Pub Date : 2025-11-26DOI: 10.1016/j.jfluchem.2025.110510
Razieh Masoomifard , Ali Darehkordi , Marziyeh Mohammadi , Mohammad Salarvand
As part of this study, we successfully synthesized trifluoromethylated thieno[3,2-d]pyrimidin-4(3H)-one derivatives, which have the potential to be biologically active. These derivatives were produced through a condensation-cyclization reaction between 3-aminothiophene-2-carboxamide derivatives and 2,2,2-trifluoroacetimidoyl chlorides. The reaction took place in the presence of a palladium catalyst. In the course of this research, good yields of 3-aminothiophene-2-carboxamide intermediates were achieved by utilizing morpholine as a catalyst in the condensation of a cyclic ketone, cyanoacetamide, and sulfur. Based on the results of molecular docking tests conducted with cyclic nucleotide phosphodiesterases (PDEs) receptors, it was discovered that the dimethoxyphenyl derivative 6a exhibited the lowest binding energy, with a value of -1453.42 kJ/mol. Furthermore, a theoretical investigation was carried out by employing density functional theory (DFT) with the 6–311++G(d, p) basis set in order to analyze the electronic structures, geometries, and reactivity features of molecular compounds. The findings showed that compounds (5a-5d) have a better level of stability in comparison to compounds (6a-6f), with compound 5d displaying noteworthy reactivity as a result of its reduced energy gap (7.957 eV) and higher electrophilicity (2.327).
{"title":"Palladium catalyst synthesis, computational chemical study and molecular docking of a new series of (aryl)-2-(trifluoromethyl) tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidin-4(3H)-one derivatives","authors":"Razieh Masoomifard , Ali Darehkordi , Marziyeh Mohammadi , Mohammad Salarvand","doi":"10.1016/j.jfluchem.2025.110510","DOIUrl":"10.1016/j.jfluchem.2025.110510","url":null,"abstract":"<div><div>As part of this study, we successfully synthesized trifluoromethylated thieno[3,2-d]pyrimidin-4(3H)-one derivatives, which have the potential to be biologically active. These derivatives were produced through a condensation-cyclization reaction between 3-aminothiophene-2-carboxamide derivatives and 2,2,2-trifluoroacetimidoyl chlorides. The reaction took place in the presence of a palladium catalyst. In the course of this research, good yields of 3-aminothiophene-2-carboxamide intermediates were achieved by utilizing morpholine as a catalyst in the condensation of a cyclic ketone, cyanoacetamide, and sulfur. Based on the results of molecular docking tests conducted with cyclic nucleotide phosphodiesterases (PDEs) receptors, it was discovered that the dimethoxyphenyl derivative 6a exhibited the lowest binding energy, with a value of -1453.42 kJ/mol. Furthermore, a theoretical investigation was carried out by employing density functional theory (DFT) with the 6–311++<em>G</em>(d, p) basis set in order to analyze the electronic structures, geometries, and reactivity features of molecular compounds. The findings showed that compounds (5a-5d) have a better level of stability in comparison to compounds (6a-6f), with compound 5d displaying noteworthy reactivity as a result of its reduced energy gap (7.957 eV) and higher electrophilicity (2.327).</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"289 ","pages":"Article 110510"},"PeriodicalIF":1.9,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145617277","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 : 2025-11-20DOI: 10.1016/j.jfluchem.2025.110509
Nafi Farzana , Roman Glaznev , Guanyu Wang , Sumit Agarwal , Ravi Fernandes , Joachim Beeckmann , Bo Shu
As global climate goals drive the transition away from high-GWP refrigerants, understanding the combustion behavior of low- and medium-GWP alternatives is essential for emissions control and fire safety assessment. This study presents a combined experimental and modeling investigation of difluoromethane (CH2F2, R32), methane (CH4, R50), and their blends. Shock tube experiments were performed over 1477-2236 K at 0.98-1.15 bar for ϕ = 0.5-2.0, with ignition delay times (IDTs) determined from time-resolved CO measurements using laser absorption spectroscopy. Complementary laminar flame speed data for CH2F2 and CH2F2/CH4 blends supported model validation. CH2F2 ignited 4-10 times faster than CH4, while blends exhibited intermediate but nonlinear IDTs due to radical cross-interactions. Time-resolved CO profiles showed broad peaks for CH2F2-containing mixtures, unlike the sharp CO peaks of CH4, indicating prolonged intermediate chemistry involving CHF, CHF2, CHFO, CF2O, and HF. Laminar flame speeds confirmed slower propagation for CH2F2 compared to CH4, while CH4 addition increased sensitivity to oxidizer composition. Kinetic analysis revealed that CH2F2 ignition is dominated by fluorine-centered pathways involving unimolecular decomposition and H-abstraction forming CHF/CHF2 radicals, with CF2O and HF as major termination products, whereas CH4 follows conventional H/O chain branching. Genetic algorithm optimization of 18 sensitive reactions within uncertainty bounds reduced IDT prediction errors by 71 % for CH2F2 and 63 % for CH2F2/CH4 blends. The optimized mechanism improved CO and flame speed predictions, achieving good agreement with experimental data within reported uncertainties. This integrated framework refines the high-temperature oxidation chemistry of fluorinated refrigerants and provides a validated mechanism for reliable fire safety evaluation.
