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PubMed2006

Chiral and achiral macrocyclic copper(II) complexes: Synthesis, characterization, and comparative binding studies with calf-thymus DNA.

The new chiral macrocyclic complexes [1,2-bis(1H-benzimidazol-2-yl)-1-(1,8-dihydro-1,3,5,8,10,12-hexaazacyclotetradecane)-2-hydroxyethanolate] copper(II) and -nickel(II) perchlorate, 3 and 4, respectively, were synthesized by the reaction of 1,2-bis(1H-benzimidazol-2-yl)ethane-1,2-diol (L) and (1,8-dihydro-1,3,5,8,10,12-hexaazacyclotetradecane)copper(II) and -nickel(II) diperchlorate complexes, 1 and 2, respectively. All complexes were characterized by various spectroscopic techniques. Molar-conductance measurements showed that all of the complexes are ionic in nature. In complexes 3 and 4, the metal center is encapsulated by the ligand L in a pentacoordinated environment. The optical-rotation values ([alpha](D)) of 3 and 4 at 25 degrees indicate that the complexes are chiral. Absorption- and fluorescence-spectral studies, cyclic voltammetry, and viscosity measurements have been carried out to assess the comparative binding of complexes 1 and 3 with calf thymus (CT)-DNA. Analysis of the results suggests that the new chiral complex 3 binds to CT-DNA through a partial intercalation mode that is different from the binding mode of parent achiral complex 1. The complexes 1 and 3 bind to CT-DNA with binding constants K(b) of 2.7 x 10(4) and 6.6 x 10(4) M(-1), respectively. Circular-dichroism (CD) studies have been further employed to ascertain the binding mode of complex 3, which is consistent with the other spectral studies.

Animals↗
PubMed2005

Control of helix sense by composition of chiral-achiral copolymers of N-propargylbenzamides.

N-Propargylbenzamides 1-7 were polymerized with (nbd)Rh(+)[eta(6)-C(6)H(5)B(-)(C(6)H(5))(3)] to afford polymers with moderate molecular weights (M(n) = 26,000-51,000) in good yields. The (1)H NMR spectra demonstrated that the polymers have fairly stereoregular structures (81-88 % cis). The optically active polymers, poly(1) and poly(2), were proven by their intense CD signals and large optical rotations to adopt a stable helical conformation with an excess of one-handed screw sense when heated in CHCl(3) or toluene. The sign of Cotton effect could be controlled by varying the content in the copolymers of either chiral bulky 1 and achiral nonbulky 3, or chiral nonbulky 2 and achiral bulky 7. The smaller the pendant group in the copolymerization of achiral monomers with 1, the more easily did the preferential helical sense change with the copolymer composition. However, the copolymers of chiral nonbulky 2 and achiral nonbulky 3 did not change the helical sense, irrespective of the composition. The free energy differences between the plus and minus helical states, as well as the excess free energy of the helix reversal, of those chiral-achiral random copolymers were estimated by applying a modified Ising model.

Benzamides↗
PubMed2006

Chemistry of anthracene-acetylene oligomers: synthesis and enantiomeric resolution of a chiral 1,8-anthrylene-ethynylene cyclic tetramer.

To construct a new type of chiral pi-conjugated system, the title anthracene-acetylene oligomer containing two octyl groups at position 10 of 1,2-alternating anthracene groups was synthesized. Each anthracene unit was connected by Sonogashira coupling, and the tetrameric precursor was cyclized by a cross-coupling reaction to form the desired C2-symmetric compound. Its enantiomers were resolved by chiral HPLC with a Chiralcel OD column, and the chiroptical properties were investigated by optical rotation ([alpha]D(23) = -95 and +91) and circular dichroism (CD) measurements. The structural and spectroscopic features of this oligomer were discussed in terms of the molecular symmetry and the dynamic behavior of the macrocyclic framework.

Journal Article↗
PubMed2001

Chiral HPLC separation and CD spectra of the enantiomers of the alkaloid tacamonine and related compounds.

The HPLC enantiomeric separation of racemic indole alkaloids tacamonine, 17 alpha-hydroxytacamonine, deethyleburnamonine, and vindeburnol was accomplished using Chiralpak AD and Chiralcel OD as chiral stationary phases. Small structural differences affect the enantioselectivity ability of these phases. Single enantiomers of tacamonine and vindeburnol were isolated by semipreparative HPLC and their CD spectra and optical rotations were measured.

Chromatography, High Pressure Liquid↗
PubMed2001

Melatonin receptor agents: synthesis, resolution by HPLC on polysaccharides chiral stationary phases, absolute configuration, and pharmacology of the enantiomers of (+/-)-N-[[2[(7-fluoro-1,2,3,4-tetrahydronaphthalen-1-yl)ethyl]acetamide.

