Trans-1,2-difluoroethylene (R-1132(E)) is expected as a next-generation refrigerant component because of its ultra-low global warming potential (GWP) compared to previous refrigerants. However, R-1132(E) is unstable and self-decomposed in the presence of an ignition source similar to tetrafluoroethylene (TFE) and trifluoroethylene (HFO-1123). In this reseach, the self-decomposition of R-1132(E) and its mixture was investigated by spark generator to elucidate the self-decomposition limit conditions in terms of initial gas pressure (p0) and spark discharge energy (Ed). It was found that the Ed for self-decomposition of R-1132(E) and its mixture depends on the p0 and there is the relationship of Ed ∝ 1/p02. The self-decomposition boundary (SDB) in Ed was increased with increasing discharge duration. The study of SDB in p0 for R-1132(E) mixed with 2,3,3,3-tetrafluoropropene (R-1234yf) indicated the relationship of R-1132(E) density ∝ R-1234yf density. From the above two relationships it was possible to predict SDB in p0 for any Ed.
{"title":"Evaluation of self-decomposition of trans-1,2-difluoroethylene by spark ignition","authors":"Takashi Usui , Tomoyuki Goto , Takashi Yoshimura , Yasufu Yamada , Kaito Santa , Yasuhiro Oshime , Kenji Takizawa , Takaaki Mizutani","doi":"10.1016/j.jfluchem.2025.110463","DOIUrl":"10.1016/j.jfluchem.2025.110463","url":null,"abstract":"<div><div>Trans-1,2-difluoroethylene (R-1132(E)) is expected as a next-generation refrigerant component because of its ultra-low global warming potential (GWP) compared to previous refrigerants. However, R-1132(E) is unstable and self-decomposed in the presence of an ignition source similar to tetrafluoroethylene (TFE) and trifluoroethylene (HFO-1123). In this reseach, the self-decomposition of R-1132(E) and its mixture was investigated by spark generator to elucidate the self-decomposition limit conditions in terms of initial gas pressure (<em>p</em><sub>0</sub>) and spark discharge energy (<em>E</em><sub>d</sub>). It was found that the <em>E</em><sub>d</sub> for self-decomposition of R-1132(E) and its mixture depends on the <em>p</em><sub>0</sub> and there is the relationship of <em>E</em><sub>d</sub> ∝ 1/<em>p</em><sub>0</sub><sup>2</sup>. The self-decomposition boundary (SDB) in <em>E</em><sub>d</sub> was increased with increasing discharge duration. The study of SDB in <em>p</em><sub>0</sub> for R-1132(E) mixed with 2,3,3,3-tetrafluoropropene (R-1234yf) indicated the relationship of R-1132(E) density ∝ R-1234yf density. From the above two relationships it was possible to predict SDB in <em>p</em><sub>0</sub> for any <em>E</em><sub>d</sub>.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110463"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145027549","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-10-08DOI: 10.1016/j.jfluchem.2025.110486
Yi Hu , Hao Yan , Jian Liu , Wensheng Chen , Xiaomeng Zhou
Trifluoroiodomethane (CF₃I), due to its environmental friendliness, has emerged as a promising PFAS-Alternative refrigerant. In practical applications, the compatibility between CF₃I and rubber materials is a critical parameter to ensure its long-term and safe operation in refrigeration systems. Therefore, this study systematically investigates the compatibility of CF₃I with two commonly used sealing elastomers in refrigeration systems—chloroprene rubber (CR) and acrylic rubber (ACM)—under conditions of 25 °C and 0.1 MPa. The elastomers were subjected to comprehensive physical and mechanical property evaluations, including weight, volume, hardness, tensile strength, elongation at break, and crosslinking density, as well as surface morphology analysis, elemental and functional group characterization. Additionally, molecular dynamics (MD) simulations were employed to analyze interfacial interactions. Experimental results revealed notable degradation in mechanical performance and microstructural integrity of both CR rubber and ACM rubber upon exposure to CF₃I. This degradation was primarily attributed to CF₃I-induced swelling and the disruption of chain packing due to non-covalent interactions between CF₃I molecules and polymer chains. MD simulations further showed that CF₃I exhibited a higher diffusion coefficient in ACM (16.53 × 10⁻⁶ cm²/s) compared to CR (7.25 × 10⁻⁶ cm²/s). CF₃I predominantly adsorbs onto polar groups in the rubber matrix (such as C–Cl and C = O) via van der Waals interactions, promoting interfacial accumulation and migration, which may compromise material stability. Integrating experimental and simulation findings, the compatibility of CF₃I with both CR and ACM is concluded to be relatively poor.
