Carbon nano peapods, with their electronic properties and spintronics, have attracted great attention regarding their potential applications when combined with fullerenes or their derivatives encapsulated inside. Herein, we have designed and synthesized a series of fullerene derivatives with different functional groups, which are then encapsulated into single-walled carbon nanotubes (SWCNTs). Accurate morphological characterization with high-resolution TEM reveals a clear correlation between the filling ratio of the peapods and the steric bulk of the functionalized groups. Further spectroscopic characterizations reveal diameter-selective interactions between the fullerene derivatives and SWCNTs, which, in turn, influence the electronic structures of the nanotubes. Our results have shed new light on the controlled synthesis and property-tuning of nano peapods.
{"title":"Diameter-Selective Host-Guest Interactions between Functionalized Fullerenes and Single-Walled Carbon Nanotubes","authors":"Rui Zhang, Wanru Gao, Chang Sun, Yiwen Liu, Xiaojun Lu, Xing Lu","doi":"10.3390/inorganics11100386","DOIUrl":"https://doi.org/10.3390/inorganics11100386","url":null,"abstract":"Carbon nano peapods, with their electronic properties and spintronics, have attracted great attention regarding their potential applications when combined with fullerenes or their derivatives encapsulated inside. Herein, we have designed and synthesized a series of fullerene derivatives with different functional groups, which are then encapsulated into single-walled carbon nanotubes (SWCNTs). Accurate morphological characterization with high-resolution TEM reveals a clear correlation between the filling ratio of the peapods and the steric bulk of the functionalized groups. Further spectroscopic characterizations reveal diameter-selective interactions between the fullerene derivatives and SWCNTs, which, in turn, influence the electronic structures of the nanotubes. Our results have shed new light on the controlled synthesis and property-tuning of nano peapods.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":"4 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135536620","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-09-27DOI: 10.3390/inorganics11100385
Uğur Tutar, Cem Çelik, Elvan Üstün, Namık Özdemir, Neslihan Şahin, David Sémeril, Nevin Gürbüz, İsmail Özdemir
Five silver(I) complexes, namely chloro[1-methallyl-3-benzyl)benzimidazol-2-ylidene] silver (6), chloro[1-methallyl-3-(2,3,5,6-tetramethylbenzyl)benzimidazol-2-ylidene]silver (7), chloro[1-methallyl-3-(3,4,5-trimethoxylbenzyl)benzimidazol-2-ylidene]silver (8), chloro[1-methallyl- 3-(naphthylmethyl)benzimidazol-2-ylidene]silver (9), and chloro [1-methallyl-3-(anthracen-9-yl- methyl)benzimidazol-2-ylidene]silver (10), were prepared starting from their corresponding benzimidazolium salts and silver oxide in 71–81% yields. A single-crystal X-ray structure of 7 was determined. These five Ag-NHC complexes were evaluated for their antimicrobial and biofilm formation inhibition properties. Complex 10 exhibited high antimicrobial activities comparable to those obtained with standard drugs such as Fluconazole in contact with Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, Acinetobacter baumannii, and Candida albicans. The latter complex has been shown to be very efficient in antibiofilm activity, with 92.9% biofilm inhibition at 1.9 μg/mL on Escherichia coli. Additionally, the molecules were optimized with DFT-based computational methods for obtaining insight into the structure/reactivity relations through the relative energies of the frontier orbitals. The optimized molecules were also analyzed by molecular docking method against DNA gyrase of Escherichia coli and CYP51 from Candida albicans.
