A new way to prepare cellulose-type chiral stationary phases （CSPs） has been established in the present work.Cellulose microspheres with a volume-average diameter of 11.5 m were prepared by an emulsion-solidificatio...A new way to prepare cellulose-type chiral stationary phases （CSPs） has been established in the present work.Cellulose microspheres with a volume-average diameter of 11.5 m were prepared by an emulsion-solidification method.Three new CSPs were obtained by crosslinking the cellulose microspheres with terephthaloyl chloride （TPC）,and then modifying the crosslinked microspheres with 4-methylbenzoyl chloride,3,5-dimethylbenzoyl chloride and 3,5-dichlorobenzoyl chloride,respectively.The microspheres and the CSPs were characterized by FT-IR,element analysis and scanning electronic microscopy （SEM）.The chiral recognition ability of the CSPs was evaluated with high-performance liquid chromatography （HPLC）.The chromatographic results demonstrate that the CSP prepared from 3,5-dichlorobenzoyl chloride possesses better chiral recognition ability compared with two other CSPs.展开更多
The development of a single analytical platform with different functions is highly desirable but remains a challenge at present.Here,a paper-based device based on fluorescent carbon dots(CDs)functionalized paper/MnO_(...The development of a single analytical platform with different functions is highly desirable but remains a challenge at present.Here,a paper-based device based on fluorescent carbon dots(CDs)functionalized paper/MnO_(2)nanosheets(MnO_(2)NS)hybrid devices(PCD/NS)was proposed for single-device multi-function applications.MnO_(2)NS functioned as a fluorescence quencher of CDs and recognizer of H_(2)O_(2)released from the oxidase catalyzed system.Fluorescence recovery would occur after the decomposition of MnO_(2)NS induced by H_(2)O_(2),by which a simple and effective strategy could be developed for fluorescence monitoring multiplex biological events.Xanthine(XA)sensing,xanthine oxidase(XOD)inhibitors screening analysis and chiral recognition of glucose enantiomers were performed on PCD/NS to investigate the multifunctional application of the paper-based device.By means of PCD/NS,XA could be determined in the range of 0.1–40μmol/L with a low detection of limit of 0.06μmol/L.The IC_(50)value of allopurinol,the model inhibitor of XOD,was sensitively detected to be 7.4μmol/L.Glucose enantiomers were also recognized in terms of the specific fluorescence response to d-glucose.This work firstly presented a paper-based device capable of biomarkers detection,inhibitors screening and chiral recognition,which enlightened a promising strategy for the construction of multifunctional devices and hold the great potential application in clinical diagnosis and drug discovery.展开更多
Understanding the regulatory mechanism of self-assembly processes is a necessity to modulate nanostructures and their properties. Herein, we have studied the mechanism of self-assembly in the C3 symmetric 1,3,5-benzen...Understanding the regulatory mechanism of self-assembly processes is a necessity to modulate nanostructures and their properties. Herein, we have studied the mechanism of self-assembly in the C3 symmetric 1,3,5-benzentricarboxylic amino acid methyl ester enantiomers(TPE) in a mixed solvent system consisting of methanol and water. The resultant chiral structure was used for chiral recognition. The formation of chiral structures from the synergistic effect of multiple noncovalent interaction forces was confirmed by various techniques. Molecular dynamics simulations were used to characterize the time evolution of TPE structure and properties in solution. The theoretical results were consistent with the experimental results. Furthermore, the chiral structure assembled by the building blocks of TPE molecules was highly stereoselective for diamine compounds.展开更多
Three novel types of chiral calixarene derivatives 5, 8, and 10 were designed and synthesized by introducing chiral units to parent calixarenes. Their chiralities were confirmed by rotational analysis. Chiral recognit...Three novel types of chiral calixarene derivatives 5, 8, and 10 were designed and synthesized by introducing chiral units to parent calixarenes. Their chiralities were confirmed by rotational analysis. Chiral recognition properties of these host compounds towards L- and D-threonine were studied by UV-Vis spectroscopy. The results indicated that calixarene derivatives 5 and 8 exhibited good chiral recognition capabilities toward L- or D-threonine. Although calixarene derivative 10 had no evident chiral recognition ability, the supramolecules of calixarene derivative 10 with L- or D-threonine showed a hypochromic effect or hyperchromic effect respectively. Therefore, calixarene derivative 10 might serve as a good chiral UV-indicator.展开更多
This study investigates the effect of counterions on the chiral recognition of 1,1'-Binaphthyl-2,2'-diamine (BNA) and 1,1'-Binaphthyl-2,2'-diyl hydrogenphosphate (BNP) enantiomers when using an amino a...This study investigates the effect of counterions on the chiral recognition of 1,1'-Binaphthyl-2,2'-diamine (BNA) and 1,1'-Binaphthyl-2,2'-diyl hydrogenphosphate (BNP) enantiomers when using an amino acid-based surfactant undecanoyl L-leucine (und-Leu) as the chiral pseudostationary phase in capillary electrophoresis. The effects of using two different counterions (sodium and lysine) on the chiral recognition of binaphthyl derivatives were compared at varying pH conditions. The enantiomeric separation of BNA and BNP enantiomers via capillary electrophoresis, using und-Leu as the chiral recognition medium, significantly improved the enantiomeric resolution in capillary electrophoresis at pH 7 when using Lysine counterions as compared to using sodium as the counterion. More specifically, at a surfactant concentration of 45 mM, at pH 7, a significant increase in chiral selectivity was observed when lysine was used as the counterion compared to sodium. The enantiomeric resolution of BNA and BNP increased by 6-fold and 1.1-fold, respectively, in capillary electrophoresis experiments when lysine was utilized as the counterion compared to using sodium. Furthermore, the retention factor of BNA and BNP enantiomers also increased approximately 3.5-fold and 4-fold, respectively, in the presence of lysine counterions as compared to using sodium counterions. When running buffer in capillary electrophoresis was increased to pH 11, the resolution and retention factors were nearly identical when comparing the effects of the sodium and lysine counterions. This signifies the important role of lysine’s positive net charge on chiral recognition. This study provides insight into the potential advantages of using cationic, pH-dependent counterions such as lysine to significantly improve the chiral recognition of binaphthyl derivatives when using chiral anionic surfactants as the pseudostationary phase in capillary electrophoresis.展开更多
