Role of catechin on collagen type I stability upon oxidation: a NMR approach

Abstract

The study focuses on the understanding, at molecular level, the mechanism of interaction between protein and flavonoids. Collagen and catechin interactions were investigated by NMR in solution and solid state. The effect of catechin on the stability of collagen to oxidation was also explored. Collagen was treated with two concentrations of catechin solutions. Oxidation was carried out by incubation of collagen solution with three oxidation systems: Fe(II)/H₂O₂, Cu(II)/H₂O₂, and NaOCl/H₂O₂. The effects of oxidation systems were evaluated by high resolution 1?D and 2?D proton spectroscopy and solid state NMR (¹³C CP MAS) experiments. Interactions between collagen and catechin preferentially occur between catechin B ring and the amino acids Pro and Hyp of collagen. Results showed that both iron and copper oxidation systems were able to interact with collagen by site specific attack. Moreover, catechin protects collagen proline from oxidation by metal/H₂O₂ systems, preventing copper and iron approach to collagene molecule;this behaviour was more evident for the copper/H₂O₂ system.     

Circular‐Dichroism Studies on Artemisinin and Epiartemisinin and Their β‐Cyclodextrin Complexes in Solution

The circular dichroism (CD) spectra of the powerful antimalarian active principle artemisinin (ART; 1 ) from Artemisia annua, and of epiartemisinin (EPI, 2), its C(7) epimer, were studied in solution in the presence and absence of β‐cyclodextrin (β‐cd). A significant inversion of sign in the region of the second electronic transition was detected. The rotational strengths were successfully calculated within the time‐dependent density functional theory (DFT), which enabled us to establish a correlation between the molecular recognition and the biological acitivities of the two isomers.     

Acetylation and molecular mass effects on barrier and mechanical properties of shortfin squid chitosan membranes

Chitosan samples with different N-deacetylation levels were obtained from β-chitin under heterogeneous alkali conditions. Oxidative depolymerisation was performed to attain low-acetylated chitosan samples with different molecular mass. Water vapour permeability, membrane swelling and tensile mechanical properties were analysed in plasticized self-supporting chitosan membranes. The main purpose was to describe unambigously the effect of the biopolymer molecular mass and acetylation degree on these properties. Commercially available chitosan samples derived from α-chitin were also studied for comparison. The equilibrium degree of swelling in water and the water vapour permeability increase by increasing the molecular mass or the degree of acetylation. Regarding the effect on the mechanical properties, generally harder and tougher membranes were obtained for chitosans with higher molecular mass or lower acetylation degree. These observations are tentatively explained based on the different structural characteristics of the polymer and can lead to a better understanding of the tools necessary to tailor a specific type of chitosan membrane.     

Preparative Droplet Counter-Current Chromatography for the Separation of the New Nor-Seco-Triterpene and Pentacyclic Triterpenoids from Qualea Parviflora

The methanolic extract of the bark of the medicinal plant Qualea parviflora (Vochysiaceae) contains new nor-seco-triterpene and pentacyclic triterpenoids. They were separated in a preparative scale using droplet counter-current chromatography. The optimum solvent used was composed of a mixture of CHCl₃/MeOH/H₂O (43:37:20, v/v) in the descending mode and led to a successful separation of the new compound 28-nor-17, 22-seco-2α, 3β, 19, 22, 23-pentahydroxy-Δ¹²-oleanane, besides the known triterpenoids bellericagenin B, bellericaside B and arjunglucoside I . Identification was performed by ESI-MS, ¹H NMR and ¹³C NMR analyses.     

On the equivalence between the energy and virial routes to the equation of state of hard-sphere fluids

The energy route to the equation of state of hard-sphere fluids is ill defined since the internal energy is just that of an ideal gas, and thus it is independent of density. It is shown that this ambiguity can be avoided by considering a square-shoulder interaction and taking the limit of vanishing shoulder width. The resulting hard-sphere equation of state coincides exactly with the one obtained through the virial route. Therefore, the energy and virial routes to the equation of state of hard-sphere fluids can be considered as equivalent.     

