Chiral Sensor Research Articles

Chiral Electrochemical Sensing Platform Constructed by Chiral Chitosan Materials for Enhanced Electrochemical Chiral Analysis

AbstractPolysaccharide materials have wide applications in the field of chiral recognition. Herein, a new series of chiral materials based on chiral polysaccharide were synthesized for electrochemical enantioselective recognition of tryptophan (Trp) enantiomers. Chiral recognition was investigated via differential pulse voltammetry (DPV). Among poly (L‐lactide) La/hydroxyapatite chitosan (PLLHC‐X) series materials (PLLHC‐0, PLLHC‐1, PLLHC‐3, PLLHC‐7 PLLHC‐9 and PLLHC‐5), PLLHC‐5 has the best recognition efficiency. And the results reveal that the PLLHC‐5 displays a stronger interaction with L‐Trp than to that of D‐Trp. The synergetic effect of chiral recognition from chitosan and signal amplification from poly (L‐lactide) (PLLA) offered an easy‐handling and effective electrochemical approach for isomers discrimination to realize the chiral recognition of Trp enantiomers. The synergetic effect results in highly efficiency and thus opens up new directions in the field of chiral materials.

Electropolymerization of a New Diketopyrrollopyrrole Derivative into Inherent Chiral Polymer Films

Electropolymerization is a convenient way to obtain conducting polymers (CPs) directly adhered to an electrode surface. CPs are well-known for their various application fields in photovoltaic cells, chemical sensors, and electronics. By implementing chirality into a CP, the application possibilities will spread further onto chiral sensors or optoelectronics. In this work, we introduce a new inherently chiral polymer based on a macrocyclic 3,4-ethylenedioxythiophene-diketopyrrolopyrrole-3,4-ethylenedioxythiophene triad (EDOT-DPP-EDOT) fused by 1,4-phenylene groups, which was prepared via oxidative electropolymerization directly on the electrode surface. The investigation of the chiroptical properties was performed by circular dichroism spectroscopy in the solid state. The enantiomeric pure polymer films obtained showed dissymmetry factors of up to −2.71 × 10−4, whereby linear dichroism contributions can be widely excluded.

Modulation of the Chirality and Dynamics of Self-Assembled Nanocellulose-Chiral C-Dot Film for Chiral Sensing Applications.

The detection and sensing of chirality using chiral biomaterials are growing areas of research in advanced bioelectronics. As a result, chiral-controlled biomaterials are crucial for advancing current technologies in chiral sensing applications within biosystems. A chiral carbon dot (C-dot) modulated self-assembled emissive cellulose nanocrystal (CNC) film is developed where the chirality of the CNC film can be tempered between left-handed and right-handed chirality after being doped with chiral L/D-C-dots in CNCs (C-dot-CNC film), transferring the chirality from C-dots to CNCs. The interaction between C-dots, CNCs, and carrier dynamics is investigated using a variety of steady-state and time-resolved PL spectroscopy techniques. The chiral C-dot enhanced the protonic conductivity across the CNC via the formation of hydrogen bonds with its surface functional groups and water molecules. Further, the chiral CNC-C-dots photoelectrodes demonstrate an excellent ability to distinguish between left-handed and right-handed small molecules. These findings on the underlying mechanism of spin selectivity between chiral CNC-C-dot and chiral ligand hold promise for the development of efficient chiral-sensing electronic devices.

Chiral Induction of a Tetrakis(porphyrin) in Various Chiral Solvents.

Non-covalent interactions offer an alternative way for developing stimulus-responsive materials such as sensors, machines, and drug-delivery systems. We recently reported that a urethane-equipped tetrakis(porphyrin) forms one-handed helical supramolecular polymers in solution in response to chirality of chiral solvents. Conformational changes in helical sense were detected using circular dichroism (CD) spectroscopy, which showed that the tetrakis(porphyrin) can possibly be used as a sensor for determining the enantiomeric excess of a chiral analyte. Hence, we studied the scope and limitations of the chiral-induction behavior of tetrakis(porphyrin) to deepen the understanding of tetrakis(porphyrin)-based chiral sensing systems. Herein, we report the chiral-induction behavior of tetrakis(porphyrin) in various chiral solvents, which was found to be CD-active in many chiral solvents. Notably, the tetrakis(porphyrin) was CD active in a cryptochiral molecular solvent, which is exciting because the chiralities of acyclic saturated hydrocarbons are hard to sense. Consequently, this study highlights the potential advantages of supramolecular chiral sensors capable of targeting a wide range of analytes, including molecules that are absorption-silent in the UV/vis region, ones devoid of anchoring functional groups, and acyclic, saturated hydrocarbons.