随着全球气候目标推动高gwp制冷剂的转型，了解低gwp和中等gwp替代品的燃烧行为对于排放控制和消防安全评估至关重要。本研究对二氟甲烷（CH2F2, R32）、甲烷（CH4, R50）及其共混物进行了实验和模型研究。激波管实验在1477-2236 K， 0.98-1.15 bar, φ = 0.5-2.0下进行，点火延迟时间（IDTs）由激光吸收光谱从时间分辨CO测量确定。CH2F2和CH2F2/CH4混合物的互补层流火焰速度数据支持模型验证。CH2F2的点燃速度是CH4的4-10倍，而共混物由于自由基交叉作用表现出中间但非线性的IDTs。时间分辨CO谱图显示含有ch2f2的混合物具有宽峰，而不像CH4的CO峰具有尖峰，这表明涉及CHF、CHF2、CHFO、CF2O和HF的中间化学反应持续时间较长。层流火焰速度证实CH2F2的传播速度比CH4慢，而CH4的加入增加了对氧化剂成分的敏感性。动力学分析表明，CH2F2的燃烧以氟为中心的单分子分解和H萃取途径为主，形成CHF/CHF2自由基，CF2O和HF是主要终止产物，而CH4则遵循常规的H/O链分支。遗传算法优化了18个不确定范围内的敏感反应，使CH2F2的IDT预测误差降低了71%，CH2F2/CH4混合物的IDT预测误差降低了63%。优化后的机制改善了CO和火焰速度的预测，在报道的不确定度范围内与实验数据吻合良好。这一综合框架完善了含氟制冷剂的高温氧化化学，并为可靠的消防安全评估提供了一种经过验证的机制。
{"title":"Shock tube and laminar flame studies of CH2F2, CH4, and their blends with genetic algorithm-based mechanism optimization","authors":"Nafi Farzana , Roman Glaznev , Guanyu Wang , Sumit Agarwal , Ravi Fernandes , Joachim Beeckmann , Bo Shu","doi":"10.1016/j.jfluchem.2025.110509","DOIUrl":"10.1016/j.jfluchem.2025.110509","url":null,"abstract":"<div><div>As global climate goals drive the transition away from high-GWP refrigerants, understanding the combustion behavior of low- and medium-GWP alternatives is essential for emissions control and fire safety assessment. This study presents a combined experimental and modeling investigation of difluoromethane (CH<sub>2</sub>F<sub>2</sub>, R32), methane (CH<sub>4</sub>, R50), and their blends. Shock tube experiments were performed over 1477-2236 K at 0.98-1.15 bar for <em>ϕ</em> = 0.5-2.0, with ignition delay times (IDTs) determined from time-resolved CO measurements using laser absorption spectroscopy. Complementary laminar flame speed data for CH<sub>2</sub>F<sub>2</sub> and CH<sub>2</sub>F<sub>2</sub>/CH<sub>4</sub> blends supported model validation. CH<sub>2</sub>F<sub>2</sub> ignited 4-10 times faster than CH<sub>4</sub>, while blends exhibited intermediate but nonlinear IDTs due to radical cross-interactions. Time-resolved CO profiles showed broad peaks for CH<sub>2</sub>F<sub>2</sub>-containing mixtures, unlike the sharp CO peaks of CH<sub>4</sub>, indicating prolonged intermediate chemistry involving CHF, CHF<sub>2</sub>, CHFO, CF<sub>2</sub>O, and HF. Laminar flame speeds confirmed slower propagation for CH<sub>2</sub>F<sub>2</sub> compared to CH<sub>4</sub>, while CH<sub>4</sub> addition increased sensitivity to oxidizer composition. Kinetic analysis revealed that CH<sub>2</sub>F<sub>2</sub> ignition is dominated by fluorine-centered pathways involving unimolecular decomposition and H-abstraction forming