{"title":"Compatibility study of PFAS-alternative refrigerant CF₃I with common refrigeration elastomers","authors":"Yi Hu , Hao Yan , Jian Liu , Wensheng Chen , Xiaomeng Zhou","doi":"10.1016/j.jfluchem.2025.110486","DOIUrl":"10.1016/j.jfluchem.2025.110486","url":null,"abstract":"<div><div>Trifluoroiodomethane (CF₃I), due to its environmental friendliness, has emerged as a promising PFAS-Alternative refrigerant. In practical applications, the compatibility between CF₃I and rubber materials is a critical parameter to ensure its long-term and safe operation in refrigeration systems. Therefore, this study systematically investigates the compatibility of CF₃I with two commonly used sealing elastomers in refrigeration systems—chloroprene rubber (CR) and acrylic rubber (ACM)—under conditions of 25 °C and 0.1 MPa. The elastomers were subjected to comprehensive physical and mechanical property evaluations, including weight, volume, hardness, tensile strength, elongation at break, and crosslinking density, as well as surface morphology analysis, elemental and functional group characterization. Additionally, molecular dynamics (MD) simulations were employed to analyze interfacial interactions. Experimental results revealed notable degradation in mechanical performance and microstructural integrity of both CR rubber and ACM rubber upon exposure to CF₃I. This degradation was primarily attributed to CF₃I-induced swelling and the disruption of chain packing due to non-covalent interactions between CF₃I molecules and polymer chains. MD simulations further showed that CF₃I exhibited a higher diffusion coefficient in ACM (16.53 × 10⁻⁶ cm²/s) compared to CR (7.25 × 10⁻⁶ cm²/s). CF₃I predominantly adsorbs onto polar groups in the rubber matrix (such as C–Cl and <em>C</em> = <em>O</em>) via van der Waals interactions, promoting interfacial accumulation and migration, which may compromise material stability. Integrating experimental and simulation findings, the compatibility of CF₃I with both CR and ACM is concluded to be relatively poor.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110486"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145332616","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-08-29DOI: 10.1016/j.jfluchem.2025.110464
Hao Huang , Jing Leng , Jie Xu , lei Zhou , Mingxing Li , Diandian Ni , Zhenzhong Ding , Xiaoyan Gao
Background
4-Hydroxyphenylpyruvate dioxygenase (HPPD) plays a crucial role in addressing issues related to plant protection research. To further our efforts in discovering new HPPD inhibitors, we adopted a bioisomerization strategy and designed a series of novel fluorinated aryloxyacetic acid scaffolds, building upon previously identified aryloxyacetic acid scaffolds. This study offers new insights into the discovery of innovative HPPD inhibitors. A series of novel HPPD inhibitor candidates (fluorinated derivatives of aryloxyacetic acids) were synthesized, and their activity was systematically evaluated using in vitro enzymatic methods and greenhouse experiments. Preliminary in vitro studies confirmed that these compounds effectively inhibit AtHPPD enzyme activity. Subsequent greenhouse experiments demonstrated that compounds 2,2-difluoro-1-(5‑hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)-2-(4-phenoxyphenoxy) ethan-1-one and 2,2-difluoro-1-(5‑hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)-2-(naphthalen-2-yloxy) ethan-1-one exhibited exceptional herbicidal activity against the tested weeds, outperforming Mesotrione under identical testing conditions. These findings suggest that fluorine-modified aryloxyacetic acid derivatives have the potential to serve as lead compounds in the development of HPPD inhibitors.