In order to obtain milligram amounts of the enantiomers of tetrahydronaphthalenic derivative 5 to be tested for binding to the melatonin sites, preparative HPLC employed a mobile phase consisting of n-hexane-alcohol and a silica-based cellulose tris-methylbenzoate (Chiralcel OJ) using isocratic conditions and multiple repetitive injections. The preparative separation was optimized by adjusting the sample size from a scale-up of the analytical method. The enantiomeric elution order was reversed by the change from the carbamate type phase (Chiralcel OD-H) to the benzoate type phase (Chiralcel OJ) in analytical mode. The optical rotation and the circular dichroism spectra of the single enantiomers were determined after separation. The absolute stereochemistry of the two enantiomers of (+/-)-N-[2-(7-fluoro-1,2,3,4-tetrahydronaphthalen-1-yl)ethyl]acetamide 5 was established by X-ray crystallographic analysis. The purity obtained was sufficient for a first screen of their biochemical properties: the (-)-(S) enantiomer shows more affinity for melatonin receptors MT1, MT2 and is responsible of the selectivity towards MT2.

Cell Line↗
PubMed2004

Online monitoring of preferential crystallization of enantiomers.

Polarimetry is used for continuous online monitoring of optical resolution by preferential crystallization. In combination with refractometry the liquid phase composition is determined, allowing one to follow the resolution progress quantitatively. The measurement techniques were calibrated up to relatively high solution concentrations and combined with the crystallizer. The resolution of DL-threonine was performed by preferential crystallization experiments in aqueous solution varying several process parameters like supersaturation, seed amount, initial enantiomeric excess, and scale. The resolution progress can be conveniently described by profiles of the optical rotation (polarimetric signal) and the crystallization pathway in the corresponding ternary phase diagram. The method outlined is applicable for dynamic process optimization and control purposes in "quasi-continuous" chiral separation processes.

Calibration↗
PubMed2005

Analysis of chiral pharmaceuticals using HPLC with CD detection.

Recent American Food and Drug Administration guidelines have effectively determined that mixtures of chiral compounds can no longer be brought to the pharmaceuticals marketplace. These guidelines require a means for chiral detection and compound separation. This article describes separation and detection of chiral pharmaceuticals using HPLC with circular dichroism detection. Two over-the-counter (OTC) medications, Prilosec and naproxen sodium, along with the prescription drugs Naproxen, Nexium, and Coumadin were analyzed using HPLC with CD, UV, and optical rotation (OR) detection. In all cases the CD and UV detectors displayed a much greater sensitivity than the OR detector. Although in many cases the UV detector did have a slightly better sensitivity than the CD detector, the CD detector had the advantage of only responding to the chiral compounds, eliminating the possibility of interference with the peaks of interest.

Journal Article↗
PubMed2005

Computational study of conformational and chiroptical properties of (2R,3S,4R)-(+)-3,3',4,4',7-flavanpentol.

Conformational analysis of (2R,3S,4R)-(+)-3,3',4,4',7-flavanpentol, a flavonoid compound displaying both antioxidant and pro-oxidant properties, is performed by molecular mechanics and density functional theory calculations both in the gas phase and in methanol solution by using the Polarizable Continuum Model. Nine different conformations are identified. Absorption (UV) and circular dichroism (CD) spectra and optical rotations are calculated by means of time dependent density functional theory (TDDFT) and compared with experiments. The effects of a complex environment formed by water and proline-rich peptide molecules on the conformational characteristics of (2R,3S,4R)-(+)-3,3',4,4',7-flavanpentol and therefore on its UV and CD spectra are investigated by atomistic molecular dynamics simulations.

Catechin↗
PubMed2006

Tracking of enantioselective solubility of rac-norgestrel in the presence of cyclodextrin by a CD spectroscopic method.

Dissolution of hydrophobic rac-norgestrel in aqueous gamma-cyclodextrin (gamma-CyD) and hydroxypropyl-gamma-cyclodextrin (HP-gamma-CyD) solutions was investigated, and enantioselective dissolution was observed. (-)-Norgestrel, the eutomer molecule, was dissolved to a greater extent using each of the CyDs, although the effect was more significant in the case of HP-gamma-CyD. A circular dichroism (CD) spectroscopic method based on measurement of the anisotropy factor was applied for the determination of the enantiomer ratio. The concentration and the enantiomer ratio of norgestrel were determined indirectly in octanol after extraction. Optical rotation dispersion (ORD) measurements could confirm that neither the free CyDs nor their inclusion complexes could get into the organic phase during transport to octanol. Only the norgestrel molecules were able to get into the organic phase, although the enantiomer ratio remained the same as was obtained in the aqueous CyD solution.

Circular Dichroism↗
PubMed2006

Separation and aquatic toxicity of enantiomers of the organophosphorus insecticide trichloronate.

