Pub Date : 2022-05-30DOI: 10.1080/02603594.2022.2075859
S. Majidi, Zahra Aramesh-Boroujeni, Majid Moghadam, S. Jahani
ABSTRACT In this paper, the biological applications of synthetic dysprosium(III) complex, with 4,5-diazafluoren-9-one (dafone) ligand, including DNA/BSA interaction, antibacterial and anticancer activity were studied in vitro. The bovine serum albumin (BSA) and fish DNA (FS-DNA) binding of the dysprosium complex were studied by multi-spectrophotometric as well as computational calculation. Its DNA and BSA binding ability were estimated by fluorescence, absorption, circular dichroism spectroscopy, and viscosity measurements (only for DNA). The Dy-complex binds to DNA and BSA presenting high binding constants. For both DNA/BSA binding, the negative signs of thermodynamic parameter confirmed that hydrogen bonds and van der Waals forces play a main role in the interaction process. The competitive experiments with ethidium bromide (EtBr) and rhodamine B exhibited that the Dy-complex interacts with DNA via groove binding. The BSA competitive experiments showed that Dy-complex interacts with site 3 of BSA, which was completely arranged by docking studies. This complex showed high antimicrobial and cytotoxicity. Besides, nanocarriers of Dy-complex were produced, and the anticancer activities of these compounds were measured. (This paper provides a manifestation of a new tradition by which Comments on Inorganic Chemistry starts publishing original research content that, nonetheless, preserves the Journal’s identity as a niche for a critical discussion of contemporary literature in inorganic chemistry) (For previous manifestations, see Comments Inorg. Chem. 2018, 38, 1–35; 2019, 39, 1–26; 2019, 39, 188–215; 2020, 40, 1–24; 2020, 40, 277–303; 2021, 1–46, doi: 10.1080/02603594.2021.1962310.)
{"title":"Can One Novel Lanthanide Complex and Its Nano-Encapsulated Compounds Afford Advances in Biological Inorganic Chemistry? A Biological Applications Study for Dysprosium (III) Complex and Its Nano-Encapsulated Compounds","authors":"S. Majidi, Zahra Aramesh-Boroujeni, Majid Moghadam, S. Jahani","doi":"10.1080/02603594.2022.2075859","DOIUrl":"https://doi.org/10.1080/02603594.2022.2075859","url":null,"abstract":"ABSTRACT In this paper, the biological applications of synthetic dysprosium(III) complex, with 4,5-diazafluoren-9-one (dafone) ligand, including DNA/BSA interaction, antibacterial and anticancer activity were studied in vitro. The bovine serum albumin (BSA) and fish DNA (FS-DNA) binding of the dysprosium complex were studied by multi-spectrophotometric as well as computational calculation. Its DNA and BSA binding ability were estimated by fluorescence, absorption, circular dichroism spectroscopy, and viscosity measurements (only for DNA). The Dy-complex binds to DNA and BSA presenting high binding constants. For both DNA/BSA binding, the negative signs of thermodynamic parameter confirmed that hydrogen bonds and van der Waals forces play a main role in the interaction process. The competitive experiments with ethidium bromide (EtBr) and rhodamine B exhibited that the Dy-complex interacts with DNA via groove binding. The BSA competitive experiments showed that Dy-complex interacts with site 3 of BSA, which was completely arranged by docking studies. This complex showed high antimicrobial and cytotoxicity. Besides, nanocarriers of Dy-complex were produced, and the anticancer activities of these compounds were measured. (This paper provides a manifestation of a new tradition by which Comments on Inorganic Chemistry starts publishing original research content that, nonetheless, preserves the Journal’s identity as a niche for a critical discussion of contemporary literature in inorganic chemistry) (For previous manifestations, see Comments Inorg. Chem. 2018, 38, 1–35; 2019, 39, 1–26; 2019, 39, 188–215; 2020, 40, 1–24; 2020, 40, 277–303; 2021, 1–46, doi: 10.1080/02603594.2021.1962310.)","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"50 1","pages":"337 - 367"},"PeriodicalIF":5.4,"publicationDate":"2022-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83687043","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-05-30DOI: 10.1080/02603594.2022.2083609
O. Mikhailov
ABSTRACT In this Comment, the content of the book by B.I. Kharisov, O.V. Kharissova, Carbon Allotropes: Metal-Complex Chemistry, Properties and Applications, published in 2019 by Springer Nature Publishing, has been characterized in detail. A great amount of information presented in this book is devoted to numerous varieties (allotropic modifications) of elemental carbon, each of which currently has not only purely academic, but also significant practical interest. This book is important for researchers working in the field of inorganic chemistry of carbon, as well as researchers in the field of chemistry of coordination compounds, which has traditionally been classified as inorganic chemistry since its inception.