Chiral Metal-Organic Framework Films with Ordered Macropores for Enantioselective Analysis of Proteins.

Chiral film-based sensors show great promise for discriminating between enantiomers due to their miniaturization and low power consumption. However, their practical use is hindered by the trade-off between enantioselectivity and mass transfer capability, especially concerning biomacromolecules such as proteins. In this work, we present an effective and straightforward method for creating highly organized macropores within crystalline chiral metal-organic framework (CMOF) films. This approach harnesses the shaping influence of a polystyrene nanosphere template and the crystallization induced by the liquid dielectric barrier discharge plasma. The resultant highly ordered macro-microporous structures improve mass diffusion and access to chiral active sites in the hierarchical CMOF films. Coupled with their inherent chirality, strong fluorescence emission, high crystallinity, and exceptional stability, these attributes endow these CMOF films with enhanced sensing capabilities for chiral molecules. Particularly, the macro-microporous structure facilitates efficient protein recognition, overcoming a significant challenge encountered by MOFs due to protein dimensions surpassing MOF pore sizes. These films exhibit increased enantioselectivity, better limits of detection, and wider linear ranges compared with purely microporous CMOF films. This study thus provides a powerful synthetic approach for hierarchical CMOF films, addressing the limitations of traditional thin film sensors and opening an avenue for efficient chiral sensing of large biomacromolecules.

Charge Transfer Plasmons Enabled by Supramolecular Plug: From Optoelectronic Switching to Enhanced Chiral Sensing.

Miniaturization and integration of plasmonic nanodevices are fundamentally limited by quantum tunneling, which leads to quantum plasmonics with reduced local E-field intensity. Despite significant efforts devoted to modeling and deterring the detrimental effect of quantum plasmonics, the modulation and application of electron transport through the subnanometer gaps seems rarely exploited due to the limited tunability of conventional quantum materials. Here, we establish a supramolecular plasmonic system made of pillar[5]arene complexes and plasmonic resonators (nanoparticle-on-mirror, NPoM). The supramolecular assemblies significantly enhance the gap conductance of NPoM, which results in a blue-shift of the coupled plasmons. Plasmonic hot-electron transport with laser excitation further modulates the gap plasmons, which are fully reversible and beneficial for enhanced chiroptic sensing. Such a conductive supramolecular plasmonic system not only suggests an optoelectronic switching strategy for charge transfer plasmons but also provides a superior sensing platform for single molecules.

Chiral helical polyaniline modified electrodes toward efficient enantioselective recognition of tyrosine

Enantiomeric analysis is a crucial aspect of the investigation of the properties of chiral substances, and it plays a pivotal role in the development and application of chiral substances. Therefore, the objective of this study was to develop a highly sensitive and user-friendly tyrosine (Tyr) enantiomer detector based on chiral helical polyaniline (PANI). In this study, the helical PANI was generated in an alcohol-water system and doped with Camphorsulfonic acid (CSA) to enhance its electrochemical properties. The chiral helical PANI was then obtained by eluting the CSA under alkaline conditions. The electrochemical sensors developed using this material enable selective recognition of Tyr enantiomers. The mechanism of enantioselective recognition was also explored from a molecular perspective with the help of modeling software. The chiral recognition ability and properties of the sensor were investigated using DPV, EIS, and CV. The surface characteristics of doped and de-doped chiral sensor were analyzed using FE-SEM, HR-TEM, AFM, CD, XPS, and FT-IR. Finally, an electrochemical analysis method for Tyr enantiomers was established using DPV, offering high sensitivity, superior anti-interference ability, quick analysis speed, and good long-term stability. The constructed chiral electrochemical sensor can be used for the detection of human serum and urine samples, which provides a new idea for the selective recognition of Tyr enantiomers in clinical sample.

Observation of the enhanced dual-split photonic spin Hall effect in wavelength domain via a helical fiber grating

To date, the photonic spin Hall effect (PSHE) has been studied and observed only in the space and momentum domains. Direct observation of the PSHE in the wavelength domain remains unexplored. In this work, we demonstrate both theoretically and experimentally the enhanced PSHE in the wavelength domain via a helical long-period fiber grating (HLPG), where the spin-dependent dual-split in the transmission spectrum of the utilized HLPG has been observed. This is unlike the PSHEs reported thus far, where a mono-splitting of the light is observed in either the space or the momentum domains. The proposed method provides an additional degree of freedom to observe the PSHE, which paves the way for exploiting all fiber-based HLPGs in chiral photonics, chiral sensors, and fine precise measurements.

