Pub Date : 2024-11-06DOI: 10.1016/j.molstruc.2024.140623
Emre Mudam , Ahsen Bolat , Hayriye Genc Bilgicli , Nazan Saraç , H. Özkan Toplan , Mustafa Arslan , Mustafa Zengin , Nil Toplan
Perlite, a cheap silica source with abundant reserves in countries such as Türkiye, China, and Greece, was used to produce nano Pd-doped silica aerogel powder for the first time in this study. The microstructure and morphology of the prepared silica aerogel powder were examined using SEM, FE-SEM, and TEM. The phases of the silica aerogel powders were analyzed via XRD (X-ray Diffraction) technique. The chemical bonding of the surface modifier with aerogels was analyzed by Fourier transform infrared spectroscopy (FTIR, Spectrum RX-1, Perkin Elmer). Surface areas, pore volumes, distributions, and particle sizes of the alumina-silica-based aerogel powders with a porous structure were measured using a Micromeritics/ASAP 2020 brand BET (Brunauer, Emmet, and Teller) device in a liquid nitrogen gas environment at 77K.
The efficiency of this nano Pd-doped silica aerogel powder was investigated as a heterogeneous catalyst for well-known transformations in organic synthesis, such as alkene hydrogenation and cross-linking reactions. The results indicated that the developed method is chemoselective, reducing only carbon-carbon multiple bonds without affecting C-N or C-O multiple bonds, such as carbonyl and nitrile. The effectiveness of the newly developed catalyst was also investigated in Heck and Suzuki-Miyaura reactions, yielding the targeted products with high efficiency.
Thus, an inexpensive, economical, and environmentally friendly method has been developed that is potentially applicable in the hydrogenation and cross-coupling reactions of alkenes.
{"title":"Nano-Pd/SiO2 aerogel catalyst prepared via ambient pressure drying process using perlite powder in hydrogenation and cross-coupling reactions","authors":"Emre Mudam , Ahsen Bolat , Hayriye Genc Bilgicli , Nazan Saraç , H. Özkan Toplan , Mustafa Arslan , Mustafa Zengin , Nil Toplan","doi":"10.1016/j.molstruc.2024.140623","DOIUrl":"10.1016/j.molstruc.2024.140623","url":null,"abstract":"<div><div>Perlite, a cheap silica source with abundant reserves in countries such as Türkiye, China, and Greece, was used to produce nano Pd-doped silica aerogel powder for the first time in this study. The microstructure and morphology of the prepared silica aerogel powder were examined using SEM, FE-SEM, and TEM. The phases of the silica aerogel powders were analyzed via XRD (X-ray Diffraction) technique. The chemical bonding of the surface modifier with aerogels was analyzed by Fourier transform infrared spectroscopy (FTIR, Spectrum RX-1, Perkin Elmer). Surface areas, pore volumes, distributions, and particle sizes of the alumina-silica-based aerogel powders with a porous structure were measured using a Micromeritics/ASAP 2020 brand BET (Brunauer, Emmet, and Teller) device in a liquid nitrogen gas environment at 77K.</div><div>The efficiency of this nano Pd-doped silica aerogel powder was investigated as a heterogeneous catalyst for well-known transformations in organic synthesis, such as alkene hydrogenation and cross-linking reactions. The results indicated that the developed method is chemoselective, reducing only carbon-carbon multiple bonds without affecting C-N or C-O multiple bonds, such as carbonyl and nitrile. The effectiveness of the newly developed catalyst was also investigated in Heck and Suzuki-Miyaura reactions, yielding the targeted products with high efficiency.</div><div>Thus, an inexpensive, economical, and environmentally friendly method has been developed that is potentially applicable in the hydrogenation and cross-coupling reactions of alkenes.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140623"},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142656916","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 : 2024-11-06DOI: 10.1016/j.molstruc.2024.140586
Ahmed I. Khodair , Dalia R. Imam , Nabila A. Kheder , Asmaa M. Fahim , Ahmed A. El-Barbary
In this study, we constructed twenty novel imidazolidinone derivatives via the reaction of 2-(methylthio)-3,5-dihydro-4H-imidazol-4-one derivatives (1a-c) with some active methylene reagents and nitrogen nucleophiles. The synthesized compounds were confirmed through spectral analysis such as 1H NMR, 13C NMR, FT-IR, and MS. Moreover, the synthesized compounds were optimized and utilizing the DFT/B3LYP/6–31(G) basis set to investigate their energies and the presence of two forms of isomers (E and Z). The results confirmed the stability of the E form. ADMET of new imidazolidinones was also studied to investigate their lipophilicity and Lipinski's rule for determination of their physiological biological analysis. Also, the antimicrobial activity of new compounds on Escherichia coli, Klebsiella pneumonia, Staphylococcus aureus, Streptococcus mutans, Candida albicans, and Aspergillus Nigar using the inhibition zone technique were evaluated. The results demonstrate that compound 11c showed higher activity rather than other compounds due to the presence of piperazine moiety out of the plane of the benzene ring. Additionally, the docking study showed an electrostatic bonding interaction of the hydrogen of 11c and the amino acids of two proteins such as PDBID: 3t88 and 2wje.
