查找使用阿拉丁产品的科研文献

Unveiling Halogenated and Nitrogenous DBPs in Chloramination-Ozonation Process: DFT-Driven Formation Pathways from Tyrosine and Toxicity Assessment

Yao Lu,Pin Wang,Hui-Xian Hu,Yu-En Guo,Shu-Xi Guo,Hua Li,Ye Du

The prechloramination followed by ozonation (NH2Cl–O3) process effectively mitigates bromate (BrO3–) formation in bromide-containing waters but inadvertently enhances the production of halogenated and nitrogenous disinfection byproducts (DBPs). Cytotoxicity assays revealed that the presence of precursors such as L-tyrosine (Tyr), L-tryptophan (Trp) and tannic acid during the NH2Cl–O3 process contributed to this increase in nitrogenous and halogenated DBPs and resulted in elevated overall toxicity. Nontargeted ultrahigh performance liquid chromatography-Orbitrap tandem mass spectrometry identified diverse halogenated DBPs, with NH2Cl–O3 yielding up to 5-fold more structures and higher abundances than NH2Cl or O3 alone. Taking Tyr as an example, proposed DBP (4-bromophenol, 4-hydroxyphenylacetamide, etc.) formation pathways, involving haloamine-mediated N-halogenation, O3-driven oxidation, decarboxylation, and deamination, were supported by density functional theory (DFT) calculations, confirming both thermodynamic and kinetic feasibility. Matrix-dependent quantitative validation in Suwannee River humic acid (SRHA) and wastewater effluents showed that concentrations of some identified DBPs reached tens of μg/L, dominated by aromatic halo-phenolics and brominated derivatives. In silico quantitative structure–activity relationship (QSAR) models and cytotoxicity assays indicated that these aromatic halo-DBPs exhibited comparable toxicities to conventional DBPs (e.g., dichloroacetonitrile, N-nitrosodimethylamine), but had a higher toxicity index than BrO3–. These findings highlight trade-offs in water disinfection, underscoring the need for optimized strategies to co-control BrO3– and toxic organic DBPs.

Electrochemical hydrogenation of halogenated disinfection byproducts in drinking water purification

Baoquan Liu,Lianchong Shao,Jiayun Yu,Feipeng Huang,Chengpu Chu,Shaoping Tong,Laiquan Li,Huan Wu,Yinghua Xu,Bin Liu

Halogenated disinfection byproducts (DBPs) pose significant health risks owing to their widespread occurrence and high toxicity in drinking water. Traditional water treatment technologies often fail to remove these toxic compounds without generating secondary pollutants. Herein, we report a sustainable and highly efficient electrochemical hydrogenation (ECH) strategy using a delicately designed ruthenium nanoparticle-modified electrochemical‑hydrogen-membrane (Ru NPs-EHM) reactor, which enables the complete conversion of halogenated DBPs into non-toxic products without the need for supporting electrolyte. The reactor achieves >99.9% conversion of 12 representative halogenated DBPs, with minimal formation of hazardous intermediates. The exceptional catalytic performance is attributed to the strong adsorption capability of Ru nanoparticles and the unique EHM configuration, which enhances both ECH selectivity and efficiency. This work presents a breakthrough in water treatment technology, offering a cost-effective, environmentally friendly, and scalable solution for the safe purification of drinking water.

Dynamic chloride coordination enables selective pulsed electrocatalytic upcycling of 4-chlorophenol on FeN2O2 single-atom catalyst

Wang Jiachen,Li Jinxin,Xie Mengjiao,Quan Xie,Liu Yanbiao

The electrocatalytic upcycling of halogenated pollutants into value-added chemicals presents a sustainable frontier, yet precise transformation pathways remain challenging. Here, we report a pulsed electrocatalytic strategy that exploits a temporal modulation to realize a dynamic coordination mechanism, enabling the sequential conversion of 4-chlorophenol (4-CP) to para -benzoquinone ( p -BQ) over an N, O-dual coordinated Fe single-atom catalyst (FeN 2 O 2 SAC). Diverging from conventional continuous electrolysis, pulsed catalysis spatiotemporally decouples cathodic dechlorination and anodic oxidation, exerting precise control over transient intermediate populations. In situ spectroscopy and density functional theory reveal that pulse polarization drives a dynamic chloride-coordination process at the Fe center. This transient ligand-field modulation optimizes the adsorption energetics and lowers the thermodynamic barrier. Consequently, the FeN 2 O 2 SAC achieves a 4-CP conversion of 94.8% and a p -BQ yield of 62.6%, outperforming the FeN 4 architecture. This system demonstrates long-term durability in flow electrolyzers alongside a reduced carbon footprint. By coupling pulsed electrocatalysis with dynamic coordination chemistry, this work establishes a paradigm for “pollutant-to-product” conversion, offering a scalable blueprint for circular chemical economies.

