Pub Date : 2023-11-19DOI: 10.3390/inorganics11110445
Ívina P. de Souza, Júlia R. L. Silva, Amanda O. Costa, J. T. J. Freitas, Renata Diniz, Rodrigo B. Fazzi, A. M. da Costa Ferreira, E. Pereira-Maia
Two ternary copper(II) complexes with an anthraquinone and a N,N-heterocyclic donor, [Cu(dmp)(L)(H2O)](ClO4) (1), [Cu(bpy)(L)(dmso)](ClO4) (2), in which dmp = 2,9-dimethyl-1,10-phenanthroline, bpy = 2,2′-bipyridine, and HL = 1-hydroxyanthracene-9,10-dione were synthesized and fully characterized by conductivity, elemental, and spectral analyses (FTIR and UV-Vis; EPR and ESI-MS). The structure of 1 reveals that Cu(II) is bound to two oxygens of L, two nitrogens of dmp, and a molecule of water in the fifth position. In complex 2.1, Cu(II) is also pentacoordinated with an O-bonded dmso in the axial position. The presence of the heteroleptic complexes in solution was evidenced by ESI-MS, EPR in dmso solution and UV-Vis spectrophotometry. All complexes bind to CT-DNA with affinity constants of approximately 104. Complex 2 can nick plasmid DNA but no cleavage was performed by complex 1. The investigation of DNA interactions by spectrofluorimetry using ethidium bromide (EB) showed that it was displaced from DNA sites by the addition of the complexes. The complexes inhibited the growth of chronic myelogenous leukemia and human squamous carcinoma cells with low IC50 values, complex 1 being the most effective.
{"title":"Heteroleptic Copper(II) Complexes Containing an Anthraquinone and a Phenanthroline as Synthetic Nucleases and Potential Anticancer Agents","authors":"Ívina P. de Souza, Júlia R. L. Silva, Amanda O. Costa, J. T. J. Freitas, Renata Diniz, Rodrigo B. Fazzi, A. M. da Costa Ferreira, E. Pereira-Maia","doi":"10.3390/inorganics11110445","DOIUrl":"https://doi.org/10.3390/inorganics11110445","url":null,"abstract":"Two ternary copper(II) complexes with an anthraquinone and a N,N-heterocyclic donor, [Cu(dmp)(L)(H2O)](ClO4) (1), [Cu(bpy)(L)(dmso)](ClO4) (2), in which dmp = 2,9-dimethyl-1,10-phenanthroline, bpy = 2,2′-bipyridine, and HL = 1-hydroxyanthracene-9,10-dione were synthesized and fully characterized by conductivity, elemental, and spectral analyses (FTIR and UV-Vis; EPR and ESI-MS). The structure of 1 reveals that Cu(II) is bound to two oxygens of L, two nitrogens of dmp, and a molecule of water in the fifth position. In complex 2.1, Cu(II) is also pentacoordinated with an O-bonded dmso in the axial position. The presence of the heteroleptic complexes in solution was evidenced by ESI-MS, EPR in dmso solution and UV-Vis spectrophotometry. All complexes bind to CT-DNA with affinity constants of approximately 104. Complex 2 can nick plasmid DNA but no cleavage was performed by complex 1. The investigation of DNA interactions by spectrofluorimetry using ethidium bromide (EB) showed that it was displaced from DNA sites by the addition of the complexes. The complexes inhibited the growth of chronic myelogenous leukemia and human squamous carcinoma cells with low IC50 values, complex 1 being the most effective.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"24 7","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139260629","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-11-18DOI: 10.3390/inorganics11110441
Tengfei Yan, Qingyun Wan
In the past decade, there have been significant advancements in the investigation of coherence-related phenomena in organic systems such as biological photosynthetic reaction centers. The d8 Pt(II) dinuclear complex or molecular aggregate with a metal–metal-to-ligand charge transfer (MMLCT) or metal-centered (MC) excited state was reported to show the vibrational coherence phenomenon in the intersystem crossing (ISC) process, due to the Metal–metal (M-M) interaction at excited state. In this study, we review the coherence effect in the Pt(II)-Pt(II) complexes which are speculated to be a coherent energy conversion system. The impacts of coherence on the photo-physics of Pt(II) dinuclear complexes have been discussed and reviewed, including the intersystem crossing process and vibrational wavepacket dynamics.