CHF/CHF<sub>2</sub> radicals, with CF<sub>2</sub>O and HF as major termination products, whereas CH<sub>4</sub> follows conventional H/O chain branching. Genetic algorithm optimization of 18 sensitive reactions within uncertainty bounds reduced IDT prediction errors by 71 % for CH<sub>2</sub>F<sub>2</sub> and 63 % for CH<sub>2</sub>F<sub>2</sub>/CH<sub>4</sub> blends. The optimized mechanism improved CO and flame speed predictions, achieving good agreement with experimental data within reported uncertainties. This integrated framework refines the high-temperature oxidation chemistry of fluorinated refrigerants and provides a validated mechanism for reliable fire safety evaluation.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"289 ","pages":"Article 110509"},"PeriodicalIF":1.9,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145617184","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 : 2025-11-18DOI: 10.1016/j.jfluchem.2025.110507
Jiaxin He , Shuo Sun , Hongjun Li , Wei Du , Hongwei Zhang , Danying Zuo
Flat porous membranes of polyvinylidene fluoride (PVDF) were synthesized utilizing a water-soluble polyester (WSPET) as a pore-forming agent through immersion precipitation phase inversion. The influence of different WSPET contents on the thermodynamic stability of the casting solution, membrane structure, and performance was investigated. The findings indicated that the incorporation of WSPET diminished the thermodynamic stability of the casting solution, thereby increasing its susceptibility to immediate liquid-liquid phase separation. The mobility of the chain segments was hindered and the crystallinity of the membranes decreased with the α-crystal content decreasing and the β-crystal content increasing. With increasing WSPET content, the porosity, mean pore size and water fluxes of the membranes increased and the contact angle on the surface decreased. The top surface of the membranes with added WSPET exhibited a porous structure and a finger-like macroporous structure in the membrane. Dynamic cyclic filtration experiments showed that with WSPET content increasing, the rejection rate of the PVDF membranes decreased, the flux recovery rates of the PVDF membranes exceeded those of the blank membrane, while both the reversible and irreversible fouling rates of the membranes were lower in comparison to the blank membrane. These results indicate that using WSPET as a pore-forming agent improved PVDF membrane hydrophilicity and enhanced the water flux and antifouling properties.
