Identification of metabolites of geniposide in rat urine using ultra-performance liquid chromatography combined with electrospray ionization quadrupole time-of-flight tandem mass spectrometry

Geniposide, an iridoid glycoside, is an important and characteristic compound in the fruits of Gardenia jasminoides Ellis, a commonly used medicinal herb in Chinese traditional and folk medicine for the treatment of inflammation and jaundice. However, few studies have been carried out on the metabolism of geniposide. In this study, we have established a rapid and sensitive method using ultra‐performance liquid chromatography coupled with electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry (UPLC/ESI‐QTOF‐MS) for analysis of the metabolic profile of geniposide in rat urine after oral administration. A total of ten metabolites were detected and identified by comparing their fragmentation patterns with that of geniposide using Metabolynx? and MassFragment? software tools. The results revealed that the principal metabolism pathways of geniposide in rat occurred after deglycosylation of the irdoid glycoside take place and this is followed by glucuronidation and the pyran‐ring cleavages. The major metabolite, the glucuronic acid conjugate of genipin as observed in vivo, was further confirmed by the in vitro enzymatic study. The results of this work have demonstrated the feasibility of the UPLC/ESI‐QTOF‐MS approach for rapid and reliable characterization of metabolites from iridoid compounds. Copyright © 2011 John Wiley & Sons, Ltd.     

Strong axiality and Ising exchange interaction suppress zero-field tunneling of magnetization of an asymmetric Dy2 single-molecule magnet

The high axiality and Ising exchange interaction efficiently suppress quantum tunneling of magnetization of an asymmetric dinuclear Dy(III) complex, as revealed by combined experimental and theoretical investigations. Two distinct regimes of blockage of magnetization, one originating from the blockage at individual Dy sites and the other due to the exchange interaction between the sites, are separated for the first time. The latter contribution is found to be crucial, allowing an increase of the relaxation time by 3 orders of magnitude.     

Novel lanthanide-based polymeric chains and corresponding ultrafast dynamics in solution

Two types of structurally related one-dimensional coordination polymers were prepared by reacting lanthanide trichloride hydrates [LnCl(3)·(H(2)O)(m)] with dibenzoylmethane (Ph(2)acacH) and a base. Using cesium carbonate (Cs(2)CO(3)) and praseodymium, neodymium, samarium, or dysprosium salts yielded [Cs{Ln(Ph(2)acac)(4)}](n) (Ln = Pr (1), Nd (2), Sm (3), Dy (4)) in considerable yields. Reaction of potassium tert-butoxide (KOtBu) and the neodymium salt [NdCl(3)·(H(2)O)(6)] with Ph(2)acacH resulted in [K{Nd(Ph(2)acac)(4)}](n) (5). All polymers exhibit a heterobimetallic backbone composed of alternating lanthanide and alkali metal atoms which are bridged by the Ph(2)acac ligands in a linear fashion. ESI-MS investigations on DMF solutions of 1-5 revealed a dissociation of all the five compounds upon dissolution, irrespective of the individual lanthanide and alkali metal present. Temporal profiles of changes in optical density were acquired performing pump/probe experiments with DMF solutions of 1-5 via femtosecond laser spectroscopy, highlighting a lanthanide-specific relaxation dynamic. The corresponding relaxation times ranging from seven picoseconds to a few hundred picoseconds are strongly dependent on the central lanthanide atom, indicating an intramolecular energy transfer from ligands to lanthanides. This interpretation also demands efficient intersystem crossing within one to two picoseconds from the S(1) to T(1) level of the ligands. Magnetic studies show that [Cs{Dy(Ph(2)acac)(4)}](n) (4) has slow relaxation of the magnetization arising from the single Dy(3+) ions and can be described as a single-ion single molecule magnet (SMM). Below 0.5 K, hysteresis loops of the magnetization are observed, which show weak single chain magnet (SCM) behavior.     

Thermal affected zone obtained in machining steel XC42 by high-power continuous CO2 laser

A high-power continuous CO₂ laser (4 kW) can provide energy capable of causing melting or even, with a special treatment of the surface, vaporization of an XC42-steel sample. The laser–metal interaction causes an energetic machining mechanism, which takes place according to the assumption that the melting front precedes the laser beam, such that the laser beam interacts with a preheated surface whose temperature is near the melting point. The proposed model, obtained from the energy balance during the interaction time, concerns the case of machining with an inert gas jet and permits the calculation of the characteristic parameters of the groove according to the characteristic laser parameters (absorbed laser energy and impact diameter of the laser beam) and allows the estimation of the quantity of the energy causing the thermal affected zone (TAZ). This energy is equivalent to the heat quantity that must be injected in the heat propagation equation. In the case of a semi-infinite medium with fusion temperature at the surface, the resolution of the heat propagation equation gives access to the width of the TAZ.     

Acid and scratch resistant coatings for melamine based OEM applications

Increasing the mar resistance of OEM clear coats has been one of the main R&D priorities of paint manufacturers over the last years. Reaching a good mar resistance level without compromising other coating properties such as acid resistance proves to be a major challenge. We investigated the use of branched glycidyl esters in melamine based OEM acrylic formulations. Our results show that systems based on this type of esters lead to good overall coating properties as well as a good balance between acid and scratch resistance.