RESUMEN
Different enantiomer forms of amino acids play different roles in multifarious fields, and improper use will cause irreversible effects. Therefore, the identification of chiral amino acids is a vital issue in the field of pharmaceutical analysis. Herein, a chiral sensing system of ß-cyclodextrin coated silver nanoparticle (ß-CD@AgNPs) with peroxidase-like activity was designed for the fast and efficient colorimetric identification of tryptophan (Trp) enantiomers based on the difference in binding capacity between D/L-Trp and ß-CD. The results showed the satisfactory linearity for detecting D/L-Trp over the concentration range from 0.2 to 4 mM with a LOD of 0.16 and 0.18 mM, respectively. Moreover, the absorbance increased linearly with the rise of D-Trp concentration percentage in the Trp enantiomer mixture. The proposed method avoided the use of natural enzymes and improved the stability due to the protective effect of cyclodextrin, which provided a new idea for selective colorimetric recognition and detection of D/L-Trp based on cyclodextrin.
Asunto(s)
Colorimetría , Nanopartículas del Metal , Plata , Triptófano , beta-Ciclodextrinas , Triptófano/análisis , Triptófano/química , Colorimetría/métodos , beta-Ciclodextrinas/química , Plata/química , Nanopartículas del Metal/química , Estereoisomerismo , Espectrofotometría Ultravioleta , Límite de DetecciónRESUMEN
It is known that extracellular free radical reactive oxygen species (ROS) rather than intracellular ROS plays a non-substitutable role in regulation of tumor-suppressing (M1) tumor-associated macrophages (TAMs) polarization. However, most therapeutic nanoplatforms mainly provide intracellular ROS and exhibit insufficient accumulation near TAMs, which strongly limits the macrophage-based immunotherapeutic effects. Here we design and synthesize chiral MoS2 /CoS2 nanozymes with peroxidase (POD)-like and catalase (CAT)-like activities to efficiently modulate TAMs polarization and reverse tumor immunosuppression by harnessing their chirality-specific interactions with biological systems. MoS2 /CoS2 nanoparticles coordinated with d-chirality (d-NPs, right-handed) show improved pharmacokinetics with longer circulating half-life and higher tumor accumulation compared with their l (left-handed)- and dl (racemate)-counterparts. Further, d-NPs can escape from macrophage uptake in the tumor microenvironment (TME) with the aid of cell-unpreferred opposite chirality and act as extracellular hydroxyl radicals (â OH) and oxygen (O2 ) generators to efficiently repolarize TAMs into M1 phenotype. On the contrary, l-NPs showed high cellular uptake due to chirality-driven homologous adhesion between l-NPs and macrophage membrane, leading to limited M1 polarization performance. As the first example for developing chiral nanozymes as extracellular-localized ROS generators to reprogram TAMs for cancer immunotherapy, this study opens an avenue for applications of chiral nanozymes in immunomodulation.