Stereoselective synthesis of the lituarine tricyclic spiroacetal

[reaction: see text] Oxidative cyclizations of 2-(4-hydroxybutyl)furan derivatives provide spirobutenolide acetals directly; on the basis of this methodology, we describe an asymmetric synthesis of a tricyclic spirobutenolide precursor to the C(7-18) fragment common to lituarines A-C.     

New caffeoyl derivatives from the leaves of Davidia involucrata

Three new caffeoyl galactoic acid derivatives, davidiosides A-C (1-3) together with four known caffeoyl derivatives such as: caffeic acid (4), methyl caffeate (5), chlorogenic acid (6), and methyl chlorogenate (7) were isolated from the leaves of Davidia involucrate. The new structures were determined by spectroscopic data and chemical evidence.     

Three New Coumarins from Micromelum integerrimum

Micromelum integerrimum (Rutaceae) is a shrub growing in Yunnan Province. Leaves and barks of this plant have been used for the treatment of dysentery, and arthritis1. Previous researches revealed that this plant contained coumarins2-8. Micromelin, the main chemical constituent of this plant, showed significant inhibition against leukaemia P-388 cell line (T/C 149% at 10 mg/kg) but was inactive in lower doses, and also showed significant activity (T/C 228% at 1.25 mg/kg) against Lewis lung…     

Application of dansyl derivatization to the high pressure liquid chromatographic identification of equine estrogens

The HPLC qualitative analysis of conjugated estrogens is accomplished by a two-step procedure involving the formation of the corresponding dansyl derivatives. The first step involves the acid hydrolysis of the conjugated estrogens, followed by dansyl derivatization and HPLC separation of these derivatives on a liChrosorb Si-60 column with 50% (v/v) chloroform-n-heptane as the mobile phase. All of the dansyl estrogens are well separated except for the 17-keto estrogens, estrone, equilin, and equilenin. The second step, designed to detect the three 17-keto estrogens, begins with the selective sodium borohydride reduction of the conjugated 17-keto estrogens to the corresponding 17-hydroxyl compounds (the beta-epimer being formed in vast predominance over the alpha-epimer), followed by acid hydrolysis, dansyl derivatization, and HPLC separation of the derivatives as in the first step. Detection of the 17-keto estrogens is possible by determining differences in peak heights between the chromatograms of the first and second analyses. The The proposed method is sensitive, the dansyl derivatives stable, and nine different estrogens can be readily identified.     

Determination of N-nitrosamines by HPTLC with Fluorescence Detection — Use of Non-Ionic Surfactants as Enhancing Agents

JPC – Journal of Planar Chromatography – Modern TLC - The dansyl derivatives of N-nitrosodimethylamine, N-nitrosodi-ethylamine, and N-nitrosodibuthylamine have been separated by HPTLC...     

Pressurized planar electrochromatography of DNS amino acids derivatives in silica gel and silanized silica gel systems with formic acid addition to the water mobile phase

JPC – Journal of Planar Chromatography – Modern TLC - Pressurized planar electrochromatography (PPEC) of dansyl (DNS) derivatives of amino acids in normal- and reversed-phase systems is...     

Determination of amine-containing phosphonic acids and amino acids as dansyl derivatives

Conditions are selected for the analytical separation of (N-phosphonomethyl glycine), products of its microbiological conversion, glutamic acid, and alanine as dansyl derivatives using reversed-phase HPLC: column (250 × 4.6 mm) ReproSil-PAH EPA; mobile phase, methanol + 20 mM CH₃COONa (pH 5.1) (20: 80); rate of mobile phase, 1 mL/min; working detector wavelength, 330 nm. The duration of separation is 35 min. The lower limits of the analytical range (in ng) for dansyl derivatives are as follows: glyphosate, 8.2; aminomethyl phosphonic acid, 24.2; glutamic acid, 9.4; alanine, 12.6: glycine, 17.7; and sarcosine, 19.3. The TLC study of dansyl derivatives of amino acids was performed on sorbfil plates PTSH-P-V using two-dimensional chromatography in the systems ethyl acetate-isopropanol-24% aqueous ammonia (45: 35: 20) in the first direction and chloroform-methanol-acetic acid (25: 5: 1) in the second one. For determining phosphonic acids (glyphosate and aminomethyl phosphonic acid), a version of one-dimensional chromatography with the sequential use of two systems, chloroform-methanol-acetic acid (25: 5: 0.2) and ethanol-24% aqueous ammonia (7: 3), was proposed.     