{"title":"Encyclopedia of the Elemental Carbon (with a Commentary Tailored for Inorganic Chemists)","authors":"O. Mikhailov","doi":"10.1080/02603594.2022.2083609","DOIUrl":"https://doi.org/10.1080/02603594.2022.2083609","url":null,"abstract":"ABSTRACT In this Comment, the content of the book by B.I. Kharisov, O.V. Kharissova, Carbon Allotropes: Metal-Complex Chemistry, Properties and Applications, published in 2019 by Springer Nature Publishing, has been characterized in detail. A great amount of information presented in this book is devoted to numerous varieties (allotropic modifications) of elemental carbon, each of which currently has not only purely academic, but also significant practical interest. This book is important for researchers working in the field of inorganic chemistry of carbon, as well as researchers in the field of chemistry of coordination compounds, which has traditionally been classified as inorganic chemistry since its inception.","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"41 1","pages":"402 - 408"},"PeriodicalIF":5.4,"publicationDate":"2022-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83433548","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-01-14DOI: 10.1080/02603594.2021.2013827
Tarun F. Parangi
ABSTRACT Hydrogen (H2) is examined as a fuel and as one of the most extensively studied substitute energy resources for available sources that are being consumed rapidly. Thus, the growing interest in the development of competitive, low-cost hydrogen production leads us to devote particular efforts to establish efficient processes in an economical and environmentally benign way. In this view, both photochemical and electrochemical processes have been exclusively investigated as greener paths for hydrogen production. The present review article highlights the process established for hydrogen generation over the last few years. The overall thrust of the present theme is a discussion of the efforts that have been made so far for finding hydrogen as an alternative fuel from different feedstock through photochemical and electrochemical processes.
{"title":"A Review on Electrochemical and Photochemical Processes for Hydrogen Production","authors":"Tarun F. Parangi","doi":"10.1080/02603594.2021.2013827","DOIUrl":"https://doi.org/10.1080/02603594.2021.2013827","url":null,"abstract":"ABSTRACT Hydrogen (H2) is examined as a fuel and as one of the most extensively studied substitute energy resources for available sources that are being consumed rapidly. Thus, the growing interest in the development of competitive, low-cost hydrogen production leads us to devote particular efforts to establish efficient processes in an economical and environmentally benign way. In this view, both photochemical and electrochemical processes have been exclusively investigated as greener paths for hydrogen production. The present review article highlights the process established for hydrogen generation over the last few years. The overall thrust of the present theme is a discussion of the efforts that have been made so far for finding hydrogen as an alternative fuel from different feedstock through photochemical and electrochemical processes.","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"28 1","pages":"271 - 336"},"PeriodicalIF":5.4,"publicationDate":"2022-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91027987","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-12-24DOI: 10.1080/02603594.2021.1971203
A. Balch, G. Everett, P. Power, W. Armstrong, J. Kovacs, T. Stack, J. P. Donahue, Thomas G. Gray, Stanislav Groysman, L. Deng