In this study, the chiral separation mechanisms of Dansyl amino acids, including Dansyl-Leucine (Dans-Leu), Dansyl-Norleucine (Dans-Nor), Dansyl-Tryptophan (Dans-Trp) and Dansyl-Phenylalanine (Dans-Phe) binding to pol...In this study, the chiral separation mechanisms of Dansyl amino acids, including Dansyl-Leucine (Dans-Leu), Dansyl-Norleucine (Dans-Nor), Dansyl-Tryptophan (Dans-Trp) and Dansyl-Phenylalanine (Dans-Phe) binding to poly-sodium </span><span style="font-family:Verdana;"><i></span><i><span style="font-family:Verdana;">N</span></i><i><span style="font-family:Verdana;"></i></span></i><span style="font-family:Verdana;">-undecanoyl-(L)-Leucylvalinate, poly (SULV), were investigated using molecular dynamics simulations. Micellar electrokinetic chromatography (MEKC) has previously shown that when separating the enantiomers of these aforementioned Dansyl amino acids, the L-enantiomers bind stronger to poly (SULV) than the D-enantiomers. This study aims to investigate the molecular interactions that govern chiral recognition in these systems using computational methods. This study reveals that the computationally-calculated binding free energy values for Dansyl enantiomers binding to poly (SULV) are in agreement with the enantiomeric order produced in experimental MEKC studies. The L-enantiomers of Dans-Leu, Dans-Nor, Dans-Trp, and Dans-Phe binding to their preferred binding pockets in poly (SULV) yielded binding free energy values of </span><span style="font-family:Verdana;">-</span><span style="font-family:Verdana;">21.8938, </span><span style="font-family:Verdana;">-</span><span style="font-family:Verdana;">22.1763, </span><span style="font-family:Verdana;">-</span><span style="font-family:""><span style="font-family:Verdana;">21.3329 </span><span style="font-family:Verdana;">and </span></span><span style="font-family:Verdana;">-</span><span style="font-family:Verdana;">13.3349 kJ</span><span style="font-family:Verdana;">·</span><span style="font-family:Verdana;">mol</span><sup><span style="font-family:Verdana;">-</span></sup><sup><span style="font-family:Verdana;">1</span></sup><span style="font-family:Verdana;">, respectively. The D-enantiomers of Dans-Leu, Dans-Nor</span><span style="font-family:Verdana;">, Dans-Trp, and Dans-Phe binding to their preferred binding pockets in poly (SULV) yielded binding free energy values of </span><span style="font-family:Verdana;">-</span><span style="font-family:Verdana;">14.5811, </span><span style="font-family:Verdana;">-</span><span style="font-family:Verdana;">15.9457, </span><span style="font-family:Verdana;">-</span><span style="font-family:Verdana;">13.6408, and </span><span style="font-family:Verdana;">-</span><span style="font-family:""><span style="font-family:Verdana;">12.0959</span><b> </b><span style="font-family:Verdana;">kJ</span></span><span style="font-family:Verdana;">·</span><span style="font-family:Verdana;">mol</span><sup><span style="font-family:Verdana;">-</span></sup><sup><span style="font-family:Verdana;">1</span></sup><span style="font-family:Verdana;">, respectively. Furthermore, hydrogen bonding analyses w</span><span style="font-family:Verdana;">ere</span><span style="font-family:Verdana;"> used to investigate and elucidate the molecular interactions that govern chiral recognition in these molecular systems.展开更多
Dynamic chiral materials with noncontactable,lightactivated,and reversible features have attracted considerable attention in photoprogrammable liquid crystals and chiral optoelectronic devices.However,most attempts to...Dynamic chiral materials with noncontactable,lightactivated,and reversible features have attracted considerable attention in photoprogrammable liquid crystals and chiral optoelectronic devices.However,most attempts to construct three-dimensional(3D)supramolecular chiral nanocages are limited to using nonresponsive chiral building blocks,which often results in the formation of architectures in shortage of tunable capacity,especially for the desirable dynamic,photoresponsive,and reversible chirality modulation.Here we report the construction of the first photoswitchable intrinsic chiral metallacages,(P)-and(M)-MOC1 and MOC_(2) based on sterically hindered diarylethene-based subcomponents,thereby achieving the unique light-driven reversible enantiospecific transformation between axial helicity and central asymmetry in 3D cages.Given the increasing cage tension during cyclization,it can be explored as a chiral encapsulant in nanocavity windows while possessing prominent enantioselectivity toward a pair of chiral camphor sulfonate vips.This work opens a new avenue to construct the unprecedented light-activated intrinsic chiral metallacages,aiming at their potential applications for chiral recognition,separation,and asymmetric catalysis.展开更多
Precise enantiomer discrimination is crucial across diverse fields;however,developing a rapid and solvent-free strategy for chiral discrimination is still difficult to achieve.Here,we present a chirality-dependent F&#...Precise enantiomer discrimination is crucial across diverse fields;however,developing a rapid and solvent-free strategy for chiral discrimination is still difficult to achieve.Here,we present a chirality-dependent Förster resonance energy transfer(FRET)system for enantiomer discrimination in the solid state.Perylene diimide(PDI)enantiomers serve as fluorescent selectands(vips),while chiral naphthalimide(NMI)or naphthalene diimide(NDI)act as chiral selectors(hosts).Photophysical studies reveal that host and vip with homochirality exhibit markedly enhanced fluorescence compared to heterochiral counterparts,attributed to more efficient FRET.In contrast,control experiments under FRET-suppressed conditions fail to effectively discern molecular chirality.Molecular dynamics simulations reveal that homochiral host and vip tend to adopt more compact molecular packing,thereby promoting FRET.This work provides a noncovalent fluorescence-based platform for real-time enantioselective recognition in the solid state.展开更多
