Nanoparticle-based Chemiluminescence for Chiral Discrimination of Thiol-Containing Amino Acids

Abstract

The ability to recognize the molecular chirality of enantiomers is extremely important owing to their critical role in drug development and biochemistry. Convenient discrimination of enantiomers has remained a challenge due to lack of unsophisticated methods. In this work, we have reported a simple strategy for chiral recognition of thiol-containing amino acids including penicillamine (PA), and cysteine (Cys). We have successfully designed a nanoparticle-based chemiluminescence (CL) system based on the reaction between cadmium telluride quantum dots (CdTe QDs) and the enantiomers. The different interactions of CdTe QDs with PA enantiomers or Cys enantiomers led to different CL intensities, resulting in the chiral recognition of these enantiomers. The developed method showed the ability for determination of enantiomeric excess of PA and Cys. It has also obtained an enantioselective concentration range from 1.15 to 9.2 mM for PA. To demonstrate the potential application of this method, the designed platform was applied for the quantification of PA in urine and tablet samples. For the first time, we presented a novel practical application of nanoparticle-based CL system for chiral discrimination.

Chirality Transfer from Sub‐Nanometer Biochemical Molecules to Sub‐Micrometer Plasmonic Metastructures: Physiochemical Mechanisms, Biosensing, and Bioimaging Opportunities

“…A large number of analytical methods, including liquid‐phase separation, [ 10 ] mass spectrometric techniques, [ 11 ] gas chromatography, [ 12 ] capillary electrophoresis, [ 13 ] and nuclear magnetic resonance protocols [ 14 ] have been used for enantiomer discrimination. [ 11,15 ] However, most of these conventional techniques suffer from unavoidable disadvantages such as complex experimental setup, long‐time sample pretreatment, expensive chiral stationary phases or chiral selectors. Fortunately, the chirality of biomolecules can manifest itself optically, which has made optical spectroscopic measurements of molecular chiral–optical (chiroptical) effects attractive as they provide label‐free, noninvasive and cost‐efficient characterizations.…”

Rapid chiral analysis based on liquid-phase cyclic chemiluminescence

“…These results demonstrate that CCL can distinguish some chiral host–guest systems, which would be difficult for NMR and fluorescence spectroscopy. Compared with the method for chiral discrimination using a QD enhanced-CL system, 41 the commercial chiral metal–organic complexes used in the present work are easily available. In addition, they allow facile discrimination between a wide range of enantiomeric pairs.…”

Enantiomeric Recognition and Separation by Chiral Nanoparticles

“…NP-based enantiomeric recognition and separation have been widely discussed and studied in the past decade. Studies reported chiral -modified nanomaterials for catalysis [70,71], chiral drug separation [71] and sensing [54,55,56,57,58,59,60,63,68,72,73,74]. In this section, we will focus on the enantiomeric recognition and the fabrication of most commonly used gold and silver materials for chiral NPs.…”

“…The working principle is that interactions with specific enantiomers occur on the surface of metal NPs, which means that interactions can be monitored according to changes in surface plasmon resonance (SPR). Furthermore, chiral ligand-capped quantum dots (QDs) have also received considerable attention in this field, due to the size-dependent optical properties, bright chemiluminescence, and excellent chemical stability [63,64,65]. Beside the applications of magnetic nanoparticles (MNPs) such as catalysts, targeted administration and magnetic resonance imaging (MRI) [66,67], researchers have even capped the surfaces of MNPs with chiral ligands to promote specific interactions with the target enantiomers.…”