Synergistic effect of inner filtering effect and host-guest interaction based on β-cyclodextrin fluorophore for promoted 4-nitrophenol detection

Zhaolei Zhang,Fengyan Fang,Pingping Zhang,Xiaokang Zhang,Hongchao Ma,Yanhui Wei

Efficient detection of 4- nitrophenol (4-NP) organic pollutant is always a very important issue due to the rapid development of chemical industry and the abuse of pesticides and so on. Here, we designed and synthesized a novel supramolecular fluorescent probe , 4-[4-(acetylamino)styryl]-1-cyclodextrin pyridinium p-toluenesulfonate (ASPT-β-CD), for the selective and sensitive detection of 4-NP. The introduction of β-CD not only improves the water solubility of probe and can also be used as a host to encapsulate 4-NP. In alkaline aqueous solution, the absorption spectrum of 4-NP overlaps the excitation spectrum of ASPT-β-CD and suggests that an internal filtration effect occurs between them. We explored the possible response mechanism and speculated that the high selectivity and high sensitivity were derived from the synergistic effect of inner filtering effect and host-guest interaction. Benefiting from the synergistic effect, the proposed sensor ASPT-β-CD displayed significant "turn-off" after adding 4-NP, while showing a fast response to 4-NP within 2 min and low LOD about 0.01 μM. In addition, this method has been successfully applied to the determination of 4-NP in lake water samples, indicating that the obtained ASPT-β-CD has great practical application potential in the environmental field.

Deciphering the Environmental Fate of Halogenated Organic Compounds in Cold Seep Sediments: Insights from Non-targeted Analysis and Metagenomics across Vertical Redox Gradients

Hao Yu,Xiaoyan Zhang,Yanpeng Liang,Qinglin Mu,Xiaolei Shi,Zhaochao Deng,Jiawang Chen,Jun Cao,Yinan Deng,Zhiqiang Han,Haixin Chen,Chunfang Zhang

Halogenated organic compounds (HOCs) are pervasive in marine environments, yet their molecular diversity, vertical distribution, and fate in deep-sea ecosystems remain largely uncharted. Here, we integrated non-targeted analysis, geochemical profiling, and metagenomics to systematically analyze a 500-cm sediment core from the Haima deep-sea cold seep, deciphering these key aspects and their controlling factors. Non-targeted analysis identified 669 HOCs (at molecular formula level), predominantly of marine origin with saturated structures. The highest HOC diversity was found in the oxic/suboxic (OS) zone, where 73.4% of the frequently detected HOCs reached their peak abundance. Concurrently, a marked decrease in organochlorines was observed at the OS–suboxic/anoxic (SA) interface, followed by level stabilization below this transition, suggesting regulation by abrupt redox shifts. Correlation analyses revealed co-regulation of HOC distribution by geochemical (e.g., depth, pH, and SO 4 2- ) and microbial (e.g., reductive and hydrolytic dehalogenases) factors. Metagenomics combined with redundancy analysis further demonstrated significant interactions between HOCs and dehalogenating microbial community along the vertical profile. In summary, this study provided an integrated perspective on the biogeochemical cycling of HOCs in the deep-sea cold seep, linking their removal at redox boundaries, long-term burial, and spatial organization to underlying microbial and geochemical drivers.

Comparative studies of transformation behaviors and mechanisms of halophenols in multiple chemical oxidative systems

Xiaoxue Pan,Junyan Wei,Min Wang,Jie Zhang,Zhiming Xu,Haojie Wei,Nami Lai,Kainan Nian,Rui Zhang,Xuesheng Zhang