{"title":"Vibrational Coherence in the Metal–Metal-Bonded Excited State of Pt(II) Complexes","authors":"Tengfei Yan, Qingyun Wan","doi":"10.3390/inorganics11110441","DOIUrl":"https://doi.org/10.3390/inorganics11110441","url":null,"abstract":"In the past decade, there have been significant advancements in the investigation of coherence-related phenomena in organic systems such as biological photosynthetic reaction centers. The d8 Pt(II) dinuclear complex or molecular aggregate with a metal–metal-to-ligand charge transfer (MMLCT) or metal-centered (MC) excited state was reported to show the vibrational coherence phenomenon in the intersystem crossing (ISC) process, due to the Metal–metal (M-M) interaction at excited state. In this study, we review the coherence effect in the Pt(II)-Pt(II) complexes which are speculated to be a coherent energy conversion system. The impacts of coherence on the photo-physics of Pt(II) dinuclear complexes have been discussed and reviewed, including the intersystem crossing process and vibrational wavepacket dynamics.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"7 3","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139262068","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-11-18DOI: 10.3390/inorganics11110443
A. Kola, Ginevra Vigni, D. Valensin
Lycorine (LYC) is an active alkaloid first isolated from Narcissus pseudonarcissus and found in most Amaryllidaceae plants. It belongs to the same family as galantamine, which is the active component of a drug used for the treatment of Alzheimer’s disease. Similarly to galantamine, LYC is able to suppress induced amyloid β (Aβ) toxicity in differentiated SH-SY5Y cell lines and it can weakly interact with the N-terminal region of Aβ via electrostatic interactions. The N-terminal Aβ domain is also involved in Cu(II)/Cu(I) binding and the formed complexes are known to play a key role in ROS production. In this study, the Aβ–LYC interaction in the absence and in the presence of copper ions was investigated by using the N-terminal Aβ peptide encompassing the first 16 residues. NMR analysis showed that Aβ can simultaneously interact with Cu(II) and LYC. The Cu(II) binding mode remains unchanged in the presence of LYC, while LYC association is favored when an Aβ–Cu(II) complex is formed. Moreover, UV-VIS studies revealed the ability of LYC to interfere with the catalytic activities of the Aβ–Cu(II) complexes by reducing the ascorbate consumption monitored at 265 nm.
{"title":"Exploration of Lycorine and Copper(II)’s Association with the N-Terminal Domain of Amyloid β","authors":"A. Kola, Ginevra Vigni, D. Valensin","doi":"10.3390/inorganics11110443","DOIUrl":"https://doi.org/10.3390/inorganics11110443","url":null,"abstract":"Lycorine (LYC) is an active alkaloid first isolated from Narcissus pseudonarcissus and found in most Amaryllidaceae plants. It belongs to the same family as galantamine, which is the active component of a drug used for the treatment of Alzheimer’s disease. Similarly to galantamine, LYC is able to suppress induced amyloid β (Aβ) toxicity in differentiated SH-SY5Y cell lines and it can weakly interact with the N-terminal region of Aβ via electrostatic interactions. The N-terminal Aβ domain is also involved in Cu(II)/Cu(I) binding and the formed complexes are known to play a key role in ROS production. In this study, the Aβ–LYC interaction in the absence and in the presence of copper ions was investigated by using the N-terminal Aβ peptide encompassing the first 16 residues. NMR analysis showed that Aβ can simultaneously interact with Cu(II) and LYC. The Cu(II) binding mode remains unchanged in the presence of LYC, while LYC association is favored when an Aβ–Cu(II) complex is formed. Moreover, UV-VIS studies revealed the ability of LYC to interfere with the catalytic activities of the Aβ–Cu(II) complexes by reducing the ascorbate consumption monitored at 265 nm.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"41 04","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139261883","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-11-18DOI: 10.3390/inorganics11110442
M. Wang, J. Hua, Pei Zheng, Yuanzhi Tian, Shaodan Kang, Junjun Chen, Yifan Duan, Xiang Ma
For decades, amyloid β-peptide (Aβ) misfolding aggregates with β-sheet structures have been linked to the occurrence and advancement of Alzheimer’s disease (AD) development and progression. As a result, modulating the misfolding mode of Aβ has been regarded as an important anti-amyloid protein misfolding strategy. A polyoxometalate based on {Co(H2O)4}2+ complex and [P2Mo5O23]6− fragments, K8{[Co(H2O)4][HP2Mo5O23]2}·8H2O (abbreviated as CoPM), has been synthesized and structurally characterized using elemental analysis, single-crystal X-ray diffraction (SXRD), IR, UV spectra, bond valence sums (Σs) calculation, and powder XRD (PXRD). CoPM’s primary component, as revealed by structural analysis, is a nanoscale polyoxoanion made of [Co(H2O)4]2+ sandwiched between two [P2Mo5O23]6− pieces. Notably, it is demonstrated that CoPM efficiently modulates Aβ aggregates’ β-sheet-rich conformation.