{"title":"The structure and performance of polyvinylidene fluoride membranes by using water-soluble polyester as an additive via immersion precipitation phase inversion","authors":"Jiaxin He , Shuo Sun , Hongjun Li , Wei Du , Hongwei Zhang , Danying Zuo","doi":"10.1016/j.jfluchem.2025.110507","DOIUrl":"10.1016/j.jfluchem.2025.110507","url":null,"abstract":"<div><div>Flat porous membranes of polyvinylidene fluoride (PVDF) were synthesized utilizing a water-soluble polyester (WSPET) as a pore-forming agent through immersion precipitation phase inversion. The influence of different WSPET contents on the thermodynamic stability of the casting solution, membrane structure, and performance was investigated. The findings indicated that the incorporation of WSPET diminished the thermodynamic stability of the casting solution, thereby increasing its susceptibility to immediate liquid-liquid phase separation. The mobility of the chain segments was hindered and the crystallinity of the membranes decreased with the α-crystal content decreasing and the β-crystal content increasing. With increasing WSPET content, the porosity, mean pore size and water fluxes of the membranes increased and the contact angle on the surface decreased. The top surface of the membranes with added WSPET exhibited a porous structure and a finger-like macroporous structure in the membrane. Dynamic cyclic filtration experiments showed that with WSPET content increasing, the rejection rate of the PVDF membranes decreased, the flux recovery rates of the PVDF membranes exceeded those of the blank membrane, while both the reversible and irreversible fouling rates of the membranes were lower in comparison to the blank membrane. These results indicate that using WSPET as a pore-forming agent improved PVDF membrane hydrophilicity and enhanced the water flux and antifouling properties.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"289 ","pages":"Article 110507"},"PeriodicalIF":1.9,"publicationDate":"2025-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145617278","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 : 2025-11-01DOI: 10.1016/j.jfluchem.2025.110503
Martin Möbs , Jan Moritz , Thomas Schwarze , Michael Pittroff , Florian Kraus
We investigated whether diluted fluorine gas (Solvaclean N, 30 % F2, 40 % N2, 30 % Ar) escaping from test leaks in prepassivated tubes or unpassivated disks can cause a metal fluorine fire. Tested tubes and disks were made out of stainless steel, 316 L (1.4404) or 316Ti (1.4571). For the simulation of damage leading to tube leaks, cuts were made using a hacksaw and an angle grinder, or a tube was squeezed together at its open end. A metal drill bit was used to make holes into test disks. Visual observations were made to determine whether corrosion, sparking, or a metal fluorine fire would occur when F2 flows through the leaks. The tests were documented photographically, and the temperature changes close to the test leaks were tracked using a thermocouple. Under the conditions selected here, no ignition could be observed in any case, whether the F2 escaped at 7 bars within 90 s or at 93 bars within a single second in a burst-like scenario. In addition, no temperature increase was detected.
{"title":"Fluorine gas (30%) escaping through leaks in stainless steels at 7 and 93 bars of pressure did not cause metal-fluorine fires","authors":"Martin Möbs , Jan Moritz , Thomas Schwarze , Michael Pittroff , Florian Kraus","doi":"10.1016/j.jfluchem.2025.110503","DOIUrl":"10.1016/j.jfluchem.2025.110503","url":null,"abstract":"<div><div>We investigated whether diluted fluorine gas (Solvaclean N, 30 % F<sub>2</sub>, 40 % N<sub>2</sub>, 30 % Ar) escaping from test leaks in prepassivated tubes or unpassivated disks can cause a metal fluorine fire. Tested tubes and disks were made out of stainless steel, 316 L (1.4404) or 316Ti (1.4571). For the simulation of damage leading to tube leaks, cuts were made using a hacksaw and an angle grinder, or a tube was squeezed together at its open end. A metal drill bit was used to make holes into test disks. Visual observations were made to determine whether corrosion, sparking, or a metal fluorine fire would occur when F<sub>2</sub> flows through the leaks. The tests were documented photographically, and the temperature changes close to the test leaks were tracked using a thermocouple. Under the conditions selected here, no ignition could be observed in any case, whether the F<sub>2</sub> escaped at 7 bars within 90 s or at 93 bars within a single second in a burst-like scenario. In addition, no temperature increase was detected.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"288 ","pages":"Article 110503"},"PeriodicalIF":1.9,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145464220","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 : 2025-11-01DOI: 10.1016/j.jfluchem.2025.110488
Yasser Ahmad
Per- and polyfluoroalkyl substances (PFAS) are a broad range of synthetic organofluorine compounds with >10,000 structures identified to date. Among them, only a limited subset of water-soluble compounds, specifically perfluoroalkyl acids (PFAAs, as PFCAs and PFSAs) and perfluoroether carboxylic acids (PFECAs, e.g. GenX), are relevant to adsorptive water and wastewater treatment. Many of these compounds are highly persistent, some subclasses bioaccumulate and several subclasses have been linked to adverse health and ecological effects. Conventional adsorbents like granular activated carbon (GAC), ion-exchange resins (IER), and membranes provide low efficiencies especially for short- and ultra-short-chain PFAAs, highlighting the need for next-generation solutions.
