Contributions to the Gelling Process in the Bi-Sr-Ca-Cu-O System, Via Acetate Route

Metal acetates represent suitable precursors in the sol-gel method. Generally, acetates are used in multicomponent systems with alkoxides or other carboxylic salts. However, Bi−Sr−Ca−Cu−O superconductors have been obtained by the sol-gel method starting only from acetate mixture. This work was intended to study the gelling process of acetates involved in the formation of bismuth-based superconducting phases, both individually and in the bi-and multicomponent systems. Probably, copper acetate is mainly responsible for the gel formation in these systems. The gelling process was monitored by measuring the pH, density and viscosity changes. The gels obtained were characterized by UV-VIS and IR spectra, DTA/TGA and powder X-ray diffraction.     

Orbitrap mass spectrometry for monitoring the ganglioside pattern in human cerebellum development and aging

We have developed here a superior approach based on high‐resolution (HR) mass spectrometry (MS) for monitoring the changes occurring with development and aging in the composition and structure of cerebellar gangliosidome. The experiments were focused on the comparative screening and structural analysis of gangliosides expressed in fetal and aged cerebellum by Orbitrap MS with nanoelectrospray ionization (nanoESI) in the negative ion mode. The employed ultrahigh‐resolution MS platform allowed the discrimination, without the need of previous separation, of 159 ions corresponding to 120 distinct species in the native ganglioside mixtures from fetal and aged cerebellar biopsies, many more than detected before, when MS platforms of lower resolution were employed. A number of gangliosides, in particular polysialylated belonging to GT, GQ, GP, and GS classes, modified by O‐fucosylation, O‐acetylation, or CH₃COO^? were discovered here, for the first time in human cerebellum. These components, found differently expressed in fetal and aged tissues, indicated that the ganglioside profile in cerebellum is development stage‐ and age‐specific. Following the fragmentation analysis by high‐energy collision‐induced dissociation (HCD) tandem MS (MS/MS), we have also observed that the intimate structure of certain compounds has not changed during the development and aging of the brain, an aspect which could open new directions in the investigation of ganglioside biomarkers in cerebellar tissue.     

Identification and structural characterization of novel O‐ and N‐glycoforms in the urine of a Schindler disease patient by Orbitrap mass spectrometry

Schindler disease is an inherited metabolic disorder caused by the deficient activity of α‐N‐acetylgalactosaminidase enzyme. An accurate diagnosis requires, besides clinical examination, complex and costly biochemical and molecular genetic tests. In the last years, mass spectrometry (MS) based on nanofluidics and high‐resolution instruments has become a successful alternative for disease diagnosis based on the investigation of O‐glycopeptides in patient urine. A complex mixture of glycoforms extracted from the urine of a 3‐year‐old patient was investigated by Orbitrap MS equipped with Nanospray Flex Ion Source in the negative ion mode. For structural characterization of several molecular species, collision‐induced dissociation MS²–MS³ was carried out using collision energy values within 20–60 eV range. By our approach, 39 novel species associated to this condition were identified, among which O‐glycopeptides, free O‐glycans and one structure corresponding to an N‐glycan never characterized in the context of Schindler disease. The experiments conducted at a resolution of 60 000 allowed the discrimination and identification of a total number of 69 different species with an average mass accuracy of 9.87 ppm, an in‐run reproducibility of almost 100%, an experiment‐to‐experiment and day‐to‐day reproducibility of about 95%. This study brings contributions in the diagnosis of Schindler disease through the elucidation of potential biomarker species in urine. Our multistage MS results completed with 39 new glycoforms the inventory of potential biomarker structures associated to Schindler disease. For the first time, an N‐glycan was identified and structurally characterized in Schindler patient urine, which opens new research directions in the field. Copyright © 2015 John Wiley & Sons, Ltd.     

Primal‐dual active set methods for Allen–Cahn variational inequalities with nonlocal constraints

We propose and analyze a primal‐dual active set method for discretized versions of the local and nonlocal Allen–Cahn variational inequalities. An existence result for the nonlocal variational inequality is shown in a formulation involving Lagrange multipliers for local and nonlocal constraints. Local convergence of the discrete method is shown by interpreting the approach as a semismooth Newton method. Properties of the method are discussed and several numerical simulations demonstrate its efficiency. © 2012 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2013     

Manufacturing and Assessing the New Orally Disintegrating Tablets,Containing Nimodipine-hydroxypropyl-β-cyclodextrin and Nimodipine-methyl-β-cyclodextrin Inclusion Complexes

The aim of the present study was to manufacture new orally disintegrating tablets containing nimodipine–hydroxypropyl-β-cyclodextrin and nimodipine–methyl-β-cyclodextrin inclusion complexes. For obtaining a better quality of the manufactured tablets, three methods of the preparation of inclusion complexes, in a 1:1 molar ratio, were used comparatively; namely, a solid-state kneading method and two liquid state coprecipitation and lyophilization techniques. The physical and chemical properties of the obtained inclusion complexes, as well as their physical mixtures, were investigated using Fourier transformed infrared spectroscopy, scanning electron microscopy, X-ray diffraction analyses, and differential scanning calorimetry. The results showed that the lyophilization method can be successfully used for a better complexation. Finally, the formulation and precompression studies for tablets for oral dispersion, containing Nim–HP-β-CD and Nim–Me-β-CD inclusion complexes, were successfully assessed.     

