Isolation and characterization of flavonols from blackcurrant by high-performance counter-current chromatography and electrospray ionization tandem mass spectrometry

Blackcurrant is considered as a natural high-value food raw material and possesses a variety of therapeutic properties. The health benefits of blackcurrant have generally been credited to its high anthocyanin content; however, the therapeutic properties of other minor flavonoids constituents have not yet been investigated due the difficulties related to their isolation. Multiple steps of high-performance counter-current chromatography in combination with ESI tandem mass spectrometry (MS(n)) were successfully used for the preparative isolation of flavonols from blackcurrant extract, to study their electrospray ionization mass spectrometry fragmentation behavior. Seven flavonols, namely myricetin-3-O-rutinoside (145.5 mg), myricetin-3-O-hexoside (79.7 mg), myricetin-3-O-(6″-malonyl)-glucoside (17.4 mg), kaempferol-3-O-glucoside (20.5 mg), quercetin-3-O-rutinoside (55.1 mg), quercetin-3-O-hexoside (25.8 mg), and myricetin (129.1 mg) have been successfully isolated and their multistage MS(n) data were used for detailed structure characterization. The results of these experiments demonstrated that high-performance counter-current chromatography along with ESI-MS(n) is a sensitive, selective, and effective technology for isolation and characterization of minor constituents from a complex mixture.     

Theoretical investigation of the electrochemical mechanism of water splitting on a titanium oxide cluster model

The step-by-step electrochemical mechanism of water splitting by removal of protons and electrons is examined for the reaction of one and two water molecules on a Ti(2)O(4) cluster. Density functional theory (B3LYP) and coupled cluster single point calculations are employed to compute gas phase reaction energies. The polarizable continuum model (PCM) is utilized to calculate energies in the aqueous phase. Both neutral and alkaline media are considered. Proton and electron removal steps are generally found to be highly endothermic, with the exception of proton removal steps in alkaline medium. The effect of an external potential on reaction energies is considered. Oxygen-oxygen bonds form after the removal of only two electrons.     

The Ultrasound-Promoted Aluminum Amalgam Reduction of Phthalimides to Hydroxy Lactams

A new method for the reduction of N-substituted phthalimides to the corresponding hydroxy lactams is described which utilizes aluminum amalgam and is promoted by high-intensity ultrasound. The ultrasonic irradiation serves to rapidly fragment the amalgam creating a reactive dispersion as well as increasing mass transport between solution and surface thereby accelerating the reaction rate. While the yields of hydrbxy lactams derived from the corresponding phthalimides are in the range of 69–94%, both N-benzyl glutarimide and N-benzyl succinimide are not reduced. The reduction does not affect the double bond or ester function of a representative α,β-enoate ester.     

Stability of the stationary motion of a spherical pendulum interacting with a string

The equation of motion of a spherical pendulum suspended at some point of a horizontal string is derived using a hybrid model of this mechanical system. The conditions for the asymptotic stability of the stationary motion of the spherical pendulum interacting with the elastic string are established     

Peptide fractionation by acid pH SDS-free electrophoresis

SDS-free polyacrylamide gel electrophoresis is an effective alternative approach to peptide fractionation. Here we describe a discontinuous buffer system at acid pH that improves the separation of acidic peptides from tryptic digestion. MOPS and chloride act as trailing and leading ions, respectively, in this system, while histidine operates as counterion and buffers all solutions. In these electrophoretic conditions, peptides with pI below 5.5 migrate with low overall electrophoretic mobilities but high differences from one another, which allows for their efficient resolution. In silico analysis of several proteomes shows that the acid pH system allows a peptide simplification of 2.5-fold with respect to the total peptide mixture, and still a proteome coverage of about 95% is achievable. A straightforward method with a protocol including proteomic studies was achieved for SDS-PAGE of proteins, enzyme treatment and further peptide fractionation by SDS-free acid PAGE.     

Comparative AFM nanoscratching tests in air of bulk copper and electrogenerated cuprous oxide films

The normal and lateral spring constants of rectangular silicon AFM cantilevers bearing pyramidal silicon tips were accurately calibrated using a procedure that takes into account their tilt compared to horizontal orientation and their trapezoidal cross section. Such systems were used to carry out nanoscratching tests in air on technical substrates presenting a moderate roughness (RMS ≈ 40 nm) and made either from bulk copper or from cuprous oxide thin films electrogenerated on copper. The various events occurring during these nanoscratching procedures were characterized in details. In particular, the features of the scars appearing on the scratched zones and SEM observations of the AFM tips used during the nanoscratching procedures are described and exploited to establish a better understanding of the effects of the nanoscratching procedures on the targeted samples. In the case of electrodeposited Cu₂O films, these effects are discussed with the help of chemical and structural characterizations using XPS and XRD studies. All this set of information is used i) to describe the history of the nanoscratching tests and ii) to compare mechanical resistance of bulk copper and electrogenerated Cu₂O thin films using these nanoscratching tests carried out in air. The wear mechanism occurring during nanoscratching tests is discussed for both kinds of samples and compared with the one observed during erosion in erosion–corrosion tests.     

Novel Spray Dried Algae-Rosemary Particles Attenuate Pollution-Induced Skin Damage

The present study investigated the effect of spray-dried algae-rosemary particles against pollution-induced damage using ex-vivo human biopsies exposed to diesel engine exhaust (DEE). For this, the complexation of hydroalcoholic rosemary extract with Chlorella (RCH) and Spirulina (RSP) protein powders was conducted. The process efficiency and concentration of rosmarinic acid (RA), carnosic acid (CA), and carnosol (CR) phenolic compounds of both products were compared. The RSP spray-dried production was more efficient, and RSP particles presented higher CR and CA and similar RA concentrations. Therefore, spray-dried RSP particles were prioritized for the preparation of a gel formulation that was investigated for its ability to mitigate pollution-induced skin oxinflammatory responses. Taken altogether, our ex-vivo data clearly demonstrated the ability of RSP gel to prevent an oxinflammatory phenomenon in cutaneous tissue by decreasing the levels of 4-hydroxynonenal protein adducts (4HNE-PA) and active matrix metalloproteinase-9 (MMP-9) as well as by limiting the loss of filaggrin induced by DEE exposure. Our results suggest that the topical application of spirulina-rosemary gel is a good approach to prevent pollution-induced skin aging/damage.