Pub Date : 2023-11-14DOI: 10.3390/inorganics11110436
Yunliang Yu, Xiaoxia Wang, Yuliang Liu, Chao Zou
During the last two decades, metal-organic cages (MOCs) have been extensively investigated and well documented. Meanwhile, phosphorescent MOCs have emerged as a kind of new MOC material but have not been given much attention. The diversity of their structures and their flexibility of self-assembly result in various luminescent behaviors. Additionally, their special photoactive properties are quite attractive in the background of photochemistry and worthy of discussion. Here, we would like to introduce the recent development of phosphorescent MOCs, including their structures, syntheses, photophysical properties and possible applications. This minireview may hopefully inspire the development of novel phosphorescent MOCs and also facilitate promising applications.
{"title":"Metal-Organic Cages Based on Phosphorescent Organometallics","authors":"Yunliang Yu, Xiaoxia Wang, Yuliang Liu, Chao Zou","doi":"10.3390/inorganics11110436","DOIUrl":"https://doi.org/10.3390/inorganics11110436","url":null,"abstract":"During the last two decades, metal-organic cages (MOCs) have been extensively investigated and well documented. Meanwhile, phosphorescent MOCs have emerged as a kind of new MOC material but have not been given much attention. The diversity of their structures and their flexibility of self-assembly result in various luminescent behaviors. Additionally, their special photoactive properties are quite attractive in the background of photochemistry and worthy of discussion. Here, we would like to introduce the recent development of phosphorescent MOCs, including their structures, syntheses, photophysical properties and possible applications. This minireview may hopefully inspire the development of novel phosphorescent MOCs and also facilitate promising applications.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"134901292","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}
Herein, the structural and photophysical features of two N-based polydentate ligands and the corresponding Zn(II) complexes are investigated. The obtained compounds were characterized using different spectroscopic techniques and their optical properties are discussed in relation to their chemical structure, defined by single-crystal X-ray diffraction and mass spectrometry. The spontaneous and quantitative complexation, investigated by UV-Vis, fluorescence, NMR, IR spectroscopies and mass spectrometry, makes these N-based polydentate ligands interesting candidates for possible applications in chelation therapy and in Zn(II) sensors.
{"title":"N-Based Polydentate Ligands and Corresponding Zn(II) Complexes: A Structural and Spectroscopic Study","authors":"Giorgio Volpi, Stefano Zago, Roberto Rabezzana, Eliano Diana, Emanuele Priola, Claudio Garino, Roberto Gobetto","doi":"10.3390/inorganics11110435","DOIUrl":"https://doi.org/10.3390/inorganics11110435","url":null,"abstract":"Herein, the structural and photophysical features of two N-based polydentate ligands and the corresponding Zn(II) complexes are investigated. The obtained compounds were characterized using different spectroscopic techniques and their optical properties are discussed in relation to their chemical structure, defined by single-crystal X-ray diffraction and mass spectrometry. The spontaneous and quantitative complexation, investigated by UV-Vis, fluorescence, NMR, IR spectroscopies and mass spectrometry, makes these N-based polydentate ligands interesting candidates for possible applications in chelation therapy and in Zn(II) sensors.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135137126","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 : 2023-11-09DOI: 10.3390/inorganics11110434
Sofia A. Basova, Maxim S. Molokeev, Aleksandr S. Oreshonkov, Maksim A. Zhernakov, Nikolay A. Khritokhin, Aleksandr S. Aleksandrovsky, Alexander S. Krylov, Elena I. Sal’nikova, Nikita O. Azarapin, Natalia A. Shelpakova, Klaus Müller-Buschbaum, Yuriy G. Denisenko
A new polymorphic modification of lanthanum sulfate was obtained by thermal dehydration of the respective nonahydrate. According to powder X-ray diffraction, it was established that β-La2(SO4)3 crystallized in the C2/c space group of the monoclinic system with the KTh2(PO4)3 structure type (a = 17.6923(9), b = 6.9102(4), c = 8.3990(5) Å, β = 100.321(3)°, and V = 1010.22(9) Å3). Temperature dependency studies of the unit cell parameters indicated almost zero expansion along the a direction in the temperature range of 300–450 K. Presumably, this occurred due to stretching of the [LaO9]n chains along the c direction, which occurred without a significant alteration in the layer thickness over the a direction. A systematic study of the formation and destruction processes of the lanthanum sulfates under heating was carried out. In particular, the decisive impact of the chemical composition and formation energy of compounds on the thermodynamic and kinetic parameters of the processes was established. DFT calculations showed β-La2(SO4)3 to be a dielectric material with a bandgap of more than 6.4 eV. The processing of β-La2(SO4)3 with the Kubelka–Munk function exhibited low values below 6.4 eV, which indicated a fundamental absorption edge above this energy that was consistent with LDA calculations. The Raman and infrared measurements of β-La2(SO4)3 were in accordance with the calculated spectra, indicating that the obtained crystal parameters represented a reliable structure.
