Velocimetry of GHz elastic surface waves in quartz and fused silica based on full-field imaging of pump-probe reflectometry.

This study reports an imaging method for gigahertz surface acoustic waves in transparent layers using infrared subpicosecond laser pulses in the ablation regime and an optical pump-probe technique. The reflectivity modulations due to the photoelastic effect of generated multimodal surface acoustic waves were imaged by an sCMOS camera illuminated by the time-delayed, frequency-doubled probe pulses. Moving the delay time between 6 . 0 n s to 11 . 5 n s , image stacks of wave field propagation were created. Two representative samples were investigated: wafers of isotropic fused silica and anisotropic x-cut quartz. Rayleigh (SAW) and longitudinal dominant high-velocity pseudo-surface acoustic wave (HVPSAW) modes could be observed and tracked along a circular grid around the excitation center, allowing the extraction of angular profiles of the propagation velocity. In quartz, the folding of a PSAW was observed. A finite element simulation was developed to predict the measurement results. The simulation and measurement were in good agreement with a relative error of 2 % to 5 %. These results show the potential for fast and full-field imaging of laser-generated ultrasonic surface wave modes, which can be utilized for the characterization of thin transparent samples such as semiconductor wafers or optical crystals in the gigahertz frequency range.

A photothermal effect-based chiral sensor for chiral discrimination and sensitive detection.

Chiral analysis with simple devices is of great importance for analytical chemistry. Based on the photothermal (PT) effect, a simple chiral sensor with a portable laser device as the light source and a thermometer as the detection tool was developed for the chiral recognition of tryptophan (Trp) isomers and the sensitive sensing of one isomer (L-Trp). Gold nanorods (GNRs), which have outstanding photo-thermal conversion ability due to their localized surface plasma resonance (LSPR) effect, are used as PT reagents, and biomacromolecules bovine serum albumin (BSA) are used as natural chiral sources, and thus, GNRs@BSA was obtained through Au-S bonds. The resultant GNRs@BSA displays higher affinity toward L-Trp than D-Trp owing to the inherent chirality of BSA. Under the irradiation of near-infrared (NIR) light, the temperature of GNRs@BSA//L-Trp is greatly lower than that of GNRs@BSA//D-Trp due to its greatly decreased thermal conductivity, and thus chiral discrimination of Trp isomers can be achieved. In addition, the developed PT effect-based chiral sensor can be used for sensitive detection of L-Trp, and the linear range and limit of detection (LOD) are 1 µM-10 mM and 0.43 µM, respectively.

π-π+ Interaction Promoting the Absorption of Electroactive Chiral Selectors into the Cavity of Conductive Covalent Organic Framework for Enantioselective Sensing of Electrochemically Silent Molecules.

To date, achieving enantioselective electroanalysis for electrochemically silent chiral molecules is still highly desired. Here, an ionic covalent organic framework (COF) consisting of the pyridinium cation was derived from the tripyridinium Zincke salt and 1,4-phenylenediamine in a one-pot reaction. The electrochemical measurements revealed that the ionic backbone contributed to the electron transfer with a low charge transfer resistance. Besides, the π-π+ interaction between the pyridinium cation and ferrocenyl unit can promote the absorption of electroactive chiral ferrocenyl reagents into the hole of COF, so as to afford the electrochemical signals by themselves, replacing the testing enantiomers. As a result, the electroactive complex used as an electrochemical platform was highly effective at enantiomerically recognizing amino alcohols (prolinol, valinol, leucinol, and alaninol) and amino acids (methionine, serine, and penicillamine), giving the ratios of current intensity between l- and d-enantiomers in the range of 1.46-1.72. Moreover, the density functional theory calculations determined the possible intermolecular interactions between the testing enantiomers and chiral selector: namely, hydrogen bonds and electrostatic attractions. Overall, the present work offers an effective strategy to enlarge the electrochemical scope for chiral recognition based on electroactive chiral COFs.

Visual and electrochemical chiral discrimination of tryptophan isomers with shikimic acid chiral ionic liquids-copper ions complex.

