A fluorescent chiral chemosensor for the recognition of the two enantiomers of chiral carboxylates

A new 7-nitrobenz-2-oxa-1,3-diazole (NBD)-based fluorescent chiral chemosensor (NBD-1) was prepared and applied to the recognition of the two enantiomers of the tetrabutylammonium salts of N-t-Boc-α-amino acids and chiral carboxylic acids including naproxen. In particular, the chiral recognition by the new fluorescent chiral chemosensor for the two enantiomers of N-t-Boc-threonine (tetrabutylammonium salt) was quite excellent, the Stern-Volmer constant ratio (K(D)/K(L)) for the two enantiomers being as high as 4.89.     

Optically active crown ether‐based fluorescent sensor molecules: A mini‐review

This mini‐review focuses on fluorescent optically active crown ethers (polymeric derivatives are not included) reported in the literature (according to our knowledge), of which enantiomeric recognition ability, and in some cases, also inorganic cation complexation properties, were investigated by the sensitive and versatile fluorescence spectroscopy. These crown ether‐based chemosensors contain various fluorophore signaling units such as binaphthyl, anthracene, pyrene, tryptophan, benzimidazole, terpyridine, acridine, phenazine, acridone, BODIPY, and another conjugated aromatic one.     

A novel colorimetric fluorescence sensor for Fe3+ based on quinoline Schiff base

A novel fluorescent sensor bearing a quinoline and an anisidine moiety has been developed for highly selective detection of Fe³⁺, which shows photo‐induced electron transfer (PET) behavior induced by Fe³⁺. Binding of Fe³⁺ to the sensor induced the electron of C = N group transfer from quinoline to iron, the result exhibits fluorescent enhancement. With the features of easy synthesis, simple structural skeleton and excellent sensing ability, the newly synthesized chemosensor also applied as a highly selective fluorescent probe in complex samples containing various competitive metal ions. The probe could fulfill various needs in biological and environmental fields.     

A colorimetric sensor array based on natural pigments for the discrimination of saccharides

A colorimetric sensor array based on natural pigments was developed to discriminate between various saccharides. Anthocyanins, pH‐sensitive natural pigments, were extracted from fruits and flowers and used as components of the sensor array. Variation in pH, due to the reaction between saccharides and boronic acids, caused obvious colour changes in the natural pigments. Only by observing the difference map with the naked eye could 11 common saccharides be divided into independent individuals. In conjunction with pattern recognition, the sensor array clearly differentiated between sugar and sugar alcohol with highly accuracy and allowed rapid quantification of different concentrations of maltitol and fructose. This sensor array for saccharides is expected to become a promising alternative tool for food monitoring. The link between anthocyanin and saccharide detection opened a new guiding direction for the application of anthocyanins in foods.     

A colorimetric sensor for the selective detection of fluoride ions

A colorimetric receptor L was prepared. Receptor L can selectively sense F^? based on distinct color changes among a series of ions. It can selectively sense F^? through an intramolecular hydrogen bond interaction. A Job plot indicated a 1:1 complexation stoichiometry between receptor L and F^?. The association constant for L –F^? in CH₃CN was determined as 9.70 × 10⁴ M^?1 using a Stern–Volmer plot.     

Synthesis and crystal structure of a highly selective colorimetric and fluorometric sensor for hydrogen sulfide

A novel Cu(II) complex chemosensor for hydrogen sulfide with azo as the colorimetric group has been synthesized. The complex and ligand crystals were obtained and the molecular structures were characterized by X‐ray diffraction and Electrospray ionization High resolution mass spectrometer (ESI‐HRMS). The photophysical and recognition properties were examined. The complex can recognize S^2?, with an obvious color change from yellow to red based on a copper ion complex displacement mechanism. By contrast, no obvious changes were observed in the presence of other anions (AcO^?, H₂PO₄^?, F^?, Cl^?, Br^? and I^?). We present a simple, easily prepared, yet efficient, inorganic reaction‐based sensor for the detection of S^2?. The complex should have many chemical and analytical applications in the sensing of hydrogen sulfide.     