Department of Chemistry, University of California, Davis, California, USA; Department of Chemistry, University of Kansas, Lawrence, Kansas, USA; Department of Chemistry, Boston College, Chestnut Hill, Massachusetts, USA; Department of Chemistry, University of Washington, Seattle, Washington, USA; Department of Chemistry, Stanford University, Stanford, California, USA; Department of Chemistry, Tulane University, New Orleans, Louisiana, USA; Department of Chemistry, Case Western Reserve University, Cleveland, Ohio, USA; Department of Chemistry, Wayne State University, Detroit, Michigan, USA; State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China
{"title":"Richard Hadley Holm: A Remembrance and A Tribute","authors":"A. Balch, G. Everett, P. Power, W. Armstrong, J. Kovacs, T. Stack, J. P. Donahue, Thomas G. Gray, Stanislav Groysman, L. Deng","doi":"10.1080/02603594.2021.1971203","DOIUrl":"https://doi.org/10.1080/02603594.2021.1971203","url":null,"abstract":"Department of Chemistry, University of California, Davis, California, USA; Department of Chemistry, University of Kansas, Lawrence, Kansas, USA; Department of Chemistry, Boston College, Chestnut Hill, Massachusetts, USA; Department of Chemistry, University of Washington, Seattle, Washington, USA; Department of Chemistry, Stanford University, Stanford, California, USA; Department of Chemistry, Tulane University, New Orleans, Louisiana, USA; Department of Chemistry, Case Western Reserve University, Cleveland, Ohio, USA; Department of Chemistry, Wayne State University, Detroit, Michigan, USA; State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"2 1","pages":"61 - 108"},"PeriodicalIF":5.4,"publicationDate":"2021-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79164575","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-11-18DOI: 10.1080/02603594.2021.1992399
Shan Li, Kurt Bodenstedt, M. Kharma, Claire M. Burson, Dieaa Alhmoud, Catherine A. Moulder, Seyedmajid Farvid, Mukunda M. Ghimire, A. Rawashdeh, M. El Bouanani, M. Omary
ABSTRACT This paper provides the sixth manifestation of a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that, nonetheless, preserves the Journal’s identity as a niche for critical discussion of contemporary literature in inorganic chemistry. (For the previous manifestations, see: Comments Inorg. Chem. 2018, 38, 1–35; 2019, 39, 1–26; 2019, 39, 188–215; 2020, 40, 1–24; 2020, 40, 277–303.) Coordination compounds are responsible for multiple quantum leaps in the performance of organic light-emitting diodes (OLEDs). The first breakthrough was via the green-fluorescent main-group complex tris-(8-hydroxyquinoline)aluminum (Alq3) which acts as both light-emitting and electron-transporting material in combination with triarylamine as a hole-transporter. To optimize the performance of such standard bilayer devices, herein we provide a double-doped structure into the emissive region consisting of 20 nm N,N’-diphenyl-N,N’-bis(1,1ʹ-biphenyl)-4,4ʹ-diamine (NPB) and 10 nm Alq3 utilized as buffer layers for facilitating charge injection from the electrodes, and a broad emissive region stacked by two doped layers with a 5% Alq3 doped in a 50-nm thick NPB layer – as well as a 5% NPB doped in a 40-nm-thick Alq3 layer from the anode side to the cathode side. The double-doped device achieves a decreased turn-on voltage of 2.44 V and maximum brightness of 17,300 cd/m2 as well as enhanced electroluminescence efficiency and moderately reduced efficiency roll-off over single-doped and standard bilayer devices. We have also found ~50% improvement of the photoluminescence quantum yield, with some subtle color shift upon doping 10% of NPB or Alq3 into the other vs. neat Alq3 (~0.3 vs. ~0.2 ) which nonetheless led only to ~20% improvement in EQE (~1.0% vs. ~0.8%), suggesting additional device optimization is warranted. Furthermore, two typical fluorescent OLEDs