Journal of Fluorine Chemistry最新文献

英文中文

Fluorinated porous materials for PFAS remediation: fluoroaffinity as a central design principle 用于PFAS修复的氟化多孔材料：以氟亲和为中心设计原则

IF 1.9 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-11-01 Epub Date: 2025-10-21 DOI: 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.

全氟和多氟烷基物质（PFAS）是一种范围广泛的合成有机氟化合物，迄今已确定有1万种结构。其中，只有一小部分水溶性化合物，特别是全氟烷基酸（PFAAs，如PFCAs和pfsa）和全氟醚羧酸（PFECAs，如GenX）与吸附性水和废水处理有关。其中许多化合物具有高度持久性，一些亚类具有生物蓄积性，一些亚类与不利的健康和生态影响有关。颗粒活性炭（GAC）、离子交换树脂（IER）和膜等传统吸附剂的效率较低，特别是对于短链和超短链PFAAs，这凸显了对下一代解决方案的需求。本文综述了氟化多孔材料（FPMs）作为新兴的吸附剂，具有吸引人的性能，并强调了它们利用氟-氟（F···F）相互作用、疏水亲和和静电的独特能力。与传统的吸附剂相比，FPMs具有优越的性能，特别是短链和超短链PFAS。我们将氟亲和性概念化，不仅是一种相互作用，而且是连接PFAS持久性和吸附剂设计的统一设计原则。我们提出了结构-性能关系、定量阈值、应用指标和尺度、可再生性、技术经济和监管方面的考虑。通过将机理理解与实际应用相结合，本工作通过设计导向的角度重新构建了可溶性PFAS修复，以指导下一代选择性捕获材料的开发。

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引用次数: 0

Practical battery boost: 2,2,2-Trifluoroethyl acetate-based fluorinated electrolyte for extended life and high voltage stability 实用电池升压：2,2,2-三氟乙酸乙酯基氟化电解质，延长寿命和高电压稳定性

IF 1.9 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-11-01 Epub Date: 2025-11-10 DOI: 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

本研究评估了1 M LiPF6 TFEtAc/FEC（体积比9:1）相对于碳酸盐基电解质在4.4 V和4.5 V的高截止电压下石墨b| NMC811锂离子电池中的性能。该调查探讨了不同的循环方案如何在增加活性材料负载的情况下提高整体效率。0.4 Ah袋状电池的实验结果表明，在2.7 ~ 4.4 V电压范围内，tfetac基电解质在600次循环内的容量保持率为79.5%，在2.7 ~ 4.5 V电压范围内，在300次循环内的容量保持率为75.4%，并伴有定量的库仑效率。D: 10。1016 / j。摩根富林明luchem

引用次数: 0

Potentiometric determination of fluoride in animal feed after microwave-induced combustion: A simple, efficient, and accurate approach 微波燃烧后动物饲料中氟化物的电位测定：一种简单、高效、准确的方法

IF 1.9 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-11-01 Epub Date: 2025-11-06 DOI: 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.

本文提出了一种简单、准确的动物饲料消化方法，即微波诱导燃烧（MIC）后离子选择电极电位法测定氟化物，以替代AOAC官方方法(no。975.08)。MIC法仅用氧气（20 bar）和几微升NH4NO3溶液（6 mol l-1）消化动物饲料（500 mg）。氟在稀释的NH4OH溶液（100 mmol l-1）中回收。MIC和AOAC方法的准确性使用牡蛎组织标准参比物质（NIST 1566a）进行验证。利用MIC进行样品制备显示出良好的一致性（接近100%），而AOAC方法产生的结果不准确（约30%的一致性）。MIC法和AOAC法的回收率分别为95%和35%。因此，MIC和电位测定法的结合被认为是替代AOAC法测定动物饲料中氟化物的可行方法。检测限和定量限较低，分别为0.5µg -1和1.6µg -1。最后，与AOAC法相比，MIC法具有消化效率高、污染风险低、防止氟损失等优点。此外，MIC需要最少的试剂使用，从而减少实验室废物的产生，符合绿色分析化学实践的趋势。

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引用次数: 0

Synthetic, structural and magnetic studies of a fluorinated chloro-bridged Cu(II) dimeric complex, [((C2F5CH2OCH2)2py)CuCl2]2, with unusual non–covalent interactions 具有异常非共价相互作用的氟化氯桥接Cu（II）二聚物[((C2F5CH2OCH2)2py)CuCl2]2的合成、结构和磁性研究

IF 1.9 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-11-01 Epub Date: 2025-11-07 DOI: 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.