{"title":"Synthesis, DFT investigation, molecular docking analysis, ADMET studies, and biological evaluation of a novel series of imidazolidinone derivatives as potential antimicrobial agents","authors":"Ahmed I. Khodair , Dalia R. Imam , Nabila A. Kheder , Asmaa M. Fahim , Ahmed A. El-Barbary","doi":"10.1016/j.molstruc.2024.140586","DOIUrl":"10.1016/j.molstruc.2024.140586","url":null,"abstract":"<div><div>In this study, we constructed twenty novel imidazolidinone derivatives via the reaction of 2-(methylthio)-3,5-dihydro-4<em>H</em>-imidazol-4-one derivatives (<strong>1a-c</strong>) with some active methylene reagents and nitrogen nucleophiles. The synthesized compounds were confirmed through spectral analysis such as <sup>1</sup>H NMR, <sup>13</sup>C NMR, FT-IR, and MS. Moreover, the synthesized compounds were optimized and utilizing the DFT/B3LYP/6–31(G) basis set to investigate their energies and the presence of two forms of isomers (<em>E</em> and <em>Z</em>). The results confirmed the stability of <em>the E</em> form. ADMET of new imidazolidinones was also studied to investigate their lipophilicity and Lipinski's rule for determination of their physiological biological analysis. Also, the antimicrobial activity of new compounds on <em>Escherichia coli, Klebsiella pneumonia, Staphylococcus aureus, Streptococcus mutans, Candida albicans, and Aspergillus Nigar</em> using the inhibition zone technique were evaluated. The results demonstrate that compound <strong>11c</strong> showed higher activity rather than other compounds due to the presence of piperazine moiety out of the plane of the benzene ring. Additionally, the docking study showed an electrostatic bonding interaction of the hydrogen of <strong>11c</strong> and the amino acids of two proteins such as <strong>PDBID:</strong> 3t88 and 2wje.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140586"},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142659671","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 : 2024-11-06DOI: 10.1016/j.molstruc.2024.140614
Sunusi Y. Hussaini , Mohd R. Razali
Gold(I)-N-heterocyclic carbenes (NHCs) complexes have undergone rapid development and developed as useful tools for the design of various scaffolds in diverse applications such as biological, catalytic and photophysical applications. This review covers photoluminescence transition properties of gold complexes containing NHC ligands, which give resulted in high energy emissions with desired blue colour needs for new optical devices, bioimaging and organic light emitting diodes (OLEDs). In addition, the great versatility in the structural morphology of the complexes with aurophilic interactions, provides numerous possibilities in the synthesis of desired luminescence complexes with lifetimes corresponding to a fluorescence or phosphorescence process that depends on the origin of the emissions. Herein, we present an overview on structural and electronic properties of NHC ligand, metal-NHC complexes, gold(I)-NHC complexes and photoluminescence properties reported from various research works.
