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ENVIRONMENTAL RESEARCH · 2022 · IF 8.431

Electrochemical removal of 4-chlorophenol in water using a porous Magnéli-phase (Ti4O7) electrode

Zhiyuan Zhao,Jinna Zhang,Jie Yao,Shijie You

Electro-oxidation is a promising technology for removal of refractory organic pollutants. While the appeal of this technology lies in its chemical-free nature, commercially scale-up application may be limited by the availability of electrode materials and mass transport. Here we report the development of a flow-through electro-oxidation system for removal of chlorophenols in water using Magnéli-phase (Ti 4 O 7 ) tubular anode and a 304 stainless steel (SS) tubular cathode. The key to this system was the porous and conductive Magnéli-phase Ti 4 O 7 anode, the structure and composition of which was confirmed by scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. System efficacy was evaluated by using 4-chlorophenol (4-CP) as a typical refractory contaminant and model chlorophenol. Under optimized conditions, a complete removal of 4-CP could be obtained within 120 min in 0.04 mol L −1 Na 2 SO 4 solution. Electro-produced HO • and direct electron transfer were both shown to contribute to the 4-CP electro-oxidation process due to the high selectivity and oxygen evolution potential of the Ti 4 O 7 anode. The intermediates of 4-CP degradation were identified and a pathway for its electro-oxidation was proposed. When challenged with industrial wastewater containing 4-CP, chemical oxygen demand (COD) and total organic carbon removal efficiencies of 67.5% and 63.1% respectively could be obtained, accounting for energy consumption of 85.1 kWh·kg COD −1 for degradation of 1 kg of COD in industrial wastewater. This study provides an effective and robust solution for the removal of refractory emerging contaminants from industrial wastewaters using a continuous-flow electro-oxidation system.

研究领域: 环境科学 · 电化学工程
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Materials Science and Engineering B-Advanced Functional Solid-State Materials · 2022 · IF 3.407

Dy3+:Ca3Gd2(BO3)4 single crystal with disordered structure: A promising yellow laser candidate

Xiaoting Chen,Lehui Liu,Yisheng Huang,Feifei Yuan,Lizhen Zhang,Zhoubin Lin

In this article, a series of Dy x Ca 3 Gd 2-x (BO 3 ) 4 (x = 0.02–0.2) polycrystalline compounds were synthesized by solid-state reaction to select the optimum concentration for single crystal growth, after then a 6.36 at.% Dy 3+ :Ca 3 Gd 2 (BO 3 ) 4 (Dy:CGB) single crystal with a disordered structure was successfully grown by the Czochralski method . The spectroscopic properties and Judd-Ofelt analyses of the crystal were carried out. Focusing on the absorption cross-section at 453 nm corresponding to the emission bands of InGaN laser diodes, the Dy:CGB crystal has a comparatively large value of 0.95 × 10 -21 cm 2 with a full width at half maximum (FWHM) of 10.2 nm. The yellow light emission cross-section at 576 nm is 2.2 × 10 -21 cm 2 with a FWHM of 14.0 nm. The Judd-Ofelt parameters Ω 2 , Ω 4 and Ω 6 were obtained to be 2.79 × 10 -20 cm 2 , 2.10 × 10 -20 cm 2 and 2.28 × 10 -20 cm 2 , respectively. The fluorescence lifetime of 4 F 9/2 → 6 H 13/2 transition was measured to be 0.26 ms. These results reveal that the Dy:CGB crystal is a promising yellow laser candidate.

研究领域: 材料科学 · 光学
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JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY · 2023 · IF 3.4

Recovery of high-purity-4-chloroguaiacol from bleaching wastewater by a heterogeneous extraction method

Ping Hu,Shengwen Lei,Weiyan Luo,Xiaoqing Huang,Wei Ruan,Yueyuan Ye,Zhifeng Zheng,Dechao Wang,Duo Wang

