Are metals made from molecules?

In the traditional view, covalently bound materials differ in a fundamental way from metallic substances. Though both are built from more basic units that are, in turn, constructed from a small number of atoms, for these two materials classes the nature of these units is thought to be quite different. For covalent solids and liquids, these units are considered to be molecular, meaning that they possess properties and bonding that are retained in the condensed phase and thus they continue to be identifiable within the larger system. For metallic materials, these basic units are considered to be mere constructs that are not observable against the delocalized bonding of metals or alloys. The perceived dissimilarity of metallic and covalently bound materials has fostered distinctly different approaches to their design and improvement. Here, the delocalized view of metallic bonding is examined. This examination suggests that much of the rationale used in the design of molecular materials my be applied to metals and alloys as well.     

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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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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Chromatographic determination of nitrophenols in aqueous media after two-stage preconcentration using an N-vinylpyrrolidone-based polymer

Two-stage procedures for the preconcentration of nitrophenols (4-nitrophenol, 2,4- and 2,5-dinitrophenol, and 2,4,6-trinitrophenol) from aqueous solutions are proposed. At the first stage, the preconcentration and desorption of nitrophenols under dynamic conditions is carried out. At the second stage, depending on the nature of the desorption solution, the eluate is evaporated (acetonitrile) or saturated with ammonium sulfate and extracted with acetone (aqueous NH₃ solution). The concentration factors are 4000 and 910, respectively. Nitrophenols are determined in concentrates by thin layer chromatography and HPLC, the limits of detection are 1.0–1.8 and 0.25–0.45 μg/L, respectively. The duration of analysis is 200 min.     

Detection and quantification of chitosan aggregates by pressure-assisted capillary zone electrophoresis

An approach to the detection and determination of chitosan aggregates in acetic acid solutions is proposed using pressure-assisted capillary zone electrophoresis. Processes of chitosan aggregation are studied depending on the composition of dispersion medium and storage time. The presence of several species of positively charged chitosan aggregates is revealed for the first time. Particle sizes in the range 20–2500 nm are determined by scanning electron microscopy and static and dynamic light scattering. The dependence of the shape of electropherograms on particle size distribution obtained under the same conditions is found. A trend to changing electrophoretic mobility depending on the size of the aggregate is observed, which enables the approximate evaluation of the polydispersity of chitosan solutions. Chitosan is used for the effective dynamic modification of capillaries, which does not require the introduction of a modifier into the background electrolyte.     

Determination of the surface area of loose metal deposits by impedance spectroscopy

The surface area and fractal dimensions of the surface of loose copper and zinc deposits obtained within 30 and 300 s at direct current sixfold exceeding limiting diffusion current on a smooth electrode were in situ determined by impedance spectroscopy. Impedance measurements were performed in 0.5 M Na₂SO₄ solution. A constant phase element taking into account the distribution of double-layer capacitance over the fractal surface of the electrode was used in the equivalent impedance scheme. Specific surface calculated with regard to the weight of the released metal slightly varied within 300 s (from 6.16 to 6.55 and from 7.12 to 5.89 m²/g for copper and zinc deposits, respectively). Fractal dimensions estimated by chronopotentiometry were given for comparison. Fractal dimensions found by two methods for loose copper and zinc deposits agree with each other; their values (2.19–2.75) testify that the surface of the deposits densely fills the space.     

A New Approach to Increasing the Resolution of a Mass Spectrometer with Wedge-Shaped Reflectors

The paper describes the investigation of the ion-optical properties of a laser TOF mass spectrometer including two successively positioned wedge-shaped ion mirrors. Some specific properties of the configuration of ion trajectories near their reflection in the second ion reflector are found. The dependence of aberrations on ion energy acquired toothed shape for the resolution of the analyzer higher than 3000–5000. The approximation of the dependence gave a 15^th degree polynomial. The calculation of polynomial coefficients showed a great contribution to the duration of ion packets for aberrations of higher order. The discovered features allowed us to suggest a way of the local correction of nearby trajectories in the total ion flux. By correcting the local motion of individual groups of ions, we could reduce temporary aberration to 1–1.6 ns, depending on ion energy. For the time of ion flight ~35 μs, such duration limits the resolution of the analyzer by a value not less than 10000. The real length of ion drift path was about 30 cm. The total overall sizes of the ionoptical system were ~24 × 19 × 5 cm.     

Determination of explosive vapor concentrations with remote sampling in the control of objects

A procedure is proposed for the determination of the vapor concentration of 2,4,6-trinitrotoluene (TNT) in air at a level of 10^–16 g/cm³ in the control of objects for the presence of TNT. The procedure includes preconcentration of TNT vapors and gas chromatographic determination with a limit of TNT detection at a level of 0.08 ± 0.02 pg in a sample. The procedure was applied to the control objects in cells of typical automatic luggage locker with sampling through sampling air ducts. A measure of sample losses as the breakthrough of vapors through sampling air ducts and gas dynamic conditions for the reduction of vapor losses as the ratio of diffusion coefficient to the air duct flow rate were proposed. The time constant of the saturation of the sampling system with TNT vapors and the time constant of its cleaning were determined. It was shown that TNT vapors can be detected virtually satisfactorily near TNT-containing objects with sampling through long channels.     

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.     

Alkylation of phenol with olefins in the presence of catalysts based on mesoporous aromatic frameworks

Mesoporous polyaromatic frameworks (PAFs) based on tetraphenylmethane were obtained and modified with sulfonic acid groups. The compounds were characterized by solid-state ¹³C NMR and IR spectroscopy, low-temperature nitrogen adsorption-desorption, and transmission electron microscopy. The acidities of the PAF-1-SO₃H and PAF-2-SO₃H samples determined by titration were 3.99 mmol g^–1 and 0.91 mmol g^–1, respectively. The catalytic activity of PAF-SO₃H for alkylation of phenol with linear terminal olefins was investigated. The reaction products were isomeric monoalkylphenols (C-alkylates), and alkyl phenyl ethers (O-alkylates).