{"title":"Photoluminescence properties of Gold(I)-N-Heterocyclic carbene complexes","authors":"Sunusi Y. Hussaini , Mohd R. Razali","doi":"10.1016/j.molstruc.2024.140614","DOIUrl":"10.1016/j.molstruc.2024.140614","url":null,"abstract":"<div><div>Gold(I)-<em>N</em>-heterocyclic carbenes (NHCs) complexes have undergone rapid development and developed as useful tools for the design of various scaffolds in diverse applications such as biological, catalytic and photophysical applications. This review covers photoluminescence transition properties of gold complexes containing NHC ligands, which give resulted in high energy emissions with desired blue colour needs for new optical devices, bioimaging and organic light emitting diodes (OLEDs). In addition, the great versatility in the structural morphology of the complexes with aurophilic interactions, provides numerous possibilities in the synthesis of desired luminescence complexes with lifetimes corresponding to a fluorescence or phosphorescence process that depends on the origin of the emissions. Herein, we present an overview on structural and electronic properties of NHC ligand, metal-NHC complexes, gold(I)-NHC complexes and photoluminescence properties reported from various research works.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140614"},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142659606","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 : 2024-11-06DOI: 10.1016/j.molstruc.2024.140591
Feng Su , Peng-Ze Cheng , Ya-Hui Liu , Xin-Yu Liu , Yan Sun , Shu-Xin Li , Shao-Dong Li , Long Sun , Zhi-Jun Wang
The efficient detection of pollutants in aqueous solutions, such as Cu2+, H2PO4− and CTC, holds significant implications for human health and environmental preservation. Two new heterometallic ZnII-EuIII-MOFs {[ZnEu(BITA)2(H2O)Cl]·H2O}n (ZnII-EuIII-1) and {[ZnEu(BITA)1.5(H2O)2Cl2]·CH3CN·H2O}n (ZnII-EuIII-2) were successfully synthesized by using a π-conjugated imidazolyl-carboxylate H2BITA ligand under solvothermal conditions. ZnII-EuIII-1 exhibits a distinctive 3D framework with 1D homochiral right- and left-handed helical chains constructed based on Zn2+ ions. ZnII-EuIII-2 presents a 3D network with rhombic channels, wherein heterometallic ZnII-EuIII ions are interconnected via carboxylate and imidazolyl groups to generate 1D zigzag chains. The ZnII-EuIII-MOFs exhibit bright red luminescence emissions in the solid state. Moreover, ZnII-EuIII-1 demonstrates exceptional thermal and chemical stability as well as excellent luminescence properties in aqueous solutions. ZnII-EuIII-1 can act as a multi-responsive luminescence sensor for the detection of Cu2+, H2PO4− and CTC in aqueous solutions through luminescence quenching and enhancement with significant red shifts. Notably, the sensing mechanism for H2PO4− can be attributed to hydrogen bonding interactions and the formation of exciplexes between H2PO4− and ZnII-EuIII-1. Furthermore, the sensing mechanism for CTC may be explained by intermolecular interactions, the existence of competition absorption, IFE and the formation of exciplex between CTC and ZnII-EuIII-1.
{"title":"Heterometal–organic frameworks as highly sensitive and highly selective luminescent probes to detect Cu2+, H2PO4− ions and CTC in aqueous solutions","authors":"Feng Su , Peng-Ze Cheng , Ya-Hui Liu , Xin-Yu Liu , Yan Sun , Shu-Xin Li , Shao-Dong Li , Long Sun , Zhi-Jun Wang","doi":"10.1016/j.molstruc.2024.140591","DOIUrl":"10.1016/j.molstruc.2024.140591","url":null,"abstract":"<div><div>The efficient detection of pollutants in aqueous solutions, such as Cu<sup>2+</sup>, H<sub>2</sub>PO<sub>4</sub><sup>−</sup> and CTC, holds significant implications for human health and environmental preservation. Two new heterometallic Zn<sup>II</sup>-Eu<sup>III</sup>-MOFs {[ZnEu(BITA)<sub>2</sub>(H<sub>2</sub>O)Cl]·H<sub>2</sub>O}<sub>n</sub> (Zn<sup>II</sup>-Eu<sup>III</sup>-<strong>1</strong>) and {[ZnEu(BITA)<sub>1.5</sub>(H<sub>2</sub>O)<sub>2</sub>Cl<sub>2</sub>]·CH<sub>3</sub>CN·H<sub>2</sub>O}<sub>n</sub> (Zn<sup>II</sup>-Eu<sup>III</sup>-<strong>2</strong>) were successfully synthesized by using a π-conjugated imidazolyl-carboxylate H<sub>2</sub>BITA ligand under solvothermal conditions. Zn<sup>II</sup>-Eu<sup>III</sup>-<strong>1</strong> exhibits a distinctive 3D framework with 1D homochiral right- and left-handed helical chains constructed based on Zn<sup>2+</sup> ions. Zn<sup>II</sup>-Eu<sup>III</sup>-<strong>2</strong> presents a 3D network with rhombic channels, wherein heterometallic Zn<sup>II</sup>-Eu<sup>III</sup> ions are interconnected via carboxylate and imidazolyl groups to generate 1D zigzag chains. The Zn<sup>II</sup>-Eu<sup>III</sup>-MOFs exhibit bright red luminescence emissions in the solid state. Moreover, Zn<sup>II</sup>-Eu<sup>III</sup>-<strong>1</strong> demonstrates exceptional thermal and chemical stability