BACKGROUND During the pulping and bleaching processes, 4-chloroguaiacol accounts for a large proportion of chlorine containing pollutants. In this study, a heterogeneous extraction method for extracting 4-chloroguaiacol from the bleaching wastewater by using the intermediate as the solid phase extraction agent is proposed. RESULTS The solid intermediate with the molar ratio of 4-chloroguaiacol to calcium 2:1 is firstly prepared. It is used for reacting with the crude 4-chloroguaiacol in the bleaching wastewater to generate the end solid complex with the molar ratio of 4-chloroguaiacol to calcium 4:1. It is verified to be that the high-purity 4-chloroguaiacol can be released from the simple thermal decomposition of the end solid complex. CONCLUSION At an optimum extraction condition including 30 °C reaction temperature, the pH value of 7, using the deionized water as the solvent, the extraction yield and the purity of 4-chloroguaiacol reached 89.2% and 97.8%. Furthermore, after 15 cycle extraction times, the extraction rate of 4-chloroguaiacol can still reach 86.3%. The extraction yield and the purity of 4-chloroguaiacol reached 68.15% and 99.56% when the guaiacol content was lower than 25 mg/L at the bleaching wastewater. © 2023 Society of Chemical Industry (SCI).

研究领域: 环境科学 · 化学工程 · 废水处理
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ACS Sustainable Chemistry & Engineering · 2023 · IF 8.4

One-Pot Photocatalytic Cleavage of Lignin β–O–4 Models by Dehydrogenation–Hydrogenolysis

Zhenlong Song,Yuzhen Hu,Song Li,Jianguo Liu,Xinghua Zhang,Longlong Ma,Lungang Chen,Qi Zhang

Valorizing lignin into valuable chemicals requires the selective breaking of a large number of C–O bonds found in the β–O–4 structure. In this study, we present a one-pot strategy that utilizes two NiO/TiO2 catalysts for the photocatalytic depolymerization of β–O–4 alcohols. The S-1.6%NiO/TiO2 catalyst is used for the dehydrogenation of β–O–4 alcohols at 450 nm. Then, the L-0.8%NiO/TiO2 catalyst is employed for the hydrogenolysis of β–O–4 ketones at 365 nm. Remarkably, the dehydrogenation–hydrogenolysis tandem reaction can be conducted in one pot, which affords high yields of ketones and phenols (up to 89%) from β–O–4 alcohols. Additionally, the L-0.8%NiO/TiO2 catalyst prepared in this article is the smallest NiO/TiO2 photocatalyst reported to date, and the size of NiO in the S-1.6%NiO/TiO2 catalyst is even small enough to enter the lattice of TiO2. We successfully regulated the reaction selectivity by controlling the loading method and the amount of NiO. Our work offers a promising solution for efficiently cleaving target bonds in lignin and provides insights into the design of efficient photocatalysts.

研究领域: 化学工程 · 材料科学 · 可再生资源转化
✓ 已验证 DOI 高影响因子
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Polymers · 2025 ·Vol. 17 ·期 3 ·318 · IF 4.9

Thermal, Crystallization, and Toughness Behavior of Polyamide 4/Long-Chain Hyperbranched Polymer Blends

Linyi Shui,Xianxin Guo,Jinrong Li,Zimeng Li,Qinghua Zhao,Guohua Chen,Xiaomin Zhao

Long-chain hyperbranched polyesters (LHBPx, x = 1, 2, 3) with varying lengths of branched chains were synthesized through a thiol-ene click reaction. Subsequently, LHBPx was incorporated into PA4 via the solution method to prepare a LHBPx/PA4 polymer blend, aiming to address the limitations of PA4, such as its narrow thermal processing window (△T = Td5−Tm) and high brittleness. The results demonstrated that the addition of LHBPx enhanced the △T of PA4 from 1.6 °C to 14.5 °C (LHBP3/PA4), increasing the rheological properties of LHBPx/PA4 polymer blends, thereby improving its thermal processability. Compared with PA4, the elongation at the break of the LHBP3/PA4 polymer blend was increased by 20.4%, and the brittle fracture was changed into a ductile fracture. The crystallinity of PA4 was greatly decreased, from 54.41% to 37.42%, owing to the incorporation of LHBPx, whereas Tmof PA4 had almost no change. It was explained that LHBPx hindered the crystal growth stage, whereas it promoted the nucleation stage of PA4, resulting in no significant change in crystal type. Moreover, the longer the branched chain of LHBPx was, the more pronounced the improvement in the thermal processability and toughness of PA4 became. Above all, this work was meaningful for the potential application of PA4 in industrial plastics.

