Application of preparative high-speed counter-current chromatography for the separation of flavonoids from the leaves of Byrsonima crassa Niedenzu (IK)

The methanolic extract of the leaves of the medicinal plant Byrsonima crassa (Malpighiaceae) contain flavonoids with antioxidant activity. They were separated in a preparative scale using high-speed counter-current chromatography. The optimum solvent system used was composed of a mixture of ethyl acetate-n-propanol-water (140:8:80 (v/v/v)) and led to a successful separation between monoglucosilated flavonoids (quercetin-3-O-alpha-L-arabinoside, quercetin-3-O-beta-D-galactoside) and the biflavonoid amentoflavone in only 3.5 h. The purities of quercetin-3-O-alpha-L-arabinoside (95 mg), quercetin-3-O-beta-D-galactoside (16 mg) and the biflavonoid amentoflavone (114 mg) were all isolated at purity over 95%. Identification was performed by 1H NMR, 13C NMR and UV analyses.     

Development of a simplified method for the simultaneous determination of retinol, α-tocopherol,and β-carotene in serum by liquid chromatography–tandem mass spectrometry with atmospheric pressure chemical ionization

A new and simple method for the determination of fat-soluble vitamins (retinol, alpha-tocopherol, and beta-carotene) in human serum was developed and validated by using liquid chromatography-tandem mass spectrometry with atmospheric pressure chemical ionization (LC-APCI-MS-MS). Different solvent mixtures were tested to obtain deproteinization and extraction of the analytes from the matrix. As a result, a volume of 240 microL of a 1:1 (v/v) ethanol/ethyl acetate mixture added to 60 microL of serum was found to be suitable for both protein precipitation and antioxidants solubilization, giving the best recovery for all three analytes. Deproteinized samples (20 microL) were injected after dilution, without the need for concentration or evaporation to dryness and reconstruction of the sample. Vitamins were separated on a C-8 column using a 95:5 (v/v) methanol/dichloromethane mixture and ionized in the positive-ion mode; detection was performed in the selected-reaction monitoring mode. Linearity of the LC-APCI-MS-MS method was established over 5 orders of magnitude for retinol and alpha-tocopherol, whereas in the case of beta-carotene it was limited to 4 orders. Lower limits of quantitation were 1.7, 2.3, and 4.1 nM for retinol, alpha-tocopherol, and beta-carotene, respectively. Serum concentrations of retinol, alpha-tocopherol, and alpha+beta-carotene determined in a group of healthy volunteers were 2.48, 38.07, and 0.50 microM, respectively, in samples collected in winter ( n=122) and 2.69, 45.88, and 0.90 microM during summer ( n=66).     

Simultaneous determination of the urinary metabolites of benzene, toluene, xylene and styrene using high-performance liquid chromatography/hybrid quadrupole time-of-flight mass spectrometry

A simple and rapid method using reversed-phase liquid chromatography/tandem mass spectrometry (LC/MS/MS) for the simultaneous determination of the urinary metabolites of benzene, toluene, xylene and styrene in human urine specimens and standard solutions is described. A hybrid quadrupole/time-of-flight (QqTOF) mass spectrometer was compared for the determination of metabolite of aromatic solvents in urine samples. The metabolites selected were: trans,trans-muconic acid, hippuric acid, o-, m- and p-methylhippuric acid and phenylglyoxylic acid. The compounds were well separated from each other on narrow-bore 1-mm i.d. reversed-phase LC C-18 columns. Average recoveries for loading 100 microL of urine samples varied from 88-110% and the quantification limits were less than 30 ng/mL for each analyte (3 ng/mL for trans,trans-muconic acid). The qualitative information obtained (mass accuracy, resolution and full-scan spectra) with the QqTOF mass spectrometer allows a secure identification of analytes in biological matrices.     

Small molecule control of bacterial biofilms

Bacterial biofilms are defined as a surface attached community of bacteria embedded in a matrix of extracellular polymeric substances that they have produced. When in the biofilm state, bacteria are more resistant to antibiotics and the host immune response than are their planktonic counterparts. Biofilms are increasingly recognized as being significant in human disease, accounting for 80% of bacterial infections in the body and diseases associated with bacterial biofilms include: lung infections of cystic fibrosis patients, colitis, urethritis, conjunctivitis, otitis, endocarditis and periodontitis. Additionally, biofilm infections of indwelling medical devices are of particular concern, as once the device is colonized infection is virtually impossible to eradicate. Given the prominence of biofilms in infectious diseases, there has been an increased effort toward the development of small molecules that will modulate bacterial biofilm development and maintenance. In this review, we highlight the development of small molecules that inhibit and/or disperse bacterial biofilms through non-microbicidal mechanisms. The review discuses the numerous approaches that have been applied to the discovery of lead small molecules that mediate biofilm development. These approaches are grouped into: (1) the identification and development of small molecules that target one of the bacterial signaling pathways involved in biofilm regulation, (2) chemical library screening for compounds with anti-biofilm activity, and (3) the identification of natural products that possess anti-biofilm activity, and the chemical manipulation of these natural products to obtain analogues with increased activity.     

