Spherical Sampler Probes Enhance the Robustness of Ambient Ionization Mass Spectrometry for Rapid Drugs Screening

Ambient ionization mass spectrometry has become one of the most promising approaches for rapid and high-throughput screening of small molecules in complex biological matrices for emergency medicine, forensics, and food and agriculture applications. The simple procedures for sample collection and ionization without additional pretreatment are vital in these fields. Many efforts have been devoted to modifying various ambient ionization techniques to simplify the procedures and improve the robustness and sensitivity of the methods. Here, we demonstrate the implementation of rigid spherical sampler probes to improve the robustness of touch spray ionization mass spectrometry. The sphericity of the probes increases the stability of the cone-jet mode of electrospray, reduces the requirements for fine positioning of a sampler in the ion source, and decreases the possibility of corona discharge occurrence. The utilization of spherical sampler probes allows fast, non-invasive sampling, followed by rapid analysis for various drugs of different chemical classes in complex biological matrices, such as the whole blood or sebum collected from the skin surface. The linearity of the analytical signal response from drug concentration confirms the possibility of creating a simple semiquantitative method for small molecules monitoring using spherical sampler probes.     

Synthesis of Spin-Labeled Ibuprofen and Its Interaction with Lipid Membranes

Ibuprofen is a non-steroidal anti-inflammatory drug possessing analgesic and antipyretic activity. Electron paramagnetic resonance (EPR) spectroscopy could be applied to study its interaction with biological membranes and proteins if its spin-labeled analogs were synthesized. Here, a simple sequence of ibuprofen transformations—nitration, esterification, reduction, Sandmeyer reaction, Sonogashira cross-coupling, oxidation and saponification—was developed to attain this goal. The synthesis resulted in spin-labeled ibuprofen (ibuprofen-SL) in which the spin label TEMPOL is attached to the benzene ring. EPR spectra confirmed interaction of ibuprofen-SL with 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) bilayers. Using ²H electron spin echo envelope modulation (ESEEM) spectroscopy, ibuprofen-SL was found to be embedded into the hydrophobic bilayer interior.     

Novel Copper(II) Complexes with Dipinodiazafluorene Ligands: Synthesis,Structure, Magnetic and Catalytic Properties

The reactions of CuX₂ (X = Cl, Br) with dipinodiazafluorenes yielded four new complexes [CuX₂L₁]₂ (X = Cl (1), Br (2), L₁ = (1R,3R,8R,10R)-2,2,9,9-Tetramethyl-3,4,7,8,9,10-hexahydro-1H-1,3:8,10-dimethanocyclopenta [1,2-b:5,4-b’]diquinolin-12(2H)-one) and [(CuX₂)₂L₂]n (X = Cl (3), Br (4), L₂ = (1R,3R,8R,10R,1’R,3’R,8’R,10’R)-2,2,2’,2’,9,9,9’,9’-Octamethyl-1,1’,2,2’,3,3’,4,4’,7,7’,8,8’,9,9’,10,10’-hexadecahydro-1,3:1’,3’:8,10:8’,10’-tetramethano-12,12’-bi(cyclopenta [1,2-b:5,4-b’]diquinolinylidene). The complexes were characterized by IR and EPR spectroscopy, HR-ESI-MS and elemental analysis. The crystal structures of compounds 1, 2 and 4 were determined by X-ray diffraction (XRD) analysis. Complexes 1–2 have a monomeric structure, while complex 4 has a polymeric structure due to additional coordinating N,N sites in L₂. All complexes contain a binuclear fragment {Cu₂(μ-X)_2×2} (X = Cl, Br) in their structures. Each copper atom has a distorted square-pyramidal coordination environment formed by two nitrogen atoms and three halogen atoms. The Cu-N_ax distance is elongated compared to Cu-N_eq. The EPR spectra of compounds 1–4 in CH₃CN confirm their paramagnetic nature due to the d⁹ electronic configuration of the copper(II) ion. The magnetic properties of all compounds were studied by the method of static magnetic susceptibility. For complexes 1 and 2, the effective magnetic moments are µ_eff ≈ 1.87 and 1.83 µ_B (per each Cu²⁺ ion), respectively, in the temperature range 50–300 K, which are close to the theoretical spin value (1.73 µ_B). Ferromagnetic exchange interactions between Cu(II) ions inside {Cu₂(μ-X)₂X₂} (X = Cl, Br) dimers (J/k_B ≈ 25 and 31 K for 1 and 2, respectively) or between dimers (θ′ ≈ 0.30 and 0.47 K for 1 and 2, respectively) were found at low temperatures. For compounds 3 and 4, the magnetic susceptibility is well described by the Curie–Weiss law in the temperature range 1.77–300 K with µ_eff ≈ 1.72 and 1.70 µ_B for 3 and 4, respectively, and weak antiferromagnetic interactions (θ ≈ −0.4 K for 3 and −0.65 K for 4). Complexes 1–4 exhibit high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The maximum yield of cyclohexane oxidation products reached 50% (complex 3). Based on the data on the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play a decisive role in the oxidation reaction. The initial products in reactions with alkanes are alkyl hydroperoxides.     

