Transport properties of metacomposites in eutectic MAO<Subscript>4</Subscript>–V<Subscript>2</Subscript>O<Subscript>5</Subscript> systems (M = Ca,Sr; A = W,Mo)

Metal molybdates MMoO₄ (M = Ca, Sr) and their composites with vanadium oxide V₂O₅ were synthesized. An X-ray diffraction analysis confirmed that the obtained molybdates were single-phase, and the heterogeneous systems were two-phase. The temperature dependences of the total conductivity of the composites were studied. The ion transport numbers in the {CaMoO₄ · xV₂O₅} composites (x = 1–30 mol %) were studied by the EMF method. The conductivity of the composites at x ≤ 5 mol % was shown to be ionic. The conductivity of the composites was described using the mixing equation.     

Quantitative Proteomic Analysis of Optimal Cutting Temperature (OCT) Embedded Core-Needle Biopsy of Lung Cancer

With recent advances in understanding the genomic underpinnings and oncogenic drivers of pathogenesis in different subtypes, it is increasingly clear that proper pretreatment diagnostics are essential for the choice of appropriate treatment options for non-small cell lung cancer (NSCLC). Tumor tissue preservation in optimal cutting temperature (OCT) compound is commonly used in the surgical suite. However, proteins recovered from OCT-embedded specimens pose a challenge for LC-MS/MS experiments, due to the large amounts of polymers present in OCT. Here we present a simple workflow for whole proteome analysis of OCT-embedded NSCLC tissue samples, which involves a simple trichloroacetic acid precipitation step. Comparisons of protein recovery between frozen versus OCT-embedded tissue showed excellent consistency with more than 9200 proteins identified. Using an isobaric labeling strategy, we quantified more than 5400 proteins in tumor versus normal OCT-embedded core needle biopsy samples. Gene ontology analysis indicated that a number of proliferative as well as squamous cell carcinoma (SqCC) marker proteins were overexpressed in the tumor, consistent with the patient’s pathology based diagnosis of “poorly differentiated SqCC”. Among the most downregulated proteins in the tumor sample, we noted a number of proteins with potential immunomodulatory functions. Finally, interrogation of the aberrantly expressed proteins using a candidate approach and cross-referencing with publicly available databases led to the identification of potential druggable targets in DNA replication and DNA damage repair pathways. We conclude that our approach allows LC-MS/MS proteomic analyses on OCT-embedded lung cancer specimens, opening the way to bring powerful proteomics into the clinic.

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Transferring Ions from Solution to the Gas Phase: The Two Basic Principles

The efficient formation of gaseous ions is the crucial step in all successful mass spectrometric experiments. The invention of electrospray ionization (ESI) has strongly facilitated this step by transferring preformed ions directly from solution to the gas phase – thereby circumventing the need to first convert analytes to the gas phase and then ionize them – and therefore ESI has become an extremely useful and widely applied MS technique. The invention of sonic spray ionization (SSI) has also allowed for the transfer of ions from solution into the gas phase, but without the assistance of a voltage or heating. Numerous ionization techniques, using similar principles to those applied in either ESI or SSI, have subsequently been developed. Although experimental conditions used in such techniques vary markedly, herein we argue that they are all based on either one of two basic principles by which ions can be transferred from solution to the gas phase, that is: via (1) neutralizing the counter ion, or (2) separating the ions. We have selected 35 such techniques and categorized them accordingly. This article thereby aims to establish the basic principles by which gaseous ions can be obtained from solvated ions. We further propose that any new ionization technique used to transfer solvated ions to the gas phase will similarly fall into one of these two mechanistic categories.