as well as excellent luminescence properties in aqueous solutions. Zn<sup>II</sup>-Eu<sup>III</sup>-<strong>1</strong> can act as a multi-responsive luminescence sensor for the detection of Cu<sup>2+</sup>, H<sub>2</sub>PO<sub>4</sub><sup>−</sup> and CTC in aqueous solutions through luminescence quenching and enhancement with significant red shifts. Notably, the sensing mechanism for H<sub>2</sub>PO<sub>4</sub><sup>−</sup> can be attributed to hydrogen bonding interactions and the formation of exciplexes between H<sub>2</sub>PO<sub>4</sub><sup>−</sup> and Zn<sup>II</sup>-Eu<sup>III</sup>-<strong>1</strong>. Furthermore, the sensing mechanism for CTC may be explained by intermolecular interactions, the existence of competition absorption, IFE and the formation of exciplex between CTC and Zn<sup>II</sup>-Eu<sup>III</sup>-<strong>1</strong>.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140591"},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657622","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}
Owing to the tremendous physicochemical and quantum confinement characteristics of carbon quantum dots (CQDs), they have revealed exciting and essential visions in the field of energy conversion and energy storage. However, due to their low photoluminescence quantum yield (PLQY) and/or short Stokes-shift, limits their application in photovoltaic (PV). In this regard, a novel and cost-effective method was used to synthesize the CQDs using waste biomass. Furthermore, a comprehensive study was made to explore the applicability of the CQDs as photon downconverters/downshifters in PVs. The average size of the CQDs are 5.1, 4.4, and 3.9 nm for the synthesis temperature of 160, 180, and 200 ℃, respectively. The EDS analysis revealed that C, O, Mg, Na, Cl, and K are present in all the CQDs. The PL emission peak position is blue-shifted with the rise in the synthesis temperature. The Stokes-shift is reduced with a rise in the synthesis temperature. The highest Stokes-shift was obtained at excitation wavelength of 300 nm for CQDs synthesized at 160 ℃. The PLQY increased by 3.5 and 7.2-folds for the rise in the temperature from 160 to 180 and 200 ℃, respectively. The investigation revealed that the applicability of CQDs can be enriched via the selection of the synthesis parameters.
{"title":"Attaining a wide photoluminescence Stokes-shift of carbon dots obtained from waste biomass","authors":"Masoud Al-Rasheidi , Arwa Alabdulhadi , Firoz Khan","doi":"10.1016/j.molstruc.2024.140627","DOIUrl":"10.1016/j.molstruc.2024.140627","url":null,"abstract":"<div><div>Owing to the tremendous physicochemical and quantum confinement characteristics of carbon quantum dots (CQDs), they have revealed exciting and essential visions in the field of energy conversion and energy storage. However, due to their low photoluminescence quantum yield (PLQY) and/or short Stokes-shift, limits their application in photovoltaic (PV). In this regard, a novel and cost-effective method was used to synthesize the CQDs using waste biomass. Furthermore, a comprehensive study was made to explore the applicability of the CQDs as photon downconverters/downshifters in PVs. The average size of the CQDs are 5.1, 4.4, and 3.9 nm for the synthesis temperature of 160, 180, and 200 ℃, respectively. The EDS analysis revealed that C, O, Mg, Na, Cl, and K are present in all the CQDs. The PL emission peak position is blue-shifted with the rise in the synthesis temperature. The Stokes-shift is reduced with a rise in the synthesis temperature. The highest Stokes-shift was obtained at excitation wavelength of 300 nm for CQDs synthesized at 160 ℃. The PLQY increased by 3.5 and 7.2-folds for the rise in the temperature from 160 to 180 and 200 ℃, respectively. The investigation revealed that the applicability of CQDs can be enriched via the selection of the synthesis parameters.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140627"},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142659609","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 optical-structural correlated properties of the system, where 2, 4, and 6 mol%, were studied. Differential scanning calorimetry (DSC) and X-ray diffraction (XRD) confirmed the glassy and amorphous nature of the samples. Adding promoted the formation of bridging oxygens (upto 4 mol%) by converting into units, however, above 4 mol% act as a modifier. The optical band gap increased from 3.70 to 4.01 eV, while the refractive index decreased from 2.23 to 2.16. The CIE coordinates indicated that the emission spectra fall within the green-blue region. The as-prepared sample exhibited the highest correlated colour temperature value above 5000 K, suggesting its suitability for cool light-emitting diodes sensitive to human vision. These glasses have potential applications in light-emitting diodes and optoelectronic devices.