CAS / MDL: 98-88-4
研究领域: 材料科学 · 高分子化学
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Current Protocols · 2021 ·Vol. 1 ·期 10 ·e274 · IF 0

Post-Synthetic Modification of Oligonucleotides Through Oxidative Amination of 4-Thio-2′-Deoxyuridine

Jingyi Wang,Jiachen Shang,Yu Xiang,Aijun Tong

Functionalized oligonucleotides (ONs) are widely applied as target recognition molecules for biosensing and gene regulation. Herein, we describe a general method for post-synthetic modification of ONs based on the oxidative amination of 4-thio-2′-deoxyuridine (4SdU) with sodium periodate and several amines. Alkyne-/azide-, biotin-, and fluorophore-modified ONs were prepared by modifying 4SdU-containing ONs with the corresponding amines and characterized for their bioorthogonal reactivity, streptavidin-binding affinity, and fluorescence properties, respectively. We synthesized three fluorophore-modified ONs with and without the aromatic fluorophores conjugated to modified nucleobases and investigated their emission properties. © 2021 Wiley Periodicals LLC. Basic Protocol 1 : Post-synthetic modification of ONs Supporting Protocol : Preparation of dansyl ethylenediamine Basic Protocol 2 : Quantification of ON reaction yields Basic Protocol 3 : Characterization of modified ONs

研究领域: 生物化学 · 分子生物学 · 化学生物学
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Drug Design Development and Therapy · 2017 · IF 2.822

Synthesis and cytotoxic activities of novel 4-methoxy-substituted and 5-methyl-substituted (3′S,4′S)-(−)-cis-khellactone derivatives that induce apoptosis via the intrinsic pathway

Jingrun Chen,Junjie Liu,Dongxiao Cui,Chaoqun Yan,Liqiang Meng,Liqian Sun,Shurong Ban,Rui Ge,Taigang Liang,Qingshan Li

This study deals with the design and synthesis of a series of novel 4-methoxy-substituted and 5-methyl-substituted (3′S,4′S)-(−)-cis-khellactones. The newly synthesized compounds were characterized by 1H nuclear magnetic resonance (NMR), 13C-NMR, mass spectrometry, and elemental analysis. All the derivatives were subjected to in vitro cytotoxicity screening against HEPG-2 (human liver carcinoma), SGC-7901 (human gastric carcinoma), and LS174T (human colon carcinoma), by using the MTT assay. The results revealed that several of the 4-methoxy-substituted compounds exhibited potent cytotoxicity. Among these, compound 12e showed the highest activity against cancer cells which 50% inhibitory concentration (IC50) values were in the range of 6.1–9.2 μM with low toxicity on normal human hepatocyte. Preliminary investigation of possible mechanisms of action of compound 12e against HEPG-2 cells indicated possible induction of apoptosis, as determined by morphological observations and Annexin V/propidium iodide (PI) double staining, in addition to apparent dissipation of mitochondrial membrane potential (MMP), as measured by 5,5′,6,6′-tetrachloro-1,1′,3,3′-tetraethyl-imidacarbocyanine iodide (JC-1) staining in combination with the activation of caspase-9 and caspase-3 by Western blot analysis. Overall, the data suggest that compound 12e may be a promising potential anti-cancer agent that could act primarily by inducing apoptosis through the mitochondria-mediated intrinsic pathway in human hepatoma cells.

研究领域: 药理学 · 肿瘤学 · 药物化学
✓ 已验证 DOI PubMed 高影响因子
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INORGANIC CHEMISTRY · 2021 · IF 5.165

Linkage Isomers of 4-Methylimidazolate Mn(II) Porphyrinates: Hindered or Unhindered?