Ion Mobility Mass Spectrometry Reveals Rare Sialylated Glycosphingolipid Structures in Human Cerebrospinal Fluid

Gangliosides (GGs) represent an important class of biomolecules associated with the central nervous system (CNS). In view of their special role at a CNS level, GGs are valuable diagnostic markers and prospective therapeutic agents. By ion mobility separation mass spectrometry (IMS MS), recently implemented by us in the investigation of human CNS gangliosidome, we previously discovered a similarity between GG profiles in CSF and the brain. Based on these findings, we developed IMS tandem MS (MS/MS) to characterize rare human CSF glycoforms, with a potential biomarker role. To investigate the oligosaccharide and ceramide structures, the ions detected following IMS MS separation were submitted to structural analysis by collision-induced dissociation (CID) MS/MS in the transfer cell. The IMS evidence on only one mobility feature, together with the diagnostic fragment ions, allowed the unequivocal identification of isomers in the CSF. Hence, by IMS MS/MS, GalNAc-GD1c(d18:1/18:1) and GalNAc-GD1c(d18:1/18:0) having both Neu5Ac residues and GalNAc attached to the external galactose were for the first time discovered and structurally characterized. The present results demonstrate the high potential of IMS MS/MS for biomarker discovery and characterization in body fluids, and the perspectives of method implementation in clinical analyses targeting the early diagnosis of CNS diseases through molecular fingerprints.     

Assessment of the impact of a phosphatic fertilizer plant on the adjacent environment using fuzzy logic

The impact of a phosphatic fertilizer plant on the adjacent environment was examined. Selected rare earth elements, heavy metals and metalloids were determined in substrates and products, waste by-product, and grass and soil samples. Concentration gradients of elements in grass and soil samples along the southerly and easterly directions were examined and compared with the content of interior soil and grass samples, substrates, and products. Results were compared with available data on soil permissible element concentration levels. Two fuzzy principal component analysis (FPCA) methods for robust estimation of principal components were applied and compared with classical PCA. The efficiency of the new algorithms is illustrated. The investigation explored the impact of the plant on the adjacent environment. The most reliable results, in good agreement with types of samples, were produced using the FPCA-O algorithm     

Ganglioside analysis in body fluids by liquid-phase separation techniques hyphenated to mass spectrometry

The expression of gangliosides in central nervous system is a few times higher than in the extraneural tissue, a characteristic highlighting their major role at this level. Although in very low amounts, gangliosides are ubiquitously distributed in body fluids too, where, depending on many factors, including pathological states, their composition fluctuates, thus having diagnostic value. Ganglioside investigation in biological fluids, which, except for cerebrospinal fluid (CSF), may be sampled noninvasively, was for years impeded by the limited sensitivity of the analytical instrumentation available in glycomics. However, because the last decade has witnessed significant developments in biological mass spectrometry (MS) and the hyphenated separation techniques, marked by a major increase in sensitivity, reproducibility, and data reliability, ganglioside research started to be focused on biofluid analysis by separation techniques coupled to MS. In this context, our review presents the achievements in this emerging field of gangliosidomics, with a particular emphasis on modern liquid chromatography (LC), thin-layer chromatography, hydrophilic interaction LC, and ion mobility separation coupled to high-performance MS, as well as the results generated by these systems and allied experimental procedures in profiling and structural analysis of gangliosides in healthy or diseased body fluids, such as CSF, plasma/serum, and milk.     

Emulsion polymerization of vinyl chloride, 2 potassium persulfats decomposition in the presence of PVC latex

The decomposition rate of potassium persulfate (KPS) in aqueous solutions, in the presence of sodium dodecyl sulfate (SDS) and poly(vinyl chloride) latex (PVC) was studied. The dissolved SDS increases the decomposition rate constant (k_d) while the SDS aggregation as micella and/or its adsorption on the polymer hydrophobic surface results in a decreasing k_d. The emulsifier - free surface of the polymer particles increases the decomposition rate. A reaction mechanism based on emulsifier - emulsifier and emulsifier - polymer hydrophobic interactions is put forward.