Noble metal surfaces with intrinsic chirality serve as an ideal candidate for investigating enantioselective chemistry due to their superior chemical durability and high catalytic activity.Recently,significant advance...Noble metal surfaces with intrinsic chirality serve as an ideal candidate for investigating enantioselective chemistry due to their superior chemical durability and high catalytic activity.Recently,significant advance has been made in synthesizing metal nanocrystals with intrinsic chirality.Nonetheless,the majority reports are limited to gold.Herein,through a heteroepitaxial growth strategy,the synthesis of metal nanocrystals with intrinsic chirality to palladium was extended for the first time and their application in enantioselective recognition was demonstrated.The heteroepitaxial growth strategy allows for transferring the chirality of homochiral Au nanocrystals to Au@Pd core–shell nanocrystals.By employing the chiral Au@Pd nanocrystals as enantiomeric recognizing elements,a series of electrochemical sensors for chiral discrimination were developed.Under optimal conditions,the peak potential between D-dihydroxyphenylalanine(D-DOPA)and L-dihydroxyphenylalanine(L-DOPA)is about 80 m V,and the peak current of D-DOPA is 2 times as much as that of L-DOPA,which enables the determination of the enantiomeric excess(EE,%)of L-DOPA.Overall,this report not only introduces a heteroepitaxial growth strategy to synthesize metal nanocrystals with intrinsic chirality,but also demonstrates the superior capability of integrating intrinsic chirality and catalytic properties into metal nanocrystals for chiral recognition.展开更多
A novel BINOL-based fluorescence probe(S)-6 featuring a sodium sulfonate fragment at the 2'-position was designed and synthesized via simple synthetic procedures under mild reaction conditions.The watersoluble pro...A novel BINOL-based fluorescence probe(S)-6 featuring a sodium sulfonate fragment at the 2'-position was designed and synthesized via simple synthetic procedures under mild reaction conditions.The watersoluble probe(S)-6 displays excellent enantioselective recognition toward 15 common amino acids,and it can be used for enantiomeric excess determination of amino acids.The fluorescence intensity of(S)-6 treated with amino acids reaches the maximum after standing for only 30 min at room temperature and remains stable in the following 5.5 h,which has great potential in the application of chiral fluorescence analysis due to its timeliness and outstanding fluorescent stability.展开更多
A novel and readily available binaphthyl-based fluorescent probe(S)-1 was designed and synthesized.(S)-1 can be used to not only chemoselectively discriminate 3 basic amino acids out of common amino acids,but also ena...A novel and readily available binaphthyl-based fluorescent probe(S)-1 was designed and synthesized.(S)-1 can be used to not only chemoselectively discriminate 3 basic amino acids out of common amino acids,but also enantioselectively recognize histidine.Encouragingly,enantioselective imaging of histidine in cells was achieved for the first time by the probe(S)-1.These performances endowed it potential application in the chiral analysis of basic amino acids in asymmetric synthesis and cell imaging for diagnosis of diseases caused by racemization of histidine.Nuclear magnetic resonance(NMR)and mass spectrometry investigations suggested that different reaction extent of(S)-1 with L/D-histidine and different product structures generated the observed enantioselective fluorescent response.The molecular structures and thermodynamic stability of the complexes,formed from(S)-1+Zn2+and enantiomers of histidine,were calculated by Gaussian 16 based on density functional theory(DFT)to validate the above action mechanism.展开更多
Two chiral fluorescent receptors 1 and 2 based on(R)-1,1'-binaphthylene-2,2’bisthiourea were synthesized,and their chiral rec ognition properties for enan tiomeric man delate anions were studied by fluorescence s...Two chiral fluorescent receptors 1 and 2 based on(R)-1,1'-binaphthylene-2,2’bisthiourea were synthesized,and their chiral rec ognition properties for enan tiomeric man delate anions were studied by fluorescence spectra an d mo。lecular modeling.Addition of the L-and D-mandelate anions caused considerable fluorescent increases in the fluo。rescent intensity of the host solution.The L-enantiomer can enhance the fluorescence intensity of 1 much more than the D.enantiomer can do,and 1 shows a better enantioselective recognition ability than 2.展开更多
Chiral nitrogen-containing calix[4]arene was easily synthesized by the reaction of 25,27-di（2-bromoethoxy）- 26,28-dihydroxy-5,11,17,23-tetrakis（t-butyl）calix[4]arene with S-（-）-1-phenylethylamine in excellent yi...Chiral nitrogen-containing calix[4]arene was easily synthesized by the reaction of 25,27-di（2-bromoethoxy）- 26,28-dihydroxy-5,11,17,23-tetrakis（t-butyl）calix[4]arene with S-（-）-1-phenylethylamine in excellent yield, and showed good ability to recognize the enantiomers of mandelic acid and 2,3-dibenzoyltartaric acid. This finding has potential application to assay and separation of enantiomers of the carboxylic acids.展开更多
A novel gelator that contained both Schiffbase and L-lysine moieties was synthesized and its gelation behavior was tested. This gelator can form gels in various organic solvents. The resulting gel can be applied as a ...A novel gelator that contained both Schiffbase and L-lysine moieties was synthesized and its gelation behavior was tested. This gelator can form gels in various organic solvents. The resulting gel can be applied as a fascinating platform for visual recognition of enantiomeric 1 -（2-hydroxynaphthalen- 1-yl）naphthalen-2-ol （B1NOL） through selective gel collapse. In addition, the mechanism for the reaction of the gel with chiral BINOL was investigated by scanning electron microscope and 1H nuclear magnetic resonance.展开更多