{"title":"Tunable green-blue luminescence of Dy2O3 doped borosilicate glasses for optoelectronic devices","authors":"Jaspreet Kaur , Santosh Kumar , Isha Mudahar , K. Singh","doi":"10.1016/j.molstruc.2024.140574","DOIUrl":"10.1016/j.molstruc.2024.140574","url":null,"abstract":"<div><div>The optical-structural correlated properties of the <span><math><mn>40</mn><msub><mrow><mi>B</mi></mrow><mrow><mn>2</mn></mrow></msub><msub><mrow><mi>O</mi></mrow><mrow><mn>3</mn></mrow></msub><mo>−</mo><mn>40</mn><mi>S</mi><mi>i</mi><msub><mrow><mi>O</mi></mrow><mrow><mn>2</mn></mrow></msub><mo>−</mo><mn>10</mn><msub><mrow><mi>V</mi></mrow><mrow><mn>2</mn></mrow></msub><msub><mrow><mi>O</mi></mrow><mrow><mn>5</mn></mrow></msub><mo>−</mo><mo>(</mo><mn>10</mn><mo>−</mo><mi>x</mi><mo>)</mo><mi>F</mi><msub><mrow><mi>e</mi></mrow><mrow><mn>2</mn></mrow></msub><msub><mrow><mi>O</mi></mrow><mrow><mn>3</mn></mrow></msub><mo>−</mo><mi>x</mi><mi>D</mi><msub><mrow><mi>y</mi></mrow><mrow><mn>2</mn></mrow></msub><msub><mrow><mi>O</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span> system, where 2, 4, and 6 mol%, were studied. Differential scanning calorimetry (DSC) and X-ray diffraction (XRD) confirmed the glassy and amorphous nature of the samples. Adding <span><math><mi>D</mi><msub><mrow><mi>y</mi></mrow><mrow><mn>2</mn></mrow></msub><msub><mrow><mi>O</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span> promoted the formation of bridging oxygens (upto 4 mol%) by converting <span><math><mi>B</mi><msub><mrow><mi>O</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span> into <span><math><mi>B</mi><msub><mrow><mi>O</mi></mrow><mrow><mn>4</mn></mrow></msub></math></span> units, however, above 4 mol% <span><math><mi>D</mi><msub><mrow><mi>y</mi></mrow><mrow><mn>2</mn></mrow></msub><msub><mrow><mi>O</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span> act as a modifier. The optical band gap increased from 3.70 to 4.01 eV, while the refractive index decreased from 2.23 to 2.16. The CIE coordinates indicated that the emission spectra fall within the green-blue region. The as-prepared sample exhibited the highest correlated colour temperature value above 5000 K, suggesting its suitability for cool light-emitting diodes sensitive to human vision. These glasses have potential applications in light-emitting diodes and optoelectronic devices.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140574"},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142656926","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 : 2024-11-06DOI: 10.1016/j.molstruc.2024.140580
Hui Wang , Haoliang Wang , Siyamak Shahab , Fulei Shang , Meng Ye
Six new charge-transfer complexes using ofloxacin (OFL) and sulfamethazine (SMR) as electron donors and coumaric acid (COA), cinnamic acid (CNA), and salicylic acid (SAA) as acceptors via equimolar mixture have been synthesized. The experiment used UV–vis spectroscopy to determine the formation of the complex in methanol through the presence of a new broad absorption band with a maximum wavelength in the 200–400 nm range. The molecular composition of the charge-transfer complexes was determined by the spectrophotometric titration method and found to be 1:1 (donor: acceptor). These complexes have been characterized by infrared (FTIR) and scanning electron microscopy (SEM). In the FTIR spectra, the CT complexes showed a wavelength shift compared to the reactants. The complexes exhibited various morphologies by SEM, including spherical particles, short rods, and flattened shapes. Additionally, quantum chemical calculations at the DFT/B3LYP level of theory investigated the complexes' steady-state structures, energies, and charge densities. The intermolecular binding energies was negative, indicating that the reactions of the six complexes proceeded spontaneously. There was strong van der Waals forces and hydrogen bonds between the donor and acceptor, which contributed to the complexes' strong molecular stability. The CN and NH groups in the donor molecule, and the -COOH group in the acceptor molecule, played key roles in the complexation process. DFT calculation results were appropriate to support our experimental results. This study highlights the molecular mechanisms of donor and acceptor action in charge-transfer interactions, providing a theoretical basis for the synthesis of antibiotic complexes and the removal of antibiotics.
