Mass Spectrometry for the Monitoring of Lipoprotein Oxidations by Myeloperoxidase in Cardiovascular Diseases

Oxidative modifications of HDLs and LDLs by myeloperoxidase (MPO) are regularly mentioned in the context of atherosclerosis. The enzyme adsorbs on protein moieties and locally produces oxidizing agents to modify specific residues on apolipoproteins A-1 and B-100. Oxidation of lipoproteins by MPO (Mox) leads to dysfunctional Mox-HDLs associated with cholesterol-efflux deficiency, and Mox-LDLs that are no more recognized by the LDL receptor and become proinflammatory. Several modification sites on apoA-1 and B-100 that are specific to MPO activity are described in the literature, which seem relevant in patients with cardiovascular risk. The most appropriate analytical method to assess these modifications is based on liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). It enables the oxidized forms of apoA-1and apoB-100 to be quantified in serum, in parallel to a quantification of these apolipoproteins. Current standard methods to quantify apolipoproteins are based on immunoassays that are well standardized with good analytical performances despite the cost and the heterogeneity of the commercialized kits. Mass spectrometry can provide simultaneous measurements of quantity and quality of apolipoproteins, while being antibody-independent and directly detecting peptides carrying modifications for Mox-HDLs and Mox-LDLs. Therefore, mass spectrometry is a potential and reliable alternative for apolipoprotein quantitation.     

Determination of persistence lengths and mark-houwink constants of aromatic polyesters from GPC-differential viscometric coupling

The introduction of lateral substituents and/or twisted biphenylylene units increase the solubility of aromatic para-linked polyesters. Two polyesters of this type of structure were characterized by gel permeation chromatography (GPC), low angle laser light scattering (LALLS) and viscometry. From the molecular weights and limiting viscosity numbers obtained by universal calibration and LALLS/viscometry the Mark-Houwink constants and persistence lengths were determined. The values of these parameters indicated that the polyesters can be described as wormlike chains in dilute solution.     

An abstract Nash–Moser theorem with parameters and applications to PDEs

We prove an abstract Nash–Moser implicit function theorem with parameters which covers the applications to the existence of finite dimensional, differentiable, invariant tori of Hamiltonian PDEs with merely differentiable nonlinearities. The main new feature of the abstract iterative scheme is that the linearized operators, in a neighborhood of the expected solution, are invertible, and satisfy the “tame” estimates, only for proper subsets of the parameters. As an application we show the existence of periodic solutions of nonlinear wave equations on Riemannian Zoll manifolds. A point of interest is that, in presence of possibly very large “clusters of small divisors”, due to resonance phenomena, it is more natural to expect solutions with only Sobolev regularity.     

Calix[4]tubes: a new class of potassium-selective ionophore

A new class of cryptand-like ionophore based on a bis calix[4]arene structure has been developed. These molecules proved highly selective for complexation of potassium over all group I metal cations and barium. A range of symmetric and asymmetric calix[4]tubes featuring either alkyl or phenyl substituents at the upper rim have been synthesized in exceptional yield. Alteration of the calix[4]arene upper rim environment enables fine-tuning of the rate of potassium uptake, which can be evaluated through the conformational change on binding by NMR studies. Selectivity of potassium complexation has been demonstrated using NMR and electrospray mass spectral techniques. Molecular modeling studies, derived from crystallographic data, confirm that the potassium metal cation is complexed via the axial route, passing through the calix[4]arene annulus, and provide evidence for complexation rate and selectivity.     

Application of the Maximum Entropy Formalism on Sprays Produced by Ultrasonic Atomizers

A recent application of the Maximum Entropy Formalism on liquid atomization problems led to the development of a mathematical volume‐based drop‐size distribution. This function, which depends on three parameters, is a reduction of the four‐parameter generalized Gamma function. The aim of the present work is to investigate the relevance of the three parameters in the characterization of liquid atomization processes. To achieve this, a variety of experimental drop‐size distributions of ultrasonic sprays were analyzed with the mathematical function. Firstly, it is found that the mathematical drop‐size distribution is very suitable to represent the volume‐based drop‐size distribution of ultrasonic sprays. Furthermore, it is seen that when considering the three parameters introduced by the function, one of them is constant for all the situations investigated, and the other two are linked to a non‐dimensional group that includes the main parameters controlling the drop production. These results are very important, since they suggest a possible development of physical models of primary atomization based on the M.E.F., which would allow for the prediction of the spray drop‐size distribution. Thusfar, such a model does not exist.     

Sunlight-induced DNA Damage in Marine Micro-organisms Collected Along a Latitudinal Gradient from 70°N to 68°S

We examined ultraviolet radiation (UVR)-induced DNA damage in marine micro-organisms collected from surface seawater along a latitudinal transect in the Central Pacific Ocean from 70°N to 68°S. Samples were collected predawn and incubated under ambient UVR in transparent incubators at in situ temperatures until late afternoon at which time they were filtered into primarily bacterioplankton and eukaryotic fractions. Cyclobutane pyrimidine dimers (CPDs) and (6-4) photoproducts [(6-4)PDs] were quantified in DNA extracts using radioimmunoassays. UVB was lowest in the polar regions and highest near the equator and correlations between UVB and DNA damage were observed. The eukaryotic fraction showed significant CPDs across the entire transect; (6-4)PDs were detected only in the tropics. The bacterial fraction showed no accumulation of (6-4)PDs at any latitude, although residual (6-4)PDs were observed. Bacterial cell volumes were greatest in the sub-Arctic and northern temperate latitudes and lower in the tropics and southern hemisphere, a unique observation that parallels Bergmann's rule. A strong negative correlation was observed between cell volume and CPDs. The environmental impact of solar UVR on marine micro-organisms in the open ocean is complex and our results suggest that several factors such as DNA repair, cell size, temperature, salinity, nutrients and species composition are important in determining relative sensitivity.     

Strong Solid‐state Luminescence Enhancement in Supramolecular Assemblies of Polyoxometalate and “Aggregation‐Induced Emission”‐active Phospholium

Two new supramolecular fluorescent hybrid materials, combining for the first time [M₆O₁₉]^2? (M=Mo, W) polyoxometalates (POMs) and aggregation‐induced emission (AIE)‐active 1‐methyl‐1,2,3,4,5‐pentaphenyl‐phospholium ( 1⁺ ), were successfully synthesized. This novel molecular self‐assembling strategy allows designing efficient solid‐state emitters, such as (1)₂[W₆O₁₉] , by directing favorably the balance between the AIE and aggregation‐caused quenching (ACQ) effects using both anion‐π⁺ and H‐bonding interactions in the solid state. Combined single‐crystal X‐ray diffraction, Raman, UV‐vis and photoluminescence analyses highlighted that the nucleophilic oxygen‐enriched POM surfaces strengthened the rigidity of the phospholium via strong C?H???O contacts, thereby exalting its solid‐state luminescence. Besides, the bulky POM anions prevented π–π stacking interactions between the luminophores, blocking detrimental self‐quenching effects.     

Periodic Solutions of Nonlinear Wave Equations with General Nonlinearities

We present a variational principle for small amplitude periodic solutions, with fixed frequency, of a completely resonant nonlinear wave equation. Existence and multiplicity results follow by min-max variational arguments. Supported by M.U.R.S.T. Variational Methods and Nonlinear Differential Equations.