由于Cu（II）配合物的结构通用性和磁性可调性以及氟化配体独特的超分子性质，我们报道了一种新型氟化CuCl2二聚体配合物[((C2F5CH2OCH2)2py)CuCl2]2[或缩写为[(5F-CuCl2)2]的合成和结构表征。其单晶x射线衍射显示为中心对称二聚体结构，由氯配体桥接的扭曲方锥体Cu（II）中心。氟化配合物在三斜空间群P-1中结晶，每个Cu（II）采用τ = 0.15的几何形状。其结构分析揭示了一个罕见的非共价相互作用网络，包括C-H···F、C-H⋯Cl （-Cu）蓝移氢键（HBs）、sp3 C-F⋯F - c卤素键等，稳定了晶格。Hirshfeld表面分析和指纹图谱进一步证实了这些相互作用在稳定其晶格中的意义。很少报道sp3杂化氟体系中观察到的C-H⋯X和C-F⋯F-C基序，证明了氟调节配位环境和诱导独特组装模式的能力。测定了（5F-CuCl2）2二聚体的磁化率。此外，Bent法则也被用来解释碳碳键和碳氧键长度的变化。这些发现将丰富我们对氟驱动的超分子化学、氟化配合物的应用的认识，并为短链氟化钳状金属配合物的设计提供新的原则。

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引用次数: 0

Difluoromethylation of N-heterocyclic biomolecules n -杂环生物分子的二氟甲基化

IF 1.9 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-11-01 Epub Date: 2025-10-30 DOI: 10.1016/j.jfluchem.2025.110499

Sandeep Kumawat, Chitrarekha Dewangan, Kallakuri Leela Manikya Naga Siva Jyothi, Km Sadhana, Kishore Natte

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.

我们报道了一种温和和通用的方案，使用BrCF₂CO₂H和K₂CO₃在DMF中对不同的N-杂环进行N-和o -二氟甲基化。这种操作简单的方法具有广泛的底物范围，并且与结构复杂的药物相关分子兼容。该策略为后期二氟甲基化提供了一个实用的平台，扩大了药物化学的合成工具箱。

引用次数: 0

Corrigendum to “Difluoromethylation of N-heterocyclic biomolecules” [Journal of Fluorine Chemistry, 2025, 288, 110499] “ n -杂环生物分子的二氟甲基化”的勘误表[氟化学杂志，2025,288,110499]

IF 1.9 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-11-01 Epub Date: 2025-11-26 DOI: 10.1016/j.jfluchem.2025.110508

Sandeep Kumawat, Chitrarekha Dewangan, Kallakuri Leela Manikya Naga Siva Jyothi, Km Sadhana, Kishore Natte

引用次数: 0

Preparation and characterization of PAPP@MF microcapsules for enhancing the safety of PVDF 提高PVDF安全性的PAPP@MF微胶囊的制备与表征

IF 1.9 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-11-01 Epub Date: 2025-10-30 DOI: 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.

聚偏氟乙烯（PVDF）的可燃性造成了重大的火灾安全隐患，限制了其应用。一种常见的解决方案是添加阻燃剂，由于添加剂与聚合物基体之间的界面相容性差，这通常会损害材料的机械性能。为了解决这一挑战，本研究通过原位聚合方法将焦磷酸哌嗪（PAPP）包裹在三聚氰胺甲醛（MF）树脂中，制备了一种新型核壳阻燃剂PAPP@MF。得益于核壳结构的桥接作用，阻燃剂与PVDF基体的相容性得到显著改善。因此，PAPP@MF/PVDF复合材料的抗拉强度比未经处理的PAPP复合材料提高了35.4%。同时，阻燃性能得到了显著提高。微尺度燃烧量热法（MCC）测试证实了这一点，显示总放热量（总HR）急剧减少85.2%。当wt% PAPP@MF为3.0 wt%时，极限氧指数（LOI）也由20.5%提高到29.5%。进一步探讨了增效阻燃机理。本研究为解决聚合物复合材料的阻燃性和力学性能之间的内在矛盾提供了新的有效途径，为开发更安全、高性能的含氟聚合物材料提供了新的见解和参考。

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引用次数: 0

Absolute configuration and an improved automated cGMP production of a clinically promising radiotracer for imaging VAChT 绝对配置和改进的自动化cGMP生产的临床有前途的放射性示踪剂成像VAChT

IF 1.9 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-11-01 Epub Date: 2025-11-11 DOI: 10.1016/j.jfluchem.2025.110506

Yanbo Yu , Anil Kumar Soda , Christopher Bognar , Gregory G. Gaehle , Stephen M. Moerlein , Michael L. Nickels , Jagan Rajamoni , Joel S. Perlmutter , Zhude Tu

The vesicular acetylcholine transporter (VAChT), primarily located in presynaptic cholinergic nerve terminals, serves as a key target in neuroimaging studies and neuropathological assessments to quantify cholinergic neuron decline. [¹⁸F]VAT has been demonstrated as a selective and specific radiotracer to quantify VAChT expression in the brains of patients with neurological diseases. Herein, we report the absolute configuration of the chemical structure and development of a straightforward cGMP protocol to produce[¹⁸F]VAT for clinical use. The absolute configuration was unambiguously determined by X-ray crystallography of the VAT phenolic analogue, establishing its (2R,3R) stereochemistry for the first time. The radiotracer production was successfully accomplished using a simple one-pot and one-step approach under cGMP conditions, achieving an average radiochemical yield of 16.9% ± 1.8% (decay-corrected to the end of synthesis), a molar activity of 61.9 ± 19.6% GBq /μmol, with a total synthesis time of approximately 60 min (n = 3). The final product met all established quality control criteria for human use.