{"title":"A Nanoscale Cobalt Functionalized Strandberg-Type Phosphomolybdate with β-Sheet Conformation Modulation Ability in Anti-Amyloid Protein Misfolding","authors":"M. Wang, J. Hua, Pei Zheng, Yuanzhi Tian, Shaodan Kang, Junjun Chen, Yifan Duan, Xiang Ma","doi":"10.3390/inorganics11110442","DOIUrl":"https://doi.org/10.3390/inorganics11110442","url":null,"abstract":"For decades, amyloid β-peptide (Aβ) misfolding aggregates with β-sheet structures have been linked to the occurrence and advancement of Alzheimer’s disease (AD) development and progression. As a result, modulating the misfolding mode of Aβ has been regarded as an important anti-amyloid protein misfolding strategy. A polyoxometalate based on {Co(H2O)4}2+ complex and [P2Mo5O23]6− fragments, K8{[Co(H2O)4][HP2Mo5O23]2}·8H2O (abbreviated as CoPM), has been synthesized and structurally characterized using elemental analysis, single-crystal X-ray diffraction (SXRD), IR, UV spectra, bond valence sums (Σs) calculation, and powder XRD (PXRD). CoPM’s primary component, as revealed by structural analysis, is a nanoscale polyoxoanion made of [Co(H2O)4]2+ sandwiched between two [P2Mo5O23]6− pieces. Notably, it is demonstrated that CoPM efficiently modulates Aβ aggregates’ β-sheet-rich conformation.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"25 3","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139262211","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-11-18DOI: 10.3390/inorganics11110444
Y. Kuo, Hsin-Kuan Liu, Chen-I Yang
By employing semi-flexible multi-N donor auxiliary ligands, namely 1,4-bis(5-pyrimidyl)benzene (bpmb) in conjunction with azide, novel Co(II) 2D coordination polymers have been successfully synthesized and structurally characterized, along with magnetic analysis. The resulting compound, {Co(N3)(bpmb)(H2O)2·H2O}n (1), exhibits a unique 2D structure comprised of interconnected Co(II) chains bridged by single end-to-end (EE) azide moieties. These chains are further linked by twisted trans-μ2-N,N′-bpmb auxiliary ligands, forming a grid-like network. Additionally, the layers are held together in a 3D arrangement through hydrogen bonding interactions between the coordination water and the N atom of the bpmb ligands. Importantly, magnetic investigations reveal that compound 1 displays weak ferromagnetism attributed to spin canting, with a critical temperature (Tc) of 12 K.
