ANALYTICAL CHEMISTRY
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2023
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IF 7.4
Bin Huang,Kuan Li,Qi-Yu Ma,Tuan-Xiu Xiang,Rui-Xue Liang,Ya-Nan Gong,Bang-Jin Wang,Jun-Hui Zhang,Sheng-Ming Xie,Li-Ming Yuan
Metallacycles are a novel class of supramolecular materials with circular structures, internal cavities, and abundant host–guest chemical properties that have exhibited good application prospects in many fields. However, to the best of our knowledge, no research on the use of metallacycles as stationary phases for gas chromatographic (GC) separations has been published yet. In this work, we report for the first time the use of a homochiral metallacycle, [ZnCl2L]2, as a stationary phase for GC separations. [ZnCl2L]2 was synthesized by reaction of (S)-(1-isonicotinoylpyrrolidin-2-yl)methyl-isonicotinate (L) with ZnCl2 via coordination-driven self-assembly. The [ZnCl2L]2-coated column displayed an excellent separation performance not only of organic isomers but also of racemic compounds. Sixteen racemates (including alcohols, esters, amino acid derivatives, ethers, organic acids, and epoxides) and 21 isomeric compounds (including positional, structural, and cis/trans-isomers) were well separated on the [ZnCl2L]2-coated column. Impressively, some racemates were resolved with high resolution values (Rs), including 1,2-butanediol diacetate (Rs = 25.86), ethyl 3-hydroxybutyrate (Rs = 20.97), 1,3-butanediol diacetate (Rs = 18.09), and threonine derivative (Rs = 18.61). Compared with the commercial β-DEX 120 column for separation of the tested racemates, the [ZnCl2L]2-coated column exhibited good enantioseparation complementarity, enabling separation of some racemates that could not be separated, or were not well resolved, by the β-DEX 120 column. In addition, many organic mixtures, such as n-alkanes, alkylbenzenes, n-alcohols, and a Grob test mixture, were also well separated on the [ZnCl2L]2-coated column. The column also has good reproducibility and thermal stability on separation. This work not only reveals the great potential of metallacycles for GC separations but also opens up a new application of metallacycles in separation science.
研究领域:
分析化学
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材料科学
✓ 已验证
DOI
PubMed
高影响因子
INORGANIC CHEMISTRY
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2025
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IF 4.7
Qiang-Qiang Ma,Peng Zhou,Yizhen Liu,Zuowei Xie
Transition metal catalyzed selective cage B–H functionalization of carboranes has made significant progress in recent years, giving rise to the efficient synthesis of a large variety of cage B-functionalized carboranes including alkenylation, arylation, alkynylation, borylation, hydroxylation, acyloxylation, amination, and halogenation. However, the mechanisms of these catalytic B–X coupling reactions are not well understood. Herein, we describe the isolation and characterization of the catalytically relevant o-carborane based palladium(II) metallacycle, disclosing the details of Pd-catalyzed B–H functionalization of o-carboranes. As a result, highly selective catalytic B(3,6)-dihalogenation, -dimethylation, and -diarylation of o-carboranes have been achieved.
研究领域:
有机化学
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过渡金属催化
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材料化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Ya-Lan Kou,Jin Tong,Cong Meng,Qing Yuan,Ji Wang,Shu-Yan Yu
Luminescent supramolecular metallacycles have attracted great interest as a new promising class of sensing substrates. In this work, two tetraphenylethene (TPE)-based diimidazole and dipyrazole ligands with the aggregation-induced emission (AIE) feature were designed for the construction of supramolecular tetragonal metallacycles 1–4 with two 90° mononuclear [(bpy)M]2+ or dinuclear [(bpy)2M2]4+ acceptors (bpy = 2,2′-dipyridine; M = Pd, Pt), in which the fluorescence can be quenched to an “off” state due to the ligand-to-metal charge transfer (LMCT). Metallacycle 1 was utilized as a fluorescence sensor for phosphate (PO43–) detection in aqueous solution by means of disassembly, leading to the release of the ligand. Additionally, the metallacycle can be regenerated through self-assembly via the introduction of Pd(II) acceptors. PO43– was detected using TPE-based metallacycles over a wide concentration range, with a detection limit as low as 2.1 × 10–8 M. Furthermore, sensor 1 also presented the semiquantitative visual detection ability for PO43– in the test paper mode via fluorescence changes. The aforementioned studies not only enhance the current research on fluorescent materials but also offer a strategy for the creation of stimuli-responsive supramolecular coordination complexes.
研究领域:
化学
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生物医学
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材料科学
✓ 已验证
DOI
PubMed
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2013
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IF 2.206
Jianxiang Feng,Xiaomin Zhang,Songqi Ma,Zhu Xiong,Chuanzhi Zhang,Yanhua Jiang,Jin Zhu
Maleated cyclodexdrin (MC) and its metal salts (Metal MC) were synthesized and added into poly(vinyl alcohol)–intumescent flame retardant (PVA–IFR) composites as synergists. Results of thermogravimetric analysis (TGA) and differential thermal analysis (DTG) showed that the thermal stability of the composites was greatly improved. The initial decomposition temperature of PVA–IFR composites was increased by 16 °C with the addition of metal MC. UL-94 vertical burning test indicated that the metallic cyclodextrin (metal MC) can catalyze the PVA–IFR system to form strong intumescent char and reach V0 rating at the proper proportion. The morphology and compositions of the char residue of PVA–IFR composites were characterized by scanning electron microscopy (SEM), Raman spectra, FTIR, and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the metal ions could boost the formation of organized and compact char layer in the condensed phase during the degradation of PVA.
研究领域:
材料科学
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高分子化学
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消防安全工程
✓ 已验证
产品关联
DOI
高影响因子
LANGMUIR
·
2024
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IF 3.7
Chao-Yu Wang,Bai-Chen Liu,Tao Tu,Bo Tu,Dong-Jin Qian
Molecular structure, external stimuli, and environmental factors all have a strong effect on the internal molecular rotation and vibration of aggregate-induced emission (AIE) luminogens. Here, we report the AIE effect for several newly synthesized amphiphilic tetra(benzimidazole)phenylethene (TBiPE) derivatives and their binuclear N-heterocyclic carbene silver (NHC-Ag) metallacycles in solutions, aggregates, and Langmuir–Blodgett (LB) films. Monolayer behaviors and microscopic images indicate that introducing alkyl chains and binuclear NHC-Ag metallacycles can facilitate the formation of a well-defined insoluble monomolecular layer at the air–water interface. Absorption and luminescence spectral features suggest that both the TBiPEs’ cyclization structure and binuclear NHC-Ag metallacycles can provide additional driving forces to restrict the internal molecular motion of the tetraphenylethene (TPE) unit, thus enhancing the AIE effects. Further, external stimuli and environmental factors such as poor solvent addition and LB film deposition also play important roles in the photoluminescent intensity, maximum wavelength, and lifetime. These internal and external factors can result in around 30–40 nm blue-shift for the maximum luminescence wavelength and 2–3 times shorter for the luminescent lifetime. These phenomena can be attributed to the reason that the nonradiative energy transfer efficiency is weakened because of the enhanced hydrophobic interaction and metal–carbene coordination as well as the closely packed arrangement of AIEgens in the LB films; consequently, the radiation energy transfer efficiency increased.
研究领域:
材料科学
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物理化学
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光化学
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表面科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）