通过对各自的非水合物进行热脱水，得到了一种新的硫酸盐镧的多晶改性物。根据粉末x射线衍射，确定β- la2 (SO4)3在单斜晶系的C2/c空间群中结晶，结构类型为KTh2(PO4)3 (a = 17.6923(9)， b = 6.9102(4)， c = 8.3990(5) Å， β = 100.321(3)°，V = 1010.22(9) Å3)。温度依赖性研究表明，在300-450 K温度范围内，沿a方向膨胀几乎为零。据推测，这是由于[la9]n链沿c方向拉伸造成的，而a方向上的层厚没有明显变化。对硫酸镧在加热条件下的形成和破坏过程进行了系统的研究。特别是，化合物的化学组成和生成能对过程的热力学和动力学参数有决定性的影响。DFT计算表明β-La2(SO4)3是一种带隙大于6.4 eV的介电材料。Kubelka-Munk函数对β-La2(SO4)3的处理表现出低于6.4 eV的低值，表明其基本吸收边缘高于该能量，与LDA计算结果一致。β-La2(SO4)3的拉曼和红外测量与计算光谱一致，表明所得晶体参数代表了可靠的结构。
{"title":"Thermochemistry, Structure, and Optical Properties of a Newβ-La2(SO4)3 Polymorphic Modification","authors":"Sofia A. Basova, Maxim S. Molokeev, Aleksandr S. Oreshonkov, Maksim A. Zhernakov, Nikolay A. Khritokhin, Aleksandr S. Aleksandrovsky, Alexander S. Krylov, Elena I. Sal’nikova, Nikita O. Azarapin, Natalia A. Shelpakova, Klaus Müller-Buschbaum, Yuriy G. Denisenko","doi":"10.3390/inorganics11110434","DOIUrl":"https://doi.org/10.3390/inorganics11110434","url":null,"abstract":"A new polymorphic modification of lanthanum sulfate was obtained by thermal dehydration of the respective nonahydrate. According to powder X-ray diffraction, it was established that β-La2(SO4)3 crystallized in the C2/c space group of the monoclinic system with the KTh2(PO4)3 structure type (a = 17.6923(9), b = 6.9102(4), c = 8.3990(5) Å, β = 100.321(3)°, and V = 1010.22(9) Å3). Temperature dependency studies of the unit cell parameters indicated almost zero expansion along the a direction in the temperature range of 300–450 K. Presumably, this occurred due to stretching of the [LaO9]n chains along the c direction, which occurred without a significant alteration in the layer thickness over the a direction. A systematic study of the formation and destruction processes of the lanthanum sulfates under heating was carried out. In particular, the decisive impact of the chemical composition and formation energy of compounds on the thermodynamic and kinetic parameters of the processes was established. DFT calculations showed β-La2(SO4)3 to be a dielectric material with a bandgap of more than 6.4 eV. The processing of β-La2(SO4)3 with the Kubelka–Munk function exhibited low values below 6.4 eV, which indicated a fundamental absorption edge above this energy that was consistent with LDA calculations. The Raman and infrared measurements of β-La2(SO4)3 were in accordance with the calculated spectra, indicating that the obtained crystal parameters represented a reliable structure.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135241802","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 : 2023-11-08DOI: 10.3390/inorganics11110433
Matthias Weil, Thomas Häusler, Barbara Bonneau, Ekkehard Füglein