{"title":"Spin Canting and Weak Ferromagnetism in a New 2D Coordination Polymer with the Co(II) Chain Bridged by a Single End-to-End Azide","authors":"Y. Kuo, Hsin-Kuan Liu, Chen-I Yang","doi":"10.3390/inorganics11110444","DOIUrl":"https://doi.org/10.3390/inorganics11110444","url":null,"abstract":"By employing semi-flexible multi-N donor auxiliary ligands, namely 1,4-bis(5-pyrimidyl)benzene (bpmb) in conjunction with azide, novel Co(II) 2D coordination polymers have been successfully synthesized and structurally characterized, along with magnetic analysis. The resulting compound, {Co(N3)(bpmb)(H2O)2·H2O}n (1), exhibits a unique 2D structure comprised of interconnected Co(II) chains bridged by single end-to-end (EE) azide moieties. These chains are further linked by twisted trans-μ2-N,N′-bpmb auxiliary ligands, forming a grid-like network. Additionally, the layers are held together in a 3D arrangement through hydrogen bonding interactions between the coordination water and the N atom of the bpmb ligands. Importantly, magnetic investigations reveal that compound 1 displays weak ferromagnetism attributed to spin canting, with a critical temperature (Tc) of 12 K.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"70 2","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139262291","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Singlet oxygen (1O2), representing an important reactive oxygen species, has promising applications in biomedical, material, and environmental sciences. Photosensitized production of 1O2 using organic dyes is highly desirable and the exploration of highly efficient photosensitizers has received considerable attention. Herein, two tridentate Pt(II) complexes, i.e., cationic 1(PF6) and neutral 2, modified with the ethynylnaphthalimide chromophore, were designed and prepared for the application in 1O2 generation. Spectroscopic studies and computational results suggest that 1(PF6) and 2 display the lowest-energy absorption bands centered at 435–465 nm with the molar extinction coefficients of 0.6–3.2 × 104 M−1 cm−1, originating from the singlet ligand-to-ligand charge transfer (1LLCT) and a mixture of 1LLCT and singlet ligand-centered (LC) transitions, respectively. Moreover, they show similar phosphorescence at 620–640 nm assigned to the Pt-perturbed triplet LC emission of the ethynylnaphthalimide moiety. Thanks to the relatively long phosphorescence lifetimes, these complexes exhibit O2-dependent phosphorescence intensities with good reversibility and stability. They are able to behave as efficient triplet photosensitizers to promote the 1O2 generation with high quantum yields (84–89%). This work indicates that the combination of an organic chromophore with Pt(II) complexes provides an effective method to obtain photosensitizers for 1O2 generation.
{"title":"Naphthalimide-Modified Tridentate Platinum(II) Complexes: Synthesis, Characterization, and Application in Singlet Oxygen Generation","authors":"Zhongliang Gong, Qing-Jun Pan, Dian-Xue Ma, Yu‐Wu Zhong","doi":"10.3390/inorganics11110438","DOIUrl":"https://doi.org/10.3390/inorganics11110438","url":null,"abstract":"Singlet oxygen (1O2), representing an important reactive oxygen species, has promising applications in biomedical, material, and environmental sciences. Photosensitized production of 1O2 using organic dyes is highly desirable and the exploration of highly efficient photosensitizers has received considerable attention. Herein, two tridentate Pt(II) complexes, i.e., cationic 1(PF6) and neutral 2, modified with the ethynylnaphthalimide chromophore, were designed and prepared for the application in 1O2 generation. Spectroscopic studies and computational results suggest that 1(PF6) and 2 display the lowest-energy absorption bands centered at 435–465 nm with the molar extinction coefficients of 0.6–3.2 × 104 M−1 cm−1, originating from the singlet ligand-to-ligand charge transfer (1LLCT) and a mixture of 1LLCT and singlet ligand-centered (LC) transitions, respectively. Moreover, they show similar phosphorescence at 620–640 nm assigned to the Pt-perturbed triplet LC emission of the ethynylnaphthalimide moiety. Thanks to the relatively long phosphorescence lifetimes, these complexes exhibit O2-dependent phosphorescence intensities with good reversibility and stability. They are able to behave as efficient triplet photosensitizers to promote the 1O2 generation with high quantum yields (84–89%). This work indicates that the combination of an organic chromophore with Pt(II) complexes provides an effective method to obtain photosensitizers for 1O2 generation.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"1 1","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139263014","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-11-17DOI: 10.3390/inorganics11110440
Dae Hyun Kim, Seul Gi Kang, Bo Jung Kim, Heegyoun Lee, Jinmo Kim, Chang-Bun Yoon
Practical applications of Li-metal anodes are limited by dendrite formation, Li loss, and poor reaction, resulting in a low Coulombic efficiency. In this study, we investigated the effects of island-shaped Ag atoms on the electrochemical behavior of Li-metal anodes. A Ag–Cu film was co-deposited through sputtering and subsequent annealing to anchor the Ag atoms with an island shape on a Cu substrate. The Ag target was co-sputtered with Cu with controlled atomic ratios in the Ag–Cu alloy. The sputtering thickness was set to 100 nm, and various annealing conditions were applied. The embedded island-shaped Ag atoms provided effective nucleation sites for Li deposition during the electrochemical nucleation of Li, increasing the nucleation density and spatial uniformity while decreasing the nucleation size and potential. Compact dendrite-free high-density Li deposition was achieved by annealing the Ag–Cu current collector (CC) at 600 °C. Under repetitive Li plating and stripping for 110 cycles at a current density of 0.5 mAcm−2 and capacity of 1 mAhcm−2, a high Coulombic efficiency of 98.5% was achieved. Conversely, the bare Cu CC had a life of up to 67 cycles under the same test conditions.