A Luminescent and Sublimable Dy(III) -Based Single-Molecule Magnet

The reaction of [Ln(hfac)(3) ]?2?H(2) O and pyridine-N-oxide (PyNO) leads to isostructural dimers of the formula [Ln(hfac)(3) (PyNO)](2) (Ln=Eu, Gd, Tb, Dy). The Dy derivative shows a remarkable single-molecule magnet behavior with complex hysteresis at 1.4?K. The dynamics of the magnetization features are two relaxation regimes: a thermally activated one at high temperature (τ(0) =(5.62±0.4)×10(-11) s and Δ=(167±1)?K) and a quantum tunneling regime at low temperature with a tunneling frequency of 0.42?Hz. The analysis of the Gd derivative evidences intradimer antiferromagnetic interactions (J=(-0.034±0.001)?cm(-1) ). Moreover, the Eu, Tb, and Dy derivatives are luminescent with quantum yield of 51, 53, and 0.1?%, respectively. The thermal investigation of [Dy(hfac)(3) (PyNO)](2) shows that the dimers can be sublimated intact, suggesting their possible exploit as active materials for surface-confined nanostructures to be investigated by fluorimetry methods.     

Cavitand-functionalized porous silicon as an active surface for organophosphorus vapor detection

This paper reports on the preparation of a porous silicon-based material covalently functionalized with cavitand receptors suited for the detection of organophosphorus vapors. Two different isomeric cavitands, both containing one acid group at the upper rim, specifically designed for covalent anchoring on silicon, were grafted on H-terminated porous silicon (PSi) by thermal hydrosilylation. The covalently functionalized surfaces and their complexation properties were characterized by combining different analytical techniques, namely X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and mass spectroscopy analysis coupled with thermal desorption experiments. Complexation experiments were performed by exposing both active surfaces and a control surface consisting of PSi functionalized with a structurally similar but inactive methylene-bridged cavitand (MeCav) to dimethyl methylphosphonate (DMMP) vapors. Comparison between active and inactive surfaces demonstrated the recognition properties of the new surfaces. Finally, the nature of the involved interactions, the energetic differences between active and inactive surfaces toward DMMP complexation, and the comparison with a true nerve gas agent (sarin) were studied by DFT modeling. The results revealed the successful grafting reaction, the specific host-guest interactions of the PSi-bonded receptors, and the reversibility of the guest complexation.     

Copper-catalyzed amination of potassium aryl trifluoroborates using aqueous ammonia

The conversion of potassium aryl trifluoroborates containing different functionalities into the corresponding aryl amines using a catalytic amount of CuSO₄·5H₂O is described. The methodology uses water as a solvent under aerobic conditions to give the products in good yields.     

Dinuclear Cu(II) complexes of isomeric bis-(3-acetylacetonate)benzene ligands: synthesis, structure, and magnetic properties

Highly versatile coordinating ligands are designed and synthesized with two β-diketonate groups linked at the carbon 3 through a phenyl ring. The rigid aromatic spacer is introduced in the molecules to orient the two acetylacetone units along different angles and coordination vectors. The resulting para, meta, and ortho bis-(3-acetylacetonate)benzene ligands show efficient chelating properties toward Cu(II) ions. In the presence of 2,2'-bipyridine, they promptly react and yield three dimers, 1, 2, and 3, with the bis-acetylacetonate unit in bridging position between two metal centers. X-ray single crystal diffraction shows that the compounds form supramolecular chains in the solid state because of intermolecular interactions. Each of the dinuclear complexes shows a magnetic behavior which is determined by the combination of structural parameters and spin polarization effects. Notably, the para derivative (1) displays a moderate antiferromagnetic coupling (J = -3.3 cm(-1)) along a remarkably long Cu···Cu distance (12.30 ?).     

The correct assignment of stereochemistry in di‐μ‐dichlorido‐bis{bis[2‐(5‐benzylsulfonyl)‐3‐fluoro‐2‐(pyridin‐2‐yl)phenyl‐κ2N,C1]iridium(III)} toluene monosolvate

The title complex, [Ir₂(C₁₈H₁₃FNO₂S)₄Cl₂]·C₇H₈, was crystallized from dichloromethane solution under a toluene atmosphere. It is a dimeric complex in which each of the two Ir^III centres is octahedrally coordinated by two bridging chloride ligands and by two chelating cyclometalated 2‐(4‐benzylsulfonyl‐2‐fluorophenyl)pyridine ligands. The crystal structure analysis unequivocally establishes the trans disposition of the two cyclometalated ligands bound to each Ir^III centre, contrary to our previous hypothesis of a cis disposition. The latter was based on the ¹H NMR spectra of a series of dimeric benzylsulfonyl‐functionalized dichloride‐bridged iridium complexes, including the compound described in the present work [Ragni et al. (2009). Chem. Eur. J. 15 , 136–148]. The toluene solvent molecules, embedded in cavities in the crystal structure, are highly disordered and could not be modelled successfully; their contribution was removed from the refinement using the SQUEEZE routine in the program PLATON [Spek (2009). Acta Cryst. D 65 , 148–155].