{"title":"Benzimidazol-2-ylidene Silver Complexes: Synthesis, Characterization, Antimicrobial and Antibiofilm Activities, Molecular Docking and Theoretical Investigations","authors":"Uğur Tutar, Cem Çelik, Elvan Üstün, Namık Özdemir, Neslihan Şahin, David Sémeril, Nevin Gürbüz, İsmail Özdemir","doi":"10.3390/inorganics11100385","DOIUrl":"https://doi.org/10.3390/inorganics11100385","url":null,"abstract":"Five silver(I) complexes, namely chloro[1-methallyl-3-benzyl)benzimidazol-2-ylidene] silver (6), chloro[1-methallyl-3-(2,3,5,6-tetramethylbenzyl)benzimidazol-2-ylidene]silver (7), chloro[1-methallyl-3-(3,4,5-trimethoxylbenzyl)benzimidazol-2-ylidene]silver (8), chloro[1-methallyl- 3-(naphthylmethyl)benzimidazol-2-ylidene]silver (9), and chloro [1-methallyl-3-(anthracen-9-yl- methyl)benzimidazol-2-ylidene]silver (10), were prepared starting from their corresponding benzimidazolium salts and silver oxide in 71–81% yields. A single-crystal X-ray structure of 7 was determined. These five Ag-NHC complexes were evaluated for their antimicrobial and biofilm formation inhibition properties. Complex 10 exhibited high antimicrobial activities comparable to those obtained with standard drugs such as Fluconazole in contact with Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, Acinetobacter baumannii, and Candida albicans. The latter complex has been shown to be very efficient in antibiofilm activity, with 92.9% biofilm inhibition at 1.9 μg/mL on Escherichia coli. Additionally, the molecules were optimized with DFT-based computational methods for obtaining insight into the structure/reactivity relations through the relative energies of the frontier orbitals. The optimized molecules were also analyzed by molecular docking method against DNA gyrase of Escherichia coli and CYP51 from Candida albicans.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":"40 7 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135536769","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-09-25DOI: 10.3390/inorganics11100381
Greg Brewer, Cynthia Brewer, Raymond J. Butcher, Peter Zavalij
The Schiff base reaction of imidazole-2-carboxaldehydes with the anion of alanine, leucine and phenylalanine in the presence of nickel(II) ion gives the neutral NiL2 complexes. The Schiff base ligand, L, binds through an imidazole nitrogen, NIm, the amino acid nitrogen, NAA, and a carboxylate oxygen, O, atom. The two N2O ligands bind to the nickel(II) in a meridional fashion with the NIm and O of each ligand in trans positions. These ligands can exist as the anticipated aldimine, Im − CH = NAA − CH(R) − CO2−, or the ketimine, Im − CH2NAA = C(R) − CO2−, tautomer. Tautomerization of the initially formed aldimine Schiff base results in movement of the hydrogen atom of the alpha carbon of the amino acid to the aldehyde carbon, CAld, atom of the imidazole carboxaldehyde with resultant relocation of the imine double bond in the reverse direction. Ten structures of the structurally unprecedented ketimine tautomer, prepared from imidazole-2-carboxaldehydes and a pyrazole-3-carboxaldehyde, were presented. The structural data supported the formation of the ketimines in each case, while the aldimine tautomer was observed with imidazole-4-carboxaldehydes. A rationale of this can be explained on the basis of charge distribution in the likely intermediate in the tautomerization.
在镍离子存在下，咪唑-2-羧醛与丙氨酸、亮氨酸和苯丙氨酸阴离子发生席夫碱反应，得到中性的NiL2配合物。席夫碱配体L通过咪唑氮NIm、氨基酸氮NAA和羧酸氧O原子结合。两个N2O配体沿子午方向与镍(II)结合，每个配体的NIm和O位于反式位置。这些配体可以作为预期的醛胺(Im - CH = NAA - CH(R) - CO2 -)或氯胺(Im - CH2NAA = C(R) - CO2 -)互变异构体存在。最初形成的醛胺席夫碱的互变异构导致氨基酸α碳的氢原子移动到咪唑甲醛的醛碳(CAld)原子上，从而导致亚胺双键在相反方向上的重新定位。介绍了咪唑-2-羧基和吡唑-3-羧基合成的十种结构。在每种情况下，结构数据都支持酮胺的形成，而醛胺的互变异构体是与咪唑-4-羧醛一起观察到的。其基本原理可以根据互变异构化过程中可能中间体的电荷分布来解释。
