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Controllable synthesis of chiral hierarchical porous Co(OH)2 and its application in rapid chiral recognition and separation

Journal 2025 · IF 6 · 发表于 2025 年 5 月 20 日
作者: Jinhua Xu,Jinyu Zhang,Wenmin Zhang,Shiye Xie,Lan Zhang
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摘要

Background Chiral pollutants present significant environmental and health concerns, with neurotoxic amino acid analogs like β-N-methylamino-L-alanine (BMAA) demonstrating enantiomer-specific bioaccumulation in aquatic ecosystems. Current analytical approaches for chiral environmental contaminants rely predominantly on chromatographic techniques that require extensive sample preparation (typically 24 h), limiting field deployment and high-throughput screening capabilities. Detection thresholds for these compounds (0.1–10 μg/L) necessitate sensitive methodologies that maintain stereochemical integrity. This study addresses these analytical challenges through the rational design of chiral cobalt hydroxide (CF–Co(OH) 2 ) nanomaterials engineered for dual-mode detection and separation functionality. Results A hierarchical porous α-Co(OH) 2 with tunable chirality (R/S/RS configurations) and morphologies (square, rough surface, snowflake, flower-like) via micelle-templated growth strategies. The materials demonstrated dual functionality: (1) Rapid colorimetric amino acid discrimination within 5 min with precision (RSD = 4.9 %, n = 6), validated through urinary l -tryptophan quantification (17.1 ± 0.4 μg/mL); (2) Ultrasensitive BMAA separation via SPE-HPLC-MS/MS with significantly improved detection limits (LOD = 0.02 μg/kg) and processing speed (144 × faster than conventional methods). The colorimetric detection mechanism exploits BMAA's ability to form cobalt-amine complexes that produce concentration-dependent yellow coloration, enabling visual detection at 50 μg/kg in freshwater samples. Field testing successfully detected BMAA in crucian carp (0.39 ± 0.03 μg/kg), confirming food-chain biomagnification with excellent recovery (90.1–102.7 %) across diverse matrices. The system's chiral specificity exhibited distinct affinity patterns (BMAA: R–Co(OH) 2 ; DAB: S–Co(OH) 2 ) with 91.4 % enantiomeric excess in just 10 min through configuration-specific “three-point binding” mechanisms (intramolecular binding energy: 18.7 kcal/mol). Significance This research establishes morphology-programmable chiral materials as a versatile analytical platform for rapid on-site environmental monitoring and high-throughput toxin analysis. The developed methodology directly addresses World Health Organization guidelines for algal toxin detection in drinking water while providing a generalizable approach for chiral pollutant discrimination in complex environmental and biological samples.

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