Due to wide applications, halophenols (HPs), especially bromophenols, chlorophenols, and fluorophenols, are commonly detected but resistant to biological removal in wastewater treatment plants (WWTPs). This study investigated the overall transformation behaviors of three representative HPs (2,4-dichlorophenol: 24-DCP, 2,4-dibromophenol: 24-DBP, 2,4-difluorophenol: 24-DFP) in six chemical oxidative systems (KMnO 4 , K 2 FeO 4 , NaClO, O 3 , UV, and persulfate (PS)). The results revealed fast removal of selected HPs by O 3 , PS and K 2 FeO 4 , while a large discrepancy in their removal efficiencies occurred under UV irradiation, KMnO 4 oxidation and particularly chlorination. Based on the analysis of the identified intermediates and products, coupling among the five routes was the general route, and dimers were the main intermediates for HP oxidation. The effect of the halogen atom on the transformation pathways of HPs was highly reaction type dependent. Among the six chemical treatments, PS could induce HPs to yield relatively low-molecular-weight polymers and obtain the highest coupling degree. Transition state (TS) calculations showed that the H atom linked to the phenoxy group of HPs was the most easily abstracted by hydroxyl radicals to form the coupling precursor, i.e., phenoxy radicals. This high coupling behavior further resulted in the increased toxicity to green algae. Characterization revealed that HP reaction solutions treated with PS had a severely negative effect on algae growth, photosynthetic pigment synthesis, and the antioxidant enzyme system. These findings can shed light on the reaction mechanisms of advanced oxidation technologies and some risk management and control of PS technique may be considered when treating phenolic pollutants.

Magnetic Large-Mesoporous Nanoreactors Enable Enzymatically Regulated Background-Free and Persistently Signalling Diseases Diagnosis

Juan Li,Jinhua Huang,Yongjian Jiang,Limin Wu,Yonghui Deng

Diverse diseases and increasing prevalence pose a serious threat to public health. Point-of-care testing (POCT) techniques have imposed superior requirements over sensitivity, selectivity, robustness, affordability, and high-throughput. However, transient signal, complex sample pretreatment, and low signal-to-noise ratio make POCT severely limited in detection accuracy, efficiency, and sensitivity. Here, an enzyme-assisted magnetic large-mesoporous nanoreactor (FS) is constructed for achieving persistent-chemiluminescence signal output and eliminating matrix interference in disease diagnosis. The core-shell structured FS synthesized via an interface coassembly method exhibits uniform size, large and open mesopores (≈22 nm), and intrinsic magnetic separability. Such unique FS acts as efficient nanoreactor for confined cascade reactions enable efficient persistent-chemiluminescence (pCL) signal transduction and high-SNR chromogenic analysis of diverse biomarkers. The developed pCL assays facilitate high-sensitive determination of chronic disease biomarkers glucose and uric acid with detection limits (DL) of 5.4 mg L −1 and 151.2 ng L −1 , respectively. The proposed chromogenic immunoassay enables an ultrasensitive and visual determination of alpha-fetoprotein with a DL of 1.2 ng L −1 , which is superior to previously published immunoassays. The feasibility of the developed methods for real-world applications are demonstrated in 159 clinical serum samples, and the determination results agree well with the clinical data. The proposed technique is expected to promote highly sensitive disease diagnosis in primary medical institutions and resource-limited areas since not relying on expensive automatic sampling and testing instruments. The good flexibility of the customizable nanoreactor makes it a powerful tool for developing various POCT techniques for rapid, sensitive, and accurate diseases diagnosis.

Temperature-Responsive Deep Eutectic Solvents for Highly Selective Separation of 5-Hydroxymethylfurfural from Reaction Mixture

Dazhen Xiong,Yang Wang,Huihui Ma,Lige Lu,Qian Zhang,Yunlei Shi,Yang Zhao,Jianji Wang

5-Hydroxymethylfurfural (HMF) is a key biobased platform compound for the production of high-value chemicals and fuels. However, separation and purification of HMF is currently the bottleneck for HMF production. In this work, a novel class of temperature-responsive deep eutectic solvent (DES)–water systems have been explored to selectively separate HMF from reaction mixtures. The fructose dehydration reaction was conducted in homogeneous DES–H2O systems, and then, the produced HMF was migrated to the DES-rich phase while the unreacted fructose was retained in the H2O-rich phase upon cooling. Thus, selective separation of HMF was realized. It was found that water–water and DES–DES interactions predominate over DES–water interactions during cooling, thus resulting in upper critical solution temperature phase separation. Under optimal conditions, the partition coefficient and separation factor of HMF could reach up to 78 and 609, respectively, which is about 5 and 13 times those reported in ionic liquid-based aqueous biphasic systems. Furthermore, HMF could be removed from the DES-rich phase, giving a high recovery efficiency of 69%, which is much higher than the best value reported in the literature. At the same time, DES was regenerated and reused in the next process, and no obvious decrease in partition coefficient of HMF was observed after six cycles.

