Solid-state glycation of beta-lactoglobulin monitored by electrospray ionisation mass spectrometry and gel electrophoresis techniques

Glycation of beta-lactoglobulin (beta-Lg) with either lactose or galactose in a solid-state medium was monitored using gel electrophoresis techniques and liquid chromatography coupled to electrospray ionisation mass spectrometry (LC/ESI-MS). The kinetics of glycation monitored by SDS polyacrylamide gel electrophoresis showed a molecular weight increase over time of the beta-Lg bands for both sugars, but no significant amounts of aggregated proteins were observed. The isoelectric point of the protein, observed by isoelectric focusing gel electrophoresis, was dramatically affected by galactosylation. LC/MS measurements of beta-Lg variants A and B, over the whole glycation reaction time, showed a larger extent of glycation with galactose (from 4 up to 22 adducts) as compared with lactose (from 0 up to 14 adducts), and confirmed that early Maillard reaction products were the main species observed. Based on the relative abundances obtained from the deconvoluted mass spectra after a 8 h 15 min incubation time at 60 degrees C, the mean values of lactose and galactose molecules bound to the protein species were calculated to be 10.4 and 17.9, and 10.5 and 18.6, for variants A and B, respectively. Furthermore, the charge state distribution data obtained by ESI-MS was studied using different methanol percentages, and indicated that adduct formation with lactose, but more significantly galactose, tends to improve the stability properties of the native protein towards denaturation.     

The first self-assembled trimetallic lanthanide helicates driven by positive cooperativity

The segmental tris-tridentate ligand L7 reacts with stoichiometric quantities of Ln(III) (Ln=La-Lu) in acetonitrile to give the complexes [Ln(2)(L7)(3)](6+) and [Ln(3)(L7)(3)](9+). Formation constants point to negligible size-discriminating effects along the lanthanide series, but Scatchard plots suggest that the self-assembly of the trimetallic triple-stranded helicates [Ln(3)(L7)(3)](9+) is driven to completion by positive cooperativity, despite strong intermetallic electrostatic repulsions. Crystallization provides quantitatively [Ln(3)(L7)(3)](CF(3)SO(3))(9) (Ln=La, Eu, Gd, Tb, Lu) and the X-ray crystal structure of [Eu(3)(L7)(3)](CF(3)SO(3))(9).(CH(3)CN)(9).(H(2)O)(2) (Eu(3)C(216)H(226)N(48)O(35)F(27)S(9), triclinic, P1, Z=2) shows the three ligand strands wrapped around a pseudo-threefold axis defined by the three metal ions rigidly held at about 9 A. Each metal ion is coordinated by nine donor atoms in a pseudo-trigonal prismatic arrangement, but the existence of terminal carboxamide units in the ligand strands differentiates the electronic properties of the terminal and the central metallic sites. Photophysical data confirm that the three coordination sites possess comparable pseudo-trigonal symmetries in the solid state and in solution. High-resolution luminescence analyses evidence a low-lying LMCT state affecting the central EuN(9) site, so that multi-metal-centered luminescence is essentially dominated by the emission from the two terminal EuN(6)O(3) sites in [Eu(3)(L7)(3)](9+). New multicenter equations have been developed for investigating the solution structure of [Ln(3)(L7)(3)](9+) by paramagnetic NMR spectroscopy and linear correlations for Ln=Ce-Tb imply isostructurality for these larger lanthanides. NMR spectra point to the triple helical structure being maintained in solution, but an inversion of the magnitude of the second-rank crystal-field parameters, obtained by LIS analysis, for the LnN(6)O(3) and LnN(9) sites with respect to the parameters extracted for Eu(III) from luminescence data, suggests that the geometry of the central LnN(9) site is somewhat relaxed in solution.     

Luminescence-detected phase transitions in lanthanide-containing liquid crystals

Complexes between lanthanide nitrates and a pro-mesogenic 18-membered diaza-substituted coronand are luminescent both as powders and liquid crystals (between 87 and 195 degrees C), and the phase transitions are detected by monitoring luminescence intensity and lifetime.     

A difluorosulfide as a Freon-free source of phosphonodifluoromethyl carbanion

The synthesis of difluoromethylphosphonates is becoming difficult due to environmental protective laws restricting the use of HCFCs and CFCs as starting chemicals. To circumvent this limitation, we report the preparation of a thioether as a new source of the lithiodifluoromethylphosphonate. This methodology avoiding the use of HCFCs involves a selective fluorination of sulfide followed by a thiaphilic addition of an organometallic reagent, which offers an alternative route to obtain phosphonodifluoromethyl carbanion. A contrasted reactivity, due to a medium effect, was also noted which allows addition of a wide range of electrophiles including nitroalkenes and DMF to thioethers.     

Stable lanthanide luminescence agents highly emissive in aqueous solution: multidentate 2-hydroxyisophthalamide complexes of Sm(3+), Eu(3+), Tb(3+), Dy(3+)

Efficient lanthanide (Ln) luminescent probes require good ligand-to-metal energy transfer and high aqueous stability. A family of ligands based on 2-hydroxyisophthalamide chelating units is reported. These form highly stable, eight-coordinate Ln complexes. Several of these (Ln = Sm, Eu, Tb, Dy) emit in the visible region with good ligand-to-lanthanide energy transfer. The absolute quantum yields of the two Tb complexes studies (Phi = 0.59, 0.61) and high absorbance make these the brightest luminescent probes for time-resolved detection; the emission spectrum of one complex can be seen down to 10-15 M. The low overlap of the four different Ln complexes enables their simultaneous detection and discrimination.     

Almost Connected Orders

One of the standard axioms for semiorders states that no three-point chain is incomparable to a fourth point. We refer to asymmetric relations satisfying this axiom as almost connected orders or ac-orders. It turns out that any relation lying between two weak orders, one of which covers the other for inclusion, is an ac-order (albeit of a special kind). Every ac-order is bracketed in a natural way by two weak orders, one the maximum in the set of weak orders included in the ac-order, and the other minimal, but not necessarily the minimum, in the set of weak orders that include the ac-order. The family of ac-orders on a finite set with at least five elements is not well graded (in the sense of Doignon and Falmagne, 1997). However, such a family is both upgradable and downgradable, as every nonempty ac-order contains a pair whose deletion defines an ac-order on the same set, and for every ac-order which is not a chain, there is a pair whose addition gives an ac-order.     

Electrochemical Synthesis of Trifluoromethane Sulfinic Acid Salt From CF3Br and SO2

The electroreduction of a mixture of SO₂ and CF₃Br in DMF, in an undivided cell with a soluble anode (Mg or Zn) lead to salt of trifluoromethane sulfinic acid in high yield.     

Access to new 4-fluorocyclohexa-2,5-dienimines using hypervalent iodine and pyridinium polyhydrogen fluoride

Nucleophilic para-fluorination of substituted anilines to afford 4-fluorocyclohexadieneimine derivatives is achieved in the presence of hypervalent iodine and pyridinium polyhydrogen fluoride.     

A Copper(I)-Catalyzed Sulfonylative Hiyama Cross-Coupling

An air-tolerant Cu-catalyzed sulfonylative Hiyama cross-coupling reaction enabling the formation of diaryl sulfones is described. Starting from aryl silanes, DABSO and aryliodides, the reaction tolerates a large variety of polar functional groups (amines, ketones, esters, aldehydes). Control experiments coupled with DFT calculations shed light on the mechanism, characterized by the formation of a Cu(I)-sulfinate intermediate via fast insertion of a SO₂ molecule.