Evaluation of propolis polyphenols absorption in humans by liquid chromatography/tandem mass spectrometry

Propolis has various biological activities such as antibacterial, antiviral, antioxidant, immunostimulating and antiinflammatory, which are generally ascribed to the polyphenolic fraction. The aim of this study was to evaluate the absorption of the main polyphenols [caffeic acid (CA), pinobanksin-5methyl ether (P-5ME), pinobanksin (Pb), chrysin (C), pinocembrin (P), galangin (G), pinobanksin-3-acetate, pinobanksin esters and caffeic acid phenylethyl ester (CAPE)] from a dewaxed and standardized extract of propolis (EPID). Fifteen healthy volunteers consumed 5 mL EPID in water, corresponding to 125 mg of flavonoids. Blood samples were collected before, each hour for 8 h and 24 h after EPID intake. After deconjugation by beta-glucuronidase/sulfatase the plasma samples were analyzed by a selective liquid chromatography/tandem mass spectrometry (LC/MS/MS) method using morin as internal standard (I.S.). A kinetic profile characterized by two t(max), respectively at 1 h and about 5 h post-ingestion, was observed in all the subjects. The two peaks may be due to enterohepatic cycling. Among the various polyphenols ingested, only P-5ME, Pb, C, P and G were detected in plasma and C(max)t(1h) were 65.7 +/- 13.3, 46.5 +/- 12.7, 79.5 +/- 18.6, 168.1 +/- 16.3 and 113.7 +/- 16.8 ng/mL, respectively. These levels decreased significantly after 8 h and were no longer detectable 24 h after EPID intake. The recovery of the extraction for CA, Pb, C, P, G and I.S. from spiked plasma was 95.2 +/- 3.1, 93.1 +/- 3.6, 91 +/- 2.5, 96.4 +/- 4.2, 93.4 +/- 2.4 and 85.5 +/- 2.4%, respectively. The results of this study evidence that flavonoids from EPID are absorbed, metabolized and Pb-5ME and G seem to have apparent absorption, measured as (AUC/dose), higher than C, P and Pb.     

Lignans and secoiridoid glycosides from the stem barks of Jasminum tortuosum

This paper reports on the first phytochemical analysis ever performed on Jasminum tortuosum Willd. This analysis, mainly carried out by means of column chromatography separation, NMR spectroscopy and mass spectrometry, led to the isolation and the identification of four compounds, namely the lignans ginkgool (1) and olivil-4′-O-β-glucopyranoside (2) and the secoiridoids oleoside dimethyl ester (3) and oleoside 11-methyl ester (4). The presence of these compounds is significant from a chemotaxonomic point of view, confirming the correct botanical classification of the species and, from a phytochemical standpoint, may suggest its possible use in the ethno-medicinal field.     

Silylating Agents Grafted onto Silica Derived from Leached Chrysotile

Silica from leached chrysotile fibers (SILO) was silanized with trialkoxyaminosilanes to yield inorganic–organic hybrids designated SILx (x=1–3). The greatest amounts of the immobilized agents were quantified as 2.14, 1.90, and 2.18 mmol g⁻¹ on SIL1, SIL2, and SIL3 for –(CH₂)₃NH₂,–(CH₂)₃NH(CH₂)₂NH₂, and –(CH₂)₃NH(CH₂)₂NH(CH₂)₂NH₂ groups attached to the inorganic support. The infrared spectra for all modified silicas showed the absence of the Si–OH deformation mode, originally found at 950 cm⁻¹, and the appearance of asymmetric and symmetric C–H stretching bands at 2950 and 2840 cm⁻¹. Other important bands associated with the organic moieties were assigned to ν_as(NH) at 3478 and ν_sym(NH) at 3418 cm⁻¹. The NMR spectrum of the solid precursor material suggested two different kinds of silicon atoms: silanol and siloxane groups, between −90 and 110 ppm; however, additional species of silicon that contain the organic moieties bonded to silicon at −58 and −66 ppm appeared after chemical modification. These modified silicas showed a high adsorption capacity for cobalt and copper cations in aqueous solution, in contrast to the original SILO matrix, confirming the unequivocal anchoring of silylating agents on the silica surface.     

The Pesticide 3-(3,4-Dichlorophenyl)-1,1-dimethylurea (Diuron) Immobilized on Silica Gel Surface

A route for 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron) immobilization on silica gel was established after reacting at the first stage the precursor silylant agent 3-trimethoxysilylpropylamine to the support. The pesticide was covalently bonded to available amine groups of the precursor, giving 1.03 mmol of amine per gram of silica. Infrared, (13)C, and (29)Si NMR spectra are in agreement with the proposed reaction between nitrogen of the amine group of the previously anchored silica to carbon on the para-position of the aromatic ring of the pesticide. The immobilization is clearly affected by the presence or absence of disprotonating agent, to give 12.50 and 68.40% reaction yield, respectively; these results were confirmed through elemental analysis. Copyright 2001 Academic Press.     

