Pub Date : 2023-09-09DOI: 10.3390/inorganics11090367
Celisnolia M. Leite, João H. Araujo-Neto, Adriana P. M. Guedes, Analu R. Costa, Felipe C. Demidoff, Chaquip D. Netto, Eduardo E. Castellano, Otaciro R. Nascimento, Alzir A. Batista
Four new Cu/PPh3/naphtoquinone complexes were synthesized, characterized (IR, UV/visible, 1D/2D NMR, mass spectrometry, elemental analysis, and X-ray diffraction), and evaluated as anticancer agents. We also investigated the reactive oxygen species (ROS) generation capacity of complex 4, considering the well-established photochemical property of naphthoquinones. Therefore, employing the electron paramagnetic resonance (EPR) “spin trap”, 5,5-dimethyl-1-pyrroline N-oxide (DMPO) technique, we identified the formation of the characteristic •OOH species (hydroperoxyl radical) adduct even before irradiating the solution containing complex 4. As the irradiation progressed, this radical species gradually diminished, primarily giving rise to a novel species known as •DMPO-OH (DMPO + •OH radical). These findings strongly suggest that Cu(I)/PPh3/naphthoquinone complexes can generate ROS, even in the absence of irradiation, potentially intensifying their cytotoxic effect on tumor cells. Interpretation of the in vitro cytotoxicity data of the Cu(I) complexes considered their stability in cell culture medium. All of the complexes were cytotoxic to the lung (A549) and breast tumor cell lines (MDA-MB-231 and MCF-7). However, the higher toxicity for the lung (MRC5) and breast (MCF-10A) non-tumoral cells resulted in a low selectivity index. The morphological analysis of MDA-MB-231 cells treated with the complexes showed that they could cause decreased cell density, loss of cell morphology, and loss of cell adhesion, mainly with concentrations higher than the inhibitory concentration of 50% of cell viability (IC50) values. Similarly, the clonogenic survivance of these cells was affected only with concentrations higher than the IC50 values. An antimigratory effect was observed for complexes 1 and 4, showing around 20–40% of inhibition of wound closure in the wound healing experiments.
{"title":"Copper(I)/Triphenylphosphine Complexes Containing Naphthoquinone Ligands as Potential Anticancer Agents","authors":"Celisnolia M. Leite, João H. Araujo-Neto, Adriana P. M. Guedes, Analu R. Costa, Felipe C. Demidoff, Chaquip D. Netto, Eduardo E. Castellano, Otaciro R. Nascimento, Alzir A. Batista","doi":"10.3390/inorganics11090367","DOIUrl":"https://doi.org/10.3390/inorganics11090367","url":null,"abstract":"Four new Cu/PPh3/naphtoquinone complexes were synthesized, characterized (IR, UV/visible, 1D/2D NMR, mass spectrometry, elemental analysis, and X-ray diffraction), and evaluated as anticancer agents. We also investigated the reactive oxygen species (ROS) generation capacity of complex 4, considering the well-established photochemical property of naphthoquinones. Therefore, employing the electron paramagnetic resonance (EPR) “spin trap”, 5,5-dimethyl-1-pyrroline N-oxide (DMPO) technique, we identified the formation of the characteristic •OOH species (hydroperoxyl radical) adduct even before irradiating the solution containing complex 4. As the irradiation progressed, this radical species gradually diminished, primarily giving rise to a novel species known as •DMPO-OH (DMPO + •OH radical). These findings strongly suggest that Cu(I)/PPh3/naphthoquinone complexes can generate ROS, even in the absence of irradiation, potentially intensifying their cytotoxic effect on tumor cells. Interpretation of the in vitro cytotoxicity data of the Cu(I) complexes considered their stability in cell culture medium. All of the complexes were cytotoxic to the lung (A549) and breast tumor cell lines (MDA-MB-231 and MCF-7). However, the higher toxicity for the lung (MRC5) and breast (MCF-10A) non-tumoral cells resulted in a low selectivity index. The morphological analysis of MDA-MB-231 cells treated with the complexes showed that they could cause decreased cell density, loss of cell morphology, and loss of cell adhesion, mainly with concentrations higher than the inhibitory concentration of 50% of cell viability (IC50) values. Similarly, the clonogenic survivance of these cells was affected only with concentrations higher than the IC50 values. An antimigratory effect was observed for complexes 1 and 4, showing around 20–40% of inhibition of wound closure in the wound healing experiments.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136192801","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 : 2023-08-17DOI: 10.3390/inorganics11080339