architectures – a graded or uniformly mixed device – have been exploited, which together with the double-doped approach would be feasible to boost EL efficiencies in both fluorescent and phosphorescent OLEDs with neat bilayer structures. The approach is not suitable for the more common doped phosphorescent devices, the optimization of which has been reviewed earlier by Nazeeruddin and coworkers in this Journal (Comments Inorg. Chem. 2017, 37, 117–145); in combination with this article, we hope that the reader will have an educational experience on OLED design and optimization from an inorganic chemistry perspective vis-à-vis a materials science perspective that dominates the OLED literature. GRAPHICAL ABSTRACT
{"title":"Can A Double-Doped Device Modification of A Standard Bilayer OLED Improve the Photo- And/or Electro-luminescence Efficiency? A Case Study of Architecture Design in Fluorescent Devices with A Potential Roadmap for High-Efficiency Phosphorescent Devices","authors":"Shan Li, Kurt Bodenstedt, M. Kharma, Claire M. Burson, Dieaa Alhmoud, Catherine A. Moulder, Seyedmajid Farvid, Mukunda M. Ghimire, A. Rawashdeh, M. El Bouanani, M. Omary","doi":"10.1080/02603594.2021.1992399","DOIUrl":"https://doi.org/10.1080/02603594.2021.1992399","url":null,"abstract":"ABSTRACT This paper provides the sixth manifestation of a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that, nonetheless, preserves the Journal’s identity as a niche for critical discussion of contemporary literature in inorganic chemistry. (For the previous manifestations, see: Comments Inorg. Chem. 2018, 38, 1–35; 2019, 39, 1–26; 2019, 39, 188–215; 2020, 40, 1–24; 2020, 40, 277–303.) Coordination compounds are responsible for multiple quantum leaps in the performance of organic light-emitting diodes (OLEDs). The first breakthrough was via the green-fluorescent main-group complex tris-(8-hydroxyquinoline)aluminum (Alq3) which acts as both light-emitting and electron-transporting material in combination with triarylamine as a hole-transporter. To optimize the performance of such standard bilayer devices, herein we provide a double-doped structure into the emissive region consisting of 20 nm N,N’-diphenyl-N,N’-bis(1,1ʹ-biphenyl)-4,4ʹ-diamine (NPB) and 10 nm Alq3 utilized as buffer layers for facilitating charge injection from the electrodes, and a broad emissive region stacked by two doped layers with a 5% Alq3 doped in a 50-nm thick NPB layer – as well as a 5% NPB doped in a 40-nm-thick Alq3 layer from the anode side to the cathode side. The double-doped device achieves a decreased turn-on voltage of 2.44 V and maximum brightness of 17,300 cd/m2 as well as enhanced electroluminescence efficiency and moderately reduced efficiency roll-off over single-doped and standard bilayer devices. We have also found ~50% improvement of the photoluminescence quantum yield, with some subtle color shift upon doping 10% of NPB or Alq3 into the other vs. neat Alq3 (~0.3 vs. ~0.2 ) which nonetheless led only to ~20% improvement in EQE (~1.0% vs. ~0.8%), suggesting additional device optimization is warranted. Furthermore, two typical fluorescent OLEDs architectures – a graded or uniformly mixed device – have been exploited, which together with the double-doped approach would be feasible to boost EL efficiencies in both fluorescent and phosphorescent OLEDs with neat bilayer structures. The approach is not suitable for the more common doped phosphorescent devices, the optimization of which has been reviewed earlier by Nazeeruddin and coworkers in this Journal (Comments Inorg. Chem. 2017, 37, 117–145); in combination with this article, we hope that the reader will have an educational experience on OLED design and optimization from an inorganic chemistry perspective vis-à-vis a materials science perspective that dominates the OLED literature. GRAPHICAL ABSTRACT","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"25 1","pages":"145 - 173"},"PeriodicalIF":5.4,"publicationDate":"2021-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73705428","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-11-09DOI: 10.1080/02603594.2021.1999234