In the context of investigating isostructural relationships between sulfates and monofluorophosphates, crystals of the double salts (NH4)2PO3F·NH4NO3 (AFP·AN) and (NH4)2XO4·3NH4NO3 (AX·3AN; X = Se, Cr) were grown from aqueous solutions and structurally characterized using X-ray diffraction and thermal analysis. Whereas the high-temperature forms of the two AX·3AN double salts are in fact isostructural with the sulfate analogue, AFP·AN crystallizes with a reduced amount of NH4NO3 and thus has a unique crystal structure. Both AFP·AN and the two AX·3AN compounds exhibit reversible structural phase transitions. Upon cooling, the monofluorophosphate double salt transforms from the monoclinic room-temperature polymorph (I; P21/n, Z = 4) to the intermediate triclinic polymorph (II; P1, Z = 4) that in turn transforms to the monoclinic low-temperature polymorph (III; P21/n, Z = 4). The two phase transitions (I) → (II) and (II) → (III) are characterized by a significant increase of the unit cell volumes upon cooling. The two AX·3AN double salts transform upon cooling from a disordered monoclinic crystal structure (P21, Z = 2) to a monoclinic polymorph with a doubled unit cell (P21/c, Z = 4). Such a phase transition is not observed for the sulfate analogue. All molecular moieties are fully ordered at −93 °C for the selenate double salt, whereas one of the nitrate anions remains disordered for the chromate double salt even at −173 °C. In all AFP·AN and AX·3AN crystal structures, the nitrate anions play a crucial role during the phase transitions, and an extensive network of N–H···O hydrogen-bonding interactions is responsible for the cohesion of the crystal.
在研究硫酸盐和单氟磷酸盐之间的同位结构关系的背景下，(NH4)2PO3F·NH4NO3 (AFP·AN)和(NH4)2XO4·3NH4NO3 (AX·3AN)的双盐晶体;X = Se, Cr)在水溶液中生长，并用X射线衍射和热分析对其结构进行了表征。两种AX·3AN双盐的高温形态实际上与硫酸盐类似物具有相同的结构，而AFP·AN在NH4NO3的减少量下结晶，因此具有独特的晶体结构。AFP·AN和两种AX·3AN化合物均表现出可逆的结构相变。冷却后，单氟磷酸盐双盐由单斜晶型(I;P21/n, Z = 4)到中间三斜晶型(II;P1, Z = 4)，转化为单斜低温晶型(III;P21/n, Z = 4)。两个相变(I)→(II)和(II)→(III)的特征是冷却后晶胞体积显著增加。两种AX·3AN双盐在冷却后从无序的单斜晶结构(P21, Z = 2)转变为具有双晶胞的单斜晶型(P21/c, Z = 4)。在硫酸盐类似物中没有观察到这种相变。硒酸盐在- 93°C时所有分子都是完全有序的，而铬酸盐在- 173°C时仍有一个硝酸盐阴离子无序。在所有AFP·AN和AX·3AN晶体结构中，硝酸盐阴离子在相变过程中起着至关重要的作用，N-H··O氢键相互作用的广泛网络负责晶体的内聚。
{"title":"Structural Phase Transitions in the Double Salts (NH4)2PO3F·NH4NO3 and (NH4)2XO4·3NH4NO3 (X = Se, Cr)","authors":"Matthias Weil, Thomas Häusler, Barbara Bonneau, Ekkehard Füglein","doi":"10.3390/inorganics11110433","DOIUrl":"https://doi.org/10.3390/inorganics11110433","url":null,"abstract":"In the context of investigating isostructural relationships between sulfates and monofluorophosphates, crystals