Ehab A. Abdelrahman, Faisal K. Algethami, Huda S. AlSalem, Mona S. Binkadem, Fawaz A. Saad, Gharieb S. El-Sayyad, Nadeem Raza, Khalil ur Rehman
An excessive accumulation of crystal violet dye in the human body results in an accelerated heart rate, tetraplegia, eye irritation, and long-term damage to the transparent mucous membrane that protects the eyeballs. Accordingly, in this paper, sodium manganese silicate/sodium manganese silicate hydroxide hydrate was easily fabricated as a novel type of nanostructures for the successful disposal of crystal violet dye from aqueous solutions. The formed sodium manganese silicate/sodium manganese silicate hydroxide hydrate nanostructures after the hydrothermal treatment of the gel produced from the interaction of Mn(II) ions with Si(IV) ions at 180 °C for 6, 12, 18, and 24 h were abbreviated as MS1, MS2, MS3, and MS4, respectively. The XRD showed that the average crystallite size of the MS1, MS2, MS3, and MS4 samples is 8.38, 7.43, 4.25, and 8.76 nm, respectively. The BET surface area of the MS1, MS2, MS3, and MS4 samples is 41.58, 46.15, 58.25, and 39.69 m2/g, respectively. The MS1, MS2, MS3, and MS4 samples consist of spherical and irregular shapes with average grain sizes of 157.22, 88.06, 43.75, and 107.08 nm, respectively. The best adsorption conditions of the crystal violet dye employing the MS1, MS2, MS3, and MS4 products were achieved at pH = 8, contact time = 140 min, and solution temperature = 298 kelvin. The linear pseudo-2nd-order model as well as the linear Langmuir isotherm better describe the disposal of the crystal violet dye using the MS1, MS2, MS3, and MS4 adsorbents. The studied thermodynamic parameters indicated that the disposal of the crystal violet dye employing the MS1, MS2, MS3, and MS4 adsorbents is spontaneous, exothermic, and chemical. The maximum disposal capacities of the MS1, MS2, MS3, and MS4 adsorbents towards crystal violet dye are 342.47, 362.32, 411.52, and 310.56 mg/g, respectively.
{"title":"Facile Synthesis and Characterization of Novel Nanostructures for the Efficient Disposal of Crystal Violet Dye from Aqueous Media","authors":"Ehab A. Abdelrahman, Faisal K. Algethami, Huda S. AlSalem, Mona S. Binkadem, Fawaz A. Saad, Gharieb S. El-Sayyad, Nadeem Raza, Khalil ur Rehman","doi":"10.3390/inorganics11080339","DOIUrl":"https://doi.org/10.3390/inorganics11080339","url":null,"abstract":"An excessive accumulation of crystal violet dye in the human body results in an accelerated heart rate, tetraplegia, eye irritation, and long-term damage to the transparent mucous membrane that protects the eyeballs. Accordingly, in this paper, sodium manganese silicate/sodium manganese silicate hydroxide hydrate was easily fabricated as a novel type of nanostructures for the successful disposal of crystal violet dye from aqueous solutions. The formed sodium manganese silicate/sodium manganese silicate hydroxide hydrate nanostructures after the hydrothermal treatment of the gel produced from the interaction of Mn(II) ions with Si(IV) ions at 180 °C for 6, 12, 18, and 24 h were abbreviated as MS1, MS2, MS3, and MS4, respectively. The XRD showed that the average crystallite size of the MS1, MS2, MS3, and MS4 samples is 8.38, 7.43, 4.25, and 8.76 nm, respectively. The BET surface area of the MS1, MS2, MS3, and MS4 samples is 41.58, 46.15, 58.25, and 39.69 m2/g, respectively. The MS1, MS2, MS3, and MS4 samples consist of spherical and irregular shapes with average grain sizes of 157.22, 88.06, 43.75, and 107.08 nm, respectively. The best adsorption conditions of the crystal violet dye employing the MS1, MS2, MS3, and MS4 products were achieved at pH = 8, contact time = 140 min, and solution temperature = 298 kelvin. The linear pseudo-2nd-order model as well as the linear Langmuir isotherm better describe the disposal of the crystal violet dye using the MS1, MS2, MS3, and MS4 adsorbents. The studied thermodynamic parameters indicated that the disposal of the crystal violet dye employing the MS1, MS2, MS3, and MS4 adsorbents is spontaneous, exothermic, and chemical. The maximum disposal capacities of the MS1, MS2, MS3, and MS4 adsorbents towards crystal violet dye are 342.47, 362.32, 411.52, and 310.56 mg/g, respectively.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136272646","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 : 2023-06-22DOI: 10.3390/inorganics11070265