锂金属阳极的实际应用受到枝晶形成、锂损耗和反应不良的限制，导致库仑效率较低。在本研究中，我们研究了岛状银原子对锂金属阳极电化学行为的影响。通过溅射和随后的退火共同沉积了一层银-铜薄膜，从而在铜基底上锚定了岛状的银原子。在银铜合金中，以可控的原子比将银靶与铜共同溅射。溅射厚度设定为 100 nm，并采用了不同的退火条件。在锂的电化学成核过程中，嵌入的岛状银原子为锂沉积提供了有效的成核位点，提高了成核密度和空间均匀性，同时减小了成核尺寸和电位。通过将银铜集流器（CC）在 600 °C 下退火，实现了紧凑无树枝状晶粒的高密度锂沉积。在电流密度为 0.5 mAcm-2 和容量为 1 mAhcm-2 的条件下，重复锂电镀和剥离 110 个循环，库仑效率高达 98.5%。相反，在相同的测试条件下，裸铜 CC 的寿命最长为 67 个周期。
{"title":"Effect of the Annealing Temperature of Lithiophilic Ag–Cu Co-Deposition on the Cycling Performance of Li-Metal Anodes","authors":"Dae Hyun Kim, Seul Gi Kang, Bo Jung Kim, Heegyoun Lee, Jinmo Kim, Chang-Bun Yoon","doi":"10.3390/inorganics11110440","DOIUrl":"https://doi.org/10.3390/inorganics11110440","url":null,"abstract":"Practical applications of Li-metal anodes are limited by dendrite formation, Li loss, and poor reaction, resulting in a low Coulombic efficiency. In this study, we investigated the effects of island-shaped Ag atoms on the electrochemical behavior of Li-metal anodes. A Ag–Cu film was co-deposited through sputtering and subsequent annealing to anchor the Ag atoms with an island shape on a Cu substrate. The Ag target was co-sputtered with Cu with controlled atomic ratios in the Ag–Cu alloy. The sputtering thickness was set to 100 nm, and various annealing conditions were applied. The embedded island-shaped Ag atoms provided effective nucleation sites for Li deposition during the electrochemical nucleation of Li, increasing the nucleation density and spatial uniformity while decreasing the nucleation size and potential. Compact dendrite-free high-density Li deposition was achieved by annealing the Ag–Cu current collector (CC) at 600 °C. Under repetitive Li plating and stripping for 110 cycles at a current density of 0.5 mAcm−2 and capacity of 1 mAhcm−2, a high Coulombic efficiency of 98.5% was achieved. Conversely, the bare Cu CC had a life of up to 67 cycles under the same test conditions.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"120 9","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139264394","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-11-17DOI: 10.3390/inorganics11110439
Elisa Gaggero, Arianna Giovagnoni, Alessia Zollo, Paola Calza, M. Paganini
In the present work, the photodegradation performances of N-doped TiO2 photocatalysts with enhanced absorption of visible light were exploited for the abatement of some representative contaminants of emerging concern (CECs). Pristine TiO2 and N-TiO2 were synthesized using hydrothermal (HT) and sol–gel (SG) routes, they were characterized using XRD and UV-Vis spectroscopy, and their band gaps were determined via analysis in diffuse reflectance. Their photodegradation efficiency was tested on a mixture of recalcitrant organic pollutants, namely, benzotriazole, diclofenac, sulfamethoxazole, and bisphenol A, using a solar simulator lamp with two different cut-off filters (λ > 340 nm and λ > 400 nm). The evaluation of the photocatalytic performances was initially carried out in spiked ultrapure water and subsequently in aqueous matrices of increasing complexity such as Po River water and water coming from an aquaculture plant. The exclusive utilization of visible light (λ > 400 nm) highlighted the advantage of introducing the dopant into the TiO2 photocatalyst since this modification allows for the material to be responsive to visible light, which is not sufficient in the case of pristine TiO2 and the higher efficiency of materials obtained via the sol–gel route. Thanks to the doping, improved performance was obtained in both ultrapure water and real water matrices, indicating the potential of the doped material for future applications in the field.
