Lijun Wu, P. Geddis, Kun Liu, J. Hiscocks, William Courchesne
A corrosion study examined stainless steel S31600/SS316 after exposure to the liquid metal galinstan and gases including nitrogen, n-pentane, isobutane and R245fa at 150 °C under dynamic conditions for 3.5, 9.5 and 20.5 days. Ampules partly filled with galinstan and the gas were continuously stirred to create regions of gas-only, gas-liquid, and liquid-only exposure. Post test examinations used a variety of qualitative and quantitative methods (visual observation, scanning electron microscopy with energy dispersive X-ray spectroscopy, surface profilometry and chemical analysis) to evaluate coupons and galinstan samples for evidence of corrosion. In the gas-exposed region, no corrosion was detected in any coupon. In the liquid region, galinstan constituents were found to be localized to grain boundaries for nitrogen and isobutane coupons but dispersed on n-pentane coupons; a gallium oxide layer was found on R245fa coupons. In the liquid-gas interface region, severe corrosion was found on the n-pentane 20.5-day and the isobutane 9.5 and 20.5-day coupons; fine scattered corrosion on the R245fa 9.5-day coupon but not on the 20.5-day coupon was observed. Profilometry results indicated the least roughness change for coupons in n-pentane, a higher change in nitrogen, then in isobutane, and the highest in R245fa. In the presence of refrigerants and under dynamic conditions, intergranular attack on stainless steel may be enhanced by chemical reactions combined with microsegregation of galinstan or gallium oxide elements on stainless steel grain boundaries. Further work is required to confidently identify and explain this corrosion mechanism.
{"title":"The Corrosion Effect of Dynamic Liquid Metal Galinstan on Stainless Steel S31600/SS316 in the Presence of Selected Refrigerants at Temperatures up to 150 °C","authors":"Lijun Wu, P. Geddis, Kun Liu, J. Hiscocks, William Courchesne","doi":"10.1139/cjc-2022-0284","DOIUrl":"https://doi.org/10.1139/cjc-2022-0284","url":null,"abstract":"A corrosion study examined stainless steel S31600/SS316 after exposure to the liquid metal galinstan and gases including nitrogen, n-pentane, isobutane and R245fa at 150 °C under dynamic conditions for 3.5, 9.5 and 20.5 days. Ampules partly filled with galinstan and the gas were continuously stirred to create regions of gas-only, gas-liquid, and liquid-only exposure. Post test examinations used a variety of qualitative and quantitative methods (visual observation, scanning electron microscopy with energy dispersive X-ray spectroscopy, surface profilometry and chemical analysis) to evaluate coupons and galinstan samples for evidence of corrosion. In the gas-exposed region, no corrosion was detected in any coupon. In the liquid region, galinstan constituents were found to be localized to grain boundaries for nitrogen and isobutane coupons but dispersed on n-pentane coupons; a gallium oxide layer was found on R245fa coupons. In the liquid-gas interface region, severe corrosion was found on the n-pentane 20.5-day and the isobutane 9.5 and 20.5-day coupons; fine scattered corrosion on the R245fa 9.5-day coupon but not on the 20.5-day coupon was observed. Profilometry results indicated the least roughness change for coupons in n-pentane, a higher change in nitrogen, then in isobutane, and the highest in R245fa. In the presence of refrigerants and under dynamic conditions, intergranular attack on stainless steel may be enhanced by chemical reactions combined with microsegregation of galinstan or gallium oxide elements on stainless steel grain boundaries. Further work is required to confidently identify and explain this corrosion mechanism.","PeriodicalId":9420,"journal":{"name":"Canadian Journal of Chemistry","volume":"9 1","pages":""},"PeriodicalIF":1.1,"publicationDate":"2023-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90241051","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}
Extraction of experimental spectrum features from target molecules, for purpose of their detection, can be achieved by comparison to template spectra within a database. This study continues presentation of the concept of using density functional theory (DFT). DFT-calculated spectra are well posed for comparison to measured spectra, to the extent of their scalability to larger space–time scales. Specifically, the focus of this study is the scalability of DFT-calculated IR spectra with respect to meso- and macroscales, characteristic of dielectric response as measured using different IR spectroscopies. A case-study analysis concerning IR spectra scalability for caffeine is described. Caffeine is only used as an example of analysis that can be applied to PFAS molecules, which are our major interest.