Ping Li, Xian-Xian Ji, Ming-Yao Xu, Yu-Long Liu, Liu Yang
Cations and anions are indispensable resources for the development of nature and modern industry and agriculture, and exploring more efficient technology to monitor them is urgently needed. A multifunctional fluorescent probe based on 1,8-naphthalimide, N-(2-thiophenhydrazide)acetyl-4-morpholine-1,8-naphthalimide (TMN), was successfully designed and synthesized for the detection of Co2+, F−, and CN−, with N-carboxymethyl-4-morpholine-1,8-naphthalimide and thiophene-2-carbohydrazide as starting materials. TMN displayed superior stability in MeCN with an “on–off” mode towards Co2+, F−, and CN− by the naked eye. The linear response ranges of TMN were 0–3 and 4–19 μM with a detection limit of 0.21 μM for detecting Co2+, 0–5 and 5–22 μM with a detection limit of 0.36 μM for F−, and 0–10 and 10–25 μM with a detection limit of 0.49 μM for CN−. TMN could also recognize Co2+, F−, and CN− in real samples. Finally, the possible sensing mechanisms of TMN for detecting Co2+, F−, and CN− were deeply investigated. These results implied that TMN could be a potential chemosensor for monitoring metal cations and anions sensitively and selectively and could be used in real sample detection.
{"title":"A Multifunctional Fluorescent Probe Based on 1,8-Naphthalimide for the Detection of Co2+, F−, and CN−","authors":"Ping Li, Xian-Xian Ji, Ming-Yao Xu, Yu-Long Liu, Liu Yang","doi":"10.3390/inorganics11070265","DOIUrl":"https://doi.org/10.3390/inorganics11070265","url":null,"abstract":"Cations and anions are indispensable resources for the development of nature and modern industry and agriculture, and exploring more efficient technology to monitor them is urgently needed. A multifunctional fluorescent probe based on 1,8-naphthalimide, N-(2-thiophenhydrazide)acetyl-4-morpholine-1,8-naphthalimide (TMN), was successfully designed and synthesized for the detection of Co2+, F−, and CN−, with N-carboxymethyl-4-morpholine-1,8-naphthalimide and thiophene-2-carbohydrazide as starting materials. TMN displayed superior stability in MeCN with an “on–off” mode towards Co2+, F−, and CN− by the naked eye. The linear response ranges of TMN were 0–3 and 4–19 μM with a detection limit of 0.21 μM for detecting Co2+, 0–5 and 5–22 μM with a detection limit of 0.36 μM for F−, and 0–10 and 10–25 μM with a detection limit of 0.49 μM for CN−. TMN could also recognize Co2+, F−, and CN− in real samples. Finally, the possible sensing mechanisms of TMN for detecting Co2+, F−, and CN− were deeply investigated. These results implied that TMN could be a potential chemosensor for monitoring metal cations and anions sensitively and selectively and could be used in real sample detection.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136249571","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 investigation of using medicinal plants for the production and application of silver nanoparticles (AgNPs) has attracted growing research interest. In this study, AgNPs are synthesized from the stem barks of the Pyrus pashia medicinal plant using a biosynthetic strategy. The reaction conditions were optimized under ambient conditions, including concentration, temperature, time, and pH, and various techniques were employed, such as UV-visible, FTIR, XRD, FESEM, and TEM, to characterize the synthesized AgNPs. The AgNPs produced through this biosynthesis method were found to be spherical and polydispersed, with an average size of 23.92 ± 7.04 nm. The synthesized AgNPs demonstrated an enhanced DPPH free radical scavenging capacity compared to the aqueous extract, with IC50 values of 10.67 ± 0.05 µg/mL and 13.66 ± 0.35 µg/mL, respectively. In the agar well diffusion method, the synthesized AgNPs showed higher antibacterial activity than that of the extract against Escherichia coli (ATCC 25922), Staphylococcus aureus (ATCC 25923), Enterococcus faecalis (ATCC 29212), Salmonella typhi (ATCC 14028), and Shigella sonnei (ATCC 25931). Based on these findings, the study suggests that green synthesized AgNPs from P. pashia could be used for biomedical applications.
