Profiling and quantifying polar lipids in milk by hydrophilic interaction liquid chromatography coupled with evaporative light-scattering and mass spectrometry detection

In this work, a high-performance liquid chromatography with evaporative light scattering detection method has been developed and applied for quantification of the polar content of the lipid fraction in milk samples of different origin. From a chromatographic stand-point, a 4.6-mm I.D. hydrophilic interaction liquid chromatography column was employed to attain a baseline separation of major phospholipid classes contained in the various milk samples tested. Quantitative analysis was performed by the external calibration method using reference material solutions in the 5–100 mg/L concentration range. Analytical recoveries ranging from 57 to 100 %, and repeatability data lower than 8.04 % were obtained on a skimmed cow’s milk sample. The crude cow milk was the most abundant (0.04 %) in phospholipids and donkey milk was the poorest (0.004 %). Quantitative differences were determined in the phospholipid content of the milk samples tested. Finally, characterization of phospholipid profile and fatty acid composition of the different samples was carried out by an ion trap-time of flight mass spectrometer and gas chromatography coupled to flame ionization and mass spectrometry detection. A thorough screening of the polar lipid composition of milk samples of different origin is here outlined, for the first time.     

Chemical composition and possible in vitro antigermination activity of three Hypericum essential oils

The essential oils of Hypericum perforatum, H. perfoliatum and H. hircinum, growing in Southern Italy, were analyzed by GC and GC/MS. In the three oils, 111 compounds in all were identified: 53 for the oil of H. hircinum (93.7% of the total oil), 55 for H. perforatum (96.5% of the total oil) and 63 for H. perfoliatum (98.7% of the total oil). The major fraction of the essential oils of H. perforatum and H. hircinum was represented by sesquiterpene hydrocarbons, while the monoterpene alpha-pinene, and the phenol thymol were the most abundant compounds in the essential oil of H. perfoliatum. The oils were evaluated for their potential in vitro phytotoxic activity against germination and early radicle elongation of Raphanus sativus and Lepidium sativum. The germination of this latter was significantly inhibited by the essential oil of H. hircinum, at the highest doses tested, whereas radicle elongation of garden cress was significantly inhibited by the essential oils of H. perfoliatum and H. hircinum. The radicle elongation of radish was inhibited by the essential oil of H. hircinum to a major extent and by H. perforatum and perfoliatum in a minor measure.     

Thermogravimetric and kinetic methods to date wood finds. First results

Fresh (larch and fir, in its white and red varieties) and ancient wood samples (dating respectively to the 13th, 15th and 17th centuries) were subjected to thermogravimetric analysis (TG and DTG). The resulting thermogravimetric data were then used to construct archeometric curves for the wood varieties tested. In a preliminary approach, it was attempted to correlate the onset temperature of the thermogravimetric step corresponding to cellulose decomposition with the age (expressed in centuries) of the samples, although the results obtained were anything but brilliant. More encouraging results were obtained by examining the relationship between wood sample age and the value of the (percent cellulose/percent lignin) ratio computed from the thermogravimetric data. Lastly, a procedure for processing data obtained from the TG curves was applied to a kinetic analysis of the processes that take place when wood samples are subjected to a temperature regime with a constant heating rate, obtaining values for the activation energy of the TG step corresponding to the decomposition of cellulose. Also using these data it was attempted to construct archeometric curves, obtaining results that varied quite significantly according to the wood species tested.     

Preparation of "high specific activity" radiochemical forms of vanadium,manganese and thallium for metallo-toxicological studies

In this paper are presented the production methods for very "high specific activity" radionuclides (HSA-RN) of vanadium, manganese and thallium which have been developed in our laboratories for labelling different chemical forms of these elements present in the echo-systems in ultra-trace amounts, for metallo-toxicological and bio-kinetic studies. Use was made of both cyclotron and thermal nuclear reactor. If the nuclear reaction product has atomic number different from irradiated target, it is possible separating the radioactive nuclide from irradiated target, without addition of isotopic carrier. This kind of radionuclide is named No Carrier Added, NCA, and his specific activity, As is very high and can reach values close to the theoretical Carrier Free one, CF. The experimental determination of specific activity, chemical and radiochemical purities is mandatory for all these kinds of applications.     