This review examines fluorinated porous materials (FPMs) as emerging adsorbents with attractive properties, and highlights their unique ability to leverage fluorine–fluorine (F···F) interactions, hydrophobic affinity, and electrostatics. Compared to conventional adsorbents FPMs represent a promising alternative with superior performance, particularly for short- and ultra-short-chain PFAS. We conceptualize fluoroaffinity not simply as an interaction but as a unifying design principle linking PFAS persistence and adsorbent design. We present structure-performance relationships, quantitative thresholds, and applied metrics and considerations of scaling, regenerability, techno-economics, and regulation. By merging mechanistic understanding with practical application, this work reframes soluble PFAS remediation through a design-oriented perspective to guide the development of next-generation materials for selective capture.
{"title":"Fluorinated porous materials for PFAS remediation: fluoroaffinity as a central design principle","authors":"Yasser Ahmad","doi":"10.1016/j.jfluchem.2025.110488","DOIUrl":"10.1016/j.jfluchem.2025.110488","url":null,"abstract":"<div><div>Per- and polyfluoroalkyl substances (PFAS) are a broad range of synthetic organofluorine compounds with >10,000 structures identified to date. Among them, only a limited subset of water-soluble compounds, specifically perfluoroalkyl acids (PFAAs, as PFCAs and PFSAs) and perfluoroether carboxylic acids (PFECAs, e.g. GenX), are relevant to adsorptive water and wastewater treatment. Many of these compounds are highly persistent, some subclasses bioaccumulate and several subclasses have been linked to adverse health and ecological effects. Conventional adsorbents like granular activated carbon (GAC), ion-exchange resins (IER), and membranes provide low efficiencies especially for short- and ultra-short-chain PFAAs, highlighting the need for next-generation solutions.</div><div>This review examines fluorinated porous materials (FPMs) as emerging adsorbents with attractive properties, and highlights their unique ability to leverage fluorine–fluorine (F···F) interactions, hydrophobic affinity, and electrostatics. Compared to conventional adsorbents FPMs represent a promising alternative with superior performance, particularly for short- and ultra-short-chain PFAS. We conceptualize fluoroaffinity not simply as an interaction but as a unifying design principle linking PFAS persistence and adsorbent design. We present structure-performance relationships, quantitative thresholds, and applied metrics and considerations of scaling, regenerability, techno-economics, and regulation. By merging mechanistic understanding with practical application, this work reframes soluble PFAS remediation through a design-oriented perspective to guide the development of next-generation materials for selective capture.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"288 ","pages":"Article 110488"},"PeriodicalIF":1.9,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145464221","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 : 2025-11-01DOI: 10.1016/j.jfluchem.2025.110502
Cristian R. Andriolli, Ariadne G.L.P. Gonçalves, Paola A. Mello, Erico M.M. Flores, Rochele S. Picoloto
A simple and accurate method for animal feed digestion using microwave-induced combustion (MIC) followed by fluoride determination by potentiometry with an ion-selective electrode is proposed as an alternative to the AOAC official method (no. 975.08). For the MIC method, only oxygen (20 bar) and a few microliters of NH4NO3 solution (6 mol l-1) were used for the digestion of animal feed (500 mg). Fluoride was recovered in a diluted NH4OH solution (100 mmol l-1). The accuracy of the MIC and AOAC methods was verified using a standard reference material of oyster tissue (NIST 1566a). Utilizing MIC for sample preparation showed good agreement (close to 100 %), whereas the AOAC method yielded inaccurate results (around 30 % agreement). Recovery experiments demonstrated 95 and 35 % for the MIC and AOAC methods, respectively. Consequently, the combination of MIC and potentiometry is considered a viable alternative to the AOAC method for fluoride determination in animal feed. The detection and quantification limits were low, at 0.5 and 1.6 µg g-1, respectively. Finally, the MIC method presented several advantages over the AOAC method, including high digestion efficiency, reduced risk of contamination, and prevention of fluorine loss. Additionally, MIC required minimal reagent use, resulting in lower laboratory waste generation, aligning with trends in Green Analytical Chemistry practices.