Many of the organophosphorus pesticides (OPs) currently used are chiral and therefore consist of mixture of enantiomers. Despite the fact that the biological processes of chiral pesticides are enantioselective, the acute aquatic toxicity of chiral OPs with respect to enantioselectivity has so far received limited research. In this study, the enantiomeric separation and acute aquatic toxicity of trichloronate were investigated. Baseline enantioseparation of trichloronate was successfully achieved using high-performance liquid chromatography on a Chiralcel OJ column, with a mobile phase of n-hexane/n-heptane/ethanol (90/5/5, v/v/v) at the flow rate of 1.0 ml min(-1) and room temperature. The resolved enantiomers were characterized for their optical rotation and by gas chromatography coupled with mass spectrometry. Significant differences were found between the enantiomers in acute aquatic toxicity to Ceriodaphnia dubia and Daphnia magna. The (-)-trichloronate was 8-11 times more toxic to the test organisms than its (+)-form, while the racemate showed intermediate toxicity. These results suggest that assessment of the environmental safety of chiral OPs should take stereospecificity into consideration.

Animals↗
PubMed2007

Enantioselective preparative HPLC separation of the HBCD-Stereoisomers from the technical product and their absolute structure elucidation using X-ray crystallography.

1,2,5,6,9,10-Hexabromocyclododecane (HBCD) is a widely used flame retardant, which tends to persist in the environment and accumulates in biota. The six stereoisomers (three racemates named alpha-, beta-, and gamma-HBCD) of the technical mixture were isolated with high-performance liquid chromatography (HPLC). Direct separations were performed on a chiral stationary phase containing permethylated beta-cyclodextrin (NUCLEODEX beta-PM column) and the pure enantiomers of alpha-, beta-, and gamma-HBCD were physically characterized for the first time. The absolute configurations of all six isomers were determined by anomalous dispersion using single crystal X-ray crystallography. Optical rotations alphaD in tetrahydrofuran were +4.2/-4.0 (alpha-HBCD), +26.1/-27.5 (beta-HBCD), and +68.0/-66.3 (gamma-HBCD). The sense of rotation could be correlated with the absolute configurations of alpha-, beta-, and gamma-HBCD enantiomers and their order of elution on a chiral permethylated beta-cyclodextrin-bonded stationary phase. The diastereomersalpha-, beta-, and gamma-HBCD displayed distinctly different melting points as well as (1)H-, (13)C NMR, and IR spectra.

Journal Article↗
PubMed1995

Determination of the enantiomers of citalopram, its demethylated and propionic acid metabolites in human plasma by chiral HPLC.

A stereoselective HPLC assay has been developed to analyze the enantiomers of citalopram and of its three main metabolites in plasma after their separation on a Chiracel OD column. Using a fluorescence detector, the limit of quantification in plasma samples was 15, 4, 5 and 2 ng/ml for the enantiomers of citalopram (CIT), desmethylcitalopram (DCIT), didesmethylcitalopram (DDCIT), and for the citalopram propionic acid derivative (CIT-PROP), respectively. Except for CIT, all metabolites were derivatized with achiral reagents. Identification of the enantiomers was realized with an optical rotation detector which showed that the enantiomers invert their rotation depending on the polarity and nature of the solvent. Under varying conditions, a racemization study has shown that the pure enantiomers of CIT and its demethylated metabolites are configurationally stable. Preliminary results obtained with five patients treated with CIT show a mean S/R ratio of 0.7 for both CIT and its active metabolite DCIT and of 3.6 for CIT-PROP in plasma. This suggests that the pharmacologically relevant (+)-(S)-isomers of CIT and DCIT could be preferentially and stereoselectively metabolized to CIT-PROP.

Antidepressive Agents↗
PubMed2003

Polymeric alkenoxy amino acid surfactants: I. Highly selective class of molecular micelles for chiral separation of beta-blockers.

Two amino acid-based alkenoxy micelle polymers were synthesized for this study. These include polysodium N-undecenoxy carbonyl-L-leucinate (poly-L-SUCL) and polysodium N-undecenoxy carbonyl-L-isoleucinate (poly-L-SUCIL). The polymerization time and concentration of the synthesized micelle polymers were optimized by (1)H-nuclear magnetic resonance (NMR) and capillary electrophoresis (CE) experiments. Detailed physicochemical properties ((1)H NMR, critical micelle concentration (CMC), optical rotation, partial specific volume, aggregation number, and polarity) were determined, and these molecular micelles were introduced as a pseudostationary phase in micellar electrokinetic chromatography to study the molecular recognition and to develop a method for simultaneous separation of eight chiral beta-blockers. It is found that poly-L-SUCL gives overall better chiral resolution and wider chiral window than poly-L-SUCIL. After optimizing the type of micelle polymer, injection size and temperature, simultaneous separation and enantioseparation of eight beta-blockers were achieved in less than 35 min. A comparison with the amide-type surfactants of the same polar head group and alkyl chain length showed that carbamate-type surfactants always work better than the corresponding amide-type surfactant.