Formation of Catalytically Active Nanoparticles under Thermolysis of Silver Chloroplatinate(II) and Chloroplatinate(IV)

The thermal behaviour of Ag₂[PtCl₄] and Ag₂[PtCl₆] complex salts in inert and reducing atmospheres has been studied. The thermolysis of compounds in a helium atmosphere is shown to occur in two stages. At the first stage, the complexes decompose in the temperature range of 350–500 °C with the formation of platinum and silver chloride and the release of chlorine gas. At the second stage, silver chloride is sublimated in the temperature range of 700–900 °C, while metallic platinum remains in the solid phase. In contrast to the thermolysis of Ag₂[PtCl₆], the thermal decomposition of Ag₂[PtCl₄] at 350 °C is accompanied by significant heat release, which is associated with disproportionation of the initial salt to Ag₂[PtCl₆], silver chloride, and platinum metal. It is confirmed by DSC measurements, DFT calculations of a suggested reaction, and XRD. The thermolysis of Ag₂[PtCl₄] and Ag₂[PtCl₆] compounds is shown to occur in a hydrogen atmosphere in two poorly separable steps. The compounds are decomposed within 170–350 °C, and silver and platinum are reduced to a metallic state, while a metastable single-phase solid solution of Ag_0.67Pt_0.33 is formed. The catalytic activity of the resulting nanoalloy Ag_0.67Pt_0.33 is studied in the reaction of CO total (TOX) and preferential (PROX) oxidation. Ag_0.67Pt_0.33 enhanced Pt nano-powder activity in CO TOX, but was not selective in CO PROX.     

Conformational Dynamics of Human ALKBH2 Dioxygenase in the Course of DNA Repair as Revealed by Stopped-Flow Fluorescence Spectroscopy

Elucidation of physicochemical mechanisms of enzymatic processes is one of the main tasks of modern biology. High efficiency and selectivity of enzymatic catalysis are mostly ensured by conformational dynamics of enzymes and substrates. Here, we applied a stopped-flow kinetic analysis based on fluorescent spectroscopy to investigate mechanisms of conformational transformations during the removal of alkylated bases from DNA by ALKBH2, a human homolog of Escherichia coli AlkB dioxygenase. This enzyme protects genomic DNA against various alkyl lesions through a sophisticated catalytic mechanism supported by a cofactor (Fe(II)), a cosubstrate (2-oxoglutarate), and O₂. We present here a comparative study of conformational dynamics in complexes of the ALKBH2 protein with double-stranded DNA substrates containing N1-methyladenine, N3-methylcytosine, or 1,N6-ethenoadenine. By means of fluorescent labels of different types, simultaneous detection of conformational transitions in the protein globule and DNA substrate molecule was performed. Fitting of the kinetic curves by a nonlinear-regression method yielded a molecular mechanism and rate constants of its individual steps. The results shed light on overall conformational dynamics of ALKBH2 and damaged DNA during the catalytic cycle.     

Water as the Key to Proto‐Aragonite Amorphous CaCO3

Temperature and pH value can affect the short‐range order of proto‐structured and additive‐free amorphous calcium carbonates (ACCs). Whereas a distinct change occurs in proto‐vaterite (pv) ACC above 45 °C at pH 9.80, proto‐calcite (pc) ACC (pH 8.75) is unaffected within the investigated range of temperatures (7–65 °C). IR and NMR spectroscopic studies together with EXAFS analysis showed that the temperature‐induced change is related to the formation of proto‐aragonite (pa) ACC. The data strongly suggest that the binding of water molecules induces dipole moments across the carbonate ions in pa‐ACC as in aragonite, where the dipole moments are due to the symmetry of the crystal structure. Altogether, a (pseudo‐)phase diagram of the CaCO₃ polyamorphism in which water plays a key role can be formulated based on variables of state, such as the temperature, and solution parameters, such as the pH value.     

Check on a nonlocal Maxwellian theory of sound propagation in fluid-saturated rigid-framed porous media

A macroscopic nonlocal theory of sound propagation in homogeneous rigid-framed porous media permeated with a viscothermal fluid has been recently proposed in this journal. It accounts for the first time for the full temporal and spatial dispersion effects, independently of the nature of the microgeometry. In this paper this new Maxwellian theory is validated in the case of sound propagation in cylindrical circular tubes, by showing that it matches exactly the long-known direct Kirchhoff–Langevin’s solutions.     

Radiochemical characterization and decontamination of rare-earth-element concentrate recovered from uranium leach liquors

Journal of Radioanalytical and Nuclear Chemistry - The paper deals with two rare earth elements (REE) concentrates recovered from uranium leach liquors after sorption separation of uranium....     

Sigma map dynamics and bifurcations

Some interesting variants of walking droplet based discrete dynamical bifurcations arising from diffeomorphisms are analyzed in detail. A notable feature of these new bifurcations is that, like Smale horseshoes, they can be represented by simple geometric paradigms, which markedly simplify their analysis. The two-dimensional diffeomorphisms that produce these bifurcations are called sigma maps or double sigma maps for reasons that are made manifest in this investigation. Several examples are presented along with their dynamical simulations.