Spacer length effect of a chiral stationary phase based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid

A new chiral stationary phase (CSP) containing 11 methylene-unit spacer was prepared by bonding (+)-(18-crown-6)-2,3,11,12-carboxylic acid to aminoundecylsilica gel. The new CSP was superior to the one containing three methylene-unit spacer in the resolution of alpha-amino acids, beta-amino acids, amines, and amino alcohols in terms of both the separation (alpha) and the resolution factors (R(S)). In the resolution of alpha-amino acids on the new CSP containing a long spacer, the retention factors (k(1)) were quite small compared to those on the CSP containing a short spacer. However, in the resolution of relatively more lipophilic beta-amino acids, amines, and amino alcohols, the retention factors (k(1)) were generally greater on the CSP containing a long spacer than on the CSP containing a short spacer. All of these resolution behaviors have been rationalized by the effective competition of the ammonium ions (R-NH(3)(+)) generated by the residual undecylamino groups of the new CSP under acidic condition with the ammonium ions (R-NH(3)(+)) of analytes for the complexation inside the cavity of the crown ether ring of the CSP and the effective lipophilic interaction between the CSP and the relatively more lipophilic analytes.     

A highly selective fluorescent sensor for mercury ion (II) based on azathia-crown ether possessing a dansyl moiety

An intramolecular charge transfer (ICT) fluorescent sensor 1 using a dansyl moiety as the fluorophore and an azathia-crown ether as the receptor was designed, synthesized and characterized. The ions-selective signaling behaviors of the sensor 1 were investigated in CH(3) CN-H(2) O (1:1, v/v) by fluorescence spectroscopy. It exhibited remarkable fluorescence quenching upon addition of Hg(2+), which was attributed to the 1:1 complex formation between 1 and Hg(2+), while other selected metal ions induced basically no spectral changes. The sensor 1 showed a rapid and linear response towards Hg(2+) in the concentration range from 5.0 × 10(-7) to 1.0 × 10(-5) mol L(-1) with the detection limit of 1.0 × 10(-7) mol L(-1). Furthermore, the whole process could be carried out in a wide pH range of 2.0-8.0 and was not disturbed by other metal ions. Thus, the sensor 1 was used for practical determination of Hg(2+) in different water samples with satisfactory results.     

Liquid chromatographic separation of the enantiomers of fluoroquinolone antibacterials on a chiral stationary phase based on a chiral crown ether

A chiral stationary phase (CSP) recently developed by bonding (diphenyl-substituted 1,1'-binaphthyl) crown ether to silica gel for the liquid chromatographic separation of enantiomers was applied to the resolution of investigational fluoroquinolone antibacterial agents including gemifloxacin (formerly LB20304a). All fluoroquinolone compounds used in this study were resolved quite well on the CSP. Especially, the resolution of gemifloxacin and its analogs on the CSP was excellent and even greater than that on the commercial Crownpak CR(+). The resolution was found to be dependent on the type and the content of organic, acidic, and inorganic modifiers added to the mobile phase and on the column temperature.     

Chiral separation of underivatized amino acids in supercritical fluid chromatography with chiral crown ether derived column

The supercritical fluid chromatographic separation of underivatized amino acids was explored using immobilized chiral crown ether column CROWNPAK CR-I (+) and mass spectrometric detection. The type of modifier, acidic additives, and the role of water were investigated. Enantioseparation was achieved for all 18 amino acids investigated with short retention times (less than 3 minutes) and average resolution of greater than 5.0. Analysis of enantiomerically pure standards demonstrated the D enantiomer eluted first for all amino acids using a CROWNPAK CR-I (+) column.     

A colorimetric and fluorescent chemosensor for selective detection of Cu2+ based on a new diarylethene with a benzophenone hydrazone unit

A new photochromic diarylethene based on benzophenone hydrazone has been synthesized. Its photochromic and fluorescent properties changed upon alternating irradiation with UV /Vis light and adding Cu²⁺/EDTA in methanol, which showed that the diarylethene could be served as a colorimetric and fluorescent chemosensor for selective detection of Cu²⁺ based on internal charge transfer processes. The colorimetric and turn‐off fluorescent selective detection of Cu²⁺ was attributed to the 2:1 complex of the diarylethene and Cu²⁺. The binding constant (Ka ) was 1.53 × 10⁴ L mol^?1 and the limit of detection of the diarylethene for Cu²⁺ was calculated to be 1.45 × 10^?6 mol L^?1. In addition, the metal‐responsive photochromic behavior of diarylethene was applied successfully to the construction of a molecular logic circuit.     