Trace and major elements in serum of patients with chronic myelogenous leukemia

Summary Major and trace elements were determined in serum of patients with chronic myelogenous leukemia (CML) using total reflection X-ray fluorescence induced by synchrotron radiation (SRTXRF). CML affects 1 to 2 people per 100,000 and accounts for 7-20% cases of leukemia. It was possible to determine the concentrations of the following elements: P, S, Cl, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Br and Rb. Using analysis of variance (ANOVA) it was observed that the contents of the P, S, Ca, Cr, Mn, Fe, Cu and Rb elements differed significantly at a = 0.05 between groups of healthy subjects and CML patients and also genders (males and females).     

Formation of a nanostructured layer on bioglass particles of different sizes immersed in tris-buffered solution. N2 adsorption and HR-TEM/EDS analysis

Morphological and structural variations of particles of Bioglass with two different grain sizes reacted in Tris-buffered solution were analyzed by means of N(2) adsorption/desorption at 77 K and HR-TEM/EDS. A remarkable increase in specific surface area (ssa) was observed after the first hour of dissolution. A plateau value corresponding to an increase of at least 2 orders of magnitude was reached after 2 days of dissolution. The ssa increase was faster for the smaller particle size sample, and the ratio between the ssa of the starting samples was not maintained during dissolution. Both micro- and mesopores were formed at different stages of the reaction for the two samples. Increasing ssa was also connected to the formation of a microcrystalline structure rich in Ca and P, as shown by TEM images. The segregation of both a SiO(2)-rich amorphous phase and a Ca/P-rich crystalline phase was observed after the first hour of dissolution. After 2 days of reaction, Ca/P-rich particles made of fine aciculate crystals were found either in close contact with SiO(2) particles or deposited on a small SiO(2)-rich core. A preliminary analysis of TEM data showed the formation, together with hydroxy carbonate apatite, of different types of calcium phosphates not detectable by powder X-ray diffraction.     

Rapid determination of aliphatic amines in water samples by pressure-assisted monolithic octadecylsilica capillary electrochromatography-mass spectrometry

A pressure-assisted capillary chromatography-mass spectrometry method based on the use of a monolithic octadecylsilica (ODS) capillary is proposed for the determination of aliphatic amines. A 25 mM citric acid buffer containing 10% methanol is used as running electrolyte. Separation is achieved by simultaneously applying a capillary electrophoresis (CE) voltage of 13 kV and an overimposed pressure of 8 bar. The use of pressure is required to ensure stable electrospray conditions. Analysis times are reduced by using a capillary column consisting of a 30 cm long monolithic silica capillary column bound with ODS and a fused-silica capillary column also 30 cm long. The proposed method was successfully applied to the determination of low-molecular-weight aliphatic amines in tap and river water. The analysis of real samples requires cleanup and preconcentration, which can be performed automatically by inserting a minicolumn in the replenishment system of the commercial instrument.     

Determination of ambroxol in an automated multi-pumping pulsed flow system.

A new flow methodology exploiting the multi-pumping approach was developed for the spectrophotometric determination of ambroxol hydrochloride in pharmaceutical preparations. The flow manifold was implemented by using, exclusively, multiple solenoid-actuated micro-pumps, which acted simultaneously as sample insertion, solutions propelling and reagents commutation units. Linear calibration plots were obtained over an ambroxol concentration ranging from 10 to 200 mg l(-1) (r.s.d. < 0.5%, n = 15) and a sampling rate of about 60 samples per hour (flow rate = 1.92 ml min(-1), sample volume = 80 microl).     

The low-lying electronic states of YCu

The spectroscopic constants for the singlet and tripletstates of YCu below about 15 000 cm⁻¹ are determined using an internally contracted multireference configuration-interaction approach. These calculations are calibrated by studies of fewer states using higher levels of correlation treatment and/or basis sets. The computed T_c values and radiative lifetimes are in reasonable agreement with experiment. The calculations confirm the previous experimental assignment for all but one state, where theory helps resolve between two possible assignments.