Electromagnetic propulsion and separation by chirality of nanoparticles in liquids

We introduce a new mechanism for the propulsion and separation by chirality of small ferromagnetic particles suspended in a liquid. Under the action of a uniform dc magnetic field H and an ac electric field E isomers with opposite chirality move in opposite directions. Such a mechanism could have a significant impact on a wide range of emerging technologies. The component of the chiral velocity that is odd in H is found to be proportional to the intrinsic orbital and spin angular momentum of the magnetized electrons. This effect arises because a ferromagnetic particle responds to the applied torque as a small gyroscope. © 2012 American Physical Society.

Application of selective F-1 decoupled H-1 NMR for enantiomer resolution and accurate measurement of enantiomeric excess at low chiral substrate/auxiliary concentration

The higher substrate and chiral auxiliary concentration is a pre-requisite to obtain efficient separation of H-1 NMR signals of enantiomers. The higher concentration of chiral lanthanide shift reagents provides broadened spectral lines resulting in a severe loss of resolution between the enantiomer resonances. In order to circumvent such difficulties, herein we present the application and the usefulness of a selective F-1 decoupled correlation (COSY) experiment which yields proton decoupled proton spectra in the indirect dimension. The potentiality of the experiment is demonstrated on several chiral compounds possessing different functional groups, employing either a lanthanide shift reagent or a solvating reagent as chiral auxiliaries. (C) 2011 Elsevier B.V. All rights reserved.

Prediction of the senses of helical amphiphilic assemblies from effective intermolecular pair potential: Studies on chiral monolayers and bilayers

It is well-known that the senses (or the handedness) of the helical assemblies formed from compressed monolayers and bilayers of chiral amphiphiles are highly specific about the chirality of the monomers concerned. We present here a molecular approach that can successfully predict the senses of such helical morphologies. The present approach is based on a reduced tractable description in terms of an effective pair potential (EPP) which depends on the distance of separation and the relative orientations of the two amphiphiles. This approach explicitly considers the pairwise intermolecular interactions between the groups attached to the chiral centers of the two neighboring amphiphiles. It is found that for a pair of the same kind of enantiomers the minimum energy configuration favors a twist angle between molecules and that this twist from neighbor to neighbor gives rise to the helicity of the aggregate. From the known twist angles at the minimum energy configuration the successive arrangement of an array of molecules can be predicted. Therefore, the sense of the helicity can be predicted from the molecular interactions. The predicted senses of the helical structures are in complete agreement with all known experimental results.

Chiral Mitsunobu reactions with (1S)-(+)-ketopinic acid: kinetic resolutions of secondary alcohols

Several secondary alcohols undergo the Mitsunobu reaction with triphenylphosphine, diethyl azodicarboxylate and (1S)-(+)-ketopinic acid (0.5 equiv. each relative to alcohol) in CH2Cl2 solution at -23degreesC, to furnish the chiral secondary alcohol and its ketopinate ester (d.e. >95%,). Chromatographic separation of these and subsequent hydrolysis of the ketopinate ester (KOH EtOH/0degreesC) provides the chiral secondary alcohol in overall yields of similar to75% and e.e. of similar to80%. When the above Mitsunobu reaction is performed with 1 equiv. of all the reactants. an effective dynamic kinetic resolution of the alcohol is observed in two cases, the ketopinate esters being isolated in 63 and 75% yields and >95% d.e. (C) 2002 Elsevier Science Ltd. All rights reserved.

Selective double quantum resolved correlation experiment for the complete separation of entire proton NMR spectra of enantiomers

The present study reports a two dimensional NMR experiment which separates single quantum spectra of enantiomers from that of a racemic mixture. This is a blend of selective double quantum refocusing, for resolving couplings and chemical shift interactions along two dimensions followed by correlation of the selectively excited protons to the entire coupled spin network. The concept is solely based on the presence of distinct intra methyl dipolar couplings of different enantiomers when dissolved in chiral orienting media. The analysis of single enantiomer spectrum obtained from respective F-2 cross sections yield all the spectral information. (C) 2011 Elsevier Inc. All rights reserved.

A versatile resolving agent for diffusion edited separation of enantiomers, complex mixtures and constitutional isomers

The study is the first report of the utilization of a crown ether as a new and versatile resolving agent for the diffusion edited separation of enantiomers, complex mixtures and constitutional isomers. As a consequence of different binding affinities of enantiomers of a chiral molecule and individual components of the complex mixtures with the crown ether, the molecules diffuse at different rates. The enhanced separation achieved due to matrix assisted diffusion permitted their separation in the diffusion dimension. The generality and wide utility of the new resolving agent and the methodology are demonstrated on diverse examples, such as an organic chiral molecule, constitutional isomers and complex mixture of molecules possessing different functional groups that possess nearly identical molecular weights.