Biphasic recognition chiral extraction: A novel method for separation of mandelic acid enantiomers

This article reports a new chiral separation method-biphasic recognition chiral extraction for the separation of mandelic acid enantiomers. Distribution behavior of mandelic acid enantiomers was studied in the extraction system with O,O'-di-benzoyl-(2S,3S)-4-toluoyl-tartaric acid (D-(+)-DTTA) in organic phase and beta-CD derivatives in aqueous phase, and the influence of the types and concentrations of extractants and pH on extraction efficiency was investigated. Hydroxypropyl-beta-cyclodextrin (HP-beta-CD), hydroxyethyl-beta-cyclodextrin (HE-beta-CD), and methyl-beta-cyclodextrin (Me-beta-CD) have stronger recognition abilities for S-mandelic acid than those for R-mandelic acid, among which HP-beta-CD has the strongest ability. D-(+)-DTTA preferentially recognizes R-mandelic acid. pH and the concentrations of extractants have great effects on chiral separation ability. A high enantioseparation efficiency with a maximum enantioselectivity of 1.527 is obtained at pH of 2.7 and the ratio of 2:1 of [D-(+)-DTTA] to [HP-beta-CD]. The obtained results indicate that the biphasic recognition chiral extraction is of stronger chiral separation ability than the monophasic recognition chiral extraction. It may be very helpful to optimize the extraction systems and realize the large-scale production of pure enantiomers.     

Microscale HPLC enables a new paradigm for commercialization of complex chiral stationary phases

The small column size (0.3 mm i.d. x 15 cm) used in microscale HPLC contains only a small fraction (<1%) of the chromatographic packing material of a typical analytical HPLC column. Consequently, chromatographic stationary phases that are prohibitively expensive in conventional HPLC, owing either to synthetic complexity or costly starting materials, may become commercially viable in the microscale format. To illustrate this point, a previously described, synthetically complex, crown ether chiral stationary phase was prepared and evaluated in the microscale format, showing excellent separation of the enantiomers of underivatized amine analytes.     

Sensitive and selective cataluminescence‐based sensor system for acetone and diethyl ether determination

A three‐dimensional hierarchical CdO nanostructure with a novel bio‐inspired morphology is reported. The field emission scanning electronic microscopy, transmission electron microscopy and X‐ray diffractometer were employed to characterize the as‐prepared samples. In gas‐sensing measurements, acetone and diethyl ether were employed as target gases to investigate cataluminescence (CTL) sensing properties of the CdO nanostructure. The results show that the as‐fabricated CdO nanostructure exhibited outstanding CTL properties such as stable intensity, high signal/noise values, short response and recovery time. The limit of detection of acetone and diethyl ether was ca. 6.5 ppm and 6.7 ppm, respectively, which was below the standard permitted concentrations. Additionally, a principal components analysis method was used to investigate the recognizable ability of the CTL sensor, and it was found that acetone and diethyl ether can be distinguished clearly. The performance of the bio‐inspired CdO nanostructure‐based sensor system suggested the promising application of the CdO nanostructure as a novel highly efficient CTL sensing material. Copyright © 2014 John Wiley & Sons, Ltd.     

An electrochemical sensor based on cellulose nanocrystal for the enantioselective discrimination of chiral amino acids

A novel electrochemical sensor based on 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanocrystals (TOCNCs) and l-cystines (l-Cys) modified Au electrode (TOCNC/l-Cys/Au) has been fabricated for detection and discrimination of the enantiomers of phenylalanine (Phe), leucine (Leu), and valine (Val). The three amino acids are in connection with metabolism diseases. The TOCNC/l-Cys/Au electrode exhibited obvious peak current difference for the amino acid enantiomers by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The TOCNCs on the electrode surface expressed different interactions with d- and l-amino acids, so the electrochemical recognitions of the three amino acid enantiomers were achieved. TOCNCs were characterized by Fourier transform infrared (FT-IR) and scanning electron microscopy (SEM). The modified electrodes were characterized by SEM and electrochemical techniques. According to DPV, peak currents of the two enantiomers decreased linearly with their concentrations. Furthermore, satisfactory results were obtained when this electrode was applied to measure the d- and l-Phe mixture. The experimental results show that TOCNCs are suitable material for chiral sensor. The contrast of serum sample of healthy people and patients with type 2 diabetes also was proposed, and significant difference was exhibited on the modified electrode. This work is significant for the screening, diagnosis, and treatment of multiple metabolic diseases.     