Quantum mechanical calculations of NMR J coupling values in the determination of relative configuration in organic compounds

[structure: see text] An approach relying on quantum mechanical calculations of proton-proton and proton-carbon J coupling values is proposed as a tool for assigning the relative configuration on chiral organic compounds. The method is suitable for carbon frameworks containing several adjacent stereogenic centers and may allow significant advances in the extensive use of spin-spin couplings in structural elucidation.     

TBAF-catalyzed synthesis of 5-substituted 1H-tetrazoles under solventless conditions

Tetrabutylammonium fluoride (TBAF) is an efficient catalyst in the [3 + 2] cycloaddition reaction of organic nitriles 1 with trimethylsilyl azide (TMSN(3)) in solventless conditions. The corresponding 5-substituted 1H-tetrazoles 2 were obtained under mild conditions and in 80-97% yields.     

Synthesis of Lewis a and Lewis X Pentasaccharides Based on N-Trichloroethoxycarbonyl Protection 1

Abstract

Thexyldimethylsilyl 4,6-O-benzylidene-2-deoxy-2-trichloroethoxycarbonylamino-β-D- glucopyranoside (4), having the 3-hydroxy group unprotected, is a versatile starting material for the synthesis of glucosamine containing oligosaccharides. Thus, reaction with galactosyl donor 5 or fucosyl donor 6 afforded the desired β(1-3)- and α(1-3)-linked disaccharides 7 and 8, respectively, in high yields. Reductive opening of the benzylidene moieties in 7 and 8 gave access to the 4-hydroxy groups in 9 and 10. Ensuing fucosylation of 9 or galactosylation of 10 led to Lewis A (Le^a) and Lewis X (Le^x) trisaccharide building blocks 13 and 14, respectively. Their transformation into glycosyl donors 19 and 20 and subsequent reaction with 3b-O-unprotected lactose derivative 23 as acceptor furnished the Le^a? and Le^x pentasaccharide precursors 24 and 25. Exchange of the N-trichloroethoxycarbonyl group for an N-acetyl group and removal of the O-benzyl and O-acetyl protective groups afforded the desired Le^a? and Le^x? pentasaccharides 1 and 2.

     

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.     

Intramolecular Participation of Amino Groups in the Cleavage and Isomerization of Ribonucleoside 3′‐Phosphodiesters: The Role in Stabilization of the Phosphorane Intermediate

A dinucleoside‐3′,5′‐phosphodiester model, 5′‐amino‐4′‐aminomethyl‐5′‐deoxyuridylyl‐3′,5′‐thymidine, incorporating two aminomethyl functions in the 4′‐position of the 3′‐linked nucleoside has been prepared and its hydrolytic reactions studied over a wide pH range. The amino functions were found to accelerate the cleavage and isomerization of the phosphodiester linkage in both protonated and neutral form. When present in protonated form, the cleavage of the 3′,5′‐phosphodiester linkage and its isomerization to a 2′,5′‐linkage are pH‐independent and 50–80 times as fast as the corresponding reactions of uridylyl‐3′,5′‐uridine (3′,5′‐UpU). The cleavage of the resulting 2′,5′‐isomer is also accelerated, albeit less than with the 3′,5′‐isomer, whereas isomerization back to the 3′,5′‐diester is not enhanced. When the amino groups are deprotonated, the cleavage reactions of both isomers are again pH‐independent and up to 1000‐fold faster than the pH‐independent cleavage of UpU. Interestingly, the 2′‐ to 3′‐isomerization is now much faster than its reverse reaction. The mechanisms of these reactions are discussed. The rate accelerations are largely accounted for by electrostatic and hydrogen‐bonding interactions of the protonated amino groups with the phosphorane intermediate.