In situ approach for testing the enantiopurity of chiral amines and amino alcohols by H-1 NMR

An in situ approach involving a simple mix and shake method for testing the enantiopurity of primary, secondary and tertiary chiral amines and their derivatives, chiral amino alcohols, by H-1-NMR spectroscopy is developed. The protocol involves the in situ formation of chiral ammonium borate salt from a mixture of C-2 symmetric chiral BINOL, trialkoxyborane and chiral amines. The proposed concept was demonstrated convincingly on a large number of chiral and pro-chiral amines and amino alcohols, and also aids the precise measurement of enantiomeric excess. The protocol can be completed in a couple of minutes directly in the NMR sample tube, without the need for any physical separation.

Plasmonic Interactions at Close Proximity in Chiral Geometries: Route toward Broadband Chiroptical Response and Giant Enantiomeric Sensitivity

Chiral metamaterials can have diverse technological applications, such as engineering strongly twisted local electromagnetic fields for sensitive detection of chiral molecules, negative indices of refraction, broadband circular polarization devices, and many more. These are commonly achieved by arranging a group of noble-metal nanoparticles in a chiral geometry, which, for example, can be a helix, whose chiroptical response originates in the dynamic electromagnetic interactions between the localized plasmon modes of the individual nanoparticles. A key question relevant to the chiroptical response of such materials is the role of plasmon interactions as the constituent particles are brought closer, which is investigated in this paper through theoretical and experimental studies. The results of our theoretical analysis, when the particles are brought in close proximity are dramatic, showing a large red shift and enhancement of the spectral width and a near-exponential rise in the strength of the chiroptical response. These predictions were further confirmed with experimental studies of gold and silver nanoparticles arranged on a helical template, where the role of particle separation could be investigated in a systematic manner. The ``optical chirality'' of the electromagnetic fields in the vicinity of the nanoparticles was estimated to be orders of magnitude larger than what could be achieved in all other nanoplasmonic geometries considered so far, implying the suitability of the experimental system for sensitive detection of chiral molecules.

Synthesis of covalently bonded cellulose derivative chiral stationary phases with a bifunctional reagent of 3-(triethoxysilyl)propyl isocyanate

A bifunctional reagent of 3-(triethoxysilyl)propyl isocyanate (TEPI) was initially adopted as a spacer reagent to prepare the bonded types of chiral stationary phases (CSPs) with cellulose derivatives. The silica-based CSPs were chemically prepared with non-regioselective and regioselective approaches and their chiral resolving capabilities were evaluated in terms of HPLC resolution of test enantiomers. It was observed that the chiral recognition capabilities of the non-regioselectively prepared CSPs were influenced by the amount of TEPI used. And also, the regioselectively prepared CSP generally showed a slightly higher resolution power than the non-regioselectively prepared CSP, while the non-regioselective procedures were highly advantageous to rapid preparation. In addition, chiral recognition of the prepared CSPs was affected by the properties of the used silica matrices. (C) 2003 Elsevier B.V. All rights reserved.

Molecularly imprinted monolithic stationary phases for liquid chromatographic separation of enantiomers and diastereomers

The method for preparation of molecularly imprinted monolithic stationary phase has been improved to achieve liquid chromatographic separation of enantiomers and diastereomers. By adopting low polar porogenic solvents of toluene and dodecanol and optimal polymerization conditions, the molecularly imprinted monolithic stationary phases with good flow-through properties and high resolution were prepared. Enantiomers of amino acid derivatives and diastereomers of cinchona alkaloids were completely resolved using the monolithic stationary phases. The influence of porogenic composition, monomer-template ratio and polymerization conditions on the chromatographic performance was investigated. Some chromatographic conditions such as the composition of the mobile phase and the temperature were characterized. Scanning electron microscopy showed that the molecularly imprinted monolithic stationary phase has a large through-pore structure to allow the mobile phase to flow through the column at very low backpressure. Accelerated separations of enantiomers and diastereomers were therefore achieved at elevated flow rates. Finally, the chiral recognition performance of the prepared stationary phase in aqueous media was investigated. Hydrophobic interaction, and ionic and/or hydrogen bonding interactions were proposed to be responsible for the recognition mechanism. (C) 2002 Elsevier Science B.V. All rights reserved.