Adrenergic beta-Antagonists↗
PubMed2005

Polymeric alkenoxy amino acid surfactants: IV. effects of hydrophobic chain length and degree of polymerization of molecular micelles on chiral separation of beta-blockers.

Four alkenoxy leucine-based surfactants with C8-C11 chains containing a terminal double bond, and one C11 chain surfactant with a terminal triple bond are synthesized and characterized in monomeric and polymeric forms. These polymeric pseudophases are then utilized to study the influence of chain length and DP for the enantioseparations of seven beta-blockers in MEKC. Variations in chain length and concentration of polymeric surfactants showed significant effects on the chiral resolution (Rs) and efficiency (N). A relatively large elution range combined with the highest polarity and aggregation number (A) but the lowest retention time, partial specific volume, and optical rotation generated with C8-polymeric surfactant results in simultaneous enantioseparation of all seven beta-blockers with higher N and R(s). In particular, highly hydrophobic beta-blockers are better resolved with shorter hydrocarbon chain even at higher surfactant concentration, which is unachievable with longer chain surfactant. On the other hand, polymer derived from C11-triple bond provided smaller A value compared to C11-double bond surfactant. However, chiral Rs of hydrophobic beta-blockers are still achievable with the C11-triple bond surfactant with enhanced N and shorter analysis time. In addition, effect of polymerization concentration is evaluated by polymerizing all five surfactants at five times their respective CMCs and 100 mM equivalent monomer concentrations. Polymerization of shorter chain (C8 and C9) double-bonded surfactants at five times their respective CMCs results in higher A values with better chiral Rs and N compared to the same two surfactants polymerized at 100 mM.

Adrenergic beta-Antagonists↗
PubMed1976

Beta-hydroxynorleucine: separation of its isomers and biological studies.

Separation of the four isomers of beta-hydroxynorleucine was accomplished by partition column chromatography and asymmetric enzymatic hydrolysis of the N-chloroacetyl derivatives. From these, the corresponding N-chloroacetyl derivatives were made. The purity and configuration of each isomer of the free acid and N-chloroacetylated derivative were ascertained by: (a) paper chromatography in five solvent systems, (b) elemental analysis, (c) Van Slyke nitrous acid determination of alpha-carbonyl carbon, and (d) Van Slyke ninhydrin determination of alpha-carbonyl carbon, and (e) optical rotation. Comparison of the rate of enzymatic hydrolysis by hog renal acylase I of the N-chloroacetyl derivative of the L-isomers of each diastereomer showed that the acyl B isomer is a better substrate than the acyl A isomer, where A denotes the faster moving diastereomer and B denotes the slower moving diastereomer in a defined chromatographic solvent system. Microbiological assay using Lactobacillus casei in a system selected for screening for possible antitumor activity indicated that while none of the isomers as free amino acids had any growth inhibitory action, the N-acylated isomers showed modest but significant activity. The N-chloroacetyl derivative of the D-enantiomorph of diastereomer B exhibited the greatest growth inhibitory activity, showing about twice the activity of the other three isomers.

Aminocaproates↗
PubMed1988

Studies on the stability of vinblastine sulfate in aqueous solution.

A stability study on vinblastine sulfate (1) in aqueous solution at several different temperatures (in the absence of light) has been undertaken. High-performance liquid chromatography was used to obtain kinetic data for the loss of vinblastine and to monitor the order of appearance of degradation products, of which eight were observed. The two most prominent components of early heat degradation have been tentatively identified by mass spectrometry (DCl), as a C19'-oxidation product (19'-oxovinblastine, 4, MH+ 825) and an isomer of vinblastine (MH+ 811). Products appearing later in the course of degradation include a component of MH+ 809, possibly corresponding to either 19'-hydroxy-3',4'-dehydrovinblastine (5) or 3',4'-dehydrovinblastine-6'-N-oxide (6), and three other products of MH+ 636, MH+ 670, and MH+ 795. In addition, optical rotation studies have established that racemization (with a possible reduction in biological activity) does not occur prior to transformation into degradation products. Preliminary experiments on light-mediated degradation demonstrated a different sequence of transformation, with the MH+ 670 and MH+ 795 products appearing first. Contrary to reports and suggestions in the literature and based on an estimated activation energy of 27.1 kcal/mol, the results of this study indicate that vinblastine sulfate is relatively stable in aqueous solution at or below room temperature (estimated t90 values: 150 d at 25 degrees C and 10.7 years at 5 degrees C) and has a t90 value of 16.6 d at 37 degrees C. These results are important in view of current interest in the continuous iv infusion of vinblastine sulfate.(ABSTRACT TRUNCATED AT 250 WORDS)

Chromatography, High Pressure Liquid↗