Efficient discrimination of amino acids (AAs) isomers is of significant importance for life science and analytical chemistry. Here, a dual-mode chiral discrimination strategy is proposed for visual and electrochemical chiral discrimination of tryptophan (Trp) isomers. Shikimic acid chiral ionic liquids (SCIL) is coordinated with copper ions (Cu2+), and the obtained SCIL-Cu2+ can form ternary complexes with the Trp isomers. Owing to the inherent chirality of SCIL and the reverse homochirality of L-Trp and D-Trp, the ternary complex of SCIL-Cu-D-Trp has higher stability than SCIL-Cu-L-Trp, as revealed by the calculated stability constants (K) and changes in Gibbs free energy (ΔG). The difference in the stability can be utilized for the chiral discrimination of L-Trp and D-Trp, resulting in discernible differences in colors and the electrochemical signals of the Trp isomers. Besides Trp, the isomers of phenylalanine (Phe) can also be discriminated by the proposed dual-mode chiral discrimination strategy with the SCIL-Cu2+ complex.

Chiral Ru-Based Covalent Organic Frameworks as An Electrochemiluminescence-Active Platform for the Enantioselective Sensing of Amino Acids.

Although several studies related with the electrochemiluminescence (ECL) technique have been reported for chiral discrimination, it still has to face some limitations, namely, complex synthetic pathways and a relatively low recognition efficiency. Herein, this study introduces a facile strategy for the synthesis of ECL-active chiral covalent organic frameworks (COFs) employed as a chiral recognition platform. In this artificial structure, ruthenium(II) coordinated with the dipyridyl unit of the COF and enantiopure cyclohexane-1,2-diamine was harnessed as the ECL-active unit, which gave strong ECL emission in the presence of the coreactant reagent (K2S2O8). When the as-prepared COF was used as a chiral ECL-active platform, clear discrimination was observed in the response of the ECL intensity toward l- and d-enantiomers of amino acids, including tryptophan, leucine, methionine, threonine, and histidine. The biggest ratio of the ECL intensity between different configurations was up to 1.75. More importantly, a good linear relationship between the enantiomeric composition and the ECL intensity was established, which was successfully employed to determine the unknown enantiomeric compositions of the real samples. In brief, we believe that the proposed ECL-based chiral platform provides an important reference for the determination of the configuration and enantiomeric compositions.

A chiral metal-organic framework/cyclodextrin sensing interface for the chiral discrimination of tryptophan enantiomers.

A chiral metal-organic framework (CMOF) was synthesized by introducing L-histidine (L-His) to zeolitic imidazolate framework-8 (ZIF-8) and then grafting with carboxymethyl-ß-cyclodextrin (CM-ß-CD). Compared with L-His-ZIF-8, the CM-ß-CD-functionalized L-His-ZIF-8 (L-His-ZIF-8-CD) showed significantly enhanced discrimination ability for the tryptophan (Trp) enantiomers owing to the inherent chirality of CM-ß-CD. The specificity of the chiral interface was also studied, and the results indicated that the discrimination ability for Trp enantiomers is significantly stronger than that for the enantiomers of cysteine (Cys) and tyrosine (Tyr), which might be due to the better matching between the indole ring of Trp and the chiral cavity of CM-ß-CD.

A Liquid-Liquid Interfacial Strategy for Construction of Electroactive Chiral Covalent-Organic Frameworks with the Aim to Enlarge the Testing Scope of Chiral Electroanalysis.

