Edward Szłyk

Determination of antioxidant capacities of vegetable oils by ferric-ion spectrophotometric methods

Two ferric-ion-based total antioxidant capacity methods: 1,10-phenanthroline (Phen) and ferric reducing antioxidant power (FRAP) were used for determination of antioxidant capacities (AC) of the acetonic and methanolic extracts of vegetable oils. The obtained mean Phen and FRAP values for acetonic extracts of olive oils, rapeseed, rice and four sunflower oils (39.3-336.5 and 39.5-339.6 micromol Fe/100g) were higher than for methanolic extracts (22.8-307.3 and 23.5-300.1 micromol Fe/100g). However, antioxidant capacities of methanolic extracts of corn oil, blended oils and two sunflower oils with garden green flowers (56.5-312.9 and 53.9-306.5 micromol Fe/100g for Phen and FRAP methods, respectively) were higher than for acetonic extracts of these oils (54.2-249.2 and 52.9-244.7 micromol Fe/100g for Phen and FRAP methods, respectively). There is a linear and significant correlation between these two analytical methods (r=0.9989 and 0.9986 for acetonic and methanolic extracts). Also, total phenolic compounds (TPC) in the studied oils correlated with their antioxidant capacities determined by Phen and FRAP methods (r=0.9012, 0.7818 and 0.8947, 0.7830 for acetonic and methanolic extracts, respectively). The comparable precision (R.S.D.=0.8-4.6%, 0.9-4.9% and 0.7-4.0%, 0.6-4.0% for acetonic and methanolic extracts, respectively) and sensitivity (epsilon=1.27 x 10(4), 1.11 x 10(4) and 2.62 x 10(4)dm(3)mol(-1)cm(-1)) for the proposed Phen and the modified FRAP methods, demonstrate the benefit of the Phen method in the routine analysis of antioxidant capacities of vegetable oils.

Effect of refining processes on antioxidant capacity, total contents of phenolics and carotenoids in palm oils

Antioxidant capacity (AC), total phenolic content (TPC) and total carotenoid content (TCC) in palm oils at various stages of the refining process from two technological modes were determined. The obtained mean FRAP and DPPH values for the methanolic extracts of palm oils from mode 1 (19.5-102.8μmol TE/100g and 18.8-103.0μmol TE/100g) were lower than for oils from mode 2 (25.6-134.8μmol TE/100g and 25.4-135.4μmol TE/100g). The total phenolics (4.1-12.4mg GA/100g) and carotenoids (0.18-45.8mg/100g) in the studied oils were correlated with their antioxidant capacities determined by FRAP and DPPH methods (r=0.6623-0.9878). During the refining process, for both technological modes resulted in a loss of AC by 80%, TPC by 26-55% and TCC by 99%. The bleaching step caused the highest losses of AC as determined by FRAP 41% and 46%, DPPH by 43% and 48%, while TPC loss was 45% and 23% and loss of carotenoids was 49% and 56%, in mode 1 and mode 2, respectively.

The X-ray structure and spectroscopy of platinum(II) complexes with 1,2,4-triazolo[1,5-a]pyrimidines and dimethylsulfoxide

Abstract Platinum(II) complexes with 1,2,4-triazolo[1,5-a]pyrimidines of general formula trans-[PtCl2(dmso)(L)], where L=1,2,4-triazolo[1,5-a]pyrimidine (tp), 5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine (dmtp), 5,7-diphenyl-1,2,4-triazolo[1,5-a]pyrimidine (dptp), 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine (dbtp) have been prepared by direct reaction between cis-[PtCl2(dmso)2] and respective 1,2,4-triazolo[1,5-a]pyrimidine in molar ratio M:L=1:1. All new platinum(II) compounds were characterized by 1H, 13C, 15N, 195Pt NMR and IR. Significant 15N NMR upfield shifts (75–87 ppm) were observed for N(3) atom indicating this nitrogen atom as a coordination site. Crystal structure of trans-[PtCl2(dmso)(dmtp)] (2) has been determinated. The molecular structure indicates that Pt(II) ion has the square-planar geometry with N(3) bonded dmtp, S-bonded dimethylsulfoxide and two trans chloride anions.

CVD of AgI complexes with tertiary phosphines and perfluorinated carboxylates : A new class of silver precursors

C 2 F 5 COOAgPMe 3 (1) and C 2 F 5 COOAg (2) have been used as precursors for the CVD of silver layers in the temperature range 493-623 K. The thin films obtained were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), scanning tunneling electrochemical microscopy (STEM), X-ray photoelectron spectroscopy (XPS), and temperature variable infrared (IR) measurements. The SEM images of Ag films grown from 2 exhibited a surface with a grain size in the range 0.4-1.5 μm, whereas from 1 the size was ∼0.1 μm. This was confirmed by the STEM studies. The better stability of 1 in the vapor phase was proved by temperature variable IR spectra (373-523 K). Mass spectrometry (MS) images confirmed the presence of the monomeric and dimeric species, and the recombination ions transported in vapors. The XPS image analysis of the silver layers revealed the presence of some carbon impurities. The films demonstrated good adhesion to silicon substrates.