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Expanding Lipidome Coverage Using LC-MS/MS Data-Dependent Acquisition with Automated Exclusion List Generation

Untargeted omics analyses aim to comprehensively characterize biomolecules within a biological system. Changes in the presence or quantity of these biomolecules can indicate important biological perturbations, such as those caused by disease. With current technological advancements, the entire genome can now be sequenced; however, in the burgeoning fields of lipidomics, only a subset of lipids can be identified. The recent emergence of high resolution tandem mass spectrometry (HR-MS/MS), in combination with ultra-high performance liquid chromatography, has resulted in an increased coverage of the lipidome. Nevertheless, identifications from MS/MS are generally limited by the number of precursors that can be selected for fragmentation during chromatographic elution. Therefore, we developed the software IE-Omics to automate iterative exclusion (IE), where selected precursors using data-dependent topN analyses are excluded in sequential injections. In each sequential injection, unique precursors are fragmented until HR-MS/MS spectra of all ions above a user-defined intensity threshold are acquired. IE-Omics was applied to lipidomic analyses in Red Cross plasma and substantia nigra tissue. Coverage of the lipidome was drastically improved using IE. When applying IE-Omics to Red Cross plasma and substantia nigra lipid extracts in positive ion mode, 69% and 40% more molecular identifications were obtained, respectively. In addition, applying IE-Omics to a lipidomics workflow increased the coverage of trace species, including odd-chained and short-chained diacylglycerides and oxidized lipid species. By increasing the coverage of the lipidome, applying IE to a lipidomics workflow increases the probability of finding biomarkers and provides additional information for determining etiology of disease.

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Primary photophysical and photochemical processes for Pt(SCN)<Subscript>6</Subscript><Superscript>2–</Superscript> complex

Photosolvation of a Pt^IV hexathiocyanate complex Pt(SCN)₆ ^2– in water and ethanol was studied by steady-state photolysis, nanosecond laser flash photolysis, and ultrafast kinetic spectroscopy. Complexes Pt(SCN)₅(H₂O)^– and Pt(SCN)₅(C₂H₅OH)^– were found to be the only reaction products. The quantum yields of photosolvation are independent of the excitation wavelength, being equal to 0.25 and 0.5 for the solutions of the complex in water and ethanol, respectively. Photosolvation proceeds by the mechanism of heterolytic metal—ligand bond dissociation without involvement of redox processes. The characteristic time of formation of the end products for both solvents is about 10 ps. Three successive intermediates detected on the picosecond time scale were interpreted as Pt^IV complexes. The nature of the intermediates and possible mechanisms of photosolvation are discussed.     

Sulphur content estimation of Venezuelan heavy oil by fast neutron and gamma transmission technique

A compact and modern equipment for implementing the fast neutron and γ-ray transmission technique (FNGT) has been developed in order to estimate the sulphur content of crude oil. FNGT is employed for non- destructive analysis of different kinds of samples. The compact system presented in this work represents an improvement of our previous experimental set-up [1, 2]. It makes use of a ²⁵²Cf source, an EJ-301 liquid scintillator detector (2″ × 2″) with excellent n/γ discrimination capabilities, and modern nuclear electronics based on fast digitizers. The fast neutron and gamma transmission technique was employed to study a system for on-line sulphur concentration measurement in Venezuelan heavy sour oil. The range of sulphur concentrations investigated is between 0.1 and 6.5 wt%. The equipment performances and limitations are compared with those predicted by a Monte Carlo model built in GEANT4 v10.01. The results show the possibility to implement a compact unit for on-line determination of sulphur concentration in crude oil.

     

Hydrogenation of diacetyl over composite-supported egg-shell noble metal catalysts

Two composite supports with a mixed inorganic–organic structure were synthesized: BTAl and UTAl. Hydrophilic–hydrophobic dual properties of the supports were suitable for preparing egg-shell-supported metal catalysts for selective hydrogenation reactions. The catalysts were characterized by ICP, XRD, OM, TEM, EPMA, XPS and TGA. Their mechanical resistance was assessed. Activity and selectivity were tested with the hydrogenation of 2,3-butanedione (diacetyl) to 3-hydroxy-2-butanoneacetoin (acetoin). The same order of increasing metal particle size was found for the two tested supports: Pt < Ru < Pd. The XPS analysis showed that the metal/composite catalysts reduced in H2 at 503 K had two kinds of active sites: reduced (Me°) and electron-deficient (Me⁺). It was rationalized that the hydrogen bond cleavage was performed on the Me° active sites, while reactant adsorption occurred on the Me⁺ sites. The differences in activity and selectivity between the composite catalysts were attributed to electronic effects on the different metals and to different adsorptive properties of the different polymers. The high selectivity to acetoin was attributed to the preferential adsorption of diacetyl as compared to the adsorption of acetoin. The BTAl catalysts were slightly more active and selective than the UTAl ones. This was attributed to electronic effects caused by remnant organic groups on the composite supports (urethane or biphenyl on UTAl or BTAl, respectively). Pd-BTAl was the most active and selective catalyst, a fact related to electronic effects of both palladium and the support.     