{"title":"Potentiometric determination of fluoride in animal feed after microwave-induced combustion: A simple, efficient, and accurate approach","authors":"Cristian R. Andriolli, Ariadne G.L.P. Gonçalves, Paola A. Mello, Erico M.M. Flores, Rochele S. Picoloto","doi":"10.1016/j.jfluchem.2025.110502","DOIUrl":"10.1016/j.jfluchem.2025.110502","url":null,"abstract":"<div><div>A simple and accurate method for animal feed digestion using microwave-induced combustion (MIC) followed by fluoride determination by potentiometry with an ion-selective electrode is proposed as an alternative to the AOAC official method (no. 975.08). For the MIC method, only oxygen (20 bar) and a few microliters of NH<sub>4</sub>NO<sub>3</sub> solution (6 mol <span>l</span><sup>-1</sup>) were used for the digestion of animal feed (500 mg). Fluoride was recovered in a diluted NH<sub>4</sub>OH solution (100 mmol <span>l</span><sup>-1</sup>). The accuracy of the MIC and AOAC methods was verified using a standard reference material of oyster tissue (NIST 1566a). Utilizing MIC for sample preparation showed good agreement (close to 100 %), whereas the AOAC method yielded inaccurate results (around 30 % agreement). Recovery experiments demonstrated 95 and 35 % for the MIC and AOAC methods, respectively. Consequently, the combination of MIC and potentiometry is considered a viable alternative to the AOAC method for fluoride determination in animal feed. The detection and quantification limits were low, at 0.5 and 1.6 µg g<sup>-1</sup>, respectively. Finally, the MIC method presented several advantages over the AOAC method, including high digestion efficiency, reduced risk of contamination, and prevention of fluorine loss. Additionally, MIC required minimal reagent use, resulting in lower laboratory waste generation, aligning with trends in Green Analytical Chemistry practices.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"288 ","pages":"Article 110502"},"PeriodicalIF":1.9,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517582","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 : 2025-11-01DOI: 10.1016/j.jfluchem.2025.110505
Aleksei V. Petrovichev, Irina V. Kutovaya, Olga I. Shmatova
This study assesses the performance of the fluorinated electrolyte 1 M LiPF6 TFEtAc/FEC (9:1 by vol.) relative to carbonate-based counterpart in Graphite||NMC811 lithium-ion cells under elevated cutoff voltages of 4.4 V and 4.5 V. The investigation explores how varying cycling protocols improve overall efficiency at increased active material loadings. Experimental results from 0.4 Ah pouch cells show that the TFEtAc-based electrolyte achieves capacity retention of 79.5 % over 600 cycles within the 2.7–4.4 V potential range and 75.4 % over 300 cycles in the 2.7–4.5 V range, accompanied by quantitative Coulombic efficiency.D OI: 10. 1016/j.jf luchem
{"title":"Practical battery boost: 2,2,2-Trifluoroethyl acetate-based fluorinated electrolyte for extended life and high voltage stability","authors":"Aleksei V. Petrovichev, Irina V. Kutovaya, Olga I. Shmatova","doi":"10.1016/j.jfluchem.2025.110505","DOIUrl":"10.1016/j.jfluchem.2025.110505","url":null,"abstract":"<div><div>This study assesses the performance of the fluorinated electrolyte 1 M LiPF6 TFEtAc/FEC (9:1 by vol.) relative to carbonate-based counterpart in Graphite||NMC811 lithium-ion cells under elevated cutoff voltages of 4.4 V and 4.5 V. The investigation explores how varying cycling protocols improve overall efficiency at increased active material loadings. Experimental results from 0.4 Ah pouch cells show that the TFEtAc-based electrolyte achieves capacity retention of 79.5 % over 600 cycles within the 2.7–4.4 V potential range and 75.4 % over 300 cycles in the 2.7–4.5 V range, accompanied by quantitative Coulombic efficiency.D OI: 10. 1016/j.jf luchem</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"288 ","pages":"Article 110505"},"PeriodicalIF":1.9,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517583","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 : 2025-11-01DOI: 10.1016/j.jfluchem.2025.110501
Norman Lu , Vinay Belur Lokesh , Ka Long Chan , Gurumallappa Gurumallappa , Pin-Xiang Zeng , Dongge Zheng , Kazuhiro Nawa , Taku J. Sato
Driven by the structural versatility and magnetic tunability of Cu(II) complexes and the unique supramolecular properties of fluorinated ligands, we report the synthesis and structural characterization of a novel fluorinated CuCl2 dimer complex [((C2F5CH2OCH2)2py)CuCl2]2 [or abbreviated as [(5F-CuCl2)2]. Its single crystal X-ray diffraction reveals a centrosymmetric dimeric structure with distorted square–pyramidal Cu(II) centers bridged by chloride ligands. The fluorinated complex crystallizes in the triclinic space group P-1, with each Cu(II) adopting a τ = 0.15 geometry. Its structural analysis reveals a network of rare non–covalent interactions including C–H···F, C–H⋯Cl (–Cu) blue-shifting hydrogen bonds (HBs), sp3 C–F⋯F–C halogen bonds etc. stabilize the crystal lattice. Hirshfeld surface analysis and fingerprint plots further affirm the significance of these interactions in stabilizing its lattice. The observed C–H⋯X and C–F⋯F–C motifs, rarely reported for sp3-hybridized fluorine systems, demonstrate the capability of fluorine to modulate coordination environments and induce unique assembly patterns. Furthermore, the magnetic susceptibility of (5F-CuCl2)2 dimer has been measured. Additionally, the Bent’s rule has also used to explain the C–C and C–O bond length changes. These findings are believed to enrich our understanding of fluorine-driven supramolecular chemistry, application of fluorinated complex and offer new design principles for the fluorinated pincer-like metal complexes with the short-chains.