Extraction of Cesium from the Irradiated Nuclear Waste by 4(5),4''''(5'''')-Bis[1-hydroxyalkylbenzo]-21-crown-7

The fission product 137Cs accounts for a large fraction of the radioactivity in high-levelnuclear waste (HLW). Because of the hazard to environment and the widespreadapplication of 137Cs gamma radiatior1, a need has arisen to develop improved methods forthe removal and recovery of radiocesium from these wastes. Reports have shown thatsome calixcrown compounds may be highly selective for Cs cation2, but, since thesynthesis of them is difficult and the cost is high, it might obviate their use…     

Facile synthesis of positively charged monosubstituted α- and γ-cyclodextrins for chiral resolution of anionic racemates

New positively charged monosubstituted α- and γ-cyclodextrins at the primary face were synthesized in good yields by displacement of the monotosylates of α- and γ-cyclodextrin with amine, alkylamines or alkylimidazoles. The influence of CD’s cavity size on the resolution abilities of CD derivatives towards model analytes, that is, dansyl amino and carboxylic acids, were investigated. Results show that the formation of the inclusion complex might play an important role in chiral recognition, in that cationic γ-CD derivatives gave better resolution abilities than their α- and γ-CD analogues, presumably due to tight fit between CD hosts and the anionic guest racemates.     

Measurement of neutral sugars in glycoproteins as dansyl derivatives by automated high-performance liquid chromatography

Automated high-performance liquid chromatography was used to analyse dansylhydrazine derivatives of neutral sugars in unfractionated acid hydrolysates of four well-characterized glycoproteins: fetuin, ovalbumin, alpha-1-acid glycoprotein and bovine submaxillary mucin. After a simple single-step derivatization at 65 degrees C the sugar derivatives in protein hydrolysates chromatographed as single peaks on reversed-phase C18 columns. The isocratic solvent consisted of 20% (v/v) aqueous acetonitrile containing 0.01 M formic acid, 0.04 M acetic acid and 0.001 M triethylamine. The triethylamine significantly increases the sugar peak height at 254 nm. Repeated automatic sample injection without deterioration of column performance or interference from dansyl hydrazine is not possible with published methods, but was achieved by cleaning the column between each analysis with a solvent of 20% (v/v) acetonitrile and 80% (v/v) methanol. Hydrolysis with 2 M trifluoroacetic acid is superior to 2 M hydrochloric acid for both sugar recovery and convenience but must continue for 6-8 h at 105 degrees C to ensure complete sugar release. We confirmed that mannose is present in most preparations of human high-molecular-weight salivary glycoproteins, and also examined purified bovine skin proteodermatan sulphate. p-Nitrophenylhydrazine derivatives of neutral sugars are readily produced, but do not chromatograph as successfully as the dansyl derivatives while phenylhydrazine derivatives are not easily produced at 65 degrees C. Further development of the method should be possible by producing other hydrazine derivatives of neutral sugars.     

Novel phloroglucinol derivatives from the roots of Lysidice rhodostegia

[structure: see text] Three novel phloroglucinol derivatives of lysidicins A-C (1-3) have been isolated from the roots of Lysidice rhodostegia and structures were elucidated by comprehensive NMR and MS spectroscopic analysis. 1 and 2 possess spirocyclic benzodihydrofuran skeleton. Their relative stereochemistries were assigned by NOE or NOESY experiment. A plausible pathway for the biosynthesis of 1-3 from 4 and a ketose derivative was postulated.     

Extraction of biogenic amines and their dansyl derivatives with reverse microemulsions of bis [2-ethylhexyl] sulphosuccinate (AOT) prior to high-performance liquid chromatographic determination

The ability of reverse microemulsions of the surfactant bis [2-ethylhexyl] sulphosuccinate (AOT) in heptane to extract and preconcentrate eight biogenic amines present in aqueous matrices has been explored. The “phase transfer” method, in which the surfactant solution is contacted with an aqueous salt solution containing the analytes, has been used as the analytical methodology. The extraction efficiencies have been compared with those obtained by using the “cloud point” extraction technique with Triton X-114 as surfactant, and with methylene chloride as a typical extracting solvent. In order to improve extraction and detection as compared with the underivatized amines, the fluorescent reagent dansyl chloride has been used to obtain the more hydrophobic and thus, easily extractable dansyl derivatives. Although extraction of most of the biogenic amines is high, extraction of their dansyl derivatives is practically 100%. The procedure was successfully applied to the analysis of commercial fruit juices. The analytical methodology is sensitive, fast, simple and reproducible. The LOD were in the vicinity of 1 and 2 pmol, which is similar or better than other techniques. The micellar phase is compatible with reverse phase HPLC mobile phases, which allow direct injection of the analyte after extraction. This is an advantage over solid phase extraction (SPE), where incomplete recovery can occur. Moreover, AOT showed to be better extracting surfactant for biogenic amines (and their corresponding dansyl derivatives) than Triton X-114 at the same concentration.     

Cationic and fluorescent "Janus" dendrimers

Two synthetic routes to "Janus"-type dendrimers possessing ammonium groups on one side and fluorescent dansyl derivatives on the other side are described. These surface-block dendrimers are obtained by the coupling of two different dendrons, built from the hexafunctional cyclotriphosphazene core. Their characterization and their photophysical behavior are reported. The largest compound possesses 10 ammonium groups and 5 dansyl groups; it is potentially useful as a fluorescent label in materials science and biology.     