{"title":"Discovery of novel fluorine modification of aryloxyacetic acid derivatives as 4-hydroxyphenylpyruvate dioxygenase inhibitors","authors":"Hao Huang , Jing Leng , Jie Xu , lei Zhou , Mingxing Li , Diandian Ni , Zhenzhong Ding , Xiaoyan Gao","doi":"10.1016/j.jfluchem.2025.110464","DOIUrl":"10.1016/j.jfluchem.2025.110464","url":null,"abstract":"<div><h3>Background</h3><div>4-Hydroxyphenylpyruvate dioxygenase (HPPD) plays a crucial role in addressing issues related to plant protection research. To further our efforts in discovering new HPPD inhibitors, we adopted a bioisomerization strategy and designed a series of novel fluorinated aryloxyacetic acid scaffolds, building upon previously identified aryloxyacetic acid scaffolds. This study offers new insights into the discovery of innovative HPPD inhibitors. A series of novel HPPD inhibitor candidates (fluorinated derivatives of aryloxyacetic acids) were synthesized, and their activity was systematically evaluated using <em>in vitro</em> enzymatic methods and greenhouse experiments. Preliminary <em>in vitro</em> studies confirmed that these compounds effectively inhibit <em>At</em>HPPD enzyme activity. Subsequent greenhouse experiments demonstrated that compounds 2,2-difluoro-1-(5‑hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)-2-(4-phenoxyphenoxy) ethan-1-one and 2,2-difluoro-1-(5‑hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)-2-(naphthalen-2-yloxy) ethan-1-one exhibited exceptional herbicidal activity against the tested weeds, outperforming Mesotrione under identical testing conditions. These findings suggest that fluorine-modified aryloxyacetic acid derivatives have the potential to serve as lead compounds in the development of HPPD inhibitors.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110464"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144912366","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-09-04DOI: 10.1016/j.jfluchem.2025.110476
Jingjing Liu , Runlong Yang , Yang Li , Benli Liu , Ming Yang , Shuangshuang Tian
Perfluorohexanone (C6F12O) has been widely used in fire suppression systems for energy storage battery. However, toxic gases such as CO, CO2, HF, and COF2 produced during extinguishing process pose significant risks to human health and equipment safety, making it essential to monitor them. Recent studies show that metal-doped Transition Metal Dichalcogenides (TMDs) exhibit excellent gas adsorption properties, demonstrating great potential in gas sensing applications. To further explore this potential, Pd doped MoTe2 is selected in this paper, for which the doping process is simulated and the adsorption properties are systematically investigated. These configurations are analyzed using the Electron Localization Function (ELF), the Independent Gradient Model based on Hirshfeld partition (IGMH), and the Density of States (DOS). Finally, the gas sensing capabilities of Pd-MoTe2 are comprehensively evaluated to investigate its viability as a sensing material. The results reveal that Pd-MoTe2 exhibits strong adsorption for CO and COF2, with adsorption energies of -1.866 eV and -0.935 eV, respectively. Furthermore, the IGMH and ELF analyses confirm the existence of chemical bonding between the CO, COF2, and the Pd atoms. The DOS study further verifies the phenomenon of orbital hybridization. Additionally, the recovery time of Pd-MoTe2 requires high temperatures to release CO, but it is ideal for COF2, making it suitable for the adsorption of CO and the detection of COF₂. The results of this research can provide a theoretical foundation and data support for the application of Pd-MoTe2.