{"title":"Synthetic, structural and magnetic studies of a fluorinated chloro-bridged Cu(II) dimeric complex, [((C2F5CH2OCH2)2py)CuCl2]2, with unusual non–covalent interactions","authors":"Norman Lu , Vinay Belur Lokesh , Ka Long Chan , Gurumallappa Gurumallappa , Pin-Xiang Zeng , Dongge Zheng , Kazuhiro Nawa , Taku J. Sato","doi":"10.1016/j.jfluchem.2025.110501","DOIUrl":"10.1016/j.jfluchem.2025.110501","url":null,"abstract":"<div><div>Driven by the structural versatility and magnetic tunability of Cu(II) complexes and the unique supramolecular properties of fluorinated ligands, we report the synthesis and structural characterization of a novel fluorinated CuCl<sub>2</sub> dimer complex [((C<sub>2</sub>F<sub>5</sub>CH<sub>2</sub>OCH<sub>2</sub>)<sub>2</sub>py)CuCl<sub>2</sub>]<sub>2</sub> [or abbreviated as [(5F-CuCl<sub>2</sub>)<sub>2</sub>]. Its single crystal X-ray diffraction reveals a centrosymmetric dimeric structure with distorted square–pyramidal Cu(II) centers bridged by chloride ligands. The fluorinated complex crystallizes in the triclinic space group P-1, with each Cu(II) adopting a τ = 0.15 geometry. Its structural analysis reveals a network of rare non–covalent interactions including C–H···F, C–H⋯Cl (–Cu) blue-shifting hydrogen bonds (HBs), sp<sup>3</sup> C–F⋯F–C halogen bonds etc. stabilize the crystal lattice. Hirshfeld surface analysis and fingerprint plots further affirm the significance of these interactions in stabilizing its lattice. The observed C–H⋯X and C–F⋯F–C motifs, rarely reported for sp<sup>3</sup>-hybridized fluorine systems, demonstrate the capability of fluorine to modulate coordination environments and induce unique assembly patterns. Furthermore, the magnetic susceptibility of (5F-CuCl<sub>2</sub>)<sub>2</sub> dimer has been measured. Additionally, the Bent’s rule has also used to explain the C–C and C–O bond length changes. These findings are believed to enrich our understanding of fluorine-driven supramolecular chemistry, application of fluorinated complex and offer new design principles for the fluorinated pincer-like metal complexes with the short-chains.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"288 ","pages":"Article 110501"},"PeriodicalIF":1.9,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145464754","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}
We report a mild and versatile protocol for N- and O-difluoromethylation of diverse N-heterocycles using BrCF₂CO₂H and K₂CO₃ in DMF. This operationally simple method exhibits broad substrate scope and is compatible with structurally complex, drug-relevant molecules. The strategy offers a practical platform for late-stage difluoromethylation, expanding the synthetic toolbox for medicinal chemistry.