{"title":"Stem Bark-Mediated Green Synthesis of Silver Nanoparticles from Pyrus pashia: Characterization, Antioxidant, and Antibacterial Properties","authors":"Lekha Nath Khanal, Purna Prasad Dhakal, Mani Ram Kandel, Debendra Acharya, Ek Raj Baral, Kisan Chhetri, Surya Kant Kalauni","doi":"10.3390/inorganics11060263","DOIUrl":"https://doi.org/10.3390/inorganics11060263","url":null,"abstract":"The investigation of using medicinal plants for the production and application of silver nanoparticles (AgNPs) has attracted growing research interest. In this study, AgNPs are synthesized from the stem barks of the Pyrus pashia medicinal plant using a biosynthetic strategy. The reaction conditions were optimized under ambient conditions, including concentration, temperature, time, and pH, and various techniques were employed, such as UV-visible, FTIR, XRD, FESEM, and TEM, to characterize the synthesized AgNPs. The AgNPs produced through this biosynthesis method were found to be spherical and polydispersed, with an average size of 23.92 ± 7.04 nm. The synthesized AgNPs demonstrated an enhanced DPPH free radical scavenging capacity compared to the aqueous extract, with IC50 values of 10.67 ± 0.05 µg/mL and 13.66 ± 0.35 µg/mL, respectively. In the agar well diffusion method, the synthesized AgNPs showed higher antibacterial activity than that of the extract against Escherichia coli (ATCC 25922), Staphylococcus aureus (ATCC 25923), Enterococcus faecalis (ATCC 29212), Salmonella typhi (ATCC 14028), and Shigella sonnei (ATCC 25931). Based on these findings, the study suggests that green synthesized AgNPs from P. pashia could be used for biomedical applications.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135236346","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}
Sb2(S, Se)3 solar cells have shown great promise due to the advantages of low cost, non-toxic and high stability. However, traditional devices commonly use noble metal as the back electrode, which not only increases device cost but also limits device stability. Herein, carbon materials are used to replace the noble metals in Sb2(S, Se)3 solar cells. In addition, to grow high-quality Sb2(S, Se)3 films, a two-step hydrothermal method was developed. The carbon-based Sb2(S, Se)3 solar cells based on the above film achieved a power conversion efficiency (PCE) of 2.76%. After inserting a stable P3HT layer at the Sb2(S, Se)3 film/carbon interface, hole extraction was enhanced and the PCE was promoted to 4.15%. This work brings out a promising route to produce emerging solar cells with cost-effective and stable materials.
{"title":"Carbon-Based Sb2(S, Se)3 Solar Cells","authors":"Yue Deng, Huicong Liu, Hailiang Wang, Yongfa Song, Weiping Li, Liqun Zhu, Xiangfan Xie, Shuang Xiao, Haining Chen","doi":"10.3390/inorganics11040159","DOIUrl":"https://doi.org/10.3390/inorganics11040159","url":null,"abstract":"Sb2(S, Se)3 solar cells have shown great promise due to the advantages of low cost, non-toxic and high stability. However, traditional devices commonly use noble metal as the back electrode, which not only increases device cost but also limits device stability. Herein, carbon materials are used to replace the noble metals in Sb2(S, Se)3 solar cells. In addition, to grow high-quality Sb2(S, Se)3 films, a two-step hydrothermal method was developed. The carbon-based Sb2(S, Se)3 solar cells based on the above film achieved a power conversion efficiency (PCE) of 2.76%. After inserting a stable P3HT layer at the Sb2(S, Se)3 film/carbon interface, hole extraction was enhanced and the PCE was promoted to 4.15%. This work brings out a promising route to produce emerging solar cells with cost-effective and stable materials.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135648010","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 : 2017-04-12DOI: 10.3390/INORGANICS5020023
O. Bokareva, Tobias Möhle, A. Neubauer, S. I. Bokarev, S. Lochbrunner, O. Kühn
Cyclometalated Ir(III) complexes are of particular interest due to the wide tunability of their electronic structure via variation of their ligands. Here, a series of heteroleptic Ir-based photosensitizers with the general formula [Ir(C^N)2(N^N)]+ has been studied theoretically by means of an optimally-tuned long-range separated density functional. Focusing on the steady-state absorption spectra, correlations between the chemical modification of both ligand types with the natures of the relevant dark and bright electronic states are revealed. Understanding such correlations builds up a basis for the rational design of efficient photocatalytic systems.