of the double salts (NH4)2PO3F·NH4NO3 (AFP·AN) and (NH4)2XO4·3NH4NO3 (AX·3AN; X = Se, Cr) were grown from aqueous solutions and structurally characterized using X-ray diffraction and thermal analysis. Whereas the high-temperature forms of the two AX·3AN double salts are in fact isostructural with the sulfate analogue, AFP·AN crystallizes with a reduced amount of NH4NO3 and thus has a unique crystal structure. Both AFP·AN and the two AX·3AN compounds exhibit reversible structural phase transitions. Upon cooling, the monofluorophosphate double salt transforms from the monoclinic room-temperature polymorph (I; P21/n, Z = 4) to the intermediate triclinic polymorph (II; P1, Z = 4) that in turn transforms to the monoclinic low-temperature polymorph (III; P21/n, Z = 4). The two phase transitions (I) → (II) and (II) → (III) are characterized by a significant increase of the unit cell volumes upon cooling. The two AX·3AN double salts transform upon cooling from a disordered monoclinic crystal structure (P21, Z = 2) to a monoclinic polymorph with a doubled unit cell (P21/c, Z = 4). Such a phase transition is not observed for the sulfate analogue. All molecular moieties are fully ordered at −93 °C for the selenate double salt, whereas one of the nitrate anions remains disordered for the chromate double salt even at −173 °C. In all AFP·AN and AX·3AN crystal structures, the nitrate anions play a crucial role during the phase transitions, and an extensive network of N–H···O hydrogen-bonding interactions is responsible for the cohesion of the crystal.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135393143","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 : 2023-11-08DOI: 10.3390/inorganics11110432
Nikola D. Radnović, Chris S. Hawes, Branko B. Kordić, Milica G. Bogdanović, Berta Barta Holló, Mirjana M. Radanović, Dušan Đ. Škorić, Branislav D. Jović, Marko V. Rodić
In this study, the synthesis of a Schiff base containing metal–organic frameworks (MOFs) of the UiO-67 family has been investigated. MOFs featuring free amine groups were successfully synthesized under mild solvothermal conditions using 2-amino-[1,1′-biphenyl]-4,4′-dicarboxylic acid and 2,2′-diamino-[1,1′-biphenyl]-4,4′-dicarboxylic acid as bridging ligands, resulting in MOFs with amine groups covalently linked to the bridging ligands. Both types of functionalized MOFs were post-synthetically modified with 4-formylbenzonitrile that resulted in imine formation. All the obtained compounds were characterized by PXRD, TGA, DTA, BET, NMR, and FTIR spectroscopy, while stability in water was monitored with SEM, EDS, and UV–VIS spectroscopy.