Although electroactive chiral covalent-organic frameworks (CCOFs) are considered an ideal platform for chiral electroanalysis, they are rarely reported due to the difficult selection of suitable precursors. Here, a facile strategy of liquid-liquid interfacial polymerization was carried out to synthesize the target electroactive CCOFs Ph-Py+-(S,S)-DPEA·PF6- and Ph-Py+-(R,R)-DPEA·PF6-. That is, a trivalent Zincke salt (4,4',4″-(benzene-1,3,5-triyl)tris(1-(2,4-dinitrophenyl)pyridin-1-ium)) trichloride (Ph-Py+-NO2) and enantiopure 1,2-diphenylethylenediamine (DPEA) were dissolved in water and chloroform, respectively. The Zincke reaction occurs at the interface, resulting in uniform porosity. As expected, the cyclic voltammetry and differential pulse voltammetry measurements showed that the tripyridinium units of the CCOFs afforded obvious electrochemical responses. When Ph-Py+-(S,S)-DPEA·PF6- was modified onto the surface of a glassy carbon electrode as a chiral sensor, the molecules, which included tryptophan, aspartic acid, serine, tyrosine, glutamic acid, mandelic acid, and malic acid, were enantioselectively recognized in the response of the peak current. Very importantly, the discriminative electrochemical signals were derived from Ph-Py+-(S,S)-DPEA·PF6-. The best peak current ratios between l- and d-enantiomers were in the range of 1.31-2.68. Besides, a good linear relationship between peak currents and enantiomeric excess (ee) values was established, which was successfully harnessed to determine the ee values for unknown samples. In a word, the current work provides new insight and potential of electroactive CCOFs for enantioselective sensing in a broad range.

Postsynthetic Modification Strategy for Constructing Electrochemiluminescence-Active Chiral Covalent Organic Frameworks Performing Efficient Enantioselective Sensing.

Electrochemiluminescence (ECL), integrating the characteristics of electrochemistry and fluorescence, has the advantages of high sensitivity and low background. However, only a few studies have been reported for enantioselective sensing based on the ECL-active platform because of the huge challenges in constructing tunable chiral ECL luminophores. Here, we developed a facile strategy to design and prepare ECL-active chiral covalent organic frameworks (COFs) Ph-triPy+-(R)-Ru(II) for enantioselective sensing. In such an artificial structure, the ionic skeleton of COFs was beneficial to the electron transfer on the working electrode surface and the chiral Ru-ligand was used as the chiral ECL-active luminophore. It was found that Ph-triPy+-(R)-Ru(II) coupled with sodium persulfate (Na2S2O8) as the coreactant exhibited obvious ECL signals. More importantly, a clear difference toward l- and d-enantiomers was observed in the response of the ECL intensity, resulting in a uniform recognition law. That is, for amino alcohols, d-enantiomers (1 mM) measured by Ph-triPy+-(R)-Ru(II) showed a higher ECL intensity compared with l-enantiomers. Differently, amino acids (1 mM) gave an inverse recognition phenomenon. The ECL intensity ratios between l- and d-enantiomers (1 mM) are in the range of 1.25-1.94 for serine, aspartic acid, glutamic acid, valine, leucine, leucinol, and valinol. What is more interesting is that the ECL intensity was closely related to the concentration of l-amino alcohols and d-amino acids, whereas their inverse configurations remained unchanged. In a word, the present concept demonstrates a feasible direction toward chiral ECL-active COFs and their potential for efficient enantioselective sensing.

Recent advances of optically active helical polymers as adsorbents and chiral stationary phases for chiral resolution.

Chiral resolution is very important and still a big challenge due to different biological activity and same physicochemical property of one pair (R)- and (S)-isomer. There is no doubt that chiral selectors are essentially needed for chiral resolution, which can stereoselectively interact with a pair of isomers. To date, a large amount of optically active helical polymers as chiral selectors have been synthesized via two strategies. First, the target helical polymers are derived from natural polysaccharide such as cellulose and amylose. Second, they can be synthesized by polymerization of chiral monomers. Alternatively, an achiral polymer is prepared first followed by static or dynamic chiral induction. Furthermore, a part of them is harnessed as chiral stationary phases for chromatographic chiral separation and as chiral adsorbents for enantioselective adsorption/crystallization, resulting in good enantioseparation efficiency. In summary, the present review will focus on recent progress of the polymers with optical activity for chiral resolution, especially the literature published in the past 10 years. In addition, development prospects and future challenges of optically active helical polymers will be discussed in detail.

Chiral Metal-Organic Framework with Temperature-Dependent Homochirality for Chiral Discrimination.