{"title":"First-principles study of the adsorption performance of Pd-MoTe2 on decomposition products of perfluorohexanone fire extinguishing agents","authors":"Jingjing Liu , Runlong Yang , Yang Li , Benli Liu , Ming Yang , Shuangshuang Tian","doi":"10.1016/j.jfluchem.2025.110476","DOIUrl":"10.1016/j.jfluchem.2025.110476","url":null,"abstract":"<div><div>Perfluorohexanone (C<sub>6</sub>F<sub>12</sub>O) has been widely used in fire suppression systems for energy storage battery. However, toxic gases such as CO, CO<sub>2</sub>, HF, and COF<sub>2</sub> produced during extinguishing process pose significant risks to human health and equipment safety, making it essential to monitor them. Recent studies show that metal-doped Transition Metal Dichalcogenides (TMDs) exhibit excellent gas adsorption properties, demonstrating great potential in gas sensing applications. To further explore this potential, Pd doped MoTe<sub>2</sub> is selected in this paper, for which the doping process is simulated and the adsorption properties are systematically investigated. These configurations are analyzed using the Electron Localization Function (ELF), the Independent Gradient Model based on Hirshfeld partition (IGMH), and the Density of States (DOS). Finally, the gas sensing capabilities of Pd-MoTe<sub>2</sub> are comprehensively evaluated to investigate its viability as a sensing material. The results reveal that Pd-MoTe<sub>2</sub> exhibits strong adsorption for CO and COF<sub>2</sub>, with adsorption energies of -1.866 eV and -0.935 eV, respectively. Furthermore, the IGMH and ELF analyses confirm the existence of chemical bonding between the CO, COF<sub>2</sub>, and the Pd atoms. The DOS study further verifies the phenomenon of orbital hybridization. Additionally, the recovery time of Pd-MoTe<sub>2</sub> requires high temperatures to release CO, but it is ideal for COF<sub>2</sub>, making it suitable for the adsorption of CO and the detection of COF₂. The results of this research can provide a theoretical foundation and data support for the application of Pd-MoTe<sub>2</sub>.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110476"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145010586","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-09-30DOI: 10.1016/j.jfluchem.2025.110481
Suming Jing , Zhineng Wang , Keyao Li , Qianxiong Chen , Xuesong Zhang , Wei Zhang , Mingwei Liu
The design and synthesis of high-performance melt-cast explosive carriers are of strategic significance for advancing weapon system technologies. In this study, three fluorinated benzene-based melt-cast explosive carriers—3-fluoro-2,4,6-trinitroanisole (FTNAN), 3-fluoro-2,4,6-trinitrotoluene (FTNT), and 1-fluoro-2,4-dinitro-5-(trifluoromethyl)benzene (TFDNT)—were synthesized using benzene rings as the molecular scaffold, with fluorine atoms and nitro groups serving as energetic modifiers. Structural characterization was systematically conducted through Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (¹H/¹³C NMR), elemental analysis, and differential scanning calorimetry (DSC). Single-crystal X-ray diffraction unambiguously confirmed their molecular configurations. Energetic performance evaluation involved computational modeling using Gaussian 09 (heat of formation calculations) and EXPLO5 (detonation parameter predictions). Experimental and theoretical analyses demonstrated that FTNAN and FTNT exhibit superior properties.
{"title":"Synthesis and characterization of fluorinated benzene-based carriers for melt-cast explosives","authors":"Suming Jing , Zhineng Wang , Keyao Li , Qianxiong Chen , Xuesong Zhang , Wei Zhang , Mingwei Liu","doi":"10.1016/j.jfluchem.2025.110481","DOIUrl":"10.1016/j.jfluchem.2025.110481","url":null,"abstract":"<div><div>The design and synthesis of high-performance melt-cast explosive carriers are of strategic significance for advancing weapon system technologies. In this study, three fluorinated benzene-based melt-cast explosive carriers—3-fluoro-2,4,6-trinitroanisole (FTNAN), 3-fluoro-2,4,6-trinitrotoluene (FTNT), and 1-fluoro-2,4-dinitro-5-(trifluoromethyl)benzene (TFDNT)—were synthesized using benzene rings as the molecular scaffold, with fluorine atoms and nitro groups serving as energetic modifiers. Structural characterization was systematically conducted through Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (¹H/¹³C NMR), elemental analysis, and differential scanning calorimetry (DSC). Single-crystal X-ray diffraction unambiguously confirmed their molecular configurations. Energetic performance evaluation involved computational modeling using Gaussian 09 (heat of formation calculations) and EXPLO5 (detonation parameter predictions). Experimental and theoretical analyses demonstrated that FTNAN and FTNT exhibit superior properties.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110481"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145262785","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-09-02DOI: 10.1016/j.jfluchem.2025.110475
Ahmed Aldulaimi , Shakir Mahmood Saeed , Soumya V Menon , Waam Mohammed Taher , Ruya yilmaz saber , Subhashree Ray , Karthikeyan Jayabalan , Aashna Sinha , Mariem Alwan , Renu Sharma
This review gives an overview of the synthesis of difluoromethyl thioethers through the S-difluoromethylation of corresponding aromatic thiols. The review has been classified based on the type of difluoromethyling agents (i.e., organosulfur-based difluoromethylating agents, organosilicon-based difluoromethylating agents, organophosphorus-based difluoromethylating agents) and surveyed the literature up until the end of 2024.