K. Garg, D. Jain, Deepak Rajprohit, H. S. Kushwaha, H. Daima, B. J. Stephen, Abhijeet Singh, S. Mohanty
All India Network Project on Soil Biodiversity-Biofertilizers, Department of Molecular Biology and Biotechnology, Maharana Pratap University of Agriculture and Technology, Udaipur, India; Material Research Centre, Malviya National Institute of Technology, Jaipur, India; Amity Center for Nanobiotechnology and Nanomedicine (Acnn), Amity Institute of Biotechnology, Amity University Rajasthan, Jaipur, India; Department of Biosciences, Manipal University Jaipur, India; All India Network Project on Soil Biodiversity-Biofertilizers, ICAR-Indian Institute of Soil Science, Bhopal, India
{"title":"Agricultural Significance of Silica Nanoparticles Synthesized from a Silica Solubilizing Bacteria","authors":"K. Garg, D. Jain, Deepak Rajprohit, H. S. Kushwaha, H. Daima, B. J. Stephen, Abhijeet Singh, S. Mohanty","doi":"10.1080/02603594.2021.1999234","DOIUrl":"https://doi.org/10.1080/02603594.2021.1999234","url":null,"abstract":"All India Network Project on Soil Biodiversity-Biofertilizers, Department of Molecular Biology and Biotechnology, Maharana Pratap University of Agriculture and Technology, Udaipur, India; Material Research Centre, Malviya National Institute of Technology, Jaipur, India; Amity Center for Nanobiotechnology and Nanomedicine (Acnn), Amity Institute of Biotechnology, Amity University Rajasthan, Jaipur, India; Department of Biosciences, Manipal University Jaipur, India; All India Network Project on Soil Biodiversity-Biofertilizers, ICAR-Indian Institute of Soil Science, Bhopal, India","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"7 1","pages":"209 - 225"},"PeriodicalIF":5.4,"publicationDate":"2021-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77073770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-10-25DOI: 10.1080/02603594.2021.1990890
Ghazaleh Jamalipour Soufi, Parisa Iravani, A. Hekmatnia, E. Mostafavi, M. Khatami, S. Iravani
ABSTRACT MXenes and MXene-based materials exhibited unique properties such as remarkable conductivity, hydrophilicity, high ion transport features, low diffusion barrier, biocompatibility, and suitable surface area, which make them promising candidates for sensing and imaging applications in the field of biomedicine (especially cancer diagnosis/imaging), analytical chemistry, and (bio)sensing. These two-dimensional (2D) materials with suitable surface functionalization or modification can be considered as the next-generation structures for cancer diagnosis with high biocompatibility, stability, and adoption capacity. In the field of cancer diagnosis and imaging, MXenes with great potentials and unique physicochemical structures should be further evaluated by researchers, especially for their biosafety, biocompatibility, stability, and biodegradability. Future studies should move toward specific clinical evaluations as well as industrial and up-scalable production of innovative functionalized MXenes and MXene-based materials with efficient cancer diagnostic potentials. In this review, recent advances related to the cancer diagnostic applications of MXenes and MXene-based materials are highlighted, focusing on current challenges and future perspectives. GRAPHICAL ABSTRACT