{"title":"Formation of Ketimines from Aldimines in Schiff Base Condensation of Amino Acids and Imidazole-2-Carboxaldehydes: Tautomerization of Schiff Bases of Amino Acids Resulting in the Loss of Stereogenic Center","authors":"Greg Brewer, Cynthia Brewer, Raymond J. Butcher, Peter Zavalij","doi":"10.3390/inorganics11100381","DOIUrl":"https://doi.org/10.3390/inorganics11100381","url":null,"abstract":"The Schiff base reaction of imidazole-2-carboxaldehydes with the anion of alanine, leucine and phenylalanine in the presence of nickel(II) ion gives the neutral NiL2 complexes. The Schiff base ligand, L, binds through an imidazole nitrogen, NIm, the amino acid nitrogen, NAA, and a carboxylate oxygen, O, atom. The two N2O ligands bind to the nickel(II) in a meridional fashion with the NIm and O of each ligand in trans positions. These ligands can exist as the anticipated aldimine, Im − CH = NAA − CH(R) − CO2−, or the ketimine, Im − CH2NAA = C(R) − CO2−, tautomer. Tautomerization of the initially formed aldimine Schiff base results in movement of the hydrogen atom of the alpha carbon of the amino acid to the aldehyde carbon, CAld, atom of the imidazole carboxaldehyde with resultant relocation of the imine double bond in the reverse direction. Ten structures of the structurally unprecedented ketimine tautomer, prepared from imidazole-2-carboxaldehydes and a pyrazole-3-carboxaldehyde, were presented. The structural data supported the formation of the ketimines in each case, while the aldimine tautomer was observed with imidazole-4-carboxaldehydes. A rationale of this can be explained on the basis of charge distribution in the likely intermediate in the tautomerization.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":"24 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135815845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-09-25DOI: 10.3390/inorganics11100382
Mezna Saleh Altowyan, Matti Haukka, Mohammed Salah Ayoup, Magda M. F. Ismail, Nagwan G. El Menofy, Saied M. Soliman, Assem Barakat, Mona M. Sharaf, Morsy A. M. Abu-Youssef, Amal Yousri
The complex [Co(L)(H2O)4](NO3)2 of (E)-4-(2-(3-methyl-5-oxo-1-(pyridin-2-yl)-1H-pyrazol-4(5H)-ylidene)hydrazinyl)-N-(pyrimidin-2-yl)benzenesulfonamide (L) was synthesized via the self-assembly technique. Its molecular and supramolecular structures were analyzed using FTIR, elemental analyses, and single-crystal X-ray diffraction, as well as Hirshfeld calculations. This complex crystallized in the triclinic space group P1¯ with Z = 2. The crystallographic asymmetric unit comprised one complex cation and two nitrate counter anions. This complex had distorted octahedral geometry around the Co(II) ion. Numerous intermolecular interactions affecting the molecular packing of this complex were conformed using Hirshfeld investigations. The most significant contacts for the cationic inner sphere [Co(L)(H2O)4]2+ were O···H (38.8%), H···H (27.8%), and N···H (9.9%). On the other hand, the main interactions for the counter NO3¯ ions were the O···H (79.6 and 77.8%), O···N (8.0%), and O···C (9.1%). A high propensity for making interactions for each atom pair in the contacts O…H, N…C, N…H, and C…C was revealed by enrichment ratio values greater than 1. The antibacterial efficacy of the complex and the free ligand were assessed. The free ligand had higher antibacterial activity (MIC = 62.5–125 µg/mL) than the [Co(L)(H2O)4](NO3)2 complex (MIC ≥ 250 µg/mL) versus all the studied bacteria.
{"title":"Synthesis, Crystal Structure Analyses, and Antibacterial Evaluation of the Cobalt(II) Complex with Sulfadiazine-Pyrazole Prodrug","authors":"Mezna Saleh Altowyan, Matti Haukka, Mohammed Salah Ayoup, Magda M. F. Ismail, Nagwan G. El Menofy, Saied M. Soliman, Assem Barakat, Mona M. Sharaf, Morsy A. M. Abu-Youssef, Amal Yousri","doi":"10.3390/inorganics11100382","DOIUrl":"https://doi.org/10.3390/inorganics11100382","url":null,"abstract":"The complex [Co(L)(H2O)4](NO3)2 of (E)-4-(2-(3-methyl-5-oxo-1-(pyridin-2-yl)-1H-pyrazol-4(5H)-ylidene)hydrazinyl)-N-(pyrimidin-2-yl)benzenesulfonamide (L) was synthesized via the self-assembly technique. Its molecular and supramolecular structures were analyzed using FTIR, elemental analyses, and single-crystal X-ray diffraction, as well as Hirshfeld calculations. This complex crystallized in the triclinic space group P1¯ with Z = 2. The crystallographic asymmetric unit comprised one complex cation and two nitrate counter anions. This complex had distorted octahedral geometry around the Co(II) ion. Numerous intermolecular interactions affecting the molecular packing of this complex were conformed using Hirshfeld investigations. The most significant contacts for the cationic inner sphere [Co(L)(H2O)4]2+ were O···H (38.8%), H···H (27.8%), and N···H (9.9%). On the other hand, the main interactions for the counter NO3¯ ions were the O···H (79.6 and 77.8%), O···N (8.0%), and O···C (9.1%). A high propensity for making interactions for each atom pair in the contacts O…H, N…C, N…H, and C…C was revealed by enrichment ratio values greater than 1. The antibacterial efficacy of the complex and the free ligand were assessed. The free ligand had higher antibacterial activity (MIC = 62.5–125 µg/mL) than the [Co(L)(H2O)4](NO3)2 complex (MIC ≥ 250 µg/mL) versus all the studied bacteria.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":"81 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135864303","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-09-25DOI: 10.3390/inorganics11100379