{"title":"Micro-to-macroscaling of DFT-calculated IR spectra for spectrum-feature extraction and estimation of dielectric response","authors":"S. Lambrakos, A. Shabaev, S. Wallace, L. Massa","doi":"10.1139/cjc-2023-0018","DOIUrl":"https://doi.org/10.1139/cjc-2023-0018","url":null,"abstract":"Extraction of experimental spectrum features from target molecules, for purpose of their detection, can be achieved by comparison to template spectra within a database. This study continues presentation of the concept of using density functional theory (DFT). DFT-calculated spectra are well posed for comparison to measured spectra, to the extent of their scalability to larger space–time scales. Specifically, the focus of this study is the scalability of DFT-calculated IR spectra with respect to meso- and macroscales, characteristic of dielectric response as measured using different IR spectroscopies. A case-study analysis concerning IR spectra scalability for caffeine is described. Caffeine is only used as an example of analysis that can be applied to PFAS molecules, which are our major interest.","PeriodicalId":9420,"journal":{"name":"Canadian Journal of Chemistry","volume":"33 1","pages":""},"PeriodicalIF":1.1,"publicationDate":"2023-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78080744","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}
In this study, we used computational quantum chemistry to investigate the cation affinity for a range of nucleophiles to gauge the possibility of using organochalcogens as catalysts for cation transfer (reference data and geometries are provided in the repository https://github.com/armanderch/ca176 ). In general, the calculated gas-phase cation affinities decrease in the order Cl+ > Br+ > I+ > carbon-centered cation, the anionic nucleophiles have significantly larger cation affinities than the neutral ones, sulfides have larger cation affinities than selenides, and solvation lowers the cation affinities and especially for anionic nucleophiles. These observations are consistent with general chemical intuitions. The energies for the resulting condensed-phase cation transfer reactions show that transferring a carbon-centered cation from a neutral source (e.g., Me2CO3) to a chalcogen nucleophile (e.g., Me2S) is thermochemically viable. However, they are associated with large kinetic barriers. Overall, we find that SeMeC6H5 may be a suitable catalyst for transferring a carbon-centered cation from an active source such as MeCO3R or MeSO4R. In this study, we also find that double-hybrid DFT methods, e.g., DSD-PBEP86 to be reasonable for the study of these cation transfer processes.
{"title":"The prospects of cation transfer to chalcogen nucleophiles","authors":"B. Chan, S. Shirakawa","doi":"10.1139/cjc-2022-0222","DOIUrl":"https://doi.org/10.1139/cjc-2022-0222","url":null,"abstract":"In this study, we used computational quantum chemistry to investigate the cation affinity for a range of nucleophiles to gauge the possibility of using organochalcogens as catalysts for cation transfer (reference data and geometries are provided in the repository https://github.com/armanderch/ca176 ). In general, the calculated gas-phase cation affinities decrease in the order Cl+ > Br+ > I+ > carbon-centered cation, the anionic nucleophiles have significantly larger cation affinities than the neutral ones, sulfides have larger cation affinities than selenides, and solvation lowers the cation affinities and especially for anionic nucleophiles. These observations are consistent with general chemical intuitions. The energies for the resulting condensed-phase cation transfer reactions show that transferring a carbon-centered cation from a neutral source (e.g., Me2CO3) to a chalcogen nucleophile (e.g., Me2S) is thermochemically viable. However, they are associated with large kinetic barriers. Overall, we find that SeMeC6H5 may be a suitable catalyst for transferring a carbon-centered cation from an active source such as MeCO3R or MeSO4R. In this study, we also find that double-hybrid DFT methods, e.g., DSD-PBEP86 to be reasonable for the study of these cation transfer processes.","PeriodicalId":9420,"journal":{"name":"Canadian Journal of Chemistry","volume":"5 1","pages":""},"PeriodicalIF":1.1,"publicationDate":"2023-05-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91080271","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}
Antimonous oxide (Sb2O3) has intriguing physical and chemical features that make it useful in various device applications, including solar cells. Nanofilms of Sb2O3:0.02wt.% CuO were prepared onto glass and silicon substrates etched by laser using a thermal evaporation process in a vacuum, with different thicknesses of about (20, 30, and 40 nm). The deposited nanofilms have no distinguishing peaks in XRD analysis. The broadening of the peak shows due to the absence of long-range symmetry as a result, the nanocrystalline structure is disorganized. SEM analysis of the surface morphology of the formed nanofilms showed spread out uniformly and were devoid of islands and voids. The particles were all about the same size, and the new structures were created with a thickness of 40 nm. AFM scanning images showed the nanofilms' homogeneous surface morphology with granular shape. As nanofilm thickness increased, so was average roughness, root mean square value and grain diameter. Optical characteristics revealed a reduction in the transmittance spectrum with increasing thicknesses. Instead, the optical energy gap (E_g^opt) was decreased by quantum confinement from 3.56 to 3.48 eV. The electrical properties of the nanofilms were analyzed, and it was found that all were n-type and that mobility (µ) decreased with nanofilm thickness. As shown by the I-V characteristics, the solar cell's conversion efficiency increases to (6.373%) at power = 100 mW/cm2 with (0.138) filling factor, (4V) of open circuit voltage, and (2.6 mA) of short circuit.