The direct chiral separations of fungicide enantiomers on amylopectin based chiral stationary phase by HPLC

Amylopectin-tris(phenylcarbamate) was synthesized and coated to aminopropylsilica to prepare chiral stationary phase. The chiral separations of fungicide enantiomers were performed by the CSP using high-performance liquid chromatography. Mobile phase was n-hexane and isopropanol, and flow rate was 1.0 ml/min. Detection wavelength was 230 nm. The influence of the percentage of isopropanol in the mobile phase on the separations was studied. Twelve chiral fungicides were tested and seven of them were found to show stereoselectivity on the CSP. The enantiomers of metalaxyl and benalaxyl got near baseline separations and myclobutanil, hexconazole, tebuconazole, uniconazole, and paclobutrazol enantiomers were completely separated. The decreasing percentage of isopropanol in the mobile phase resulted in better separation and longer analysis time. The enantiomers were identified by a circular dichroism (CD) detector and the CD spectra of the individual enantiomers were also studied by online scanning.     

Crystallographic studies for the chiral recognition of the novel chiral stationary phase derived from (+)‐(R)‐18‐crown‐6 tetracarboxylic acid

Chiral discrimination observed in high‐performance liquid chromatography (HPLC) with the novel chiral stationary phase (CSP‐18C6I) derived from (+)‐(R)‐18‐crown‐6 tetracarboxylic acid [(+)‐18C6H₄] was investigated by X‐ray crystallographic analysis of the complex composed of the R‐enantiomer of 1‐(1‐naphthyl)ethylamine (1‐NEA) and (+)‐18C6H₄. Mixtures of 1‐NEA (the R‐ or S‐enantiomer) and (+)‐18C6H₄ were dissolved in methanol‐water (1:1) solution and allowed to stand for crystallization. The R‐enantiomer crystallized with (+)‐18C6H₄ as a co‐crystal, although the S‐enantiomer did not. This result was in good agreement with the enantiomer elution order of 1‐NEA in CSP‐18C6I. The apparent binding constants (K_a) of the enantiomers to the (+)‐18C6H₄ obtained from ¹H‐NMR experiments also supported the above‐mentioned result. The X‐ray crystal structure of the 1:1 complex of the R‐enantiomer and (+)‐18C6H₄ indicated the four sets of hydrogen bond association between the naphthylethylammonium cation and oxygen of polyether ring or carbonyl group of (+)‐18C6H₄. Chirality 11:173–178, 1999. © 1999 Wiley‐Liss, Inc.     

Design and development of chiral reagents for the chromatographic e.e. determination of chiral alcohols

(S)-Trolox methyl ether is known as a powerful chiral reagent for the e.e. determination of chiral alcohols by separation of the corresponding diastereoisomeric esters on achiral GC and SFC columns. In order to further improve his methodology, five possible candidates resultings from variation of structural elements of parent reagent have been tested for derivatization with selected alcohols and subsequent analysis of the diastereoisomeric pairs of esters. The results of this optimization procedure showing the ways to new potent reagents are discussed. © 1996 Wiley-Liss, Inc.     

Guest-dependent conformation of 18-crown-6 tetracarboxylic acid: relation to chiral separation of racemic amino acids

(+)-18-crown-6 tetracarboxylic acid (18C6H(4)) has been used as a chiral selector for various amines and amino acids. To further clarify the structural scaffold of 18C6H(4) for chiral separation, single crystal X-ray analysis of its glycine(+) (1), H3O+ (2), H5O2+ (3), NH4+ (4), and 2CH3NH3+ (5) complexes was performed and the guest-dependent conformation of 18C6H(4) was investigated. The crown ether ring of 18C6H4 in 3, 4, and 5 took a symmetrical C2 or C2-like conformation, whereas that in 1 and 2 took an asymmetric C1 conformation, which is commonly observed in complexes with various optically active amino acids. The overall survey of the present and related complexes suggests that the molecular conformation of 18C6H4 is freely changeable within an allowable range, depending on the molecular shape and interaction mode with the cationic guest. On the basis of the present results, we propose the allowable conformational variation of 18C6H4 and a possible transition pathway from its primary conformation to the conformation suitable for chiral separation of racemic amines and amino acids.