Carlos A. Peñuelas, José J. Campos-Gaxiola, Rody Soto-Rojo, Adriana Cruz-Enríquez, Edgar A. Reynoso-Soto, Valentín Miranda-Soto, Juventino J. García, Marcos Flores-Álamo, Jesús Baldenebro-López, Daniel Glossman-Mitnik
A new copper(I) complex, [Cu2(L)2dppm](PF6)2 (1) [L = 3-(2-Pyridyl)-5,6-diphenyl-1,2,4-triazine and dppm: Bis(diphenylphosphino)methane], was prepared and characterized by IR, 1H-NMR, 31P-NMR spectroscopy, elemental and thermogravimetric analysis, and a single-crystal X-ray diffraction technique. Complex 1 is a dinuclear compound, showing that L and dppm act as tridentate and bidentate chelating ligands, respectively. The two Cu(I) atoms exhibit a distorted tetrahedral coordination sphere embedded in N3P environments. The supramolecular interactions in the solid-state structure are characterized by C−H···N, C−H···F, C-H···π and π···π intermolecular interactions, which we studied using Hirshfeld surface and fingerprint tools. Additionally, the complex was studied experimentally using UV–Vis spectroscopy and cyclic voltammetry, and theoretical studies with time-dependent density functional theory (TD-DFT) were performed. Moreover, the optical and electrochemical properties were studied, focusing on the band gap. Compound 1 was used as a co-sensitizer in a dye-sensitized solar cell, showing a good photovoltaic performance of 2.03% (Jsc = 5.095 mAcm−2, Voc = 757 mV, and FF = 52.7%) under 100 mW cm−2 (AM 1.5G) solar irradiation, which is similar to that of DSSC, which was only sensitized by N719 (2.2%) under the same condition.
{"title":"Synthesis of a New Dinuclear Cu(I) Complex with a Triazine Ligand and Diphenylphosphine Methane: X-ray Structure, Optical Properties, DFT Calculations, and Application in DSSCs","authors":"Carlos A. Peñuelas, José J. Campos-Gaxiola, Rody Soto-Rojo, Adriana Cruz-Enríquez, Edgar A. Reynoso-Soto, Valentín Miranda-Soto, Juventino J. García, Marcos Flores-Álamo, Jesús Baldenebro-López, Daniel Glossman-Mitnik","doi":"10.3390/inorganics11100379","DOIUrl":"https://doi.org/10.3390/inorganics11100379","url":null,"abstract":"A new copper(I) complex, [Cu2(L)2dppm](PF6)2 (1) [L = 3-(2-Pyridyl)-5,6-diphenyl-1,2,4-triazine and dppm: Bis(diphenylphosphino)methane], was prepared and characterized by IR, 1H-NMR, 31P-NMR spectroscopy, elemental and thermogravimetric analysis, and a single-crystal X-ray diffraction technique. Complex 1 is a dinuclear compound, showing that L and dppm act as tridentate and bidentate chelating ligands, respectively. The two Cu(I) atoms exhibit a distorted tetrahedral coordination sphere embedded in N3P environments. The supramolecular interactions in the solid-state structure are characterized by C−H···N, C−H···F, C-H···π and π···π intermolecular interactions, which we studied using Hirshfeld surface and fingerprint tools. Additionally, the complex was studied experimentally using UV–Vis spectroscopy and cyclic voltammetry, and theoretical studies with time-dependent density functional theory (TD-DFT) were performed. Moreover, the optical and electrochemical properties were studied, focusing on the band gap. Compound 1 was used as a co-sensitizer in a dye-sensitized solar cell, showing a good photovoltaic performance of 2.03% (Jsc = 5.095 mAcm−2, Voc = 757 mV, and FF = 52.7%) under 100 mW cm−2 (AM 1.5G) solar irradiation, which is similar to that of DSSC, which was only sensitized by N719 (2.2%) under the same condition.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":"37 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135815562","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-09-25DOI: 10.3390/inorganics11100380
Suyang Yao, Yanxi Pu, Lulu Ren, Manli Cao, Baohui Ye