{"title":"Solar Cell of Sb2O3:CuO/Si Prepared Via Thermal Evaporation Technique: Structural, Morphological Properties, and Efficiency","authors":"A. Attia, Foaad Shakir, K. Abass","doi":"10.1139/cjc-2023-0001","DOIUrl":"https://doi.org/10.1139/cjc-2023-0001","url":null,"abstract":"Antimonous oxide (Sb2O3) has intriguing physical and chemical features that make it useful in various device applications, including solar cells. Nanofilms of Sb2O3:0.02wt.% CuO were prepared onto glass and silicon substrates etched by laser using a thermal evaporation process in a vacuum, with different thicknesses of about (20, 30, and 40 nm). The deposited nanofilms have no distinguishing peaks in XRD analysis. The broadening of the peak shows due to the absence of long-range symmetry as a result, the nanocrystalline structure is disorganized. SEM analysis of the surface morphology of the formed nanofilms showed spread out uniformly and were devoid of islands and voids. The particles were all about the same size, and the new structures were created with a thickness of 40 nm. AFM scanning images showed the nanofilms' homogeneous surface morphology with granular shape. As nanofilm thickness increased, so was average roughness, root mean square value and grain diameter. Optical characteristics revealed a reduction in the transmittance spectrum with increasing thicknesses. Instead, the optical energy gap (E_g^opt) was decreased by quantum confinement from 3.56 to 3.48 eV. The electrical properties of the nanofilms were analyzed, and it was found that all were n-type and that mobility (µ) decreased with nanofilm thickness. As shown by the I-V characteristics, the solar cell's conversion efficiency increases to (6.373%) at power = 100 mW/cm2 with (0.138) filling factor, (4V) of open circuit voltage, and (2.6 mA) of short circuit.","PeriodicalId":9420,"journal":{"name":"Canadian Journal of Chemistry","volume":"36 1","pages":""},"PeriodicalIF":1.1,"publicationDate":"2023-05-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73669938","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}
The density functional theory (DFT) was used to calculate the reaction mechanism and selectivity of nonmetallic single-atom catalysts, such as N, O, and P, doped on graphene in the direct dehydrogenation of propane (PDH). Our results show that the rate-controlling step in PDH varies with the doping atom. We also found that N, O, and P nonmetallic single-atom-doped graphene catalysts showed relatively low adsorption performance for propane and the active site was the C atom adjacent to N, O, P, rather than the doped atom itself. Interestingly, for the O-doped graphene catalysts which can reduce the reaction energy barrier by searching for multiple transition states. Finally, the results show that the energy barrier of P-doped propane direct dehydrogenation reflecting the speed control step is the lowest, which is 44.32 kcal·mol−1, and the energy barrier of deep dehydrogenation is 53.08 kcal·mol−1, so it has good selectivity. Therefore, the P-doped graphene catalyst has a promising application as a nonmetallic catalyst for the direct dehydrogenation of propane, which provides the possibility for the design of cheap and environmentally friendly catalysts.