β-Amino acids(AAs),homologs ofα-AAs,are important building blocks of biological materials.Herein,chiral recognitions ofβ-AAs with Ir(III)complexes are reported,in favor of formation of the thermodynamically stable...β-Amino acids(AAs),homologs ofα-AAs,are important building blocks of biological materials.Herein,chiral recognitions ofβ-AAs with Ir(III)complexes are reported,in favor of formation of the thermodynamically stableΛ-[Ir(pq)_(2)(D-β-AAs)]andΔ-[Ir(pq)_(2)(L-β-AAs)](pq is 2-phenylquinoline)diastereomers.The photoreactions of[Ir(pq)_(2)(β-AA)]complexes are observed in an EtOH solution in the presence of O_(2) at room temperature.The primaryβ-AAs complexes,such as rac-[Ir(pq)_(2)(β-ala)](β-ala isβ-alanine),Δ-[Ir(pq)_(2)(D-β-ma)]andΛ-[Ir(pq)_(2)(D-β-ma)](β-ma isβ-methylalanine),Δ-[Ir(pq)_(2)(D-β-pa)]andΛ-[Ir(pq)_(2)(D-β-pa)](β-pa isβ-phenylalanine),and rac-[Ir(pq)_(2)(β-dma)](β-dma is 3,3-dimethyl-β-alanine),are interligand C—N cross-coupling in situ between pq andβ-AAs ligands.The secondaryβ-AA complexesΔ-[Ir(pq)_(2)(L-β-pro)]andΛ-[Ir(pq)_(2)(L-β-pro)](β-pro isβ-proline,2-(pyrrolidin-2-yl)acetic acid)are dehydrogenatively oxidized into imino acid complexesΔ-[Ir(pq)_(2)(L-β-pro-2H^(β)’)]andΛ-[Ir(pq)_(2)(L-β-pro-2H^(β)’)](L-β-pro-2H^(β)’=2-(3,4-dihydro-2H-pyrrol-2-yl)acetic acid),respectively.Moreover,the dehydrogenative reaction inΔ-[Ir(pq)_(2)(L-β-pro)]diastereomer is regioselective depending on the reaction temperature,affordingΔ-[Ir(pq)_(2)(L-β-pro-2H^(β)’)]andΔ-[Ir(pq)_(2)(L-β-pro-2H^(β))](β-pro-2H^(β)=2-(3,4-dihydro-2H-pyrrol-5-yl)acetic acid)at low temperature.The chiral recognitions and photoreactions of Ir(III)-β-AAs complexes are much different from the previous observations in Ir(III)-α-AAs complexes.展开更多
Chiral tetraphenylethylene(TPE) dicycle tetraaldehyde and TPE dicycle tetraacids bearing optically pure groups on the cycles were designed and synthesized. Due to the propeller-like conformation immobilization of TPE ...Chiral tetraphenylethylene(TPE) dicycle tetraaldehyde and TPE dicycle tetraacids bearing optically pure groups on the cycles were designed and synthesized. Due to the propeller-like conformation immobilization of TPE unit, this new class of TPE dicycle was resolved into M-and P-enantiomers, which could emit strong circular polarized luminescence(CPL). Interestingly,these TPE helicates displayed exceptional ability of molecule recognition. While the TPE dicycle tetraaldehyde could detect the microscale water in anhydrous tetrahydrofuran, the chiral TPE dicycle tetraacid could display different fluorescent color after interacting with two enantiomers of a wide variety of chiral amines including monoamines, diamines, and aminols, which could be applied to chiral recognition of these chiral amines. Furthermore, the emission wavelength of TPE dicycle tetraacid was found to change linearly with the enantiomer purity of chiral amine from enantiomer excess(ee) percent-100% to +100%, for the first time showing the potential for quantitative chiral analysis of chiral amines based on emission wavelength change. The emission wavelength was affected less by environmental factors than fluorescence intensity, which would enable the chiral analysis based on wavelength change with higher accuracy and repeatability.展开更多
Two new chiral calixarenes bearing chiral pendants, which were from by-product of the antibiotic industry, were synthesized and characterized by 1H NMR, MS-FAB and elemental analysis. Studies of 1H NMR of the ...Two new chiral calixarenes bearing chiral pendants, which were from by-product of the antibiotic industry, were synthesized and characterized by 1H NMR, MS-FAB and elemental analysis. Studies of 1H NMR of the two calixarene derivatives indicate that they exist in cone conformation in solution. Results of chiral recognition of the two chiral ligands 2a and 2b towards the tartaric acid derivative 3 show that ligand 2a exhibited good chiral recognition abilities compared to ligand 2b.展开更多
Enantiomer identification is of paramount industrial value and physiological significance.Construction of sensitive chiral sensors with high enantiomeric discrimination ability is highly desirable.In this work,a chira...Enantiomer identification is of paramount industrial value and physiological significance.Construction of sensitive chiral sensors with high enantiomeric discrimination ability is highly desirable.In this work,a chiral covalent organic framework/anodic aluminum oxide(c-COF/AAO)membrane was prepared for electrochemical enantioselective recognition and sensing.Benefiting from the remarkable asymmetry,the asprepared nanofluidic c-COF/AAO presents a distinct ion current rectification(ICR)characteristic,enabling sensitive bioanalysis.In addition,owing to the large surface area,high chemical stability and perfect ion selectivity of chiral COF,the prepared c-COF/AAO membrane presents exceptionally selective mass transport and thereby enables excellent chiral discrimination for S-/R-Naproxen(S-/R-Npx)enantiomers.It is especially noteworthy that the detection limit is achieved as low as 3.88 pmol/L.These results raise the possibility for a facile,stable and low-cost method to carry out sensitive enantioselective recognition and detection.展开更多
Five chiral stationary phases (CSPs) were used to separate the enantiomers of a series of O,O-diethyl (p-methyl-benzenesulfonamindo)-aryl(alkyl)-methylphosphonates. A chiral recognition mechanism was presented to expl...Five chiral stationary phases (CSPs) were used to separate the enantiomers of a series of O,O-diethyl (p-methyl-benzenesulfonamindo)-aryl(alkyl)-methylphosphonates. A chiral recognition mechanism was presented to explain the resolution of these compounds. Results show that CSP with strong π-acceptor 3,5-dinitrobenzoyl group and high steric hindrance has the best resolution ability in chiral separation of O,O-diethyl (p-methylbenzenesulfonamindo)-aryl(alkyl)-methylphosphonates. When a CSP has just a strong π-acceptor 3,5-dinitrobenzoyl or high steric hindrance it does not have good chiral resolution ability. The chiral recognition is more difficult when the CSP has more than one asymmetric center.展开更多
基金Supported by the National Natural Science Foundation of China (50973086)the Research Project of Department of Education of Hubei Province (Z20081501)
文摘A new way to prepare cellulose-type chiral stationary phases （CSPs） has been established in the present work.Cellulose microspheres with a volume-average diameter of 11.5 m were prepared by an emulsion-solidification method.Three new CSPs were obtained by crosslinking the cellulose microspheres with terephthaloyl chloride （TPC）,and then modifying the crosslinked microspheres with 4-methylbenzoyl chloride,3,5-dimethylbenzoyl chloride and 3,5-dichlorobenzoyl chloride,respectively.The microspheres and the CSPs were characterized by FT-IR,element analysis and scanning electronic microscopy （SEM）.The chiral recognition ability of the CSPs was evaluated with high-performance liquid chromatography （HPLC）.The chromatographic results demonstrate that the CSP prepared from 3,5-dichlorobenzoyl chloride possesses better chiral recognition ability compared with two other CSPs.
