solubility of both compounds. In our study, a cocrystal of TM and FL with a stoichiometric ratio of 2:1 was synthesized and characterized using a suite of analytical techniques, including powder X-ray diffraction, single-crystal X-ray diffraction, FT-IR vibrational spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. Quantum chemical calculations were utilized to elucidate the weak interactions within the TM-FL cocrystal. Notably, our solubility studies revealed that the cocrystal reduced TM solubility by 66.58 % and enhanced FL solubility by 48.41 %, which offers a significant reference for the simultaneous change of the solid-state properties of both APIs.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140681"},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142659675","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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