{"title":"Charge-transfer interactions between antibiotics and small organic acids: Spectroscopic characterization and computational investigation","authors":"Hui Wang , Haoliang Wang , Siyamak Shahab , Fulei Shang , Meng Ye","doi":"10.1016/j.molstruc.2024.140580","DOIUrl":"10.1016/j.molstruc.2024.140580","url":null,"abstract":"<div><div>Six new charge-transfer complexes using ofloxacin (OFL) and sulfamethazine (SMR) as electron donors and coumaric acid (COA), cinnamic acid (CNA), and salicylic acid (SAA) as acceptors via equimolar mixture have been synthesized. The experiment used UV–vis spectroscopy to determine the formation of the complex in methanol through the presence of a new broad absorption band with a maximum wavelength in the 200–400 nm range. The molecular composition of the charge-transfer complexes was determined by the spectrophotometric titration method and found to be 1:1 (donor: acceptor). These complexes have been characterized by infrared (FTIR) and scanning electron microscopy (SEM). In the FTIR spectra, the CT complexes showed a wavelength shift compared to the reactants. The complexes exhibited various morphologies by SEM, including spherical particles, short rods, and flattened shapes. Additionally, quantum chemical calculations at the DFT/B3LYP level of theory investigated the complexes' steady-state structures, energies, and charge densities. The intermolecular binding energies was negative, indicating that the reactions of the six complexes proceeded spontaneously. There was strong van der Waals forces and hydrogen bonds between the donor and acceptor, which contributed to the complexes' strong molecular stability. The C<img>N and N<img>H groups in the donor molecule, and the -COOH group in the acceptor molecule, played key roles in the complexation process. DFT calculation results were appropriate to support our experimental results. This study highlights the molecular mechanisms of donor and acceptor action in charge-transfer interactions, providing a theoretical basis for the synthesis of antibiotic complexes and the removal of antibiotics.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140580"},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142659673","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 : 2024-11-06DOI: 10.1016/j.molstruc.2024.140610
Jiacheng Guo , Lingling Xu , Wen You , Yuze Ji , Dongying Chen
Indole-3-propionic acid (IPA), an intestinal microbiota produced metabolite, has been supposed as a promising clinical drug candidate to ameliorate progressive neurological and neuropsychiatric disorders associated with gut microbiota dysbiosis due to age-related infirmity. In this study, in order to enhance the aqueous solubility of IPA, nicotinamide (NIC) was selected as a coformer to synthesize a novel cocrystal (IPA-NIC) which was characterized by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), thermal analysis, and Fourier transform infrared spectroscopy (FT-IR). The cocrystal structure was found to be in a 2:1 stoichiometric ratio consisting of four IPA molecules and two NIC molecules linked through heteromolecular hydrogen bonds within an asymmetric unit. The physiochemical properties of solubility, dissolution and permeability were demonstrated to be simultaneously improved. Preliminary forced studies under thermal (60 °C) and humid (92.5 % RH) conditions indicated that the cocrystal remained stable which would be beneficial to the further development as a potential drug candidate.