Rapid determination for tyrosine isomers in food based on N-acetyl-L-cysteine/Upconversion nanomaterials target-induced quench by chiral Electrochemiluminescence sensor

Rapid determination of amino acid isomer is very important for the evaluation of the amino acid nutrition in different foods, so a fast and sensitive electrochemiluminescence (ECL) sensor was innovatively fabricated for the determination of tyrosine isomers in foods based on N-Acetyl-L-cysteine/upconversion nanomaterials possessed a good particular selectivity to L-tyrosine. Under the optimal conditions, for L-tyrosine, the limit of detection (LOD) of the sensor for L-tyrosine was 2.87 × 10−6 M, detection range of 5.5 × 10−5–5.5 × 10−3 M, for D-tyrosine, LOD was 2.56 × 10−5 M, detection range was from 5.5 × 10−4 to 5.5 × 10−3 M. The developed chiral sensor was used to determinate the tyrosine isomers in foods successfully, which provided a convenient method to quickly evaluate the nutritional value of amino acids in food.

Adsorption of Prochiral Solvent Molecules by Surface-Confined Chiral Supramolecular Assemblies: How Solvent Impacts on-Surface Chirality.

The understanding of supramolecular chirality in self-assembled molecular networks (SAMNs) on surfaces generates a lot of interest because of its relation to the production of chiral sensors, reactors, and catalysts. We herein report the adsorption of a prochiral solvent molecule in porous SAMNs formed by a chiral dehydrobenzo[12]annulene (cDBA) derivative. Through the prochirality recognition of a solvent molecule, the supramolecular chirality of the SAMN is switched: the cDBA exclusively forms a counter-clockwise pore through co-adsorption of the solvent molecule in prochiral 1,2,4-trichlorobenzene, while in 1-phenyloctane it produces the opposite chiral, clockwise pore. The prochirality recognition of the solvent molecule in the chiral SAMN pores is attributed to the adaptable conformational changes of the chiral chains of the cDBA molecule.

Highly sensitive intensity-type polarization chiral sensor with reference light.

Optical rotation is a special phenomenon in which the plane of polarization of polarized light is rotated after passing through a chiral medium. This work first, to our knowledge, presents and optimizes a polarization chiral sensor with a reference light on the basis of a weak measurement light path. The influences of phase shift and polarization angle difference on sensitivity were theoretically optimized and verified experimentally. The introduction of a reference light further reduced the impact of light source fluctuations on the detection signal, improving the signal-to-noise ratio and reducing the optical rotation resolution to 2 × 10-5 rad. This method has the characteristics of low cost, high sensitivity, and real-time rapid detection, making it potentially applicable in the field of chemical analysis, such as chiral molecule detection.

Enhanced Enantioselective Discrimination Regulated by Achiral Ligands in Chiral Metal-Organic Frameworks.

Enantioselective recognition is a fundamental property of chiral linkers in chiral metal-organic frameworks (CMOFs). However, clarifying the efficient enantioselective discrimination tailored by achiral linkers remains challenging to explain the chiral recognition mechanism and efficiency. Here, two CMOFs ([Zn2(l-Phe)2(bpa)2]n and [Zn2(l-Phe)2(bpe)2]n) with the completely different enantioselective recognition are synthesized from different nonchiral ligands and the same chiral ligands. The enantioselective recognition of CMOF is undoubtedly related to l-Phe, which differs in the hydrogen bonding to the Trp enantiomer. However, the electrochemical signals are weak and undifferentiated. [Zn2(l-Phe)2(bpe)2]n produces a flattened coplanar conformation with the -C═C- tether in the achiral ligand. The flattened achiral bpee ligand and its surrounding chiral phenylalanine molecules interact through multiple π-π stacking and hydrogen bonding, which together create a chiral sensor that facilitates the recognition of l-Trp. However, [Zn2(l-Phe)2(bpa)2]n produces a stepped conformation due to the -C-C- tether in the achiral ligand; despite the recognition effect of bpea, the recognition is unsatisfactory. Therefore, the chiral recognition of the two CMOFs stems from the synergistic effect between chiral and achiral ligands. This work shows that nonchiral ligands are also crucial in determining enantiomeric discrimination and opens up a new avenue for designing chiral materials.