A sustainable iron-catalyzed aerobic oxidative C–C and C–O bond cleavage of a lignin model to phenol and methyl benzoate

Shaoyuan Guo,Xinli Tong,Lingwu Meng,Guobao Yang

Selective oxidative C–C and C–O bond cleavage is of significance to the efficient utilization of biomass and biomass-derived platform compounds. In this work, the selective oxidative cleavage of C–C and C–O bonds has been developed with an iron-based catalyst (Fe–N–C) in the presence of molecular oxygen. Specifically, the β-O-4 lignin model compound was successfully converted to phenol and methyl benzoate in a methanol solvent, where the substrate conversion was 95.0% and the yields of phenol and methyl benzoate were 94.9% and 63.7%, respectively, when the reaction was performed with the Fe–N–C-850 catalyst at 120 °C for 4 h. Also, the oxidative transformations of other lignin models to phenols and methyl benzoates were achieved. Further investigations showed that the existence of the Fe3C phase in the catalyst plays an important role in the aerobic oxidative cleavage of C–C and C–O bonds in the β-O-4 lignin model.

Simultaneous detection of multiple phenolic compounds in fish by gas chromatography-mass spectrometry following a modified QuEChERS cleanup

Jiali Xing,Yang Li,Ruihang Zheng,Hao Shen,Xiaorong Xu,Lingyan Mao,Xiaohu Luo,Jian Shen,Weirong Yao

Zeolite-encaged palladium catalysts for heterogeneous Suzuki-Miyaura cross-coupling reactions

Mingyang Gao,Jiamin Wang,Weixiang Shang,Yuchao Chai,Weili Dai,Guangjun Wu,Naijia Guan,Landong Li

Suzuki-Miyaura cross-coupling reaction by homogeneous Pd complex is a powerful route to construct carbon-carbon bond and is now widely applied in the synthesis of functional organic compounds. Heterogeneous Pd catalysts are highly desired as alternatives to homogeneous ones due to their facile reusability and good compatibility. Herein, zeolite-encaged Pd particles, namely Pd@MFI, have been successfully prepared via an in-situ hydrothermal strategy and investigated as promising heterogeneous catalysts for Suzuki-Miyaura cross-coupling reactions. Characterization results demonstrate that high dispersed Pd particles with apparent sizes of 1–2 nm have been encaged in and efficiently stabilized by the matrix of MFI zeolite. The as-prepared Pd@MFI catalysts are active in the Suzuki-Miyaura coupling reaction between bromobenzene and phenylboronic acid, and the presence of basic sites adjacent to Pd sites are crucial to achieving high catalytic activity via effective cooperation. Pd@K-ZSM-5 can be optimized for the coupling between bromobenzene and phenylboronic acid and can catalyze the reaction with a low apparent activation energy value of 41.2 kJ/mol. Pd@K-ZSM-5 also shows good stability and can be recycled for at least five times without obvious loss in activity, demonstrating its great potential as a heterogeneous catalyst for Suzuki-Miyaura cross-coupling reactions. Encapsulation of metal species in zeolite matrix offers a big opportunity to the heterogenization of homogeneous metal catalysts for practical chemical transformations.

Preparation of a novel heterogeneous palladium nanocatalyst based on carboxyl modified magnetic nanoparticles and its applications in Suzuki-Miyaura coupling reactions

Fangfang Ren,Simin Li,Wenqing Zheng,Qianyi Song,Wenhui Jia,Yaqin Nan,Haijiao Jia,Jia Liu,James Jianmin Bao,Youxin Li

In this paper, an active, recyclable and stable magnetic palladium nanocatalyst (Fe 3 O 4 @SiO 2 -DTPA-Pd) was reported which could catalyze Suzuki coupling reaction. The Pd was stably hold by the three nitrogen atoms at the inside and four acetic acid groups at the outside of the chelating ligand ethylenediaminepentaacetic acid (DTPA) on the surface of core-shell magnetic Fe 3 O 4 @SiO 2 microspheres . The prepared Fe 3 O 4 @SiO 2 -DTPA-Pd was systematically characterized. Results showed its size was 10–20 nm with 0.535 mmol/g Pd 2+ /Pd 0 . It could monodisperse in liquid, was thermally stable and good magnetic response from the high saturation magnetization value at 35.9 emu/g. Its activity was evaluated through Suzuki coupling reactions between 14 types of aryl halides and phenylboronic acid under optimized reaction conditions. It exhibited excellent activities and good applicability to substituted iodobenzene and bromobenzene . The yield of 4-bromobenzonitrile was up to 97.93%. Furthermore, the Fe 3 O 4 @SiO 2 -DTPA-Pd catalyst was stable, reusable and conveniently recovered by applying an external magnetic field. After 20 consecutive reaction cycles, the yield was still above 85%, which showed a superior heterogeneous advantage over other catalysts reported in the literature and had the huge potential in actual application of industry.