采用密度泛函理论(DFT)计算了石墨烯上掺杂N、O、P等非金属单原子催化剂在丙烷直接脱氢反应中的反应机理和选择性。结果表明，PDH的速率控制步长随掺杂原子的不同而不同。我们还发现，N, O, P非金属单原子掺杂石墨烯催化剂对丙烷的吸附性能相对较低，活性位点是与N, O, P相邻的C原子，而不是掺杂原子本身。有趣的是，掺杂o的石墨烯催化剂可以通过寻找多个过渡态来降低反应能垒。结果表明，p掺杂丙烷直接脱氢反应反应速度控制阶跃的能势垒最低，为44.32 kcal·mol−1，深度脱氢反应的能势垒为53.08 kcal·mol−1，具有较好的选择性。因此，p掺杂石墨烯催化剂作为丙烷直接脱氢的非金属催化剂具有广阔的应用前景，为设计廉价环保的催化剂提供了可能。
{"title":"Density Functional Theory Study on Direct Dehydrogenation of Propane Catalyzed by N, O, P Doped Graphene Catalysts","authors":"De-min Liu, Xunchao Zhang, Lihua Kang, Mingyuan Zhu","doi":"10.1139/cjc-2023-0020","DOIUrl":"https://doi.org/10.1139/cjc-2023-0020","url":null,"abstract":"The density functional theory (DFT) was used to calculate the reaction mechanism and selectivity of nonmetallic single-atom catalysts, such as N, O, and P, doped on graphene in the direct dehydrogenation of propane (PDH). Our results show that the rate-controlling step in PDH varies with the doping atom. We also found that N, O, and P nonmetallic single-atom-doped graphene catalysts showed relatively low adsorption performance for propane and the active site was the C atom adjacent to N, O, P, rather than the doped atom itself. Interestingly, for the O-doped graphene catalysts which can reduce the reaction energy barrier by searching for multiple transition states. Finally, the results show that the energy barrier of P-doped propane direct dehydrogenation reflecting the speed control step is the lowest, which is 44.32 kcal·mol−1, and the energy barrier of deep dehydrogenation is 53.08 kcal·mol−1, so it has good selectivity. Therefore, the P-doped graphene catalyst has a promising application as a nonmetallic catalyst for the direct dehydrogenation of propane, which provides the possibility for the design of cheap and environmentally friendly catalysts.","PeriodicalId":9420,"journal":{"name":"Canadian Journal of Chemistry","volume":" 15","pages":""},"PeriodicalIF":1.1,"publicationDate":"2023-05-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72382389","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}
Hannah Valencia, A. Yeboah, Steve Turita, Kyle Joshua Muñoz, Arnold C. Gaje, Chenille Rose Siva, M. F. Paige, Concepcion P. Ponce
Luminescent carbon dots (CDs) are emerging carbon nanomaterials whose tunable and exceptional optoelectronic properties have found applications as alternatives to traditional fluorophores and metal-based catalysts. Further, they can be easily prepared from biomass and using green solvents. Biomass sources of CDs, however, often result in the formation of thousands of products which are difficult to separate. In this study, CDs were synthesized using a urea-choline chloride deep eutectic solvent (DES) and shrimp shell-derived chitin as raw materials through a low temperature solvothermal treatment. This was followed by a facile liquid-liquid extraction with acetone to improve the optical properties and narrow the size distribution of the CDs. The acetone-extracted CDs (ACDs) showed good performance in photocatalytic degradation of the aquatic pollutant, malachite green. They also show good potential in monitoring various toxic water pollutants through the quenching effect of selected pesticides, antibiotics, heavy metals and anions on the fluorescence of ACDs.
{"title":"Urea-choline chloride deep eutectic solvent-assisted synthesis of luminescent nitrogen-doped carbon dots from chitin and their photocatalytic application in decolourizing malachite green","authors":"Hannah Valencia, A. Yeboah, Steve Turita, Kyle Joshua Muñoz, Arnold C. Gaje, Chenille Rose Siva, M. F. Paige, Concepcion P. Ponce","doi":"10.1139/cjc-2023-0016","DOIUrl":"https://doi.org/10.1139/cjc-2023-0016","url":null,"abstract":"Luminescent carbon dots (CDs) are emerging carbon nanomaterials whose tunable and exceptional optoelectronic properties have found applications as alternatives to traditional fluorophores and metal-based catalysts. Further, they can be easily prepared from biomass and using green solvents. Biomass sources of CDs, however, often result in the formation of thousands of products which are difficult to separate. In this study, CDs were synthesized using a urea-choline chloride deep eutectic solvent (DES) and shrimp shell-derived chitin as raw materials through a low temperature solvothermal treatment. This was followed by a facile liquid-liquid extraction with acetone to improve the optical properties and narrow the size distribution of the CDs. The acetone-extracted CDs (ACDs) showed good performance in photocatalytic degradation of the aquatic pollutant, malachite green. They also show good potential in monitoring various toxic water pollutants through the quenching effect of selected pesticides, antibiotics, heavy metals and anions on the fluorescence of ACDs.","PeriodicalId":9420,"journal":{"name":"Canadian Journal of Chemistry","volume":"64 1","pages":""},"PeriodicalIF":1.1,"publicationDate":"2023-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72806558","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}
The structural biology renaissance has created new opportunities for both understanding mechanisms of action of many dynamic protein complexes and advancing drug discovery. 19F NMR can play a key role in both protein and ligand NMR. In particular, through judiciously labeling the protein target with CF3 reporters, functional states can be monitored as a function of ligand or drug candidate so as to understand their mechanism of action or response. At the same time, Fragment Based Drug Discovery (FBDD) using fluorinated libraries enables the rapid detection of binders and their elaboration toward lead compounds. New trends will likely employ fluorinated tags with improved chemical shift sensitivity and reporters that can be biosynthetically incorporated via AMBER stop codon technologies. At the same time, FBDD will be greatly improved by promising new fluorinated libraries in combination with improved computational methods for predicting lead compounds.