{"title":"MXenes and MXene-based Materials with Cancer Diagnostic Applications: Challenges and Opportunities","authors":"Ghazaleh Jamalipour Soufi, Parisa Iravani, A. Hekmatnia, E. Mostafavi, M. Khatami, S. Iravani","doi":"10.1080/02603594.2021.1990890","DOIUrl":"https://doi.org/10.1080/02603594.2021.1990890","url":null,"abstract":"ABSTRACT MXenes and MXene-based materials exhibited unique properties such as remarkable conductivity, hydrophilicity, high ion transport features, low diffusion barrier, biocompatibility, and suitable surface area, which make them promising candidates for sensing and imaging applications in the field of biomedicine (especially cancer diagnosis/imaging), analytical chemistry, and (bio)sensing. These two-dimensional (2D) materials with suitable surface functionalization or modification can be considered as the next-generation structures for cancer diagnosis with high biocompatibility, stability, and adoption capacity. In the field of cancer diagnosis and imaging, MXenes with great potentials and unique physicochemical structures should be further evaluated by researchers, especially for their biosafety, biocompatibility, stability, and biodegradability. Future studies should move toward specific clinical evaluations as well as industrial and up-scalable production of innovative functionalized MXenes and MXene-based materials with efficient cancer diagnostic potentials. In this review, recent advances related to the cancer diagnostic applications of MXenes and MXene-based materials are highlighted, focusing on current challenges and future perspectives. GRAPHICAL ABSTRACT","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"25 1","pages":"174 - 207"},"PeriodicalIF":5.4,"publicationDate":"2021-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87332274","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-10-12DOI: 10.1080/02603594.2021.1976759
V. Ivanova, I. D. Shurygin, V. V. Chevela, O. Ajsuvakova, V. Semenov, S. G. Bezryadin
ABSTRACT The complexation of gadolinium(III) with citric acid in aqueous solutions was studied by pH-metric titration, proton magnetic relaxation, and mathematic simulation in the pH range 2.0–10 at [Gd3+]: [H4Cit] = 1:1, 1:2, 1:3 ([Gd3+] = 1.3, 2.6, 5.0, 10.0, and 20.0 mmol L−1). In the process of simulation, the equilibrium composition, a model obtained from previously known works and including mono- and bis-citrate complexes of gadolinium(III) was taken as a basis. In this work, it is shown that a satisfactory description of the experimental data set of two independent physico-chemical methods is achieved only with the additional inclusion of citrate complexes of gadolinium(III) with higher degree of protonation and some new polynuclear complexes. The complex [GdH4Cit]3+ with the molecular form of the citrate ligand, and the polynuclear complexes [Gd2(HCit)2]°, [Gd2Cit2]2-, [Gd6(OH)2Cit6]8-, [Gd6(OH)3Cit6]9- were first detected at the molar ratio of 1:1. At two- and three-fold excess of citric acid, mononuclear bis- and tris-citrate complexes with different degrees of protonation were found, and binuclear tetrakis- and hexakis-citrate complexes [Gd2(HCit)Cit3]9-and [Gd2(HCit)4Cit2]14- at the pH > 7.5. On the example of this manuscript, the importance of applying the NMR relaxation method for identifying polynuclear complexation in systems containing paramagnetic ions is shown. GRAPHICAL ABSTRACT