Chiral metal-organic frameworks (CMOFs) have attracted considerable attention in chiral discrimination and separation. In this work, a simple CMOF is synthesized through a facile one-pot method by using Zn(II), tetra(4-carboxyphenyl)-porphyrin (TCPP), and d-phenylalanine methyl ester (d-Phe-OMe) as metal ion, organic ligand, and chiral source, respectively. Interestingly, the CMOFs synthesized at different temperatures (25 and 160 °C) display quite different morphologies and diametrically opposite chirality due to the different interaction modes between TCPP and d-Phe-OMe at 25 and 160 °C. Next, the CMOFs synthesized at 25 and 160 °C are utilized for the chiral discrimination of the isomers of tryptophan (Trp), resulting in exactly the reverse effect. The developed CMOF-based chiral sensors also exhibit excellent reproducibility, suggesting their great potential for chiral analysis.

A biodegradable pH and glutathione dual-triggered drug delivery system based on mesoporous silica, carboxymethyl chitosan and oxidized pullulan.

A simple and smart drug controlled delivery system is developed in this work. Biodegradable mesoporous silica nanoparticles (BMSN) were first synthesized by introducing disulfide during the synthesis of mesoporous silica nanoparticles (MSN), which were used for the loading of methotrexate (MTX), an anti-cancer drug. The MTX loaded BMSN (BMSN-MTX) was then encapsulated in the hydrogels of carboxymethyl chitosan (CMCS)/oxidized pullulan (OPL) generated through Schiff base reaction. The acylhydrazone bonds (-N=CH-) between CMCS and OPL are prone to be hydrolyzed in acidic medium while the disulfide linkage (-S-S-) in the BMSN can be cleaved in the presence of glutathione (GSH), and thus the delivery of MTX from the BMSN-MTX-gel can be triggered by both pH and GSH. The results of release kinetics reveal that the delivery of MTX from the biodegradable hydrogels is controlled by Higuchi model. Finally, good biocompatibility and pronounced cytotoxicity of the developed BMSN-MTX-gel are confirmed by cytotoxicity test.

A Real-Time Strategy for Chiroptical Sensing and Enantiomeric Excess Determination of Primary Amines via an Acid-Base Reaction.

Two achiral aromatic carboxylic acids that included the 1,8-naphthalimide group and an imidazolium cation were synthesized and exploited as chiroptical sensors. These compounds showed the real-time discrimination and enantiomeric excess determination of chiral amines and amino alcohols via an acid-base interaction, especially for UV-silent chiral compounds.

TiO2 Nanotubes Decorated with CdSe Quantum Dots: A Bifunctional Electrochemiluminescent Platform for Chiral Discrimination and Chiral Sensing.

Chiral analysis is of significant importance for living organisms since chirality is the fundamental phenomenon in nature. In this work, a bifunctional electrochemiluminescent (ECL) platform is constructed for chiral discrimination and chiral sensing. 3-Mercaptopropionic acid-functionalized CdSe quantum dots (CdSe QDs) are combined with aminated TiO2 nanotubes (NH2-TiNTs) via amidation. The resultant CdSe QDs/TiNTs display significantly enhanced ECL signals due to the synergistic effect between CdSe QDs and TiNTs, which are then used for the chiral discrimination of the isomers of nine chiral amino acids (AAs) in the presence of d-AA oxidase (DAAO). DAAO can selectively catalyze the oxidation of d-AAs to generate H2O2, which acts as the coreaction reagent and triggers the ECL signals of CdSe QDs/TiNTs, and thus, the isomers of the nine chiral AAs can be effectively discriminated. In addition, the as-constructed ECL platform can also be used for the sensitive detection of d-AAs in the presence of DAAO with a wide linear range and a low limit of detection. These findings suggest that the CdSe QDs/TiNTs can work as a bifunctional ECL platform (chiral discrimination and chiral sensing), which might be an advanced ECL platform for biomedical applications.

Strategies to synthesize a chiral helical polymer accompanying with two stereogenic centers for chiral electroanalysis.