Octahedral chiral-at-metal Ir(III) complexes exhibit excellent structural stability and stereoselectivity in asymmetric synthesis. Selectively oxidative dehydrogenation of amino acids could be achieved by exploiting such complexes as chiral templates. The obtaining stable imine complexes can then be utilized in nucleophilic additions to generate corresponding chiral amine compounds. In this study, a conveniently synthesized [Λ-Ir(ppy)2(MeCN)2](PF6) chiral complex (ppy is 2-phenylpyridine) was utilized as a chiral template. A series of chiral amino acid complexes Λ-[Ir(ppy)2(D/L-AA)] (AA is amino acid) were prepared in high yield and optical purity. The above amino acid complexes were then oxidized to their corresponding imino acid complexes Λ-[Ir(ppy)2(AA-2H)] under visible light. All these complexes exhibited high selectivity during the dehydrogenation process without the formation of C-N bond coupling byproducts. The photooxidative dehydrogenation rates of these complexes were studied, which show that D-configured amino acids exhibited faster dehydrogenation rates when using the Λ-configured complex as a chiral template and the substitution of electron-donating or bulky groups in the N-α position of the amino acid decreased their dehydrogenation rates. The crystal structures of Λ-Ir(ppy)2(D-Thr) (Thr is threonine) and its dehydrogenated complex Λ-Ir(ppy)2(Thr-2H) indicate the process of photooxidative dehydrogenation and the configuration stability of metal center throughout the process.
{"title":"Photooxidative Dehydrogenation of Chiral Ir (III) Amino Acid Complexes Based on [Λ-Ir(ppy)2(MeCN)2](PF6)","authors":"Suyang Yao, Yanxi Pu, Lulu Ren, Manli Cao, Baohui Ye","doi":"10.3390/inorganics11100380","DOIUrl":"https://doi.org/10.3390/inorganics11100380","url":null,"abstract":"Octahedral chiral-at-metal Ir(III) complexes exhibit excellent structural stability and stereoselectivity in asymmetric synthesis. Selectively oxidative dehydrogenation of amino acids could be achieved by exploiting such complexes as chiral templates. The obtaining stable imine complexes can then be utilized in nucleophilic additions to generate corresponding chiral amine compounds. In this study, a conveniently synthesized [Λ-Ir(ppy)2(MeCN)2](PF6) chiral complex (ppy is 2-phenylpyridine) was utilized as a chiral template. A series of chiral amino acid complexes Λ-[Ir(ppy)2(D/L-AA)] (AA is amino acid) were prepared in high yield and optical purity. The above amino acid complexes were then oxidized to their corresponding imino acid complexes Λ-[Ir(ppy)2(AA-2H)] under visible light. All these complexes exhibited high selectivity during the dehydrogenation process without the formation of C-N bond coupling byproducts. The photooxidative dehydrogenation rates of these complexes were studied, which show that D-configured amino acids exhibited faster dehydrogenation rates when using the Λ-configured complex as a chiral template and the substitution of electron-donating or bulky groups in the N-α position of the amino acid decreased their dehydrogenation rates. The crystal structures of Λ-Ir(ppy)2(D-Thr) (Thr is threonine) and its dehydrogenated complex Λ-Ir(ppy)2(Thr-2H) indicate the process of photooxidative dehydrogenation and the configuration stability of metal center throughout the process.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":"6 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135815718","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-09-25DOI: 10.3390/inorganics11100383
Chunghyeon Choi, Tae Gwang Yun, Byungil Hwang
Carbon nanotubes (CNTs), with their extraordinary combination of mechanical, electrical, and thermal properties, have emerged as a revolutionary class of nanomaterials with immense potential in energy storage and harvesting devices. Realizing this potential hinges on a fundamental challenge: the dispersion stability of CNTs within various matrices. This review paper provides a comprehensive exploration of the critical interplay between CNT dispersion stability and its far-reaching implications for the performance of energy storage and harvesting technologies. By delving into the underlying mechanisms of dispersion, the strategies to achieve stability, and the direct effects on device functionality, this review sheds light on the intricate relationship between nanotube dispersion and the advancement of energy-related applications.