吲哚-3-丙酸（IPA）是一种由肠道微生物群产生的代谢产物，被认为是一种很有前景的临床候选药物，可用于改善因年老体弱导致肠道微生物群失调而引起的进行性神经和神经精神疾病。在本研究中，为了提高 IPA 的水溶性，我们选择烟酰胺（NIC）作为共形剂合成了一种新型共晶体（IPA-NIC），并通过单晶 X 射线衍射（SCXRD）、粉末 X 射线衍射（PXRD）、热分析和傅立叶变换红外光谱（FT-IR）对其进行了表征。研究发现，这种共晶体结构的化学计量比为 2:1，由四个 IPA 分子和两个 NIC 分子组成，在一个不对称单元内通过异分子氢键连接。实验证明，这种共聚物的溶解度、溶解性和渗透性等理化性质同时得到了改善。在热（60 °C）和湿（92.5 % 相对湿度）条件下进行的初步强制研究表明，这种共晶体保持稳定，有利于进一步开发成为潜在的候选药物。
{"title":"A novel cocrystal of indole-3-propionic acid and nicotinamide: Structure design, preparation, characterization and preliminary physiochemical properties evaluation","authors":"Jiacheng Guo , Lingling Xu , Wen You , Yuze Ji , Dongying Chen","doi":"10.1016/j.molstruc.2024.140610","DOIUrl":"10.1016/j.molstruc.2024.140610","url":null,"abstract":"<div><div>Indole-3-propionic acid (IPA), an intestinal microbiota produced metabolite, has been supposed as a promising clinical drug candidate to ameliorate progressive neurological and neuropsychiatric disorders associated with gut microbiota dysbiosis due to age-related infirmity. In this study, in order to enhance the aqueous solubility of IPA, nicotinamide (NIC) was selected as a coformer to synthesize a novel cocrystal (IPA-NIC) which was characterized by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), thermal analysis, and Fourier transform infrared spectroscopy (FT-IR). The cocrystal structure was found to be in a 2:1 stoichiometric ratio consisting of four IPA molecules and two NIC molecules linked through heteromolecular hydrogen bonds within an asymmetric unit. The physiochemical properties of solubility, dissolution and permeability were demonstrated to be simultaneously improved. Preliminary forced studies under thermal (60 °C) and humid (92.5 % RH) conditions indicated that the cocrystal remained stable which would be beneficial to the further development as a potential drug candidate.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140610"},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142659674","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 : 2024-11-06DOI: 10.1016/j.molstruc.2024.140628
Weizhao Hou , Wenjuan Guo , Zhao Dai , He Ren , Xingran Luo , Junjie Fu
Baicalin is a natural active ingredient known for its medicinal properties and a broad spectrum of pharmacological activities, including antimicrobial, antioxidant, antiviral, and anticancer effects. However, its application is hindered by its poor water-solubility. In this study, we aimed to enhance the water solubility of baicalin by embedding it within the hydrophobic cavity of hydroxypropyl-β-cyclodextrin through supramolecular assembly to form inclusion complexes. The inclusion complexes were subsequently processed into nanofiber membranes suitable for application on skin and wounds using coaxial electrostatic spinning. The inclusion complexes and nanofiber membranes were analyzed and characterized using high-performance liquid chromatography (HPLC), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The combined results from XRD, FT-IR, and TGA confirmed that baicalin successfully formed inclusion complexes with cyclodextrin, resulting in an increase in water solubility from 0.0170 mg/mL to 8.9600 mg/mL, representing a 527-fold enhancement. Additionally, the inclusion complexes demonstrated superior antimicrobial activity against E. coli, S. aureus and C. albicans, as well as higher free radical scavenging rates compared to native baicalin. After the inclusion complexes were transformed into nanofiber membranes via coaxial electrospinning, their properties remained unchanged, and they continued to exhibit excellent antimicrobial and antioxidant activities. In the in vitro release assay, nearly 90 % of the drug (baicalin) was released from the nanofiber membranes over a period of time, indicating sustained release. Furthermore, the molecular docking mechanism of baicalin and cyclodextrin was elucidated through molecular docking simulations, establishing a theoretical foundation for the synthesis of inclusion complexes in the computational studies. This study reports the successful fabrication of water-soluble, antimicrobial nanofiber membranes containing bioavailable baicalin, which have potential clinical applications in the development of wound dressings and drug delivery systems utilizing plant-extracted bioactive compounds.
