Chiral capillary electrophoresis-mass spectrometry of amino acids in foods

In this work, the development of a new chiral capillary electrophoresis-mass spectrometry (CE-MS) method to separate D- and L-amino acids is shown. On-line coupling between CE and MS is established through an electrospray-coaxial sheath flow interface. Enantiomer separation is achieved by using a cheap, nonvolatile, chiral selector as beta-cyclodextrin in the background electrolyte (BGE) together with a physically coated capillary that is aimed to prevent contamination of the electrospray. The capillary coating is simple and easy to obtain as it only requires flushing of the capillary with a polymer aqueous solution for 3 min. Optimization of CE parameters (pH of BGE, type and concentration of chiral selector, and capillary inner diameter) and electrospray-MS parameters (nature and flow rate of the sheath liquid, nebulizer pressure) is carried out. Two different derivatization protocols of amino acids using dansyl chloride (DNS) and fluorescein isothiocyanate (FITC) are compared in terms of MS sensitivity and chiral resolution. Under optimum CE-MS conditions it is observed that the MS sensitivity obtained for FITC- and DNS-amino acids is similar (with limit of detection (LOD) in the microM range, corresponding to amounts injected in the fmol range) while chiral resolution is better for FITC-amino acids. The optimized method is demonstrated to provide the simultaneous analysis of 15 selected amino acids (i.e., FITC-D/L-Asp, -Glu, -Ser, -Asn, -Ala, -Pro, -Arg, and FITC-gamma-aminobutyric acid (GABA) in a single chiral CE-MS run, corresponding to the main amino acids that can be found in orange. Moreover, as a result of the high resolution achieved, it is possible to detect down to 2% of D-Asp in the presence of 98% of L-Asp. The good possibilities of chiral CE-MS in food analysis are corroborated through the detection of the main amino acids in a commercial orange juice (i.e., FITC-L-Asp, -Glu, -Ser, -Asn, -Pro, -Arg, and the nonchiral FITC-GABA) as well as the determination of the fraudulent addition of synthetic amino acids (containing D- and L-forms) to a fresh orange juice.     

Capillary electrophoresis-mass spectrometry in food analysis

This work provides an updated overview (including works published till June 2004) on the principal applications of capillary electrophoresis-mass spectrometry (CE-MS) together with their main advantages and drawbacks in food science. Thus, analysis of amino acids, peptides, proteins, carbohydrates, or polyphenols by CE-MS in different foods is reviewed. Also, other natural compounds (e.g., alkaloids) and toxins analyzed by CE-MS in foods are revised. Moreover, exogenous substances with a potential risk for human health (e.g., pesticides, drugs) detected in foods by CE-MS are included in this work. The usefulness of CE-MS for food analysis and the information that this coupling can provide in terms of processing, composition, authenticity, quality, or safety of foods is also discussed.     

Proline-catalyzed one-step asymmetric synthesis of 5-hydroxy-(2E)-hexenal from acetaldehyde.

For the first time, the L-proline-catalyzed direct asymmetric self-aldolization of acetaldehyde is described affording (+)-(5S)-hydroxy-(2E)-hexenal 2 with ee's ranging from 57 to 90%. Further transformations of 2 into synthetically valuable building blocks are presented. A mechanism for the formation of 2 is proposed.     

Validated capillary electrophoresis method for small-anions measurement in wines

A capillary electrophoresis method has been developed and validated for acetic, citric, fumaric, lactic, malic, oxalic, succinic, and tartaric acids plus the measurement of nitrate and sulfite ions in white and red wines. The separation was carried out in a neutral coated capillary. Separation was performed at -14 kV of applied potential. Temperature was maintained at 20 degrees C. The background electrolyte used was 200 mM phosphate buffer at pH 7.50. Separation was obtained in less than 13 min. Validation parameters obtained for the method permit it to be considered adequate for routine analysis.     

Amino alcohol catalyzed direct asymmetric aldol reactions: enantioselective synthesis of anti-α-fluoro-β-hydroxy ketones

Prolinol but not proline-(a recently established catalyst of simple intermolecular aldol reactions) was found to be an efficient catalyst for fluoroaldol reactions providing anti-α-fluoro-β-hydroxy ketones with good regio-, diasterio-, and enantioselectivities.     

Design and use of fluorogenic aldehydes for monitoring the progress of aldehyde transformations

We describe the first examples of fluorogenic aldehydes useful for monitoring many types of reactions including aldol reactions, allylations, and reductions. The fluorogenic aldehydes were constructed by covalent combination of a fluorophore and an aldehyde moiety via a linker. In the resulting single molecule, the aldehyde functioned as a quencher of the fluorophore's fluorescence. The reaction product, modified at the aldehyde functionality, no longer served as an effective quencher. The reaction products showed up to approximately 80-fold higher fluorescence than the aldehyde reactants.     

Towards organo-click chemistry: development of organocatalytic multicomponent reactions through combinations of aldol, Wittig, Knoevenagel, Michael, Diels-Alder and Huisgen cycloaddition reactions

Here we report on our studies on combinations of amino acids and copper(I) for catalyzing multicomponent reactions (MCRs). We aimed to prepare both diene and dienophiles simultaneously, under very mild and environmentally friendly conditions, thus giving the constituents for a stereocontrolled Diels-Alder reaction, which in turn yields compounds 4 to 8. A diversity-oriented synthesis of polysubstituted spirotriones 4 to 6 were assembled from simple substrates like 1-(triphenylphosphanylidene)-propan-2-one, two aldehydes, and cyclic-1,3-diketones through Wittig/Knoevenagel/Diels-Alder and aldol/Knoevenagel/Diels-Alder reaction sequences in one pot under stereospecific organocatalysis. Chemical diversity libraries of polysubstituted spirotrione-1,2,3-traizoles 8 were assembled from simple substrates by means of Wittig/Knoevenagel/Diels-Alder/Huisgen cycloaddition reaction sequences in one pot under stereospecific organo/Cu(I) catalysis. Functionalized dispirolactones such as 6 are biologically active antioxidants and radical scavengers, and spirotrione-1,2,3-traizoles 8 have found wide applications in chemistry, biology, and materials science. Experimentally simple and environmentally friendly, organocatalytic, asymmetric four-component Diels-Alder (AFCDA) reactions of 1-(triphenylphosphanylidene)- propan-2-one, two different aldehydes, and cyclic-1,3-diketones produced diastereospecific and highly enantioselective substituted spirotriones 4 by means of a Wittig/Knoevenagel/Diels-Alder reaction sequence in one pot. Additionally we have developed an organocatalytic, asymmetric three-component Michael (ATCM) reaction of 1-(triphenylphosphanylidene)-propan-2-one, aldehyde, and cyclic-1,3-diketones that produced Michael adducts 15, 16 through a Wittig/Michael reaction sequence in a highly enantioselective one-pot process.