{"title":"Direct S-difluoromethylation of thiols: A facile synthetic route to difluoromethyl thioethers","authors":"Ahmed Aldulaimi , Shakir Mahmood Saeed , Soumya V Menon , Waam Mohammed Taher , Ruya yilmaz saber , Subhashree Ray , Karthikeyan Jayabalan , Aashna Sinha , Mariem Alwan , Renu Sharma","doi":"10.1016/j.jfluchem.2025.110475","DOIUrl":"10.1016/j.jfluchem.2025.110475","url":null,"abstract":"<div><div>This review gives an overview of the synthesis of difluoromethyl thioethers through the <em>S</em>-difluoromethylation of corresponding aromatic thiols. The review has been classified based on the type of difluoromethyling agents (<em>i.e</em>., organosulfur-based difluoromethylating agents, organosilicon-based difluoromethylating agents, organophosphorus-based difluoromethylating agents) and surveyed the literature up until the end of 2024.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110475"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145216483","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-10-02DOI: 10.1016/j.jfluchem.2025.110483
Viktor G. Makotchenko , Alexander M. Panich , Ekaterina D. Grayfer
Fluorinated graphitic materials are widely studied for various applications including energy storage, lubricants, hydrophobic coatings, neutron reflectors, etc. Here, we investigate the F2 gas fluorination of three starting graphitic materials with different thicknesses: graphite, multi-layer graphene, and “graphene paper”. All synthesized products exhibit similar interplanar spacings, FTIR and XPS spectral characteristics, and similar compositions corresponding to graphite monofluoride CF1.12. However, the thickness of the starting compound affects the temperature required for the fluorination and the decomposition temperatures of the resulting fluorides. Fluorinated graphite CF1.12 prepared from graphite is stable up to 600 °C, while the stability drops dramatically for the fluorinated multi-layer graphene, which starts decomposing already at 100 °C. Besides, few-layer CF1.12 forms stable colloidal dispersions in organic media, unlike its thicker counterpart. The obtained results will facilitate structural engineering of fluorinated nanographite materials to optimize their properties for potential applications.
{"title":"Effect of graphene stack thickness on gaseous fluorination of graphitic materials","authors":"Viktor G. Makotchenko , Alexander M. Panich , Ekaterina D. Grayfer","doi":"10.1016/j.jfluchem.2025.110483","DOIUrl":"10.1016/j.jfluchem.2025.110483","url":null,"abstract":"<div><div>Fluorinated graphitic materials are widely studied for various applications including energy storage, lubricants, hydrophobic coatings, neutron reflectors, etc. Here, we investigate the F<sub>2</sub> gas fluorination of three starting graphitic materials with different thicknesses: graphite, multi-layer graphene, and “graphene paper”. All synthesized products exhibit similar interplanar spacings, FTIR and XPS spectral characteristics, and similar compositions corresponding to graphite monofluoride CF<sub>1.12</sub>. However, the thickness of the starting compound affects the temperature required for the fluorination and the decomposition temperatures of the resulting fluorides. Fluorinated graphite CF<sub>1.12</sub> prepared from graphite is stable up to 600 °C, while the stability drops dramatically for the fluorinated multi-layer graphene, which starts decomposing already at 100 °C. Besides, few-layer CF<sub>1.12</sub> forms stable colloidal dispersions in organic media, unlike its thicker counterpart. The obtained results will facilitate structural engineering of fluorinated nanographite materials to optimize their properties for potential applications.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110483"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145262786","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-10-07DOI: 10.1016/j.jfluchem.2025.110484
Olena Voloshyna , Bohdan Moroz , Kostiantyn P. Melnykov , Serhii Holovach , Dmytro Lesyk , Yuliia Holota , Petro Borysko , Andrey A. Filatov , Oleksandr O. Grygorenko
An expedient gram-scale synthesis of stereochemically pure exo- and endo-5,5-difluorooctahydropentalen-2-amines – valuable building blocks for medicinal chemistry – is described. The method commenced from the commercially available Weiss diketone. The compound’s stereochemistry was controlled using diastereoselective NaBH4-mediated reduction and Mitsunobu reaction at the corresponding steps. To install the gem‑difluorinated moiety, classical DAST-mediated deoxofluorination was employed. Physicochemical properties of the synthesized compounds (pKa and LogP) demonstrated their potential for applications in drug discovery as cyclohexane replacements.