基金financially supported by the National Natural Science Foundation of China (No. 21804141)“Double First-Class University” Project (Nos. CPU2018GY07 and CPU2018GY21)
文摘The development of a single analytical platform with different functions is highly desirable but remains a challenge at present.Here,a paper-based device based on fluorescent carbon dots(CDs)functionalized paper/MnO_(2)nanosheets(MnO_(2)NS)hybrid devices(PCD/NS)was proposed for single-device multi-function applications.MnO_(2)NS functioned as a fluorescence quencher of CDs and recognizer of H_(2)O_(2)released from the oxidase catalyzed system.Fluorescence recovery would occur after the decomposition of MnO_(2)NS induced by H_(2)O_(2),by which a simple and effective strategy could be developed for fluorescence monitoring multiplex biological events.Xanthine(XA)sensing,xanthine oxidase(XOD)inhibitors screening analysis and chiral recognition of glucose enantiomers were performed on PCD/NS to investigate the multifunctional application of the paper-based device.By means of PCD/NS,XA could be determined in the range of 0.1–40μmol/L with a low detection of limit of 0.06μmol/L.The IC_(50)value of allopurinol,the model inhibitor of XOD,was sensitively detected to be 7.4μmol/L.Glucose enantiomers were also recognized in terms of the specific fluorescence response to d-glucose.This work firstly presented a paper-based device capable of biomarkers detection,inhibitors screening and chiral recognition,which enlightened a promising strategy for the construction of multifunctional devices and hold the great potential application in clinical diagnosis and drug discovery.
基金supported by the National Natural Science Foundation of China(No.21962003)the Natural Science Foundation of Jiangsu Province(No.BK20190056)the“Fundamental Research Funds for the Central Universities”(No.021514380014)。
文摘Understanding the regulatory mechanism of self-assembly processes is a necessity to modulate nanostructures and their properties. Herein, we have studied the mechanism of self-assembly in the C3 symmetric 1,3,5-benzentricarboxylic amino acid methyl ester enantiomers(TPE) in a mixed solvent system consisting of methanol and water. The resultant chiral structure was used for chiral recognition. The formation of chiral structures from the synergistic effect of multiple noncovalent interaction forces was confirmed by various techniques. Molecular dynamics simulations were used to characterize the time evolution of TPE structure and properties in solution. The theoretical results were consistent with the experimental results. Furthermore, the chiral structure assembled by the building blocks of TPE molecules was highly stereoselective for diamine compounds.
基金National Natural Science Foundation of China(No. 20472065)
文摘Three novel types of chiral calixarene derivatives 5, 8, and 10 were designed and synthesized by introducing chiral units to parent calixarenes. Their chiralities were confirmed by rotational analysis. Chiral recognition properties of these host compounds towards L- and D-threonine were studied by UV-Vis spectroscopy. The results indicated that calixarene derivatives 5 and 8 exhibited good chiral recognition capabilities toward L- or D-threonine. Although calixarene derivative 10 had no evident chiral recognition ability, the supramolecules of calixarene derivative 10 with L- or D-threonine showed a hypochromic effect or hyperchromic effect respectively. Therefore, calixarene derivative 10 might serve as a good chiral UV-indicator.
文摘This study investigates the effect of counterions on the chiral recognition of 1,1'-Binaphthyl-2,2'-diamine (BNA) and 1,1'-Binaphthyl-2,2'-diyl hydrogenphosphate (BNP) enantiomers when using an amino acid-based surfactant undecanoyl L-leucine (und-Leu) as the chiral pseudostationary phase in capillary electrophoresis. The effects of using two different counterions (sodium and lysine) on the chiral recognition of binaphthyl derivatives were compared at varying pH conditions. The enantiomeric separation of BNA and BNP enantiomers via capillary electrophoresis, using und-Leu as the chiral recognition medium, significantly improved the enantiomeric resolution in capillary electrophoresis at pH 7 when using Lysine counterions as compared to using sodium as the counterion. More specifically, at a surfactant concentration of 45 mM, at pH 7, a significant increase in chiral selectivity was observed when lysine was used as the counterion compared to sodium. The enantiomeric resolution of BNA and BNP increased by 6-fold and 1.1-fold, respectively, in capillary electrophoresis experiments when lysine was utilized as the counterion compared to using sodium. Furthermore, the retention factor of BNA and BNP enantiomers also increased approximately 3.5-fold and 4-fold, respectively, in the presence of lysine counterions as compared to using sodium counterions. When running buffer in capillary electrophoresis was increased to pH 11, the resolution and retention factors were nearly identical when comparing the effects of the sodium and lysine counterions. This signifies the important role of lysine’s positive net charge on chiral recognition. This study provides insight into the potential advantages of using cationic, pH-dependent counterions such as lysine to significantly improve the chiral recognition of binaphthyl derivatives when using chiral anionic surfactants as the pseudostationary phase in capillary electrophoresis.