In most cases, the recognition efficiency of chiral electroanalysis relies on the chiral carbon center, whereas its medium is just used to transfer the electron. Differently, in this study, an ionic helical polymer with right- or left-handed configuration was prepared via an acid-base interaction between the ionic polymer and enantiopure 1,2-diphenylethane-1,2-diamine. The structure and absolute handedness of the helical polymers were well characterized by the circular dichroism spectrum, gel permeation chromatography, and Fourier transform infrared spectroscopy. The pyridinium moiety of the helical polymer contributes to the electron transfer when it was directly modified on the surface of the glassy carbon electrode as an electrochemical enantioselector for chiral electroanalysis. Results indicated that different configurations of amino acids can be recognized in the responses of different electric signals, namely peak current or peak potential. The peak current ratio between L- and d-isomer can be up to 7.5 and 23.2 for tryptophan and tyrosine, respectively. Most importantly, the reversal of the electric signal can be observed toward L- and d-isomer under the different testing conditions such as pH and metal ion content, because of two stereogenic centers (the chiral inducer and the stereogenic axis) in the helical polymer. Overall, we believe that the present study offers a great promise for the synthesis and application of the ionic helical polymers accompanying with multiple stereogenic centers.

The hybrids of perylene tetracarboxylic acid functionalized multi-walled carbon nanotubes and chitosan for electrochemical chiral sensing of tryptophan enantiomers.

To introduce abundant carboxyl (COOH) groups to the surface of multi-walled carbon nanotubes (MWCNTs) while maintaining the pristine structure of MWCNTs, 3,4,9,10-perylene tetracarboxylic acid (PTCA) was non-covalently grafted to the sidewalls of MWCNTs. The obtained PTCA functionalized MWCNTs (MWCNTs-PTCA) functioned as a scaffold for the further introduction of chitosan (CS) via electrostatic attractions and hydrogen-bonds. The resultant CS/MWCNTs-PTCA could be used for electrochemical chiral sensing of tryptophan (Trp) enantiomers due to the intrinsic chirality of CS and the high electrocatalytic activity of MWCNTs. Under optimized conditions, the Trp enantiomers could be effectively discriminated at the CS/MWCNTs-PTCA modified electrode by differential pulse voltammetry (DPV), demonstrating that the developed CS/MWCNTs-PTCA might be a potential candidate for the construction of electrochemical chiral sensors.

Competitive Self-Assembly Interaction between Ferrocenyl Units and Amino Acids for Entry into the Cavity of ß-Cyclodextrin for Chiral Electroanalysis.

At present, chiral electroanalysis of nonelectroactive chiral compounds still remains a challenge because they cannot provide an electrochemical signal by themselves. Here, a strategy based on a competitive self-assembly interaction of a ferrocene (Fc) unit and the testing isomers entering into the cavity of ß-cyclodextrin (ß-CD) was carried out for chiral electroanalysis. First of all, the Fc derivative was directly bridged to silica microspheres, followed by inclusion into the cavity of ß-CD. As expected, once it was modified onto the surface of a carbon working electrode as an electrochemical sensor, SiO2@Fc-CD-WE, its differential pulse voltammetry signal would markedly decrease compared with the uncovered Fc. Next, when l- and d-isomers of amino acids that included histidine, threonine, phenylalanine, and glutamic acid were examined using SiO2@Fc-CD-WE, it showed an enantioselective entry of amino acids into the cavity of ß-cyclodextrin instead of Fc, resulting in the release of Fc with signal enhancement. For histidine, glutamic acid, and threonine, l-isomers showed a higher peak current response compared with d-isomers. The peak current ratios between l- and d-isomers were 2.88, 1.21, and 1.40, respectively. At the same time, the opposite phenomenon occurred for phenylalanine with a peak current ratio of 3.19 between d- and l-isomers. In summary, we are assured that the recognition strategy based on the supramolecular interaction can enlarge the detection range of chiral compounds by electrochemical analysis.

A surface protein-imprinted biosensor based on boronate affinity for the detection of anti-human immunoglobulin G.