{"title":"Baicalin nanofiber membranes: A comprehensive study on preparation, characterization, and antimicrobial pharmacological activities","authors":"Weizhao Hou , Wenjuan Guo , Zhao Dai , He Ren , Xingran Luo , Junjie Fu","doi":"10.1016/j.molstruc.2024.140628","DOIUrl":"10.1016/j.molstruc.2024.140628","url":null,"abstract":"<div><div>Baicalin is a natural active ingredient known for its medicinal properties and a broad spectrum of pharmacological activities, including antimicrobial, antioxidant, antiviral, and anticancer effects. However, its application is hindered by its poor water-solubility. In this study, we aimed to enhance the water solubility of baicalin by embedding it within the hydrophobic cavity of hydroxypropyl-β-cyclodextrin through supramolecular assembly to form inclusion complexes. The inclusion complexes were subsequently processed into nanofiber membranes suitable for application on skin and wounds using coaxial electrostatic spinning. The inclusion complexes and nanofiber membranes were analyzed and characterized using high-performance liquid chromatography (HPLC), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The combined results from XRD, FT-IR, and TGA confirmed that baicalin successfully formed inclusion complexes with cyclodextrin, resulting in an increase in water solubility from 0.0170 mg/mL to 8.9600 mg/mL, representing a 527-fold enhancement. Additionally, the inclusion complexes demonstrated superior antimicrobial activity against <em>E. coli, S. aureus</em> and <em>C. albicans</em>, as well as higher free radical scavenging rates compared to native baicalin. After the inclusion complexes were transformed into nanofiber membranes via coaxial electrospinning, their properties remained unchanged, and they continued to exhibit excellent antimicrobial and antioxidant activities. In the <em>in vitro</em> release assay, nearly 90 % of the drug (baicalin) was released from the nanofiber membranes over a period of time, indicating sustained release. Furthermore, the molecular docking mechanism of baicalin and cyclodextrin was elucidated through molecular docking simulations, establishing a theoretical foundation for the synthesis of inclusion complexes in the computational studies. This study reports the successful fabrication of water-soluble, antimicrobial nanofiber membranes containing bioavailable baicalin, which have potential clinical applications in the development of wound dressings and drug delivery systems utilizing plant-extracted bioactive compounds.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140628"},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142659610","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 : 2024-11-05DOI: 10.1016/j.molstruc.2024.140609
Huizhuan Zhu , Hanrong Liu , Jiakun Bai , Jiang Peng , Huijuan Zhang , Junhui Jia
It is highly desirable and significant to integrate the remarkable properties of mechanical force-induced luminescence enhancement and aggregation-induced emission (AIE) within a single simple molecule. In this study, a new novel AIE-active anthracene-based chalcone derivative APBP ((E)-1-(4-(anthracen-9-yl)phenyl)-3-(4-bromophenyl)prop‑2-en-1-one) was designed and synthesized, and its photophysical properties, aggregation-induced emission behavior, and mechanical force-induced luminescence properties were systematically investigated. It is worth noting that, due to its high sensitivity to mechanical force, APBP exhibited reversible high-contrast turn-on mechanofluorochromism in response to mechanical force, accompanied by a substantial increase in the solid fluorescence quantum yield (QY), from 0.4 % (pristine) to 36.8 % (upon grinding). Additionally, a large red-shift of 46 nm from 488 nm to 534 nm was observed upon grinding. In other words, the prominent enhanced and larger red-shifted emission endows it with the characteristics of a high-contrast mechanofluorochromism material. The reversible phase transition between the well-ordered crystalline and amorphous states was responsible for the mechanical force-induced luminescence enhanced and chromism properties, as evidenced by powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FESEM), and differential calorimetric scanning (DSC) results. Furthermore, X-ray single-crystal diffraction results revealed that the observed fluorescence enhancement behavior was attributable to the disruption of both the π-π stacking and the H-Br interactions.
{"title":"Mechanical force-induced luminescence enhancement and chromism of AIE-active anthracene chalcone derivative","authors":"Huizhuan Zhu , Hanrong Liu , Jiakun Bai , Jiang Peng , Huijuan Zhang , Junhui Jia","doi":"10.1016/j.molstruc.2024.140609","DOIUrl":"10.1016/j.molstruc.2024.140609","url":null,"abstract":"<div><div>It is highly desirable and significant to integrate the remarkable properties of mechanical force-induced luminescence enhancement and aggregation-induced emission (AIE) within a single simple molecule. In this study, a new novel AIE-active anthracene-based chalcone derivative <strong>APBP</strong> ((<em>E</em>)-1-(4-(anthracen-9-yl)phenyl)-3-(4-bromophenyl)prop‑2-en-1-one) was designed and synthesized, and its photophysical properties, aggregation-induced emission behavior, and mechanical force-induced luminescence properties were systematically investigated. It is worth noting that, due to its high sensitivity to mechanical force, <strong>APBP</strong> exhibited reversible high-contrast turn-on mechanofluorochromism in response to mechanical force, accompanied by a substantial increase in the solid fluorescence quantum yield (QY), from 0.4 % (pristine) to 36.8 % (upon grinding). Additionally, a large red-shift of 46 nm from 488 nm to 534 nm was observed upon grinding. In other words, the prominent enhanced and larger red-shifted emission endows it with the characteristics of a high-contrast mechanofluorochromism material. The reversible phase transition between the well-ordered crystalline and amorphous states was responsible for the mechanical force-induced luminescence enhanced and chromism properties, as evidenced by powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FESEM), and differential calorimetric scanning (DSC) results. Furthermore, X-ray single-crystal diffraction results revealed that the observed fluorescence enhancement behavior was attributable to the disruption of both the π-π stacking and the H-Br interactions.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140609"},"PeriodicalIF":4.0,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657059","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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