本研究利用掺杂 N 的二氧化钛光催化剂对可见光的吸收增强的光降解性能，来消除一些具有代表性的新关注污染物（CECs）。采用水热法（HT）和溶胶-凝胶法（SG）合成了纯净的二氧化钛（TiO2）和掺氮二氧化钛（N-TiO2），使用 XRD 和紫外-可见光谱对它们进行了表征，并通过漫反射分析确定了它们的带隙。使用带有两种不同截止滤光片（λ > 340 nm 和 λ > 400 nm）的太阳模拟灯测试了它们对苯并三唑、双氯芬酸、磺胺甲噁唑和双酚 A 等难降解有机污染物混合物的光降解效率。对光催化性能的评估最初是在加标超纯水中进行的，随后又在波河水和水产养殖厂水等复杂程度越来越高的水基质中进行。对可见光（λ > 400 nm）的专门利用凸显了在二氧化钛光催化剂中引入掺杂剂的优势，因为这种改性可使材料对可见光产生反应，而原始二氧化钛对可见光的反应是不够的，而且通过溶胶-凝胶路线获得的材料效率更高。由于进行了掺杂，在超纯水和真水基质中的性能都得到了提高，这表明掺杂材料未来在该领域的应用潜力巨大。
{"title":"Photocatalytic Degradation of Emerging Contaminants with N-Doped TiO2 Using Simulated Sunlight in Real Water Matrices","authors":"Elisa Gaggero, Arianna Giovagnoni, Alessia Zollo, Paola Calza, M. Paganini","doi":"10.3390/inorganics11110439","DOIUrl":"https://doi.org/10.3390/inorganics11110439","url":null,"abstract":"In the present work, the photodegradation performances of N-doped TiO2 photocatalysts with enhanced absorption of visible light were exploited for the abatement of some representative contaminants of emerging concern (CECs). Pristine TiO2 and N-TiO2 were synthesized using hydrothermal (HT) and sol–gel (SG) routes, they were characterized using XRD and UV-Vis spectroscopy, and their band gaps were determined via analysis in diffuse reflectance. Their photodegradation efficiency was tested on a mixture of recalcitrant organic pollutants, namely, benzotriazole, diclofenac, sulfamethoxazole, and bisphenol A, using a solar simulator lamp with two different cut-off filters (λ > 340 nm and λ > 400 nm). The evaluation of the photocatalytic performances was initially carried out in spiked ultrapure water and subsequently in aqueous matrices of increasing complexity such as Po River water and water coming from an aquaculture plant. The exclusive utilization of visible light (λ > 400 nm) highlighted the advantage of introducing the dopant into the TiO2 photocatalyst since this modification allows for the material to be responsive to visible light, which is not sufficient in the case of pristine TiO2 and the higher efficiency of materials obtained via the sol–gel route. Thanks to the doping, improved performance was obtained in both ultrapure water and real water matrices, indicating the potential of the doped material for future applications in the field.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"51 3","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139265402","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-11-17DOI: 10.3390/inorganics11110437
Julian Zinke, C. Bruhn, U. Siemeling
Half-sandwich iron(II) dihalido complexes of the type [Fe(η5-Cp’)X2]− (Cp’ = C5H5 or substituted cyclopentadienyl) which are thermally stable at room temperature are extremely scarce, being limited to congeners containing the bulky C5H2-1,2,4-tBu3 ligand. We extended this to homologues [Fe(η5-Cp*)X2]− (X = Cl, Br, I) containing the particularly popular C5Me5 (Cp*) ligand. Corresponding ionic compounds ER4[Fe(η5-Cp*)X2] are easily accessible from FeX2, MCp* (M = Li, K) and a suitable halide source R4EX (E = N, P) in THF. Despite their high sensitivity towards air and moisture, the new compounds NnPr4[Fe(η5-Cp*)X2] (X = Cl, Br), NnPr4[Fe(η5-Cp*)BrCl], and PPh4[Fe(η5-Cp*)X2] (X = Cl, Br, I) were structurally characterised using single-crystal X-ray diffraction. NnPr4[Fe(η5-Cp*)Cl2] reacts readily with CO to afford [Fe(η5-Cp*)Cl(CO)2], indicating the synthetic potential of ER4[Fe(η5-Cp*)X2] in FeCp* half-sandwich chemistry.