{"title":"Chemical Tuning and Absorption Properties of Iridium Photosensitizers for Photocatalytic Applications","authors":"O. Bokareva, Tobias Möhle, A. Neubauer, S. I. Bokarev, S. Lochbrunner, O. Kühn","doi":"10.3390/INORGANICS5020023","DOIUrl":"https://doi.org/10.3390/INORGANICS5020023","url":null,"abstract":"Cyclometalated Ir(III) complexes are of particular interest due to the wide tunability of their electronic structure via variation of their ligands. Here, a series of heteroleptic Ir-based photosensitizers with the general formula [Ir(C^N)2(N^N)]+ has been studied theoretically by means of an optimally-tuned long-range separated density functional. Focusing on the steady-state absorption spectra, correlations between the chemical modification of both ligand types with the natures of the relevant dark and bright electronic states are revealed. Understanding such correlations builds up a basis for the rational design of efficient photocatalytic systems.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2017-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80973318","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 : 2016-12-09DOI: 10.3390/INORGANICS4040041
Theresia M. M. Richter, Sabine Strobel, N. Alt, E. Schlücker, R. Niewa
The treatment of excess zinc in the presence of ammonium chloride under ammonothermal conditions of 873 K and 97 MPa leads to diamminetriamidodizinc chloride [Zn2(NH3)2(NH2)3]Cl with a two-dimensionally μ-amido-interconnected substructure. Similar reaction conditions using ammonium bromide instead of the chloride (773 K, 230 MPa) result in diamminemonoamidozinc bromide [Zn(NH3)2(NH2)]Br with one-dimensional infinite μ-amido-bridged chains. Both compounds were obtained as colorless, very moisture sensitive crystals. Crystal structures and hydrogen bond schemes are analyzed. Raman spectroscopic data of the chloride are reported.
{"title":"Ammonothermal Synthesis and Crystal Structures of Diamminetriamidodizinc Chloride [Zn2(NH3)2(NH2)3]Cl and Diamminemonoamidozinc Bromide [Zn(NH3)2(NH2)]Br","authors":"Theresia M. M. Richter, Sabine Strobel, N. Alt, E. Schlücker, R. Niewa","doi":"10.3390/INORGANICS4040041","DOIUrl":"https://doi.org/10.3390/INORGANICS4040041","url":null,"abstract":"The treatment of excess zinc in the presence of ammonium chloride under ammonothermal conditions of 873 K and 97 MPa leads to diamminetriamidodizinc chloride [Zn2(NH3)2(NH2)3]Cl with a two-dimensionally μ-amido-interconnected substructure. Similar reaction conditions using ammonium bromide instead of the chloride (773 K, 230 MPa) result in diamminemonoamidozinc bromide [Zn(NH3)2(NH2)]Br with one-dimensional infinite μ-amido-bridged chains. Both compounds were obtained as colorless, very moisture sensitive crystals. Crystal structures and hydrogen bond schemes are analyzed. Raman spectroscopic data of the chloride are reported.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78527798","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 : 2016-10-24DOI: 10.3390/INORGANICS4040033
A. Taubert, Christian Balischewski, Doreen Hentrich, Thomas Elschner, Sascha Eidner, C. Günter, Karsten Behrens, T. Heinze
The effect of cellulose-based polyelectrolytes on biomimetic calcium phosphate mineralization is described. Three cellulose derivatives, a polyanion, a polycation, and a polyzwitterion were used as additives. Scanning electron microscopy, X-ray diffraction, IR and Raman spectroscopy show that, depending on the composition of the starting solution, hydroxyapatite or brushite precipitates form. Infrared and Raman spectroscopy also show that significant amounts of nitrate ions are incorporated in the precipitates. Energy dispersive X-ray spectroscopy shows that the Ca/P ratio varies throughout the samples and resembles that of other bioinspired calcium phosphate hybrid materials. Elemental analysis shows that the carbon (i.e., polymer) contents reach 10% in some samples, clearly illustrating the formation of a true hybrid material. Overall, the data indicate that a higher polymer concentration in the reaction mixture favors the formation of polymer-enriched materials, while lower polymer concentrations or high precursor concentrations favor the formation of products that are closely related to the control samples precipitated in the absence of polymer. The results thus highlight the potential of (water-soluble) cellulose derivatives for the synthesis and design of bioinspired and bio-based hybrid materials.