{"title":"Difluoromethylation of N-heterocyclic biomolecules","authors":"Sandeep Kumawat, Chitrarekha Dewangan, Kallakuri Leela Manikya Naga Siva Jyothi, Km Sadhana, Kishore Natte","doi":"10.1016/j.jfluchem.2025.110499","DOIUrl":"10.1016/j.jfluchem.2025.110499","url":null,"abstract":"<div><div>We report a mild and versatile protocol for <em>N</em>- and <em>O</em>-difluoromethylation of diverse <em>N</em>-heterocycles using BrCF₂CO₂H and K₂CO₃ in DMF. This operationally simple method exhibits broad substrate scope and is compatible with structurally complex, drug-relevant molecules. The strategy offers a practical platform for late-stage difluoromethylation, expanding the synthetic toolbox for medicinal chemistry.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"288 ","pages":"Article 110499"},"PeriodicalIF":1.9,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145415179","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 : 2025-11-01DOI: 10.1016/j.jfluchem.2025.110504
Long-Tai Qi , Lei Ma , Zhi-Xiang Xing , Ye-Cheng Liu , Wan-Zheng Lu , Han Han , Tian-Yu Zhou , Yao Wu
The flammability of polyvinylidene fluoride (PVDF) poses significant fire safety hazards, limiting its applications. A common solution involves adding flame retardants, which often compromises the material's mechanical properties due to poor interfacial compatibility between the additives and the polymer matrix. To address this challenge, this study prepared a novel core-shell flame retardant, PAPP@MF, by encapsulating piperazine pyrophosphate (PAPP) with a melamine-formaldehyde (MF) resin via an in-situ polymerization method. Benefiting from the bridging effect of the core-shell structure, the compatibility between the flame retardant and the PVDF matrix was significantly improved. Consequently, the tensile strength of the PAPP@MF/PVDF composite increased by 35.4 % compared to that of the composite with untreated PAPP. Concurrently, the flame-retardant performance was substantially enhanced. Microscale Combustion Calorimetry (MCC) tests confirmed this, revealing a drastic 85.2 % reduction in Total Heat Release (Total HR). With 3.0 wt% PAPP@MF, the Limiting Oxygen Index (LOI) also increased from 20.5 % to 29.5 %. Furthermore, the synergistic flame-retardant mechanism was investigated. This work provides a new and effective approach to resolving the inherent conflict between flame retardancy and mechanical properties in polymer composites, offering new insights and references for the development of safer, high-performance fluoropolymer materials.
{"title":"Preparation and characterization of PAPP@MF microcapsules for enhancing the safety of PVDF","authors":"Long-Tai Qi , Lei Ma , Zhi-Xiang Xing , Ye-Cheng Liu , Wan-Zheng Lu , Han Han , Tian-Yu Zhou , Yao Wu","doi":"10.1016/j.jfluchem.2025.110504","DOIUrl":"10.1016/j.jfluchem.2025.110504","url":null,"abstract":"<div><div>The flammability of polyvinylidene fluoride (PVDF) poses significant fire safety hazards, limiting its applications. A common solution involves adding flame retardants, which often compromises the material's mechanical properties due to poor interfacial compatibility between the additives and the polymer matrix. To address this challenge, this study prepared a novel core-shell flame retardant, PAPP@MF, by encapsulating piperazine pyrophosphate (PAPP) with a melamine-formaldehyde (MF) resin via an in-situ polymerization method. Benefiting from the bridging effect of the core-shell structure, the compatibility between the flame retardant and the PVDF matrix was significantly improved. Consequently, the tensile strength of the PAPP@MF/PVDF composite increased by 35.4 % compared to that of the composite with untreated PAPP. Concurrently, the flame-retardant performance was substantially enhanced. Microscale Combustion Calorimetry (MCC) tests confirmed this, revealing a drastic 85.2 % reduction in Total Heat Release (Total HR). With 3.0 wt% PAPP@MF, the Limiting Oxygen Index (LOI) also increased from 20.5 % to 29.5 %. Furthermore, the synergistic flame-retardant mechanism was investigated. This work provides a new and effective approach to resolving the inherent conflict between flame retardancy and mechanical properties in polymer composites, offering new insights and references for the development of safer, high-performance fluoropolymer materials.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"288 ","pages":"Article 110504"},"PeriodicalIF":1.9,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145464219","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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