New Factorial Designs to Evaluate Chemisorption of Divalent Metals on Aminated Silicas

Adsorption processes of Cu(II), Co(II), and Hg(II) on two aminated silica gel surfaces with immobilized ethylenediamine and diethylenediamine groups were studied by a new 2(3) full factorial design. Two metal quantity levels, temperatures of 25 and 50 degrees C, and silica amounts of 100 and 200 mg were employed. Our study indicates that higher factorial design levels increase adsorption for all metals evaluated, with the exception of the mass parameter. Adsorption is also significantly affected by important antagonistic and synergistic effects involving all factors. Both functionalized silica gel surfaces present higher interactions and good perspectives in preconcentration studies for mercury. The factorial design results are also discussed in terms of some solvation properties for each of the metals studied. Copyright 2001 Academic Press.     

Di­bromo{N-[2-(di­phenyl­phosphino)­benzyl­idene]-2,6-diiso­propyl­aniline-κ2N,P}nickel

In the title compound, [NiBr₂(C₃₁H₃₂NP)], (I), the second reported example of a nickel–imino­phosphine N,P-chelate in which the Ni atom has tetrahedral coordination, the Ni coordination is distorted as a consequence of the N—Ni—P chelate bite angle of 91.07 (6)° compensated by the Br—­Ni—­Br angle of 126.385 (18)°. In (I) and its analogue, viz. dichloro{[2-(4-isobutyloxazol-2-yl)phenyl]diphenylphos­phine-N,P}nickel(II), the Ni—N and Ni—P distances are greater and the N—Ni—P ligand bite angles smaller than those observed in a series of related complexes with square-planar nickel.     

Crystal structures and order‐disorder phenomena in polymers

The crystal structure of various polymers, presenting symmetry breaking, is discussed. Owing to the presence of disorder, the crystal structure of polymers is generally described in term of ideal modifications, a limit ordered form, characterized by ideal three‐dimensional order, and a limit disordered form, characterized by the presence of statistical disorder in the packing, while preserving the order in the parallelism of the chains. The real crystalline forms are generally intermediate between the limit ordered and limit disordered models. The occurrence of conformational disorder, which produce defects frozen in the crystals of syndiotactic polypropylene, is analyzed.     

Structural flexibility and role of vicinal 2-thienyl rings in 2,3-dicyano-5,6-di(2-thienyl)-1,4-pyrazine, [(CN)2Th2Pyz], its palladium(II) complex [(CN)2Th2Pyz(PdCl2)2], and the related pentametallic pyrazinoporphyrazines [(PdCl2)4Th8TPyzPzM] (M = Mg(II)(H2O), Zn(II))

The solid state and solution structure of 2,3-dicyano-5,6-di(2-thienyl)-1,4-pyrazine, [(CN)(2)Th(2)Pyz], and its Pd(II) derivative, [(CN)(2)Th(2)Pyz(PdCl(2))(2)]·H(2)O, formed by reaction of [(CN)(2)Th(2)Pyz] with [(C(6)H(5)CN)(2)PdCl(2)] were characterized by X-ray, UV-visible, (1)H and (13)C NMR, and extended X-ray absorption fine structure (EXAFS) spectral measurements. The X-ray crystal structure of [(CN)(2)Th(2)Pyz] shows the presence of one thienyl ring positioned orthogonal to the rest of the molecule, with the two vicinal thienyl rings lying orthogonal to each other in a rare arrangement. NMR studies of [(CN)(2)Th(2)Pyz] in the solid state and in solutions of dimethylformamide or dimethyl sulfoxide confirm a nonequivalence of the thienyl rings in the solid state and also in solution. EXAFS results indicate that two distinct Pd(II) coordination sites are formed at the di(2-thienyl)pyrazino moiety of [(CN)(2)Th(2)Pyz(PdCl(2))(2)]·H(2)O, with identical Pd-N(pyz) (2.03(3) ?) and Pd-Cl (2.36(3) ?) bond lengths but with different Pd-S1 (2.25(4) ?) and Pd-S2 (3.21(5) ?) bond distances in an overall asymmetric molecular framework. Density functional theory (DFT) and time-dependent DFT (TDDFT) theoretical studies also provide information about the structure and spectral behavior of the precursor and its metalated Pd(II) derivative. (1)H/(13)C NMR and UV-visible spectral measurements were also carried out on two heteropentametallic porphyrazine macrocycles which were prepared by a reaction of PdCl(2) with [Th(8)TPyzPzM] where Th(8)TPyzPz = tetrakis-2,3-[5,6-di-(2-thienyl)-pyrazino]porphyrazinato dianion and M = Mg(II)(H(2)O) or Zn(II). Spectroscopic data on the newly synthesized [(PdCl(2))(4)Th(8)TPyzPzM] compounds suggest that the binding of PdCl(2) involves coordination sites of the type S(2(th))PdCl(2) with the two thienyl rings of each di(2-thienyl)pyrazino fragment bound to Pd(II) in an equivalent manner ("th-th" coordination). This is similar to what was found for the corresponding octapyridinated analogues ("py-py" coordination).