Jianping Zhao,Fei Qian,Wenping Guo,Jianfeng Li,Zeyuan Lin

Three different manganese(II) porphyrins have been exploited to react with 4-methylimidazolate (4-MeIm–), and the five-coordinate products are characterized by ultraviolet–visible, single-crystal X-ray, and electronic paramagnetic resonance spectroscopies. Interestingly, 4-MeIm– is found to bond to the metal center through either of the two N atoms (N1 or N3), which yielded two linkage isomers with either an unhindered or a hindered ligand conformation, respectively. Investigations revealed it is the large metal out-of-plane displacements (Δ24 and Δ4 ≥ 0.59 Å) that have rendered the equivalence of two isomers with a small energy difference (5.2–8.3 kJ/mol). The nonbonded intra- and intermolecular interactions thus become crucial factors in the balance of linkage isomerization. All of the products in both solution and solid states show the same characteristic resonances of high-spin Mn(II) (S = 5/2) with g⊥ ≈ 5.9 and g∥ ≈ 2.0 at 4 K, consistent with the weak effects of the axial ligand on core conformation and metal electronic configurations. Zero-field splitting parameters obtained through simulations are also reported.

CAS / MDL: 1310-58-3
研究领域: 配位化学 · 材料科学 · 物理化学
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MOLECULES · 2022 ·Vol. 27 ·期 9 ·2738 · IF 4.927

Design, Synthesis, and Antifungal Activity of 4-Amino Coumarin Based Derivatives

Lu Xu,Jinmeng Yu,Lu Jin,Le Pan

A series of 30 succinate dehydrogenase inhibitors (SDHIs) of 4-amino coumarin-based derivatives were designed and synthesized. According to the analysis of fungicidal activity in vitro, most of the compounds expressed broad-spectrum antifungal activity against four plant pathogenic fungi (Alternaria alternata, Alternaria solani, Fusarium oxysporum,andBotrytis cinerea) using the mycelium growth inhibition method. The results showed that compounds3nwith the group of 2-ene-3-methyl-butyl and4ewith the group of 2-bromo-1-oxo-hexyl displayed excellent activity againstAlternaria alternataandAlternaria solani, with EC50values of 92~145 μg/mL. Molecular docking showed that the inhibitor3nwas completely locked into the cavity of SDH, forming a conventional hydrogen bond interacting with the amino acid residue TYR58. The present work indicates that these derivatives would serve as novel potential fungicides targeting SDH.Keywords:succinate dehydrogenase;inhibitor;4-amino coumarin;fungicide;antifungal activity;molecular docking

研究领域: 植物保护学 · 药物化学 · 生物化学
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ACS Applied Polymer Materials · 2023 · IF 5

Amphiphilic Hyperbranched Polymers for Selective and Sensitive Detection of 4-Nitrophenol

Siyuan Zhang,Jiao He,Xinjian Cheng

Amphiphilic hyperbranched polymers (AHBPs) possess important characteristics, such as high solubility, low viscosity, and multiple functional groups, making them of significant scientific interest. In this work, a chain transfer agent (CTA) with a styrene unit was synthesized at first. Subsequently, the CTA was polymerized with a coumarin derivative containing a −C=C bond through reversible addition-fragmentation chain transfer-self-condensing vinyl polymerization (RAFT-SCVP) to obtain the hyperbranched polymer HP-1. Finally, using HP-1 as a macromolecular CTA, amphiphilic hyperbranched fluorescent probes AHP-2 and AHP-3 were synthesized via RAFT polymerization of hydrophilic monomers poly[oligo(ethylene glycol) methacrylate] (PEGMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA). The as-prepared AHP-2 and AHP-3 were characterized and confirmed. These macromolecular fluorescent probes enable highly sensitive and specific recognition of 4-nitrophenol (4-NP) with detection limit as 0.59 μM. A unique fluorescence quenching effect, termed “enriching inner filter effect (IFE)”, was revealed through the study of the recognition mechanism of the probes for 4-NP in hyperbranched polymers. This effect has the potential to expand the preparation methods of both fluorescent probes and functional hyperbranched polymers. This work investigates the synthesis methodology of amphiphilic hyperbranched polymers and the performance of fluorescent probes, providing a valuable approach for the development of highly sensitive polymer fluorescent probes in the future.