Aqueous Two-Phase Extraction of Single-Chirality Carbon Nanotubes with Functionalized ssDNA for Biomarker-Specific Antibody Conjugation

Multiplexed detection of biomarkers for cancer and chronic inflammatory diseases is necessary to improve diagnostic sensitivity and specificity. Our prior studies and that of others has used near-infrared fluorescent single-walled carbon nanotubes (SWCNT) as sensor transducers because of their sensitivity to the local environment, photostability, and emission in the tissue-transparent window. That work engineered the SWCNT surface through non-covalent interactions with short ssDNA oligonucleotides containing a functional group to which a biomarker-specific antibody was conjugated. Further, previous work by other groups has demonstrated the ability to obtain single SWCNT chiralities using the aqueous two-phase extraction (ATPE) technique with non-functionalized ssDNA sequences. Here, we have incorporated primary amine-functionalized ssDNA sequences into the ATPE separation technique to obtain individual SWCNT chiralities with functionalized ssDNA. To those primary amine-functionalized ssDNA-SWCNT complexes, we conjugated antibodies against two inflammatory cytokines. We investigated the sensitivity and specificity of these individual SWCNT chirality sensors specific to two biomarkers together in buffer and serum, finding that each chirality responds specifically only to its cognate biomarker and not the other. This is the first demonstration of single-chirality, molecularly-specific multiplexed SWCNT sensors. It forms the basis of ongoing work to obtain additional chiral species with other functional groups, as well as to develop multiplexed cytokine sensors for in vivo diagnostics.

(Invited) Purification of Enantiomeric Pairs of DNA-Wrapped Carbon Nanotubes and Their Use in Bilateral Chiral Sensing

This presentation will focus on our recent progress in purifying enantiomeric pairs of DNA-wrapped carbon nanotubes (DNA-CNTs) via the aqueous two-phase extraction method. We will also discuss a potential application of enantiomeric pairs of DNA-CNTs in bilateral chiral sensing.

Chirality Sensing of Amino Acid Esters by S-2-Methylbutanamido-Substituted m-Phthalic Diamide-Linked Zinc Bisporphyrinate.

To understand the role of an additional coordination site in the linker in chirality sensing, we designed and synthesized an S-2-methylbutanamido-substituted m-phthalic diamide-linked zinc bisporphyrinate, [Zn2(S-MAABis)] and investigated its ability to sense the chirality of amino acid esters. The 1H NMR spectra and the crystal structure showed that the amido oxygen adjacent to the chiral carbon was coordinated with zinc. NMR and UV-vis titration showed that the binding of [Zn2(S-MAABis)] to amino acid esters occurred via two equilibria, forming 1:1 and 1:2 host-guest complexes. The CD spectra suggested that [Zn2(S-MAABis)] can effectively recognize the absolute configuration of amino acid esters. The sign of the CD spectra remained unchanged during the titration, indicating that the corresponding 1:1 and 1:2 host-guest complexes had the same chirality. This is different from previously studied amino-substituted m-phthalic diamide-linked zinc bisporphyrinate [Zn2(AmBis)], which showed chirality inversion during titration. Theoretical calculations indicated that the additional coordination sites (amido or amino) in the 1:1 host-guest complexes played different roles, leading to differences in chirality. Our studies suggest that the introduction of a coordination site can influence the chirality transfer process, but the results of chirality transfers are dependent on the specific binding modes.

Precise measurement of chiral spectrum in the ultraviolet band using weak measurement and a deep neural network model.

Circular dichroism (CD) spectrum and optical rotation (OR) spectrum, crucial for understanding molecular properties and configurations, present challenges due to limited testing methods and equipment accuracy in the ultraviolet (UV) region. This study proposes a weak measurement system for chiral signals in varying concentrations in the ultraviolet range, optimized using a deep neural network (DNN) model. Introducing different post-selections to detect the circular dichroism spectrum and optical rotation spectrum separately, with contrast as a probe, it achieves a detection resolution of up to 10-6 rad. Moreover, the fitted value of the training data can reach 0.9989, enhancing the prediction accuracy of chiral molecule concentrations. This method exhibits considerable promise for applications in chiral measurement and sensor technologies.

Highly sensitive terahertz polarization biosensor utilizing chiral metasurface

In order to achieve a highly sensitive biosensor with a simple structure, we propose a chiral metasurface polarization sensor. Using immunological surface plasmon resonance (SPR) detection, the antigen or antibody is fixed as a probe on the SPR metasurface to detect the corresponding antibody or antigen. Through the change of the refractive index of the analyte on the surface facial mask, the terahertz signal changes, and finally the sensing detection of avian influenza virus can be achieved. The designed metasurface adopts a hollow split sector chiral structure to generate chiral surface current, which can convert linearly polarized incident waves as elliptical polarized waves. The structure achieves the high sensitivity of 401 deg/RIU at frequency of 0.8 THz, and the avian influenza virus (H1N1, H5N2 and H9N2) with the same real part of the refractive index can also be distinguished. Influenza viruses belong to the family Orthomyxoviridae of RNA viruses, divided into three types: A, B, and C. In this article, avian influenza viruses belong to type A influenza viruses. It can clearly identify different Avian Influenza Viruses by the two polarization characteristic parameters of the reflection spectrum PEA (Polarization Ellipse Angle) and PRA (Polarization Rotation Angle). This method has a significant application prospect in the fields of biomedicine and food industries.