{"title":"A Beginner's Guide to 19F NMR and its Role in Drug Discovery","authors":"S. Prosser","doi":"10.1139/cjc-2023-0028","DOIUrl":"https://doi.org/10.1139/cjc-2023-0028","url":null,"abstract":"The structural biology renaissance has created new opportunities for both understanding mechanisms of action of many dynamic protein complexes and advancing drug discovery. 19F NMR can play a key role in both protein and ligand NMR. In particular, through judiciously labeling the protein target with CF3 reporters, functional states can be monitored as a function of ligand or drug candidate so as to understand their mechanism of action or response. At the same time, Fragment Based Drug Discovery (FBDD) using fluorinated libraries enables the rapid detection of binders and their elaboration toward lead compounds. New trends will likely employ fluorinated tags with improved chemical shift sensitivity and reporters that can be biosynthetically incorporated via AMBER stop codon technologies. At the same time, FBDD will be greatly improved by promising new fluorinated libraries in combination with improved computational methods for predicting lead compounds.","PeriodicalId":9420,"journal":{"name":"Canadian Journal of Chemistry","volume":"60 1","pages":""},"PeriodicalIF":1.1,"publicationDate":"2023-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86820309","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}
Cohan Huxley, Callum Lucas, Juan Manuel Mesa Bruno, Matthew J Anketell, Emma K. Davison, G. Muir, Matthew B. Nodwell, Michael Meanwell, S. Silverman, Robert Britton, Louis-Charles Campeau
α-heteroaryl acetaldehydes have become important building blocks in the synthesis of synthetic nucleosides. Novel organocatalytic cascades have enabled the rapid generation of nucleosides, which are valuable building blocks in the development of antisense oligonucleotides or as stand-alone antiviral and anticancer therapies, obviating the need for laborious synthetic routes relying on chiral pool starting materials and inefficient synthetic routes. This manuscript describes a robust and scalable protocol to α-heteroaryl acetaldehydes from readily available building blocks.
{"title":"Efficient protocol for the preparation of α-heteroaryl acetaldehydes","authors":"Cohan Huxley, Callum Lucas, Juan Manuel Mesa Bruno, Matthew J Anketell, Emma K. Davison, G. Muir, Matthew B. Nodwell, Michael Meanwell, S. Silverman, Robert Britton, Louis-Charles Campeau","doi":"10.1139/cjc-2022-0275","DOIUrl":"https://doi.org/10.1139/cjc-2022-0275","url":null,"abstract":"α-heteroaryl acetaldehydes have become important building blocks in the synthesis of synthetic nucleosides. Novel organocatalytic cascades have enabled the rapid generation of nucleosides, which are valuable building blocks in the development of antisense oligonucleotides or as stand-alone antiviral and anticancer therapies, obviating the need for laborious synthetic routes relying on chiral pool starting materials and inefficient synthetic routes. This manuscript describes a robust and scalable protocol to α-heteroaryl acetaldehydes from readily available building blocks.","PeriodicalId":9420,"journal":{"name":"Canadian Journal of Chemistry","volume":"1 1","pages":""},"PeriodicalIF":1.1,"publicationDate":"2023-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76953544","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}
Luana L.T.N. Porto, Moutasem Seifi, Nicole Johnson, R. Baker
Given the importance of fluorinated drugs and agrochemicals, fluoroalkylation of organic electrophiles that can be performed at a late stage of chemical synthesis has attracted a flurry of contributions. New fluoroalkyl groups can be obtained by insertion of fluoroalkenes into Cu–H bonds. Chlorotrifluoroethylene undergoes regioselective insertion in its reaction with Stryker's reagent, [CuH(PPh3)]6 and triphos to give [Cu(CFClCF2H)(μ−κ1,κ2-triphos)]2, which mediates the fluoroalkylation of several aroyl chlorides (triphos = bis(2-diphenylphosphinoethyl)-phenylphosphine). In contrast, attempted −RF transfer to aryl iodides instead affords aryl–aryl coupling products.