{"title":"Synthesis, Characterization, and Impact of Water on the Stability of Postmodified Schiff Base Containing Metal–Organic Frameworks","authors":"Nikola D. Radnović, Chris S. Hawes, Branko B. Kordić, Milica G. Bogdanović, Berta Barta Holló, Mirjana M. Radanović, Dušan Đ. Škorić, Branislav D. Jović, Marko V. Rodić","doi":"10.3390/inorganics11110432","DOIUrl":"https://doi.org/10.3390/inorganics11110432","url":null,"abstract":"In this study, the synthesis of a Schiff base containing metal–organic frameworks (MOFs) of the UiO-67 family has been investigated. MOFs featuring free amine groups were successfully synthesized under mild solvothermal conditions using 2-amino-[1,1′-biphenyl]-4,4′-dicarboxylic acid and 2,2′-diamino-[1,1′-biphenyl]-4,4′-dicarboxylic acid as bridging ligands, resulting in MOFs with amine groups covalently linked to the bridging ligands. Both types of functionalized MOFs were post-synthetically modified with 4-formylbenzonitrile that resulted in imine formation. All the obtained compounds were characterized by PXRD, TGA, DTA, BET, NMR, and FTIR spectroscopy, while stability in water was monitored with SEM, EDS, and UV–VIS spectroscopy.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135392285","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 : 2023-11-03DOI: 10.3390/inorganics11110431
Corinne Aubert, Pierre Mandin, Béatrice Py
Fe-S clusters are essential cofactors for the activity of a large variety of metalloproteins that play important roles in respiration, photosynthesis, nitrogen fixation, regulation of gene expression, and numerous metabolic pathways, including biosynthesis of other protein cofactors. Assembly of iron and sulfur atoms into a cluster, followed by its insertion into the polypeptide chain, is a complex process ensured by multiproteic systems. Through evolution, eukaryotes have acquired two Fe-S protein biogenesis systems by endosymbiosis from bacteria. These systems, ISC and SUF, are compartmentalized in mitochondria and plastids, respectively. The eukaryotic Fe-S protein biogenesis system (CIA) is dedicated to the biogenesis of cytosolic and nuclear Fe-S proteins. While the CIA system is absent in bacteria, at least two of its components share homologies with bacterial Fe-S protein biogenesis factors, Mrp and SufT. Here, we provide an overview of the role of Mrp and SufT in Fe-S protein biogenesis in bacteria, aiming to put forward specific but also common features with their eukaryotic CIA counterparts.
{"title":"Mrp and SufT, Two Bacterial Homologs of Eukaryotic CIA Factors Involved in Fe-S Clusters Biogenesis","authors":"Corinne Aubert, Pierre Mandin, Béatrice Py","doi":"10.3390/inorganics11110431","DOIUrl":"https://doi.org/10.3390/inorganics11110431","url":null,"abstract":"Fe-S clusters are essential cofactors for the activity of a large variety of metalloproteins that play important roles in respiration, photosynthesis, nitrogen fixation, regulation of gene expression, and numerous metabolic pathways, including biosynthesis of other protein cofactors. Assembly of iron and sulfur atoms into a cluster, followed by its insertion into the polypeptide chain, is a complex process ensured by multiproteic systems. Through evolution, eukaryotes have acquired two Fe-S protein biogenesis systems by endosymbiosis from bacteria. These systems, ISC and SUF, are compartmentalized in mitochondria and plastids, respectively. The eukaryotic Fe-S protein biogenesis system (CIA) is dedicated to the biogenesis of cytosolic and nuclear Fe-S proteins. While the CIA system is absent in bacteria, at least two of its components share homologies with bacterial Fe-S protein biogenesis factors, Mrp and SufT. Here, we provide an overview of the role of Mrp and SufT in Fe-S protein biogenesis in bacteria, aiming to put forward specific but also common features with their eukaryotic CIA counterparts.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135821475","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}
The emergence of drug resistance due to the overuse of antibiotics has made the prevention and treatment of invasive fungal infections caused by Candida albicans (C. albicans) a great challenge. Oxygen vacancy-rich inorganic materials show great promise in the antimicrobial field due to their unique physicochemical properties. Defect engineering can significantly optimize the electronic structure of inorganic materials to further enhance their antimicrobial activity. We designed oxygen vacancy defect-rich V6O13 powders using the hydrothermal-calcination method and investigated their anti-C. albicans activity. The results showed that the stronger antibacterial activity is attributed to the fact that the optimized V6O13 powder oxygen vacancy defects induced a reduction reaction of dissolved oxygen in the environment, which produced ROS with strong oxidative properties, causing damage to the wall membrane of C. albicans and leakage of intracellular material. The minimum inhibitory concentration (99% or more inhibition) of V6O13 powders is 4 mg/mL. This work not only provides a facile method for constructing oxygen-rich vacancies in V6O13 powders, but also provides new insights into the potential of inorganic materials optimized by defect engineering for efficient antimicrobial activity.