Optical activity of films based on chitosan of various molecular masses and modifications

The effect of chemical (polysalt → polybase reaction) and physicochemical (heat and vapor processing) modifications of the films of chitosan of various molecular masses and prehistories on the optical activity of the polysaccharide is studied. For both of the chitosan chemical modifications, the following dependence that is nontrivial for high-molecular compounds is established: [α] = f(log\({\bar M_\eta }\)); as the degree of polymerization decreases, the modulus of [α] of the films increases. The X-ray diffraction study shows that the differences in the optical activity of the samples with different \({\bar M_\eta }\) are caused by a restriction in the mobility of the macromolecular sections upon formation of the films of high-molecular chitosan and incompleteness of the relaxation processes of the film systems to the state with energetically favorable conformations. The comparison of humidity and optical and biological activities of the initial and dehydrated chitosan films is performed. The chitosan films in the salt modification feature moderate bactericidal activity, which decreases with an increase in \({\bar M_\eta }\) of the polymer. The thermal processing of the salt modification reduces the antibacterial action; a conversion to the base form is accompanied by the loss of bactericidal activity.     

Understanding Behavior of Polycaprolactone–Gelatin Blends under High Pressure CO<Subscript>2</Subscript>

Polycaprolactone (PCL) is widely used in biomedical applications as electrospun fibers or porous foams. As PCL is synthetic polymer, many researchers have explored blends of PCL–gelatin to combine mechanical and bioactive properties of individual components. High pressure carbon dioxide (CO2) has been studied to foam and impregnate many biocompatible polymers. In case of PCL–gelatin blends, certain compositions can be swelled reversibly under high pressure CO₂ without permanent deformation. This allows successful impregnation of PCL–gelatin blends under CO₂. This study summarizes effect of different treatments adopted during impregnation process including high pressure CO2 on several blend compositions of PCL–gelatin blends. Stress relaxation, polymer melting and dissolution were observed during several treatments which affects porosity and scaffold structure significantly. Results summarized in this study will aid in optimum selection of PCL–gelatin blend composition for biomedical applications. Furthermore, CO₂ solubility in polymers is restricted due to thermodynamic limitations but can be altered in the presence of a co-solvent to produce better foams. PCL can be foamed using supercritical CO₂. However, CO₂ foaming of PCL–gelatin blend becomes challenging to simultaneous swelling of PCL and compression of gelatin providing blend structural stability. This study has demonstrated ability of supercritical CO₂ to foam PCL–gelatin blends in presence of water to create porous structure. These foams were subjected post-fabrication crosslinking and supercritical CO₂ without losing porosity of foams. Thus, creating a strategy to use environmentally benign processes to fabricate, crosslink and impregnate porous scaffolds for biomedical applications.     

On parallel Branch and Bound frameworks for Global Optimization

Branch and Bound (B&B) algorithms are known to exhibit an irregularity of the search tree. Therefore, developing a parallel approach for this kind of algorithms is a challenge. The efficiency of a B&B algorithm depends on the chosen Branching, Bounding, Selection, Rejection, and Termination rules. The question we investigate is how the chosen platform consisting of programming language, used libraries, or skeletons influences programming effort and algorithm performance. Selection rule and data management structures are usually hidden to programmers for frameworks with a high level of abstraction, as well as the load balancing strategy, when the algorithm is run in parallel. We investigate the question by implementing a multidimensional Global Optimization B&B algorithm with the help of three frameworks with a different level of abstraction (from more to less): Bobpp, Threading Building Blocks (TBB), and a customized Pthread implementation. The following has been found. The Bobpp implementation is easy to code, but exhibits the poorest scalability. On the contrast, the TBB and Pthread implementations scale almost linearly on the used platform. The TBB approach shows a slightly better productivity.