{"title":"New Aspects of Complex Formation in the Gadolinium(III)–Citric Acid System in Aqueous Solution","authors":"V. Ivanova, I. D. Shurygin, V. V. Chevela, O. Ajsuvakova, V. Semenov, S. G. Bezryadin","doi":"10.1080/02603594.2021.1976759","DOIUrl":"https://doi.org/10.1080/02603594.2021.1976759","url":null,"abstract":"ABSTRACT The complexation of gadolinium(III) with citric acid in aqueous solutions was studied by pH-metric titration, proton magnetic relaxation, and mathematic simulation in the pH range 2.0–10 at [Gd3+]: [H4Cit] = 1:1, 1:2, 1:3 ([Gd3+] = 1.3, 2.6, 5.0, 10.0, and 20.0 mmol L−1). In the process of simulation, the equilibrium composition, a model obtained from previously known works and including mono- and bis-citrate complexes of gadolinium(III) was taken as a basis. In this work, it is shown that a satisfactory description of the experimental data set of two independent physico-chemical methods is achieved only with the additional inclusion of citrate complexes of gadolinium(III) with higher degree of protonation and some new polynuclear complexes. The complex [GdH4Cit]3+ with the molecular form of the citrate ligand, and the polynuclear complexes [Gd2(HCit)2]°, [Gd2Cit2]2-, [Gd6(OH)2Cit6]8-, [Gd6(OH)3Cit6]9- were first detected at the molar ratio of 1:1. At two- and three-fold excess of citric acid, mononuclear bis- and tris-citrate complexes with different degrees of protonation were found, and binuclear tetrakis- and hexakis-citrate complexes [Gd2(HCit)Cit3]9-and [Gd2(HCit)4Cit2]14- at the pH > 7.5. On the example of this manuscript, the importance of applying the NMR relaxation method for identifying polynuclear complexation in systems containing paramagnetic ions is shown. GRAPHICAL ABSTRACT","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"40 1","pages":"109 - 144"},"PeriodicalIF":5.4,"publicationDate":"2021-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84140539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-10-06DOI: 10.1080/02603594.2021.1973444
Thomas E. Robinson, Lucy A. Arkinstall, S. Cox, L. Grover
Hexametaphosphate (HMP) is an inorganic condensed phosphate, which has been used in a wide variety of industries for nearly a century, originally patented to deflocculate clay and soften hard water. Today, HMP is still used in the minerals processing industry as a dispersant to improve separation. It is also used in the food industry, as additive E452i, to improve the stability of whey protein drinks, prevent efflorescence in fermented sausages, and as an emulsifying salt in processed cheese. HMP is used in some toothpastes, to prevent caries and reduce the amount of fluorine required. HMP is particularly useful in these applications due to its ability to bind to surfaces to provide steric and electrostatic repulsion, and to form strong soluble complexes with multivalent cations. Indeed, studies have identified HMP as the most potent of the condensed phosphates for cation binding, however, the exact reason for this is somewhat unclear because of confusion about the structure of HMP. While important for all of these industries, understanding the structure of HMP is of particular importance for its emerging biomedical applications. These include biomaterial formulations such as cements, materials for controlled antibiotic release and nanoparticulate drug delivery vehicles, but also using HMP as the active therapeutic to combat pathological calcifications, such as heterotopic ossification and kidney stones. It is particularly important to know the precise structure of HMP for clinical applications in order to reliably and reproducibly predict efficacy and ADME (absorption, distribution, metabolism and excretion) properties, to overcome regulatory hurdles. There are currently two popular ideas for the structure of HMP. Some studies state that HMP is a 12 membered ring (Figure 1A), while others claim HMP is a linear polyphosphate (Figure 1B). It has also been suggested that both linear and cyclic products are available, but are both referred to as HMP commercially. This confusion has prevented some attempts to compare between studies, because it is not clear whether the HMP used in each is the