{"title":"Antibacterial Activity of Oxygen Vacancy-Mediated ROS Production of V6O13 Powder against Candida albicans","authors":"Li Liu, Siyu Li, Detai Shi, Qifu Bao, Tiangui Zhao, Wei Zhu, Xiaolong Li, Jianer Zhou","doi":"10.3390/inorganics11110429","DOIUrl":"https://doi.org/10.3390/inorganics11110429","url":null,"abstract":"The emergence of drug resistance due to the overuse of antibiotics has made the prevention and treatment of invasive fungal infections caused by Candida albicans (C. albicans) a great challenge. Oxygen vacancy-rich inorganic materials show great promise in the antimicrobial field due to their unique physicochemical properties. Defect engineering can significantly optimize the electronic structure of inorganic materials to further enhance their antimicrobial activity. We designed oxygen vacancy defect-rich V6O13 powders using the hydrothermal-calcination method and investigated their anti-C. albicans activity. The results showed that the stronger antibacterial activity is attributed to the fact that the optimized V6O13 powder oxygen vacancy defects induced a reduction reaction of dissolved oxygen in the environment, which produced ROS with strong oxidative properties, causing damage to the wall membrane of C. albicans and leakage of intracellular material. The minimum inhibitory concentration (99% or more inhibition) of V6O13 powders is 4 mg/mL. This work not only provides a facile method for constructing oxygen-rich vacancies in V6O13 powders, but also provides new insights into the potential of inorganic materials optimized by defect engineering for efficient antimicrobial activity.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135972931","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 : 2023-11-02DOI: 10.3390/inorganics11110430
Roberto D’Amato, Giulia Quaglia, Roberta Selvaggi, Fabio Marmottini, Loredana Latterini
Silica nanostructured materials find application in different fields, since they are cheap, versatile, and easy to functionalize as materials. However, silica reactivity has not been deeply investigated yet, mainly due to a poor understanding of how it is affected by superficial defects. In the present study, the electronic and optical properties of nanoparticles have been investigated using bare silica nanoparticles (SNP) and amino- or phosphonate-functionalized silica nanoparticles (SNP–APTES and SNP-phosphonate), prepared by a sol-gel procedure, and their morphology has been investigated using transmission electron microscopy (TEM) analysis. The prepared silica nanomaterials were characterized by means of reflectance and emission spectroscopies to determine the types of defects that can be found on silica nanoparticles’ surface. In order to understand the effect of surface defects on the reactivity of silica, the nanoparticles were employed for the photocatalytic degradation of Rhodamine 6G (R6G), upon selective irradiation at 320 nm, where only silica colloids absorb. The photoreaction was carried out in ethanol and in water and was monitored following the fluorescence signal of the dye. The evaluation of the fluorescent intensities allowed for the determination of the degradation efficiencies.
{"title":"Role of Surface Defects on Photoinduced Reactivity in SiO2 Nanoparticles","authors":"Roberto D’Amato, Giulia Quaglia, Roberta Selvaggi, Fabio Marmottini, Loredana Latterini","doi":"10.3390/inorganics11110430","DOIUrl":"https://doi.org/10.3390/inorganics11110430","url":null,"abstract":"Silica nanostructured materials find application in different fields, since they are cheap, versatile, and easy to functionalize as materials. However, silica reactivity has not been deeply investigated yet, mainly due to a poor understanding of how it is affected by superficial defects. In the present study, the electronic and optical properties of nanoparticles have been investigated using bare silica nanoparticles (SNP) and amino- or phosphonate-functionalized silica nanoparticles (SNP–APTES and SNP-phosphonate), prepared by a sol-gel procedure, and their morphology has been investigated using transmission electron microscopy (TEM) analysis. The prepared silica nanomaterials were characterized by means of reflectance and emission spectroscopies to determine the types of defects that can be found on silica nanoparticles’ surface. In order to understand the effect of surface defects on the reactivity of silica, the nanoparticles were employed for the photocatalytic degradation of Rhodamine 6G (R6G), upon selective irradiation at 320 nm, where only silica colloids absorb. The photoreaction was carried out in ethanol and in water and was monitored following the fluorescence signal of the dye. The evaluation of the fluorescent intensities allowed for the determination of the degradation efficiencies.