Synthesis and characteristics of composite chiral stationary phases based on cellulose derivatives

Composite chiral stationary phases (CSPs) were prepared on the basis of cellulose derivatives coated or bonded onto silica. "Molecular exterior" type CSPs were prepared by mixing together two different cellulose tris-derivatives before or after being coated or bonded onto silica, and the "molecular interior" type was obtained by synthesizing non-regioselectively heterosubstituted cellulose derivatives coated or bonded onto silica. For the sake of comparison, the individual phases were also prepared with corresponding cellulose derivatives by coating or bonding approaches, respectively. All of the prepared CSPs were characterized and their chiral recognition properties were evaluated by HPLC with several test racemates. The experimental results demonstrated that the "molecular exterior" CSPs generally exhibit chiral recognition capacities intermediate between those of the two individual phases. However, in the separation of some racemates higher enantioselectivity may be achieved on the "molecular interior" phases than on individual phases, thus broadening the application range of a single cellulose-based CSP.

Transient state of chiral recognition in a binary mixture of cyclodextrins in capillary electrophoresis

The transient state (as the defined point where no enantioseparation is obtained in a dual chiral selector system) of chiral recognition of aminoglutethimide in a binary mixture of neutral cyclodextrins (CDs) was studied by capillary electrophoresis (CE). The following three dual selector systems were used: alpha-cyclodextrin (alpha-CD) and beta-cyclodextrin (beta-CD); alpha-CD and heptakis(di-O-methyl-beta-cyclodextrin) (DM-beta-CD); alpha-CD and heptakis(tri-O-methyl-beta-cyclodextrin) (TM-beta-CD). The S-(-) enantiomer of the analyte was more strongly retained in the presence of either alpha-CD or TM-beta-CD at pH 2.5, 100 mM phosphate buffer, while the R-(+) enantiomer was more strongly retained in the presence of either P-CD or DM-P-CD. In the more simple case, the elution order is invariably kept if the enantiomers have the same elution order in either one of the two hosts of the binary mixture. In contrast, the elution order may be switched by varying the concentration ratio of two hosts that produce opposite elution order for this particular analyte. In such a dual selector system, the enantioselectivity will disappear at the transient state at a certain ratio of host,:host, Moreover, the migration times of the two enantiomers with host, alone (diluted in buffer) is approximately equal to the migration times at the corresponding concentration of host, alone (diluted in buffer), where the ratio of concentrations of host,:host, is the same as in the binary mixture at the transient state. As found by nuclear magnetic resonance experiments, the analyte is forming a 1:1 complex with either one of the CDs applied. From this finding, a theoretical model based on the mobility difference of the two enantiomers was derived that was used to simulate the transient state. (C) 2000 Elsevier Science B.V. All rights reserved.

Synthesis and characteristics of the human serum albumin-triazine chiral stationary phase

Human serum albumin (HSA) was successfully bonded to silica with s-triazine as activator. The coupling reaction by this method was rapid and effective. The triazine-activated silica is relatively stable and can be installed for at least 1 month without obvious loss of reactivity when stored below 30 degreesC, pH below 7. It was observed that the amount of bound HSA reached 120 mg/g silica calculated from the UV absorbance difference of the HSA solution. d,l-tryptophan was selected as the probe solute to characterize the properties of HSA bonded s-triazine chiral stationary phase, and separation factor of 9.4 was obtained for d,l-tryptophan. Furthermore, the amount of effective HSA on silica was measured by high-performance frontal analysis, and only 16.8 mg/g silica was responsible for the resolution of d,l-tryptophan. These results indicate that the amount of both the bound and effective HSA on silica with triazine as activator was much higher than those by the Schiff base coupling method. Different kinds of enantiomers were resolved successfully on the aminopropylsilica-bonded HSA s-triazine chiral stationary phase. (C) 2000 Wiley-Liss, Inc.

Synthesis of a silica-bonded bovine serum albumin s-triazine chiral stationary phase for high-performance liquid chromatographic resolution of enantiomers

A novel method of synthesizing protein chiral stationary phase (protein-CSP) is proposed with 2,4,6-trichloro-1,3,5-triazine as the activator. The bovine serum albumin (BSA) based chiral columns (150x4.6 mm I.D.) were prepared successfully within 8 h. With tryptophan as the probe solute, it was observed that the BSA immobilized by this method had a better ability to distinguish enantiomers than that activated by glutaric dialdehyde. This may be due to the well-maintained BSA conformation and the larger amount of BSA immobilized on the silica gel. The BSA-CSP prepared by this method was relatively stable under experimental conditions, and the resolution of 13 chiral compounds was achieved. The coupling reaction in this method is mild, reliable and reproducible; it is also suitable for the immobilization of various biopolymers in the preparation of bioreactor, biosensor and affinity chromatography columns. (C) 2000 Elsevier Science B.V. All rights reserved.