{"title":"Dispersion Stability of Carbon Nanotubes and Their Impact on Energy Storage Devices","authors":"Chunghyeon Choi, Tae Gwang Yun, Byungil Hwang","doi":"10.3390/inorganics11100383","DOIUrl":"https://doi.org/10.3390/inorganics11100383","url":null,"abstract":"Carbon nanotubes (CNTs), with their extraordinary combination of mechanical, electrical, and thermal properties, have emerged as a revolutionary class of nanomaterials with immense potential in energy storage and harvesting devices. Realizing this potential hinges on a fundamental challenge: the dispersion stability of CNTs within various matrices. This review paper provides a comprehensive exploration of the critical interplay between CNT dispersion stability and its far-reaching implications for the performance of energy storage and harvesting technologies. By delving into the underlying mechanisms of dispersion, the strategies to achieve stability, and the direct effects on device functionality, this review sheds light on the intricate relationship between nanotube dispersion and the advancement of energy-related applications.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":"67 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135864164","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-09-25DOI: 10.3390/inorganics11100384
Natalia S. Panina, Ilya N. Klyukin, Tatyana M. Buslaeva, Andrei I. Fischer
A detailed study on the stages of catalytic reactions involving platinum and platinum-vanadium clusters has been carried out. Minimum energy pathways (MEP) of reactions have been constructed via the DFT/PBE0/def2tzvp method using NEB functional and optimized structures, and points of minima and transition states have been calculated. A two-step process for the conversion of formamide to methylamine under the action of H2 has been considered as a test reaction. The energy barriers of this reaction, not previously described in the literature, have been evaluated. It has been shown that the main changes in the structural characteristics of the reagents, as well as the migration of single H atoms from one metal center of clusters to another or to an organic substrate, are initiated at the molecular level by shifts corresponding to the vectors of normal vibrations of systems in transition states.
{"title":"Revealing the Minimum Energy Pathways for Formamide Hydrogenation Reactions in the Presence of Platinum and Platinum–Vanadium Clusters: A Quantum Chemical DFT/Nudged Elastic Band Study","authors":"Natalia S. Panina, Ilya N. Klyukin, Tatyana M. Buslaeva, Andrei I. Fischer","doi":"10.3390/inorganics11100384","DOIUrl":"https://doi.org/10.3390/inorganics11100384","url":null,"abstract":"A detailed study on the stages of catalytic reactions involving platinum and platinum-vanadium clusters has been carried out. Minimum energy pathways (MEP) of reactions have been constructed via the DFT/PBE0/def2tzvp method using NEB functional and optimized structures, and points of minima and transition states have been calculated. A two-step process for the conversion of formamide to methylamine under the action of H2 has been considered as a test reaction. The energy barriers of this reaction, not previously described in the literature, have been evaluated. It has been shown that the main changes in the structural characteristics of the reagents, as well as the migration of single H atoms from one metal center of clusters to another or to an organic substrate, are initiated at the molecular level by shifts corresponding to the vectors of normal vibrations of systems in transition states.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":"59 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135864117","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study focuses on the computational characterization of electrochemical C-C bond formation through the CO and CHO coupling process utilizing a dioxo-coordinated Cu single atom site ([CuO2]*) supported on a Pd(111) surface. The stable intermediate, [CuO2]*(CO)2, was identified as a tetradentate-and-tetrahedral species formed upon exposure to CO gaseous molecules. Electrochemically, the hydrogenation of the carbonyl group to CHO was found to be 0.87 eV, conceivably lower than the corresponding step for conventional Cu surfaces. This study observed a considerable charge transfer effect from the top layer of Pd atoms to the adsorbate moiety, especially at the TS structure. This phenomenon resulted in an accessible C-C bond formation barrier at 0.67 eV. Furthermore, the reaction energy of C-C bond formation was found to be exothermic at −0.21 eV, indicating a favorable chemical equilibrium condition. Considering the temperature effect and pressure of the gaseous molecules (CO, CO2, O2), the [CuO2]*(CO)2 intermediate was substantially populated at room temperature and was found to be chemically resilient under dry ambient conditions, as suggested by the kinetic modeling results.