Structural correlations for 1H, 13C and 15N NMR coordination shifts in Au(III), Pd(II) and Pt(II) chloride complexes with lutidines and collidine

1H, 13C and 15N NMR studies of gold(III), palladium(II) and platinum(II) chloride complexes with dimethylpyridines (lutidines: 2,3‐lutidine, 2,3lut; 2,4‐lutidine, 2,4lut; 3,5‐lutidine, 3,5lut; 2,6‐lutidine, 2,6lut) and 2,4,6‐trimethylpyridine (2,4,6‐collidine, 2,4,6col) having general formulae [AuLCl3], trans‐[PdL2Cl2] and trans‐/cis‐[PtL2Cl2] were performed and the respective chemical shifts (δ1H, δ13C, δ15N) reported. The deshielding of protons and carbons, as well as the shielding of nitrogens was observed. The 1H, 13C and 15N NMR coordination shifts (Δ1Hcoord, Δ13Ccoord, Δ15Ncoord; Δcoord = δcomplex − δligand) were discussed in relation to some structural features of the title complexes, such as the type of the central atom [Au(III), Pd(II), Pt(II)], geometry (trans‐ or cis‐), metal‐nitrogen bond lengths and the position of both methyl groups in the pyridine ring system. Copyright

Spectroscopy and stereochemistry of the optically active copper(II), cobalt(II) and nickel(II) complexes with Schiff bases N,N′-(1R,2R)-(−)-1,2-cyclohexylenebis(3-methylbenzylideneiminato) and N,N′-(1R,2R)-(−)-1,2-cyclohexylenebis(5-methylbenzylideneiminato)

Abstract Schiff bases obtained from N,N′-(1R,2R)-1,2-cyclohexanediamine and 2-hydroxy-3-methylbenzaldehyde, 2-hydroxy-5-methylbenzaldehyde, have been used as ligands for copper(II), cobalt(II) and nickel(II). The complexes were characterized with UV–Vis, circular dichroism (CD), infrared, diamagnetic and paramagnetic 1H NMR spectroscopy. CD spectra revealed exciton coupled π→π* transitions. Assignments of LMCT and d–d transitions in CD spectra of Ni(II), Co(II) and Cu(II) complexes is proposed. CD data are characteristic for central ion tetrahedral distortion from the planarity and λ conformation of the cyclohexane ring. 1H NMR of Ni(II) complexes exhibited significant coordination shifts of CHN and ring protons which are in the closest proximity to Ni(II). The 1H NMR paramagnetic spectra of Co(II) complexes revealed the most upfield shifted resonance at −60 ppm assigned to CHN and −28 ppm to hydrogen atom at C(5′) of the phenyl ring. Results of spectral analyses suggest central ions in a distorted square-planar geometry with N2O2 chromofore group.

Determination of phosphorus in food samples by X-ray fluorescence spectrometry and standard spectrophotometric method

The Wavelength Dispersive X-ray fluorescence (WD XRF) determination of phosphorus in GMO and non GMO food samples is proposed. The tested materials included commercially available transgenic, unmodified soya-foods and popular dairy products. The WD XRF method was compared with the standard molybdenum blue method. Matrix effects were minimised by using standard reference material. Obtained results were discussed in respect of the accuracy, statistical parameters and values recommended by the Recommended Dietary Allowance (RDA). The results indicate the validity of the proposed methods to routine food analysis.

Spectrophotometric determination of total phosphorus in rape seeds and oils at various stages of technological process: calculation of phospholipids and non-hydratable phospholipids contents in rapeseed oil

Abstract A new spectrophotometric method for determination of total phosphorus in rape seeds and rapeseed oils is described. The procedure is based on formation of the ionic—associate of molybdophosphate with Malachite Green (MG) in an acidic medium and compared with the standard vanadomolybdate and molybdenum blue methods. Satisfactory values of recovery ranged between 99.1–100.3% and RSD

The X-ray structure of bis(5,7-dimethyl-1,2,4-triazolo-[1,5α]-pyrimidinium) hexachloroplatinate(IV) and spectroscopic properties of Pt(II) and Pt(IV)chloride complexes with 1,2,4-triazolo-[1,5α]-pyrimidines

Abstract Pt(II) and Pt(IV) chloride complexes with 1,2,4-triazolo-[1,5α]-pyrimidines: trans-[Pt(tp)2Cl2], trans-[Pt(dmtp)2Cl2], trans-[Pt(tp)2Cl4] and trans-[Pt(dmtp)2Cl4] where tp=1,2,4-triazolo-[1,5α]-pyrimidine and dmtp=5,7-dimethyl-1,2,4-triazolo-[1,5α]-pyrimidine were synthesised and studied by 1H, 13C, 15N, 195Pt NMR and IR spectroscopies. Significant 15N NMR upfield coordination shifts (92–96 ppm) were observed for the N(3) atom indicating that this nitrogen is the metallation site. The X-ray structure of an ionic pair (dmtpH)2[PtCl6] {bis(5,7-dimethyl-1,2,4-triazolo-[1,5α]-pyrimidinium) hexachloroplatinate(IV)} was determined, exhibiting the presence of unique (dmtpH)22+ dimeric cations, protonated at N(3), N(3′) atoms and linked by hydrogen bonding.

Determination of toxic metals by ICP-MS in Asiatic and European medicinal plants and dietary supplements.

The potentially toxic metals content was determined in selected plants, used in Traditional Chinese Medicine (Angelica sinensis, Bacopa monnieri, Bupleurum sinensis, Curcuma longa, Cola accuminata, Emblica officinalis, Garcinia cambogia, Mucuna pruriens, Ocimum sanctum, Panax ginseng, Pueraria lobata, Salvia miltiorrhiza, Schisandra sinensis, Scutellaria baicalensis, Siraitia grosvenorii, Terminalia arjuna and Terminalia chebula), and some European herbs (Echinacea purpurea, Hypericum perforatum, Vitis vinifera). Samples were mineralized in a closed microwave system using HNO3 and the concentrations of Cd, Pb, Al, As, Ba, Ni and Sb were determined by ICP-MS method. Some relevant aspects of potential toxicity of metallic elements and their compounds were also discussed. Results of metal content analysis in dietary supplements available on Polish market, containing studied plants, are presented as well. The results were analyzed by principal component analysis (PCA) and cluster analysis.