研究领域: 高分子化学 · 分析化学 · 环境科学
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FUEL · 2024 · IF 6.7

C–C bond coupling differences between β-O-4 and 4-O-5 ether bonds over hydrophobic mesoporous Ru/MY-O catalysts: from lignin model compounds to polycyclic alkanes

Zhuang Li,Zi-Chun Fan,Xiang Bai,Xian-Yong Wei,Yierxiati. Dilixiati,Qian-Qian Kong,Ji Zhao,Yong-Hui Feng,Jun-Long Wang,Xing Fan,Xiao-Yan He,Hai-Xu Zou,Zhi-Min Zong

MY zeolites with mesopores were prepared by hydrothermal method using functionalized SiO 2 (F-SiO 2 ) as a silica source, and hydrophobic bifunctional Ru/MY- O catalysts were obtained by deposition precipitation method and silylation treatment. This work aims at obtaining polycyclic alkane (PCA) based high-density hydrocarbon fuels (HDHFs). We focused on the catalytic hydroconversion (CHC) of 2-phenoxy-1-phenylethanol (PP-ol) and oxydibenzene (ODB), two typical lignin-related model compounds (LRMCs), over Ru/MY- O . The effects of different reaction conditions and catalysts on the product distribution in PP-ol and ODB were investigated. The partial hydrogenation of ODB was found to be a necessary step before achieving C-O ether bond cleavage and C-C bond coupling. The balance of metal/acidic sites is critical for maximizing PCA yields. Changes in the metal/acid ratio had a greater effect on PCA yield in PP-ol than in ODB. Poor stability of cycloalkyl cations and partial hydrogenation of ODB hinder the generation of C-C coupling products. The incorporation of mesopores and hydrophobic treatment were found to weaken the negative effects of C-C bond coupling products and water on the catalyst. The conversion of Ru 3 /MY- O was improved by nearly 10% compared to Ru 3 /Y in the fifth cycle reaction. This work provided a theoretical basis for the generation of HDHFs from lignin.

研究领域: 化学工程 · 催化 · 可再生能源 · 材料科学
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APPLIED AND ENVIRONMENTAL MICROBIOLOGY · 2016 ·Vol. 82 ·期 2 · IF 3.823

HipH Catalyzes the Hydroxylation of 4-Hydroxyisophthalate to Protocatechuate in 2,4-Xylenol Catabolism by Pseudomonas putida NCIMB 9866

Hong-Jun Chao,Yan-Fei Chen,Ti Fang,Ying Xu,Wei E. Huang,Ning-Yi Zhou

In addition to growing on p-cresol, Pseudomonas putida NCIMB 9866 is the only reported strain capable of aerobically growing on 2,4-xylenol, which is listed as a priority pollutant by the U.S. Environmental Protection Agency. Several enzymes involved in the oxidation of the para-methyl group, as well as the corresponding genes, have previously been reported. The enzyme catalyzing oxidation of the catabolic intermediate 4-hydroxyisophthalate to the ring cleavage substrate protocatechuate was also purified from strain NCIMB 9866, but its genetic determinant is still unavailable. In this study, the gene hipH, encoding 4-hydroxyisophthalate hydroxylase, from strain NCIMB 9866 was cloned by transposon mutagenesis. Purified recombinant HipH-His6 was found to be a dimer protein with a molecular mass of approximately 110 kDa. HipH-His6 catalyzed the hydroxylation of 4-hydroxyisophthalate to protocatechuate with a specific activity of 1.54 U mg−1 and showed apparent Km values of 11.40 ± 3.05 μM for 4-hydroxyisophthalate with NADPH and 11.23 ± 2.43 μM with NADH and similar Km values for NADPH and NADH (64.31 ± 13.16 and 72.76 ± 12.06 μM, respectively). The identity of protocatechuate generated from 4-hydroxyisophthalate hydroxylation by HipH-His6 has also been confirmed by high-performance liquid chromatography and mass spectrometry. Gene transcriptional analysis, gene knockout, and complementation indicated that hipH is essential for 2,4-xylenol catabolism but not for p-cresol catabolism in this strain. This fills a gap in our understanding of the gene that encodes a critical step in 2,4-xylenol catabolism and also provides another example of biochemical and genetic diversity of microbial catabolism of structurally similar compounds.

研究领域: 微生物学 · 环境科学 · 生物化学 · 遗传学
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