文摘In this study, the chiral separation mechanisms of Dansyl amino acids, including Dansyl-Leucine (Dans-Leu), Dansyl-Norleucine (Dans-Nor), Dansyl-Tryptophan (Dans-Trp) and Dansyl-Phenylalanine (Dans-Phe) binding to poly-sodium </span><span style="font-family:Verdana;"><i></span><i><span style="font-family:Verdana;">N</span></i><i><span style="font-family:Verdana;"></i></span></i><span style="font-family:Verdana;">-undecanoyl-(L)-Leucylvalinate, poly (SULV), were investigated using molecular dynamics simulations. Micellar electrokinetic chromatography (MEKC) has previously shown that when separating the enantiomers of these aforementioned Dansyl amino acids, the L-enantiomers bind stronger to poly (SULV) than the D-enantiomers. This study aims to investigate the molecular interactions that govern chiral recognition in these systems using computational methods. This study reveals that the computationally-calculated binding free energy values for Dansyl enantiomers binding to poly (SULV) are in agreement with the enantiomeric order produced in experimental MEKC studies. The L-enantiomers of Dans-Leu, Dans-Nor, Dans-Trp, and Dans-Phe binding to their preferred binding pockets in poly (SULV) yielded binding free energy values of </span><span style="font-family:Verdana;">-</span><span style="font-family:Verdana;">21.8938, </span><span style="font-family:Verdana;">-</span><span style="font-family:Verdana;">22.1763, </span><span style="font-family:Verdana;">-</span><span style="font-family:""><span style="font-family:Verdana;">21.3329 </span><span style="font-family:Verdana;">and </span></span><span style="font-family:Verdana;">-</span><span style="font-family:Verdana;">13.3349 kJ</span><span style="font-family:Verdana;">·</span><span style="font-family:Verdana;">mol</span><sup><span style="font-family:Verdana;">-</span></sup><sup><span style="font-family:Verdana;">1</span></sup><span style="font-family:Verdana;">, respectively. The D-enantiomers of Dans-Leu, Dans-Nor</span><span style="font-family:Verdana;">, Dans-Trp, and Dans-Phe binding to their preferred binding pockets in poly (SULV) yielded binding free energy values of </span><span style="font-family:Verdana;">-</span><span style="font-family:Verdana;">14.5811, </span><span style="font-family:Verdana;">-</span><span style="font-family:Verdana;">15.9457, </span><span style="font-family:Verdana;">-</span><span style="font-family:Verdana;">13.6408, and </span><span style="font-family:Verdana;">-</span><span style="font-family:""><span style="font-family:Verdana;">12.0959</span><b> </b><span style="font-family:Verdana;">kJ</span></span><span style="font-family:Verdana;">·</span><span style="font-family:Verdana;">mol</span><sup><span style="font-family:Verdana;">-</span></sup><sup><span style="font-family:Verdana;">1</span></sup><span style="font-family:Verdana;">, respectively. Furthermore, hydrogen bonding analyses w</span><span style="font-family:Verdana;">ere</span><span style="font-family:Verdana;"> used to investigate and elucidate the molecular interactions that govern chiral recognition in these molecular systems.
基金supported by the National Natural Science Foundation of China(grant nos.92356301,22338006,22305079,and 22108076)Scientific Committee of Shanghai(grant nos.21JC1401700 and 15XD1501400)+2 种基金China Postdoctoral Science Foundation(grant nos.2019M661399,2021M691006,and 2022M721143)Shanghai Sailing Program(grant nos.20YF1410500,22YF1410400,and 23YF1409000)Fundamental Research Funds for the Central Universities(grant no.JKJ01231555).
文摘Dynamic chiral materials with noncontactable,lightactivated,and reversible features have attracted considerable attention in photoprogrammable liquid crystals and chiral optoelectronic devices.However,most attempts to construct three-dimensional(3D)supramolecular chiral nanocages are limited to using nonresponsive chiral building blocks,which often results in the formation of architectures in shortage of tunable capacity,especially for the desirable dynamic,photoresponsive,and reversible chirality modulation.Here we report the construction of the first photoswitchable intrinsic chiral metallacages,(P)-and(M)-MOC1 and MOC_(2) based on sterically hindered diarylethene-based subcomponents,thereby achieving the unique light-driven reversible enantiospecific transformation between axial helicity and central asymmetry in 3D cages.Given the increasing cage tension during cyclization,it can be explored as a chiral encapsulant in nanocavity windows while possessing prominent enantioselectivity toward a pair of chiral camphor sulfonate vips.This work opens a new avenue to construct the unprecedented light-activated intrinsic chiral metallacages,aiming at their potential applications for chiral recognition,separation,and asymmetric catalysis.
基金support from the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB1300000)the Beijing Natural Science Foundation(2252054)+2 种基金the National Natural Science Foundation of China(22505012 and 22475204)the Fundamental Research Funds for the Central Universities(WK9990000099)supported by the National Center for International Research on Intelligent Nano-Materials and Detection Technology in Environmental Protection(SDGH2402).
文摘Precise enantiomer discrimination is crucial across diverse fields;however,developing a rapid and solvent-free strategy for chiral discrimination is still difficult to achieve.Here,we present a chirality-dependent Förster resonance energy transfer(FRET)system for enantiomer discrimination in the solid state.Perylene diimide(PDI)enantiomers serve as fluorescent selectands(vips),while chiral naphthalimide(NMI)or naphthalene diimide(NDI)act as chiral selectors(hosts).Photophysical studies reveal that host and vip with homochirality exhibit markedly enhanced fluorescence compared to heterochiral counterparts,attributed to more efficient FRET.In contrast,control experiments under FRET-suppressed conditions fail to effectively discern molecular chirality.Molecular dynamics simulations reveal that homochiral host and vip tend to adopt more compact molecular packing,thereby promoting FRET.This work provides a noncovalent fluorescence-based platform for real-time enantioselective recognition in the solid state.