A surface protein-imprinted biosensor was constructed on a screen-printed carbon electrode (SPCE) for the detection of anti-human immunoglobulin G (anti-IgG). The SPCE was successively decorated with aminated graphene (NH2-G) and gold nanobipyramids (AuNBs) for signal amplification. Then 4-mercaptophenylboric acid (4-MPBA) was covalently anchored to the surface of AuNBs for capturing anti-IgG template through boronate affinity binding. The decorated SPCE was then deposited with an imprinting layer generated by the electropolymerization of pyrrole. After removal of the anti-IgG template by the dissociation of the boronate ester in an acidic solution, three-dimensional (3D) cavities complementary to the anti-IgG template were formed in the imprinting layer of polypyrrole (PPy). The molecularly imprinted polymers (MIP)-based biosensor was used for the detection of anti-IgG, exhibiting a wide linear range from 0.05 to 100 ng mL-1 and a low limit of detection of 0.017 ng mL-1 (S/N = 3). In addition, the MIP-based anti-IgG biosensor also shows high selectivity, reproducibility and stability. Finally, the practicability of the fabricated anti-IgG biosensor was demonstrated by accurate determination of anti-IgG in serum sample.

Recent advances of the ionic chiral selectors for chiral resolution by chromatography, spectroscopy and electrochemistry.

Ionic chiral selectors have been received much attention in the field of asymmetric catalysis, chiral recognition, and preparative separation. It has been shown that the addition of ionic chiral selectors can enhance the recognition efficiency dramatically due to the presence of multiple intermolecular interactions, including hydrogen bond, π-π interaction, van der Waals force, electrostatic ion-pairing interaction, and ionic-hydrogen bond. In the initial research stage of the ionic chiral selectors, most of work center on the application in chromatographic separation (capillary electrophoresis, high-performance liquid chromatography, and gas chromatography). Differently, more and more attention has been paid on the spectroscopy (nuclear magnetic resonance, fluorescence, ultraviolet and visible absorption spectrum, and circular dichroism spectrum) and electrochemistry in recent years. In this tutorial review as regards the ionic chiral selectors, we discuss in detail the structural features, properties, and their application in chromatography, spectroscopy, and electrochemistry.

Ultrasensitive Electrochemical Impedance Chiral Discrimination and Sensing of Tryptophan Isomers Based on Core-Shell-Structured Au-Ag Nanoparticles.

Au-Ag nanoparticles (Au-Ag NPs) with a core-shell structure are prepared and used for ultrasensitive electrochemical impedance (EI) discrimination of the isomers of tryptophan (Trp). As revealed by circular dichroism, rotary polarization caused by the Au-Ag NPs is consistent with D-Trp but opposite to L-Trp, and thus, the Au-Ag NPs can selectively combine with D-Trp through preferential interactions. Compared with Au-Ag NPs, the composites of D-Trp and Au-Ag NPs (Au-Ag NPs/D-Trp) display significantly increased charge transfer resistance (Rct); differently, the Rct of Au-Ag NPs/L-Trp remains almost unchanged because the Au-Ag NPs exhibit poor affinity toward L-Trp. Therefore, ultrasensitive EI enantiodiscrimination of the isomers of Trp is realized even at an extremely low concentration of the Trp isomers (0.1 nM). In addition, it is successfully applied in the ultrasensitive determination of D-Trp at a low concentration level (0.1 nM∼10 µM).

Electrochemiluminescent chiral discrimination with chiral Ag2S quantum dots/few-layer carbon nitride nanosheets.

Well-dispersed chiral Ag2S quantum dots (Ag2S QDs) were facilely synthesized by using N-acetyl-L-cysteine (NALC) as the chiral ligand and loaded onto nanosheets of two-dimensional (2D) few-layer carbon nitride (C3N4). The resultant nanocomposite (Ag2S QDs/few-layer C3N4) shows enhanced electrochemiluminescence (ECL) while maintaining the chirality of Ag2S QDs, which can be used for the chiral discrimination of the enantiomers of tyrosine (Tyr). Due to the higher affinity of chiral Ag2S QDs toward L-Tyr than toward its enantiomer, the ECL intensity of Ag2S QDs/few-layer C3N4 is significantly decreased after its incubation with L-Tyr, and thus the Tyr enantiomers can be discriminated. The developed ECL chiral sensor exhibits high stability and reproducibility. The universality of the ECL chiral sensor for the discrimination of other chiral amino acids is also studied, and the results indicate that it can work only in the case of chiral aromatic amino acids.