Bionic nanopore recognition receptors for single-molecule enantioselectivity studies of chiral drugs

BackgroundEnantiodiscrimination of chiral drugs is critical for understanding physiological phenomena and ensuring medical safety. Although enantiomers of these drugs share identical physicochemical properties, they exhibit significant differences in pharmacodynamic, pharmacokinetic, and toxicological properties due to the differences in their three-dimensional shapes. Therefore, the development of effective methods for chiral recognition is of great significance and has been a hot topic in chemo/biological studies. ResultsIn this study, we designed a recognition receptor comprising a α-hemolysin (α-HL) nanopore and sulfobutyl ether-β-cyclodextrin (SBEβCD) for identifying the enantiomers of the antidepressant duloxetine at the single-molecule level. Chiral molecules were discriminated based on the different current blockages within the recognition receptor. The results indicated a strong interaction between R-duloxetine and the recognition receptor. By combining the experimental data and molecular docking results, we explored the recognition mechanism of the designed nanopore recognition receptor for chiral drug molecules. It was found that hydrophobic and electrostatic interactions play key roles in chiral recognition. Additionally, by comparing the binding kinetics of enantiomers to cyclodextrins in confined nanospace and bulk solution, we found that enantiomeric identification was better facilitated in the confined nanospace. Finally, the enantiomeric excess (ee) of the enantiomeric duloxetine mixture was measured using this recognized receptor. SignificanceThis strategy has the advantages of low cost, high sensitivity, and no need for additional derivative modifications, providing a new perspective on the development of chiral recognition sensors with excellent enantioselectivity in drug design, pharmaceuticals, and biological applications.

Electrochemical chiral sensor developed using nanofibrous polyaniline chiral Structures: Detection and differentiation of D- and L-tryptophan

In this work, a simple strategy for electrochemical detection and differentiation of D- and L- forms of tryptophan is demonstrated using nanofibrous structures of chiral polyaniline (CP). Basically, CP with desired chirality is prepared using a chiral acid namely, ± camphor sulfonic acid (±CSA) in presence of either a cationic (or) anionic surfactant (CTAB / SDS) through a simple oxidative polymerization process. Structure, morphology and phase purity of the resultant CP materials are characterized by field emission scanning electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy and X-ray diffraction studies. Moreover, the chiral properties of these conducting polymers are evaluated using circular dichroism (CD) spectroscopic studies. From these analyses it is found that CP exhibited twisted nanofibrous morphology and possesses the chirality whereas the non-chiral polyaniline (PANI), prepared in the absence of chiral acid, displayed the formation of a simple fibrous structures without any twists or chirality. Interestingly, such CP materials are found to be electrochemically selective for the detection and differentiation of D- and L- forms of tryptophan (Trp). Among the different chiral materials, CP-CT(−) prepared using CTAB displayed a much better sensing characteristics with higher IL/ID ratio, wider concentration range of detection and lower detection limit of 0.98 µM for l-Trp and 1.2 µM for d-Trp respectively. On the other hand, non-chiral PANI does not display any sensing behavior towards the differentiation of amino acid, Trp. Further, chronoamperometric studies reveal the selectivity of this chiral sensor for the detection of Trp among the other potentially interfering analytes. Although the difference in the measured peak current value is smaller, a significant difference of 70 mV peak potential is observed for the differentiation of L- and d-Trp. Moreover, the proposed CP-based sensing platform exhibits excellent stability and reproducibility with statistically negligible error values suggesting the potential use of the developed material towards electrochemical chiral detection and differentiation of amino acid, Trp.

Chirality Sensing of Chiral Carboxylic Acids by a Ureido-Linked Zinc Bisporphyrinate.

We designed and synthesized a ureido-linked zinc bisporphyrinate [Zn2(UBis)]. CD spectra show that this zinc bisporphyrinate has the ability to sense the chirality of chiral carboxylic acids without derivatization. Our studies suggest that the phenyl ring in the linker forms π-π interactions with porphyrin planes and that the carboxylic acid is coordinated to the zinc in the host-guest complex. DFT calculations show that the bisporphyrin adopts a "Z"-shaped configuration, and that the ureido group forms hydrogen bonds with carboxylic acids. The combination of π-π interactions, coordination interactions and hydrogen bonding interactions leads to the chirality sensing ability of [Zn2(UBis)].