{"title":"Water-Soluble Cellulose Derivatives Are Sustainable Additives for Biomimetic Calcium Phosphate Mineralization","authors":"A. Taubert, Christian Balischewski, Doreen Hentrich, Thomas Elschner, Sascha Eidner, C. Günter, Karsten Behrens, T. Heinze","doi":"10.3390/INORGANICS4040033","DOIUrl":"https://doi.org/10.3390/INORGANICS4040033","url":null,"abstract":"The effect of cellulose-based polyelectrolytes on biomimetic calcium phosphate mineralization is described. Three cellulose derivatives, a polyanion, a polycation, and a polyzwitterion were used as additives. Scanning electron microscopy, X-ray diffraction, IR and Raman spectroscopy show that, depending on the composition of the starting solution, hydroxyapatite or brushite precipitates form. Infrared and Raman spectroscopy also show that significant amounts of nitrate ions are incorporated in the precipitates. Energy dispersive X-ray spectroscopy shows that the Ca/P ratio varies throughout the samples and resembles that of other bioinspired calcium phosphate hybrid materials. Elemental analysis shows that the carbon (i.e., polymer) contents reach 10% in some samples, clearly illustrating the formation of a true hybrid material. Overall, the data indicate that a higher polymer concentration in the reaction mixture favors the formation of polymer-enriched materials, while lower polymer concentrations or high precursor concentrations favor the formation of products that are closely related to the control samples precipitated in the absence of polymer. The results thus highlight the potential of (water-soluble) cellulose derivatives for the synthesis and design of bioinspired and bio-based hybrid materials.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84077456","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 : 2016-09-20DOI: 10.3390/INORGANICS4030027
Adam N. Swinburne, Madeleine H. Langford Paden, T. Chan, S. Randall, F. Ortu, A. Kenwright, L. Natrajan
The construction of lanthanide(III) chelates that exhibit superior photophysical properties holds great importance in biological and materials science. One strategy to increase the luminescence properties of lanthanide(III) chelates is to hinder competitive non-radiative decay processes through perfluorination of the chelating ligands. Here, the synthesis of two families of heavily fluorinated lanthanide(III) β-diketonate complexes bearing monodentate perfluorinated tris phenyl phosphine oxide ligands have been prepared through a facile one pot reaction [Ln(hfac)3{(ArF)3PO}(H2O)] and [Ln(F7-acac)3{(ArF)3PO}2] (where Ln = Sm3+, Eu3+, Tb3+, Er3+ and Yb3+). Single crystal X-ray diffraction analysis in combination with photophysical studies have been performed to investigate the factors responsible for the differences in the luminescence lifetimes and intrinsic quantum yields of the complexes. Replacement of both bound H2O and C–H oscillators in the ligand backbone has a dramatic effect on the photophysical properties of the complexes, particularly for the near infra-red emitting ion Yb3+, where a five fold increase in luminescence lifetime and quantum yield is observed. The complexes [Sm(hfac)3{(ArF)3PO}(H2O)] (1), [Yb(hfac)3{(ArF)3PO}(H2O)] (5), [Sm(F7-acac)3{(ArF)3PO}2] (6) and [Yb(F7-acac)3{(ArF)3PO}2] (10) exhibit unusually long luminescence lifetimes and attractive intrinsic quantum yields of emission in fluid solution (ΦLn = 3.4% (1); 1.4% (10)) and in the solid state (ΦLn = 8.5% (1); 2.0% (5); 26% (6); 11% (10)), which are amongst the largest values for this class of compounds to date.