基金financially supported by the National Natural Science Foundation of China(Nos.22072144,22102171 and 21974131)the Department of Science and Technology of Jilin Province(No.20200201080JC)。
文摘Noble metal surfaces with intrinsic chirality serve as an ideal candidate for investigating enantioselective chemistry due to their superior chemical durability and high catalytic activity.Recently,significant advance has been made in synthesizing metal nanocrystals with intrinsic chirality.Nonetheless,the majority reports are limited to gold.Herein,through a heteroepitaxial growth strategy,the synthesis of metal nanocrystals with intrinsic chirality to palladium was extended for the first time and their application in enantioselective recognition was demonstrated.The heteroepitaxial growth strategy allows for transferring the chirality of homochiral Au nanocrystals to Au@Pd core–shell nanocrystals.By employing the chiral Au@Pd nanocrystals as enantiomeric recognizing elements,a series of electrochemical sensors for chiral discrimination were developed.Under optimal conditions,the peak potential between D-dihydroxyphenylalanine(D-DOPA)and L-dihydroxyphenylalanine(L-DOPA)is about 80 m V,and the peak current of D-DOPA is 2 times as much as that of L-DOPA,which enables the determination of the enantiomeric excess(EE,%)of L-DOPA.Overall,this report not only introduces a heteroepitaxial growth strategy to synthesize metal nanocrystals with intrinsic chirality,but also demonstrates the superior capability of integrating intrinsic chirality and catalytic properties into metal nanocrystals for chiral recognition.
基金financial support from the National Natural Science Foundation of China(Nos.21877087,22074114)Natural Science Foundation of Hubei Province of China(Nos.2020CFB623,2021CFB556)+3 种基金Key Laboratory for Green Chemical Process of Ministry of Education(No.GCP20200201)Hubei Key Laboratory of Novel Reactor and Green Chemical Technology(No.40201002)Wuhan Institute of Technology Graduate Education and Teaching Reform Research Project(Nos.2022JYXM09,2021JYXM07)Wuhan Institute of Technology Graduate Innovation Fund(Nos.CX2022450,CX2022009,CX2022058)are greatly appreciated.
文摘A novel BINOL-based fluorescence probe(S)-6 featuring a sodium sulfonate fragment at the 2'-position was designed and synthesized via simple synthetic procedures under mild reaction conditions.The watersoluble probe(S)-6 displays excellent enantioselective recognition toward 15 common amino acids,and it can be used for enantiomeric excess determination of amino acids.The fluorescence intensity of(S)-6 treated with amino acids reaches the maximum after standing for only 30 min at room temperature and remains stable in the following 5.5 h,which has great potential in the application of chiral fluorescence analysis due to its timeliness and outstanding fluorescent stability.
基金financial support from the National Natural Science Foundation of China(Nos.22074114,22377097,21877087)Natural Science Foundation of Hubei Province of China(Nos.2020CFB623,2021CFB556)+2 种基金Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education(No.LCX202305)Wuhan Institute of Technology Graduate Education and Teaching Reform Research Project(Nos.2022JYXM09,2021JYXM07)Wuhan Institute of Technology Graduate Innovation Fund(No.CX2022450)are greatly appreciated。
文摘A novel and readily available binaphthyl-based fluorescent probe(S)-1 was designed and synthesized.(S)-1 can be used to not only chemoselectively discriminate 3 basic amino acids out of common amino acids,but also enantioselectively recognize histidine.Encouragingly,enantioselective imaging of histidine in cells was achieved for the first time by the probe(S)-1.These performances endowed it potential application in the chiral analysis of basic amino acids in asymmetric synthesis and cell imaging for diagnosis of diseases caused by racemization of histidine.Nuclear magnetic resonance(NMR)and mass spectrometry investigations suggested that different reaction extent of(S)-1 with L/D-histidine and different product structures generated the observed enantioselective fluorescent response.The molecular structures and thermodynamic stability of the complexes,formed from(S)-1+Zn2+and enantiomers of histidine,were calculated by Gaussian 16 based on density functional theory(DFT)to validate the above action mechanism.
基金supported by the National Natural Science Foundation of China(No.20372054)
文摘Two chiral fluorescent receptors 1 and 2 based on(R)-1,1'-binaphthylene-2,2’bisthiourea were synthesized,and their chiral rec ognition properties for enan tiomeric man delate anions were studied by fluorescence spectra an d mo。lecular modeling.Addition of the L-and D-mandelate anions caused considerable fluorescent increases in the fluo。rescent intensity of the host solution.The L-enantiomer can enhance the fluorescence intensity of 1 much more than the D.enantiomer can do,and 1 shows a better enantioselective recognition ability than 2.
基金Project supported by the National Natural Science Foundation of China （No. 20072007）.
文摘Chiral nitrogen-containing calix[4]arene was easily synthesized by the reaction of 25,27-di（2-bromoethoxy）- 26,28-dihydroxy-5,11,17,23-tetrakis（t-butyl）calix[4]arene with S-（-）-1-phenylethylamine in excellent yield, and showed good ability to recognize the enantiomers of mandelic acid and 2,3-dibenzoyltartaric acid. This finding has potential application to assay and separation of enantiomers of the carboxylic acids.
基金We greatly appreciate the support of the National Natural Science Foundation of China （Grant Nos. 21272054 and 21502040）, Natural Science Foundation of Hebei Province （B2016205249 and B2016205211）, Youth Top-notch Talent Foundation of the Education Department of Hebei Province （No. BJ2014039）, Science and Technology Research Fund of the Education Department of Hebei Province （No. ZD2015030） and the Startup Foundation of Hebei Normal University （Nos. L2015B08, L2015B09, L2015k02 and L2016Z01）
文摘A novel gelator that contained both Schiffbase and L-lysine moieties was synthesized and its gelation behavior was tested. This gelator can form gels in various organic solvents. The resulting gel can be applied as a fascinating platform for visual recognition of enantiomeric 1 -（2-hydroxynaphthalen- 1-yl）naphthalen-2-ol （B1NOL） through selective gel collapse. In addition, the mechanism for the reaction of the gel with chiral BINOL was investigated by scanning electron microscope and 1H nuclear magnetic resonance.
基金support from the National Natural Science Foundation of China(grant no.21971266).