囊泡性乙酰胆碱转运蛋白（VAChT）主要位于突触前胆碱能神经末梢，是神经影像学研究和神经病理学评估中量化胆碱能神经元衰退的关键靶点。[18F]VAT已被证明是一种选择性和特异性的放射性示踪剂，可量化神经系统疾病患者大脑中VAChT的表达。在本文中，我们报告了化学结构的绝对构型，并开发了一种简单的cGMP方案来生产用于临床使用的[18F]VAT。用x射线晶体学方法确定了VAT酚类似物的绝对构型，首次建立了它的（2R,3R）立体化学。在cGMP条件下，采用简单的一锅一步法成功地完成了放射性示踪剂的生产，平均放射化学产率为16.9%±1.8%（衰变校正到合成结束），摩尔活性为61.9±19.6% GBq /μmol，总合成时间约为60 min （n = 3）。最终产品符合人类使用的所有既定质量控制标准。

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引用次数: 0

Feasibility of on-demand fluorine generation using cold atmospheric plasma from benign precursor: An optical emission spectroscopy study 利用良性前体的冷大气等离子体按需生产氟的可行性：光学发射光谱研究

IF 1.9 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-11-01 Epub Date: 2025-10-29 DOI: 10.1016/j.jfluchem.2025.110500

Rajib Kar , Vishakha Bende , Vanita Sekar , R.L. Bhardwaj , J.P. Nilaya , M.L. Mascarenhas

Fluorine gas (F₂) is indispensable in industries ranging from fluoropolymer synthesis to semiconductor fabrication, but its high toxicity, extreme reactivity, and storage hazards limit its applicability. On-demand in situ production could eliminate the need for bulk storage and transport. Here, we demonstrate fluorine generation from CF₄ using a Tesla coil–based 2 MHz cold atmospheric plasma (CAP) device. Plasma was generated with Ar (Case I), Ar + CF₄ (Case II), and Ar + CF₄ + O₂ (Case III). Optical emission spectroscopy (OES) and direct gas sensing used to detect species. Adding O₂ increased F₂ emission while reducing CF, CF₂, and C₂ bands, and simultaneously decreased stainless steel electrode erosion. The oxygen effect is attributed to carbon scavenging and oxide film formation, enhancing F₂ yield while protecting electrodes. These findings establish the feasibility of plasma-based, switch-on/switch-off fluorine production.

从含氟聚合物合成到半导体制造，氟气体（F₂）在工业中是必不可少的，但其高毒性，极端反应性和储存危害限制了其适用性。按需就地生产可以消除大量储存和运输的需要。在这里，我们演示了使用基于特斯拉线圈的2 MHz冷大气等离子体（CAP）装置从cf4生成氟。血浆由Ar（病例I）、Ar + CF₄（病例II）和Ar + CF₄+ O₂（病例III）生成。光学发射光谱（OES）和直接气体传感用于检测物种。添加O₂增加了F₂排放量，同时减少了CF、CF 2和C₂带，同时减少了不锈钢电极的腐蚀。氧效应归因于碳清除和氧化膜的形成，在保护电极的同时提高了F₂产率。这些发现确定了基于等离子体的开关氟生产的可行性。

引用次数: 0

New synthesis of meso-substituted 4,4-Difluoro-4-bora-3a, 4a-diaza-s-indacene (BODIPY) with fluorene 用芴合成介位取代4,4-二氟-4-硼-3a， 4-二氮-s-茚二烯（BODIPY）

IF 1.9 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-10-01 Epub Date: 2025-10-05 DOI: 10.1016/j.jfluchem.2025.110485

Sujun Wei, Francisco Caban , Jiayi Xue , Feruza Turobova

4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (aka BODIPY) derivatives are typically air stable, highly fluorescent with high quantum yield, low toxicity and high biocompatibility, which attract strong interest as fluorescent markers and dyes in biological research field. Herein we report a novel synthetic strategy to convert a stable dipyrrole intermediate to a BODIPY dye with a fluorene unit at its meso position. More interestingly the covalent C-C single bond is between BODIPY and fluorene’s sole sp³ hybridized carbon, which provides bulkiness around BODIPY aromatic core to reduce intermolecular π−π stacking. This new BODIPY compound is fully characterized, and its X-ray crystal structure is reported. We also extend this methodology to produce chloro substituted analog.

4,4-二氟-4-硼-3a，4 -二氮杂-s-茚二烯（BODIPY）衍生物具有空气稳定、高荧光、高量子产率、低毒性和高生物相容性等特点，作为荧光标记和染料在生物研究领域受到广泛关注。在此，我们报告了一种新的合成策略，将稳定的双吡咯中间体转化为中间体位置有芴单元的BODIPY染料。更有趣的是，共价C-C单键位于BODIPY和芴唯一的sp3杂化碳之间，这使得BODIPY芳香族核心周围的体积更大，从而减少了分子间π−π堆积。对该化合物进行了全面表征，并报道了其x射线晶体结构。我们还扩展了这种方法来生产氯取代类似物。

引用次数: 0

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