{"title":"Optical Properties of Heavily Fluorinated Lanthanide Tris β-Diketonate Phosphine Oxide Adducts","authors":"Adam N. Swinburne, Madeleine H. Langford Paden, T. Chan, S. Randall, F. Ortu, A. Kenwright, L. Natrajan","doi":"10.3390/INORGANICS4030027","DOIUrl":"https://doi.org/10.3390/INORGANICS4030027","url":null,"abstract":"The construction of lanthanide(III) chelates that exhibit superior photophysical properties holds great importance in biological and materials science. One strategy to increase the luminescence properties of lanthanide(III) chelates is to hinder competitive non-radiative decay processes through perfluorination of the chelating ligands. Here, the synthesis of two families of heavily fluorinated lanthanide(III) β-diketonate complexes bearing monodentate perfluorinated tris phenyl phosphine oxide ligands have been prepared through a facile one pot reaction [Ln(hfac)3{(ArF)3PO}(H2O)] and [Ln(F7-acac)3{(ArF)3PO}2] (where Ln = Sm3+, Eu3+, Tb3+, Er3+ and Yb3+). Single crystal X-ray diffraction analysis in combination with photophysical studies have been performed to investigate the factors responsible for the differences in the luminescence lifetimes and intrinsic quantum yields of the complexes. Replacement of both bound H2O and C–H oscillators in the ligand backbone has a dramatic effect on the photophysical properties of the complexes, particularly for the near infra-red emitting ion Yb3+, where a five fold increase in luminescence lifetime and quantum yield is observed. The complexes [Sm(hfac)3{(ArF)3PO}(H2O)] (1), [Yb(hfac)3{(ArF)3PO}(H2O)] (5), [Sm(F7-acac)3{(ArF)3PO}2] (6) and [Yb(F7-acac)3{(ArF)3PO}2] (10) exhibit unusually long luminescence lifetimes and attractive intrinsic quantum yields of emission in fluid solution (ΦLn = 3.4% (1); 1.4% (10)) and in the solid state (ΦLn = 8.5% (1); 2.0% (5); 26% (6); 11% (10)), which are amongst the largest values for this class of compounds to date.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74742416","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 : 2016-05-17DOI: 10.3390/INORGANICS4020015
Satoshi Matsunaga, Eriko Miyamae, Y. Inoue, K. Nomiya
The β,β-isomer of open-Wells–Dawson polyoxometalate (POM) containing a tetra-iron(III) cluster, K9[{Fe4(H2O)(OH)5}(β,β-Si2W18O66)]·17H2O (potassium salt of β,β-Fe4-open), was synthesized by reacting Na9H[A-β-SiW9O34]·23H2O with FeCl3·6H2O at pH 3, and characterized by X-ray crystallography, FTIR, elemental analysis, TG/DTA, UV–Vis, and cyclic voltammetry. X-ray crystallography revealed that the {Fe3+4(H2O)(OH)5}7+ cluster was included in the open pocket of the β,β-type open-Wells–Dawson polyanion [β,β-Si2W18O66]16− formed by the fusion of two trilacunary β-Keggin POMs, [A-β-SiW9O34]10−, via two W–O–W bonds. The β,β-open-Wells–Dawson polyanion corresponds to an open structure of the standard γ-Wells–Dawson POM. β,β-Fe4-open is the first example of the compound containing a geometrical isomer of α,α-open-Wells–Dawson structural POM.
{"title":"β,β-Isomer of Open-Wells–Dawson Polyoxometalate Containing a Tetra-Iron(III) Hydroxide Cluster: [{Fe4(H2O)(OH)5}(β,β-Si2W18O66)]9−","authors":"Satoshi Matsunaga, Eriko Miyamae, Y. Inoue, K. Nomiya","doi":"10.3390/INORGANICS4020015","DOIUrl":"https://doi.org/10.3390/INORGANICS4020015","url":null,"abstract":"The β,β-isomer of open-Wells–Dawson polyoxometalate (POM) containing a tetra-iron(III) cluster, K9[{Fe4(H2O)(OH)5}(β,β-Si2W18O66)]·17H2O (potassium salt of β,β-Fe4-open), was synthesized by reacting Na9H[A-β-SiW9O34]·23H2O with FeCl3·6H2O at pH 3, and characterized by X-ray crystallography, FTIR, elemental analysis, TG/DTA, UV–Vis, and cyclic voltammetry. X-ray crystallography revealed that the {Fe3+4(H2O)(OH)5}7+ cluster was included in the open pocket of the β,β-type open-Wells–Dawson polyanion [β,β-Si2W18O66]16− formed by the fusion of two trilacunary β-Keggin POMs, [A-β-SiW9O34]10−, via two W–O–W bonds. The β,β-open-Wells–Dawson polyanion corresponds to an open structure of the standard γ-Wells–Dawson POM. β,β-Fe4-open is the first example of the compound containing a geometrical isomer of α,α-open-Wells–Dawson structural POM.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73213871","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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