Simultaneous High Performance Liquid Chromatographic Determination of Theophylline and Ethylenediamine in Aminophylline Dosage Forms as Their Dansyl Derivatives

Abstract

A simple HPLC method has been developed for the assay of the components of aminophylline (theophylline: ethylenediamine 2:1) in solid and liquid dosage forms. Following the extraction of tablets into or the dilution of a liquid dosage form with water, the aqueous extract was reacted with dansyl chloride in an alkaline medium. The mixture of the dansyl derivatives of theophylline and ethylediamine was analyzed on an reversed phase μBondapak Cia column, using a methanol-water-acetic acid-triethylamine (60–65: 33–38: 1. 5:0. 5) mobile phase delivered at the rate of 1.5 mL/min, and a detection wavelength of 254 nm. In addition to exhibiting excellent accuracy and precision, the method yielded detector responses that were linearly related to concentrations of theophylline and ethylenediamine in aminophylline of up to 7 mg of theophylline, and of up to 10 mg     

Physico-chemical phenomena of double-layer spray and effect on enhancement and stabilization of fluorescence

Summary It was surprisingly found in TLC that double spraying of plates could enhance fluorescence of dansyl derivatives 200–360 fold after spraying with 20% triethanolamine in propane-2-of followed by 30% paraffin oil in hexane on a developed plate containing dansyl chloride derivatives. Visual detection limits as low as 1–6 pmole per spot even a month after spraying with a reproducibility of about 5–6% rsd were obtained. Spraying calibration graphs showed a dose-dependency of at least 1 pmole up to 1.5 nmole per spot. The stability of fluorescence of derivatives to light was increased and spectra of compounds acquired a hypochromic shift in which the color changed from yellow to blue. The graphical method employing the “organic concept” is introduced to explain this kind of synergistic effect of double spraying using different solvents.     

Separation of N1- and N8-acetylspermidine isomers by reversed-phase column liquid chromatography after derivatization with dansyl chloride

The separation of dansyl derivatives of N1- and N8-acetylspermidine by reversed-phase column liquid chromatography is reported. The influence of organic solvents on the retention of acetylspermidines was studied. Best resolutions were achieved using a C18 column and a ternary mobile phase composed of water, methanol and acetonitrile. The precolumn derivatization method permitted the detection of picomole quantities. A method for the determination of acetylspermidines in rat tissues is described.     

Determination of amino acid ratios in natural products by micellar electrokinetic chromatography

Summary Separation of dansyl and di-dansyl derivatives of amino acids present in natural products (corn seed flour, wheat flour fraction gliadine) is described. Problems with coelution of derivatization by-products and reagent with some dansyl amino acids (DNS-AA) were solved. A preconcentration step after derivatization of real sample is described. DNS-AA peak areas for different varieties of corn seed flour were compared. Di-dansyl histidine is not separated from di-dansyl lysine and didansyl tyrosine. Additional separation mechanisms have to be introduced to achieve separation of these three species.     

Triazole‐Tailored Guanosine Dinucleosides as Biomimetic Ion Channels to Modulate Transmembrane Potential

A “click” ion channel platform has been established by employing a clickable guanosine azide or alkyne with covalent spacers. The resulting guanosine derivatives modulated the traffic of ions across the phospholipid bilayer, exhibiting a variation in conductance spanning three orders of magnitude (pS to nS). Förster resonance energy transfer studies of the dansyl fluorophore with the membrane binding fluorophore Nile red revealed that the dansyl fluorophore is deeply embedded in the phospholipid bilayer. Complementary cytosine can inhibit the conductance of the supramolecular guanosine channels in the phospholipid bilayers.     

Non-protected fluid room temperature phosphorescence of several naphthalene derivatives

In our previous work, we reported that with TlNO(3) as a heavy atom perturber and Na(2)SO(3) as a deoxygenator, room temperature phosphorescence (RTP) emission of dansyl chloride and its amino acid derivatives can be induced directly from their aqueous solution without a protective medium. Is this kind of fluid luminescence phenomenon unique for the dansyl chloride compounds? The present work has shown that many naphthalene derivatives can also exhibit RTP emission in their aqueous solutions under similar conditions in the absence of a protective medium. Such an RTP emission phenomenon could be denoted as nonprotected fluid room temperature phosphorescence (NP-RTP). In order to further understand this new luminescence phenomenon, the substituent group effects and the favorable chemical structure of compounds for NP-RTP emissions are discussed in detail.     

Sartoryglabrins, analogs of ardeemins, from Neosartorya glabra

Chemical investigation of a collection of the fungus Neosartorya glabra from Thailand furnished sartoryglabins A-C (1a, 1b and 2) which are analogs of the reverse prenylated indole alkaloids known as (-) ardeemins. Structures of these compounds were established by NMR spectrometry and an X-ray analysis. Sartoryglabins A-C were evaluated for their in vitro growth inhibitory activity on three human tumor cell lines: MCF-7 (breast adenocarcinoma), NCI-H460 (non-small cell lung cancer) and A375-C5 (melanoma). All the compounds exhibited strong to moderate activity against the MCF-7 cell line but weak or no activity against the NCI-H460 and A375-C5 cell lines. Sartoryglabin B was found to exhibit selectivity towards the MCF-7 cell line.