{"title":"A Computational Perspective on Carbon-Carbon Bond Formation by Single Cu Atom on Pd(111) Surface for CO Electrochemical Reduction","authors":"Chen-Cheng Liao, Tsung-Han Tsai, Chun-Chih Chang, Ming-Kang Tsai","doi":"10.3390/inorganics11100378","DOIUrl":"https://doi.org/10.3390/inorganics11100378","url":null,"abstract":"This study focuses on the computational characterization of electrochemical C-C bond formation through the CO and CHO coupling process utilizing a dioxo-coordinated Cu single atom site ([CuO2]*) supported on a Pd(111) surface. The stable intermediate, [CuO2]*(CO)2, was identified as a tetradentate-and-tetrahedral species formed upon exposure to CO gaseous molecules. Electrochemically, the hydrogenation of the carbonyl group to CHO was found to be 0.87 eV, conceivably lower than the corresponding step for conventional Cu surfaces. This study observed a considerable charge transfer effect from the top layer of Pd atoms to the adsorbate moiety, especially at the TS structure. This phenomenon resulted in an accessible C-C bond formation barrier at 0.67 eV. Furthermore, the reaction energy of C-C bond formation was found to be exothermic at −0.21 eV, indicating a favorable chemical equilibrium condition. Considering the temperature effect and pressure of the gaseous molecules (CO, CO2, O2), the [CuO2]*(CO)2 intermediate was substantially populated at room temperature and was found to be chemically resilient under dry ambient conditions, as suggested by the kinetic modeling results.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":"7 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135924861","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-09-23DOI: 10.3390/inorganics11100376
Helena Brunckova, Erika Mudra, Ivan Shepa
Lanthanide Metal–Organic Frameworks (LnMOFs), in recent years, have developed into an interesting subclass of MOFs. While the number of published papers, in particular, were dedicated to their synthesis and functional properties, along with the application mechanisms of MOFs, only a few of them have been focused on LnMOFs thin films independently. LnMOFs have become interesting thanks to their outstanding properties, for example, excellent structural flexibility, tunable pore size, surface area, functionality, and good chemical stability. Significant progress over the past two decades in the preparation of MOF films has been achieved, especially towards the development of green, or at least greener, synthesis approaches. We begin with insight into various types of MOFs and summarize recent achievements in the production of LnMOF films, along with various film preparation approaches. Afterward, we briefly discuss the applications of luminescence features of lanthanide ions in films and their potential as white-light source materials. We also covered films based on Eu, Tb, and Gd with particular accents on different design approaches. Moreover, specifically, luminescent features applied for sensing temperature, a variety of ions, gases, and biomolecules are highlighted. The review ends with a comprehensive conclusion about the state-of-art-potential of LnMOFs together with an outlook on the future of LnMOF films in future technologies.
{"title":"Recent Advances in Lanthanide Metal–Organic Framework Thin Films Based on Eu, Tb, Gd: Preparation and Application as Luminescent Sensors and Light-Emitting Devices","authors":"Helena Brunckova, Erika Mudra, Ivan Shepa","doi":"10.3390/inorganics11100376","DOIUrl":"https://doi.org/10.3390/inorganics11100376","url":null,"abstract":"Lanthanide Metal–Organic Frameworks (LnMOFs), in recent years, have developed into an interesting subclass of MOFs. While the number of published papers, in particular, were dedicated to their synthesis and functional properties, along with the application mechanisms of MOFs, only a few of them have been focused on LnMOFs thin films independently. LnMOFs have become interesting thanks to their outstanding properties, for example, excellent structural flexibility, tunable pore size, surface area, functionality, and good chemical stability. Significant progress over the past two decades in the preparation of MOF films has been achieved, especially towards the development of green, or at least greener, synthesis approaches. We begin with insight into various types of MOFs and summarize recent achievements in the production of LnMOF films, along with various film preparation approaches. Afterward, we briefly discuss the applications of luminescence features of lanthanide ions in films and their potential as white-light source materials. We also covered films based on Eu, Tb, and Gd with particular accents on different design approaches. Moreover, specifically, luminescent features applied for sensing temperature, a variety of ions, gases, and biomolecules are highlighted. The review ends with a comprehensive conclusion about the state-of-art-potential of LnMOFs together with an outlook on the future of LnMOF films in future technologies.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":"2014 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135967113","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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