文摘β-Amino acids(AAs),homologs ofα-AAs,are important building blocks of biological materials.Herein,chiral recognitions ofβ-AAs with Ir(III)complexes are reported,in favor of formation of the thermodynamically stableΛ-[Ir(pq)_(2)(D-β-AAs)]andΔ-[Ir(pq)_(2)(L-β-AAs)](pq is 2-phenylquinoline)diastereomers.The photoreactions of[Ir(pq)_(2)(β-AA)]complexes are observed in an EtOH solution in the presence of O_(2) at room temperature.The primaryβ-AAs complexes,such as rac-[Ir(pq)_(2)(β-ala)](β-ala isβ-alanine),Δ-[Ir(pq)_(2)(D-β-ma)]andΛ-[Ir(pq)_(2)(D-β-ma)](β-ma isβ-methylalanine),Δ-[Ir(pq)_(2)(D-β-pa)]andΛ-[Ir(pq)_(2)(D-β-pa)](β-pa isβ-phenylalanine),and rac-[Ir(pq)_(2)(β-dma)](β-dma is 3,3-dimethyl-β-alanine),are interligand C—N cross-coupling in situ between pq andβ-AAs ligands.The secondaryβ-AA complexesΔ-[Ir(pq)_(2)(L-β-pro)]andΛ-[Ir(pq)_(2)(L-β-pro)](β-pro isβ-proline,2-(pyrrolidin-2-yl)acetic acid)are dehydrogenatively oxidized into imino acid complexesΔ-[Ir(pq)_(2)(L-β-pro-2H^(β)’)]andΛ-[Ir(pq)_(2)(L-β-pro-2H^(β)’)](L-β-pro-2H^(β)’=2-(3,4-dihydro-2H-pyrrol-2-yl)acetic acid),respectively.Moreover,the dehydrogenative reaction inΔ-[Ir(pq)_(2)(L-β-pro)]diastereomer is regioselective depending on the reaction temperature,affordingΔ-[Ir(pq)_(2)(L-β-pro-2H^(β)’)]andΔ-[Ir(pq)_(2)(L-β-pro-2H^(β))](β-pro-2H^(β)=2-(3,4-dihydro-2H-pyrrol-5-yl)acetic acid)at low temperature.The chiral recognitions and photoreactions of Ir(III)-β-AAs complexes are much different from the previous observations in Ir(III)-α-AAs complexes.
基金the National Natural Science Foundation of China (22072050 and 22372066) for financial support。
文摘Chiral tetraphenylethylene(TPE) dicycle tetraaldehyde and TPE dicycle tetraacids bearing optically pure groups on the cycles were designed and synthesized. Due to the propeller-like conformation immobilization of TPE unit, this new class of TPE dicycle was resolved into M-and P-enantiomers, which could emit strong circular polarized luminescence(CPL). Interestingly,these TPE helicates displayed exceptional ability of molecule recognition. While the TPE dicycle tetraaldehyde could detect the microscale water in anhydrous tetrahydrofuran, the chiral TPE dicycle tetraacid could display different fluorescent color after interacting with two enantiomers of a wide variety of chiral amines including monoamines, diamines, and aminols, which could be applied to chiral recognition of these chiral amines. Furthermore, the emission wavelength of TPE dicycle tetraacid was found to change linearly with the enantiomer purity of chiral amine from enantiomer excess(ee) percent-100% to +100%, for the first time showing the potential for quantitative chiral analysis of chiral amines based on emission wavelength change. The emission wavelength was affected less by environmental factors than fluorescence intensity, which would enable the chiral analysis based on wavelength change with higher accuracy and repeatability.
基金ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .2 0 0 72 0 2 9)
文摘Two new chiral calixarenes bearing chiral pendants, which were from by-product of the antibiotic industry, were synthesized and characterized by 1H NMR, MS-FAB and elemental analysis. Studies of 1H NMR of the two calixarene derivatives indicate that they exist in cone conformation in solution. Results of chiral recognition of the two chiral ligands 2a and 2b towards the tartaric acid derivative 3 show that ligand 2a exhibited good chiral recognition abilities compared to ligand 2b.
基金supported by grants from the National Natural Science Foundation of China(Nos.22274076,22304084)the Primary Research&Development Plan of Jiangsu Province(No.BE2022793)+1 种基金the Natural Science Foundation of Jiangsu Province of China(No.BK20230377)Jiangsu Provincial Department of Education(No.211090B52303)。
文摘Enantiomer identification is of paramount industrial value and physiological significance.Construction of sensitive chiral sensors with high enantiomeric discrimination ability is highly desirable.In this work,a chiral covalent organic framework/anodic aluminum oxide(c-COF/AAO)membrane was prepared for electrochemical enantioselective recognition and sensing.Benefiting from the remarkable asymmetry,the asprepared nanofluidic c-COF/AAO presents a distinct ion current rectification(ICR)characteristic,enabling sensitive bioanalysis.In addition,owing to the large surface area,high chemical stability and perfect ion selectivity of chiral COF,the prepared c-COF/AAO membrane presents exceptionally selective mass transport and thereby enables excellent chiral discrimination for S-/R-Naproxen(S-/R-Npx)enantiomers.It is especially noteworthy that the detection limit is achieved as low as 3.88 pmol/L.These results raise the possibility for a facile,stable and low-cost method to carry out sensitive enantioselective recognition and detection.
基金Project supported by the National Natural Science Foundation of China.
文摘Five chiral stationary phases (CSPs) were used to separate the enantiomers of a series of O,O-diethyl (p-methyl-benzenesulfonamindo)-aryl(alkyl)-methylphosphonates. A chiral recognition mechanism was presented to explain the resolution of these compounds. Results show that CSP with strong π-acceptor 3,5-dinitrobenzoyl group and high steric hindrance has the best resolution ability in chiral separation of O,O-diethyl (p-methylbenzenesulfonamindo)-aryl(alkyl)-methylphosphonates. When a CSP has just a strong π-acceptor 3,5-dinitrobenzoyl or high steric hindrance it does not have good chiral resolution ability. The chiral recognition is more difficult when the CSP has more than one asymmetric center.