{"title":"Generation of copper fluoroalkyl complexes (CuRFLn) from chlorotrifluoroethylene and −RF transfer to aroyl chlorides","authors":"Luana L.T.N. Porto, Moutasem Seifi, Nicole Johnson, R. Baker","doi":"10.1139/cjc-2022-0240","DOIUrl":"https://doi.org/10.1139/cjc-2022-0240","url":null,"abstract":"Given the importance of fluorinated drugs and agrochemicals, fluoroalkylation of organic electrophiles that can be performed at a late stage of chemical synthesis has attracted a flurry of contributions. New fluoroalkyl groups can be obtained by insertion of fluoroalkenes into Cu–H bonds. Chlorotrifluoroethylene undergoes regioselective insertion in its reaction with Stryker's reagent, [CuH(PPh3)]6 and triphos to give [Cu(CFClCF2H)(μ−κ1,κ2-triphos)]2, which mediates the fluoroalkylation of several aroyl chlorides (triphos = bis(2-diphenylphosphinoethyl)-phenylphosphine). In contrast, attempted −RF transfer to aryl iodides instead affords aryl–aryl coupling products.","PeriodicalId":9420,"journal":{"name":"Canadian Journal of Chemistry","volume":"1 1","pages":""},"PeriodicalIF":1.1,"publicationDate":"2023-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91126101","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}
Marilyne Bélanger-Bouliga, N. Kihal, Hanae Mahious, P. T. Nguyen, S. Bourgault, A. Nazemi
Gold nanoparticles (AuNPs) have found use in broad range of applications such as in catalysis and nanomedicine. Despite the fact that thiol-based AuNPs have been widely studied, they suffer from relative instability in various conditions, such as high and low temperatures, pH variations, and are prone to oxidation. Over the last decade, N-heterocyclic carbenes (NHCs) have been under spotlight as suitable ligands to stabilize metal nanoparticles and surfaces. Although NHC-functionalized AuNPs have been shown to outperform their thiol-based analogs in terms of stability, their applications in nanomedicine have not been realized. Hybrid nanomaterials, such as AuNPs tagged with π-conjugated molecules with aggregation-induced emission (AIE) property, are promising candidates to develop fluorescent materials for cellular imaging. The combination of NHC-stabilized AuNPs with AIE to form stable, fluorescent hybrid AuNPs is of significant interest to open the door to develop new NHC-based nanomaterials. Herein, we report the synthesis and characterization of water-soluble fluorescent NHC-decorated AuNPs for potential applications in nanomedicine. Their stability in biologically relevant conditions is investigated.
{"title":"Synthesis and characterization of tetraphenylethylene-functionalized N-heterocyclic carbene-stabilized gold nanoparticles with aggregation-induced emission","authors":"Marilyne Bélanger-Bouliga, N. Kihal, Hanae Mahious, P. T. Nguyen, S. Bourgault, A. Nazemi","doi":"10.1139/cjc-2022-0260","DOIUrl":"https://doi.org/10.1139/cjc-2022-0260","url":null,"abstract":"Gold nanoparticles (AuNPs) have found use in broad range of applications such as in catalysis and nanomedicine. Despite the fact that thiol-based AuNPs have been widely studied, they suffer from relative instability in various conditions, such as high and low temperatures, pH variations, and are prone to oxidation. Over the last decade, N-heterocyclic carbenes (NHCs) have been under spotlight as suitable ligands to stabilize metal nanoparticles and surfaces. Although NHC-functionalized AuNPs have been shown to outperform their thiol-based analogs in terms of stability, their applications in nanomedicine have not been realized. Hybrid nanomaterials, such as AuNPs tagged with π-conjugated molecules with aggregation-induced emission (AIE) property, are promising candidates to develop fluorescent materials for cellular imaging. The combination of NHC-stabilized AuNPs with AIE to form stable, fluorescent hybrid AuNPs is of significant interest to open the door to develop new NHC-based nanomaterials. Herein, we report the synthesis and characterization of water-soluble fluorescent NHC-decorated AuNPs for potential applications in nanomedicine. Their stability in biologically relevant conditions is investigated.","PeriodicalId":9420,"journal":{"name":"Canadian Journal of Chemistry","volume":"109 1","pages":""},"PeriodicalIF":1.1,"publicationDate":"2023-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82565169","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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