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135973360","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 : 2023-11-01DOI: 10.3390/inorganics11110428
Marianela Batistelli, Julián Bultri, Mayra Hernandez Trespalacios, María Florencia Mangiameli, Lina Gribaudo, Sebastián Bellú, María Inés Frascaroli, Juan Carlos González
Arsenic is highly toxic, affecting millions of people in many regions of the world. That is why developing economic and efficient technologies is imperative to eliminate it. Sorption techniques are attractive as efficient and inexpensive sorbents can be used. Chitosan is an abundant, naturally occurring, biodegradable, low-cost biopolymer that can be combined with metal oxide to enhance its removability. This work aimed to synthesize a new chitosan–magnetite-based sorbent for arsenic removal. The synthesized sorbent does not present pores, and when using FT-IR, functional groups of the chitosan and the presence of As(V) in the sorbent treated with arsenic were identified. The synthesized magnetite was characterized using XRD spectroscopy. Application of the central composite design model showed that 0.22 g of the sorbent at pH 6.0 could remove 27.6% of As(V). Kinetic data, fitted with the pseudo-first and -second order models, indicated an ion exchange sorption and activation energy of 28.1–31.4 kJ mol−1. The isotherms were fitted with the Langmuir model, indicating favorable monolayer adsorption with high affinity. The sorption energy calculated using Dubinin Radushkevich, 9.60–8.80 kJ mol−1, confirms a sorption mechanism mediated by ion exchange. The thermodynamic parameters of the process were ΔG° (−21.7/−19.7 kJ mol−1), ΔH°(16.7 kJ mol−1) and ΔS°(123.3 J mol−1 K−1).
{"title":"Elimination of Arsenic Using Sorbents Derived from Chitosan and Iron Oxides, Applying Factorial Designs","authors":"Marianela Batistelli, Julián Bultri, Mayra Hernandez Trespalacios, María Florencia Mangiameli, Lina Gribaudo, Sebastián Bellú, María Inés Frascaroli, Juan Carlos González","doi":"10.3390/inorganics11110428","DOIUrl":"https://doi.org/10.3390/inorganics11110428","url":null,"abstract":"Arsenic is highly toxic, affecting millions of people in many regions of the world. That is why developing economic and efficient technologies is imperative to eliminate it. Sorption techniques are attractive as efficient and inexpensive sorbents can be used. Chitosan is an abundant, naturally occurring, biodegradable, low-cost biopolymer that can be combined with metal oxide to enhance its removability. This work aimed to synthesize a new chitosan–magnetite-based sorbent for arsenic removal. The synthesized sorbent does not present pores, and when using FT-IR, functional groups of the chitosan and the presence of As(V) in the sorbent treated with arsenic were identified. The synthesized magnetite was characterized using XRD spectroscopy. Application of the central composite design model showed that 0.22 g of the sorbent at pH 6.0 could remove 27.6% of As(V). Kinetic data, fitted with the pseudo-first and -second order models, indicated an ion exchange sorption and activation energy of 28.1–31.4 kJ mol−1. The isotherms were fitted with the Langmuir model, indicating favorable monolayer adsorption with high affinity. The sorption energy calculated using Dubinin Radushkevich, 9.60–8.80 kJ mol−1, confirms a sorption mechanism mediated by ion exchange. The thermodynamic parameters of the process were ΔG° (−21.7/−19.7 kJ mol−1), ΔH°(16.7 kJ mol−1) and ΔS°(123.3 J mol−1 K−1).","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135271265","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 : 2023-10-31DOI: 10.3390/inorganics11110427
Perabathula Satish, Komalakrushna Hadagalli, Lakkimsetti Lakshmi Praveen, Mahin Saif Nowl, Asiful H. Seikh, Ibrahim A. Alnaser, Hany S. Abdo, Saumen Mandal