{"title":"Gram-scale synthesis and physicochemical properties of exo- and endo-5,5-difluorooctahydropentalen-2-amines","authors":"Olena Voloshyna , Bohdan Moroz , Kostiantyn P. Melnykov , Serhii Holovach , Dmytro Lesyk , Yuliia Holota , Petro Borysko , Andrey A. Filatov , Oleksandr O. Grygorenko","doi":"10.1016/j.jfluchem.2025.110484","DOIUrl":"10.1016/j.jfluchem.2025.110484","url":null,"abstract":"<div><div>An expedient gram-scale synthesis of stereochemically pure exo- and endo-5,5-difluorooctahydropentalen-2-amines – valuable building blocks for medicinal chemistry – is described. The method commenced from the commercially available Weiss diketone. The compound’s stereochemistry was controlled using diastereoselective NaBH<sub>4</sub>-mediated reduction and Mitsunobu reaction at the corresponding steps. To install the gem‑difluorinated moiety, classical DAST-mediated deoxofluorination was employed. Physicochemical properties of the synthesized compounds (pK<sub>a</sub> and LogP) demonstrated their potential for applications in drug discovery as cyclohexane replacements.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110484"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145262788","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-09-18DOI: 10.1016/j.jfluchem.2025.110477
Mannab Yu. Tashmetov , Normamat B. Ismatov , Shermakhmat M. Makhkamov , Sadulla.R. Allayarov , Matthew P. Confer , David A. Dixon
The effect of γ-irradiation on the post-irradiation thermoluminescent and photoluminescent properties of an industrial ethylene-tetrafluoroethylene (ETFE) copolymer was investigated. The radiothermoluminescence (RTL) curve in the temperature range of 77 to 400 K exhibits three maxima: the most intense peak occurs at 116 K, while two additional maxima appear as shoulders at 168 K and 210 K. These maxima result from the formation and subsequent quenching of electronically excited states caused by the recombination of charge carriers accumulated during γ-irradiation of the copolymer at 77 K. Photoluminescence arises from the radiative recombination of excitons formed in the copolymer upon photoexcitation with a xenon lamp at 300 K. The photoluminescence maximum occurs at 340 nm, and its intensity decreases as the γ-irradiation dose increases. Structural defects and macromolecular cross-linking induced by γ-irradiation act as centers of nonradiative exciton recombination, thereby reducing the intensity of the post-irradiation luminescence of the copolymer. Electronic structure predictions of the degradation thermodynamics indicate that polymer backbone degradation through either loss of small unsaturated molecules or carbenes is unfavorable at room temperature but is possible under γ-irradiation conditions.
{"title":"Post-Irradiation photoluminescence and thermoluminescence of the ethylene-tetrafluoroethylene copolymer","authors":"Mannab Yu. Tashmetov , Normamat B. Ismatov , Shermakhmat M. Makhkamov , Sadulla.R. Allayarov , Matthew P. Confer , David A. Dixon","doi":"10.1016/j.jfluchem.2025.110477","DOIUrl":"10.1016/j.jfluchem.2025.110477","url":null,"abstract":"<div><div>The effect of γ-irradiation on the post-irradiation thermoluminescent and photoluminescent properties of an industrial ethylene-tetrafluoroethylene (ETFE) copolymer was investigated. The radiothermoluminescence (RTL) curve in the temperature range of 77 to 400 K exhibits three maxima: the most intense peak occurs at 116 K, while two additional maxima appear as shoulders at 168 K and 210 K. These maxima result from the formation and subsequent quenching of electronically excited states caused by the recombination of charge carriers accumulated during γ-irradiation of the copolymer at 77 K. Photoluminescence arises from the radiative recombination of excitons formed in the copolymer upon photoexcitation with a xenon lamp at 300 K. The photoluminescence maximum occurs at 340 nm, and its intensity decreases as the γ-irradiation dose increases. Structural defects and macromolecular cross-linking induced by γ-irradiation act as centers of nonradiative exciton recombination, thereby reducing the intensity of the post-irradiation luminescence of the copolymer. Electronic structure predictions of the degradation thermodynamics indicate that polymer backbone degradation through either loss of small unsaturated molecules or carbenes is unfavorable at room temperature but is possible under γ-irradiation conditions.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110477"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145105781","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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