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Pub Date : 2021-08-19DOI: 10.1080/02603594.2021.1962310
Reem G. Deghadi, Ahmed E. Elsharkawy, A. Ashmawy, G. Mohamed
ABSTRACT This paper provides a manifestation of a new tradition by which Comments on Inorganic Chemistry starts publishing original research content that, nonetheless, preserves the Journal’s identity as a niche for a critical discussion of contemporary literature in inorganic chemistry; for previous manifestations, see Comments Inorg. Chem. 2020, 40, 277-303 and references cited in the abstract thereof as Yaseen W. K.; Sanders S. F.; Almotawa R. M.; Otten B. M.; Bhat S.; Alamo D. C.; Marpu S. B.; Golden T. D.; Omary M. A. “Are Metal Complexes” Organic, Inorganic, Organometallic, or Metal-Organic Materials? A case Study for the Use of Trinuclear Coinage Metal Complexes as “Metal-Organic Coatings” for Corrosion Suppression on Aluminum Substrates Comments Inorg. Chem. 2019, 39, 1-26 and also, Mohapatra R. K.; Das P. K.; Pradhan M. K.; El-Ajaily M. M.; Das D.; Salem H. F.; Mahanta U.; Badhei G.; Parhi P. K.; Maihub A. A.; Kudrat -E-Zahan Md. “Recent Advances in Urea- and Thiourea-Based Metal Complexes: Biological, Sensor, Optical, and Corrosion Inhibition Studies” Comments Inorg. Chem. 2019, 39, 127-147). In this work, the Schiff base 1-(6-(1-((4-(4-aminophenoxy)phenyl)imino)ethyl)-pyridin-2-yl)ethan-1-one (L) and eight transition metal complexes were synthesized. The reaction of 4,4-oxy-dianiline with 2,6-diacetylpyridine in 1:1 molar ratio affords to the ligand which was employed in the synthesis of the corresponding metal complexes by reacting with the Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) chlorides in 1:1 molar ratio. All the compounds were characterized by using different analytical methods. Structures of complexes were found to be octahedral as deduced from the spectroscopic and magnetic moment measurements. The ligand behaves as a neutral tridentate ligand where it coordinated to metal ions through N-azomethine, N-pyridine, and O-carbonyl group. Besides, experimental investigations for their antibacterial activity against different bacteria species were studied, molecular docking studies were reported with receptors 4ME7, 4K3V, 3T88 and 4WJ3. Density functional theory (DFT) calculations for ligand were reported. Finally, the evaluation of corrosion inhibition efficiency was measured by using different techniques such as electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and electrochemical frequency modulation (EFM). Scanning electron microscope (SEM) and energy dispersive X-Ray analysis (EDX) were measured to affirm the presence of barrier film on the carbon steel surface by inspecting the surface morphologies and elemental composition of corrosion products.
本文提供了一种新传统的表现，即《无机化学评论》开始发表原创研究内容，尽管如此，它仍保留了该杂志作为无机化学当代文学批判性讨论的利基的身份;有关以前的表现，请参阅Comments Inorg。化学，2020,40,277-303及其摘要中引用的参考文献。桑德斯s.f.;Almotawa r.m.;奥顿b.m.;Bhat美国;阿拉莫特区;马普s.b.;金博士;“金属配合物”是有机的、无机的、有机金属的还是金属-有机材料?三核金属配合物作为“金属-有机涂层”在铝基体上抑制腐蚀的案例研究[j]。化学，2019,39,1-26和also, Mohapatra R. K.;Das P. K.;Pradhan M. K.;El-Ajaily m.m.;Das d;塞勒姆H. F.;Mahanta美国;Badhei g;Parhi P. K.;Maihub A.;Kudrat - e - zahan Md.“脲基和硫脲基金属配合物的最新进展:生物、传感器、光学和缓蚀研究”。化学，2019,39,127-147)。本文合成了希夫碱1-(6-(1-(4-(4-氨基苯氧基)苯基)亚氨基)乙基)吡啶-2-基)乙比1- 1 (L)和8个过渡金属配合物。4,4-氧二苯胺与2,6-二乙酰吡啶以1:1的摩尔比反应生成配体，并与Cr(III)、Mn(II)、Fe(III)、Co(II)、Ni(II)、Cu(II)、Zn(II)和Cd(II)氯化物以1:1的摩尔比反应合成相应的金属配合物。所有化合物都用不同的分析方法进行了表征。通过光谱和磁矩测量，发现配合物的结构为八面体。该配体表现为中性三齿配体，通过n -亚甲基、n -吡啶和o -羰基与金属离子配位。此外，对其抑菌活性进行了实验研究，并报道了与受体4ME7、4K3V、3T88和4WJ3的分子对接研究。本文报道了配体的密度泛函理论(DFT)计算。最后，采用电化学阻抗谱(EIS)、动电位极化和电化学调频(EFM)等技术对其缓蚀效果进行了评价。通过扫描电镜(SEM)和能量色散x射线(EDX)分析，通过观察碳钢表面形貌和腐蚀产物的元素组成，证实了碳钢表面存在屏障膜。
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