Hydroxyapatite (HA, Ca10(PO4)6(OH)2)-based porous scaffolds have been widely investigated in the last three decades. HA, with excellent biocompatibility and osteoconductivity, has made this material widely used in bone tissue engineering. To improve the mechano-biological properties of HA, the addition of clay to develop HA-based composite scaffolds has gained considerable interest from researchers. In this study, a cost-effective method to prepare a HA–clay composite was demonstrated via the mechanical mixing method, wherein kaolin was used because of its biocompatibility. Prawn (Fenneropenaeus indicus) exoskeleton biowaste was utilized as a raw source to synthesize pure HA using wet chemical synthesis. HA–clay composites were prepared by reinforcing HA with 10, 20, and 30 wt.% of kaolin via the mechanical mixing method. A series of characterization tools such as XRD, FTIR, Raman, and FESEM analysis confirmed the phases and characteristic structural and vibrations bonds along with the morphology of sintered bare HA, HA–kaolin clay composite, and kaolin alone, respectively. The HA–clay composite pellets, uniaxially pressed and sintered at 1100 °C for 2 h, were subjected to a compression test, and an enhancement in mechanical and physical properties, with the highest compressive strength of 35 MPa and a retained open porosity of 33%, was achieved in the HA–kaolin (20 wt.%) clay composite, in comparison with bare HA. The addition of 20% kaolin to HA enhanced its compressive strength by 33.7% and increased its open porosity by 19% when compared with bare HA. The reinforcement of HA with different amounts (10, 20, 30 wt.%) of kaolin could open up a new direction of preparing biocomposite scaffolds with enhanced mechanical properties, improved wear, and better cell proliferation in the field of bone tissue engineering.
{"title":"Hydroxyapatite–Clay Composite for Bone Tissue Engineering: Effective Utilization of Prawn Exoskeleton Biowaste","authors":"Perabathula Satish, Komalakrushna Hadagalli, Lakkimsetti Lakshmi Praveen, Mahin Saif Nowl, Asiful H. Seikh, Ibrahim A. Alnaser, Hany S. Abdo, Saumen Mandal","doi":"10.3390/inorganics11110427","DOIUrl":"https://doi.org/10.3390/inorganics11110427","url":null,"abstract":"Hydroxyapatite (HA, Ca10(PO4)6(OH)2)-based porous scaffolds have been widely investigated in the last three decades. HA, with excellent biocompatibility and osteoconductivity, has made this material widely used in bone tissue engineering. To improve the mechano-biological properties of HA, the addition of clay to develop HA-based composite scaffolds has gained considerable interest from researchers. In this study, a cost-effective method to prepare a HA–clay composite was demonstrated via the mechanical mixing method, wherein kaolin was used because of its biocompatibility. Prawn (Fenneropenaeus indicus) exoskeleton biowaste was utilized as a raw source to synthesize pure HA using wet chemical synthesis. HA–clay composites were prepared by reinforcing HA with 10, 20, and 30 wt.% of kaolin via the mechanical mixing method. A series of characterization tools such as XRD, FTIR, Raman, and FESEM analysis confirmed the phases and characteristic structural and vibrations bonds along with the morphology of sintered bare HA, HA–kaolin clay composite, and kaolin alone, respectively. The HA–clay composite pellets, uniaxially pressed and sintered at 1100 °C for 2 h, were subjected to a compression test, and an enhancement in mechanical and physical properties, with the highest compressive strength of 35 MPa and a retained open porosity of 33%, was achieved in the HA–kaolin (20 wt.%) clay composite, in comparison with bare HA. The addition of 20% kaolin to HA enhanced its compressive strength by 33.7% and increased its open porosity by 19% when compared with bare HA. The reinforcement of HA with different amounts (10, 20, 30 wt.%) of kaolin could open up a new direction of preparing biocomposite scaffolds with enhanced mechanical properties, improved wear, and better cell proliferation in the field of bone tissue engineering.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135869302","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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