{"title":"Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(η5-Cp*)X2]− (X = Cl − I)","authors":"Julian Zinke, C. Bruhn, U. Siemeling","doi":"10.3390/inorganics11110437","DOIUrl":"https://doi.org/10.3390/inorganics11110437","url":null,"abstract":"Half-sandwich iron(II) dihalido complexes of the type [Fe(η5-Cp’)X2]− (Cp’ = C5H5 or substituted cyclopentadienyl) which are thermally stable at room temperature are extremely scarce, being limited to congeners containing the bulky C5H2-1,2,4-tBu3 ligand. We extended this to homologues [Fe(η5-Cp*)X2]− (X = Cl, Br, I) containing the particularly popular C5Me5 (Cp*) ligand. Corresponding ionic compounds ER4[Fe(η5-Cp*)X2] are easily accessible from FeX2, MCp* (M = Li, K) and a suitable halide source R4EX (E = N, P) in THF. Despite their high sensitivity towards air and moisture, the new compounds NnPr4[Fe(η5-Cp*)X2] (X = Cl, Br), NnPr4[Fe(η5-Cp*)BrCl], and PPh4[Fe(η5-Cp*)X2] (X = Cl, Br, I) were structurally characterised using single-crystal X-ray diffraction. NnPr4[Fe(η5-Cp*)Cl2] reacts readily with CO to afford [Fe(η5-Cp*)Cl(CO)2], indicating the synthetic potential of ER4[Fe(η5-Cp*)X2] in FeCp* half-sandwich chemistry.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"75 3","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139264739","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-09-08DOI: 10.3390/inorganics11090365
Anna Farasat, L. Labella, M. D. Di Paolo, L. Dalla Via, S. Samaritani
Some new dichloro- and dibromotriphenylphosphino isonitrile and N-acyclic (NAC) carbene complexes of platinum(II) were synthesized, starting from suitable dinuclear precursors. The reaction of cyclohexylisonitrile with trans-[Pt(μ-X)X(PPh3)]2, followed by the addition of N,N-diethylamine afforded the corresponding N-acyclic carbene (NAC)derivatives cis-[PtX2(PPh3)(NAC)] in 61–64% isolated yield. The cis geometry was attributed based on the comparison with known structures. The stability of the complexes in pure DMSO, DMSO/H2O, and DMSO/NaClaq mixtures was evaluated. While pure DMSO, as well as DMSO/H2O, did not affect the nature of either dichloro- or dibromo-compounds, dibromo derivatives were not stable in the presence of chloride ions. Since a high concentration of chloride ions is essential to perform in vitro cell assays, only dichlorocomplexes were tested as cytotoxic agents against HepG2 and human tumor cells. Among the tested complexes, NAC derivatives showed a moderate effect on MSTO-211H.
{"title":"Dibromo- and Dichlorotriphenylphosphino N-Acyclic Carbene Complexes of Platinum(II)—Synthesis and Cytotoxicity","authors":"Anna Farasat, L. Labella, M. D. Di Paolo, L. Dalla Via, S. Samaritani","doi":"10.3390/inorganics11090365","DOIUrl":"https://doi.org/10.3390/inorganics11090365","url":null,"abstract":"Some new dichloro- and dibromotriphenylphosphino isonitrile and N-acyclic (NAC) carbene complexes of platinum(II) were synthesized, starting from suitable dinuclear precursors. The reaction of cyclohexylisonitrile with trans-[Pt(μ-X)X(PPh3)]2, followed by the addition of N,N-diethylamine afforded the corresponding N-acyclic carbene (NAC)derivatives cis-[PtX2(PPh3)(NAC)] in 61–64% isolated yield. The cis geometry was attributed based on the comparison with known structures. The stability of the complexes in pure DMSO, DMSO/H2O, and DMSO/NaClaq mixtures was evaluated. While pure DMSO, as well as DMSO/H2O, did not affect the nature of either dichloro- or dibromo-compounds, dibromo derivatives were not stable in the presence of chloride ions. Since a high concentration of chloride ions is essential to perform in vitro cell assays, only dichlorocomplexes were tested as cytotoxic agents against HepG2 and human tumor cells. Among the tested complexes, NAC derivatives showed a moderate effect on MSTO-211H.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43513845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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