Employment of differential pulse polarography and adsorptive voltammetry for the determination of some sulfonamides

Reduction of sulfonamides in mineral acids was investigated using fast scan differential-pulse polarography (FSDPP). The optimal medium for sulfadimidin, sulfamethoxydin and sulfamethoxypyridazin is 0.01–0.02M HCl, while for phthalazol it is 1M HCl and the latter compound can be selectively determined in the presence of other sulfonamides. Adsorptive properties on the Hg-electrode were analytically used in the case of sulfamethoxypyridazin and phthalazol. Relative standard deviation of all determinations did not exceed 8%.     

Differential Invariants of Immersions of Manifolds with Metric Fields

The problem of finding all r^th order differential invariants of immersions of manifolds with metric fields, with values in a left (G¹_m×G¹_n)-manifold is formulated. For obtaining the basis of higher order differential invariants the orbit reduction method is used. As a new result it appears that r^th order differential invariants depending on an immersion f:M N of smooth manifolds M and N and metric fields on them can be factorized through metrics, curvature tensors and their covariant differentials up to the order (r–2), and covariant differentials of the tangent mapping Tf up to the order r. The concept of a covariant differential of Tf is also introduced in this paper. The obtained results are geometrically interpreted as well.This research is supported by grants GAR 201/03/0512 and MSM 143100006.     

Experimental techniques and terminology in gas-phase ion spectroscopy

This perspective gives an overview of the action spectroscopy methods for measurements of electronic, vibrational, and rotational spectra of mass-selected ions in the gas phase. We classify and give a short overview of the existing experimental approaches in this field. There is currently a plethora of names used for, essentially, the same techniques. Hence within this overview, we scrutinized the notations and suggested terms to be generally used. The selection was either driven by making the name unique and straightforward or the term being the most broadly used one. We believe that a simplification and a unification of the notation in ion spectroscopy can make this field better accessible for experts outside the mass spectrometry community where the applications of gas-phase action ion spectroscopy can make a large impact.     

High-temperature reactions in the Co<Subscript>3</Subscript>Cr<Subscript>4</Subscript>(PO<Subscript>4</Subscript>)<Subscript>6</Subscript>–Cr(PO<Subscript>3</Subscript>)<Subscript>3</Subscript> system

A new dichromium(III) cobalt(II) diphosphate(V) of the formula CoCr₂(P₂O₇)₂ was detected in the Co₃Cr₄(PO₄)₆–Cr(PO₃)₃ system. The new compound was obtained as a result of high-temperature solid-state reactions between CoCO₃, Cr₂O₃ and (NH₄)₂HPO₄ as well as between Cr(PO₃)₃ and Co₃Cr₄(PO₄)₆. CoCr₂(P₂O₇)₂ was characterized using XRD, DTA and IR methods. Results demonstrated that CoCr₂(P₂O₇)₂ crystallizes in the triclinic system and its unit cell parameters were calculated. Its infrared spectrum was presented. CoCr₂(P₂O₇)₂ melts incongruently at 1270±10 °C with a formation of solid α-CrPO₄. The compound Co₃Cr₄(PO₄)₆, component of the system under study, was obtained for the first time as a pure phase. Its thermal stability was also investigated. Co₃Cr₄(PO₄)₆ is stable in air up to 1410 ± 20 °C.     

Moisture transport in initially fully saturated concrete during drying

Moisture content changes during drying were investigated in the present work. Particular emphasis was placed on the initial stage of drying of saturated concrete, where moisture contents are high. For this stage of drying, experimental data are lacking, and no comprehensive theory exists to describe it. The present investigation was performed experimentally and numerically for drying of cylinders with one exposed end, made of normal weight and lightweight concrete with varying water to cement ratio (w/c). The gravimetric technique was employed to obtain the spatial distribution of moisture content. The experimental results obtained indicate that drying of concrete becomes diffusion controlled when the average moisture content decreases below 70 to 80% of the initial saturation. Typical drying rates are in the order of magnitude of 0.18 kg/day/m² and 0.02 kg/day/m² for the first and the second stage of drying, respectively. The lightweight concrete cylinders as compared to those made of normal weight concrete exhibited higher levels of moisture content throughout the process. At high w/c ratios, the moisture profiles for both types of cylinders, as expected, show steeper changes with time. Large, constant drying rates were observed both experimentally and numerically in the beginning of the drying. The numerical model developed is based on a generalized mathematical formulation for mass and heat transfer in porous media, and its predictions are in agreement with the experimental data within the uncertainty range of the input data.     

Indentation of a semi-infinite fluid-saturated poroelastic medium by an undeformable porous punch

Summary The following mixed boundary value problem in deformation theory of porous and elastic medium is considered. The bounding surface of the semiinfinite medium has a prescribed normal displacement within a circular area and prescribed stresses outside the circle. The techniques of integral transform are used. The expressions for the stresses and displacements are written down. As a special case, the indentation by a flat ended cylinder is considered and the distribution of pore-fluid pressure in the neighbourhood of the loaded area is shown graphically.     

The Endogenous Tryptophan‐derived Photoproduct 6‐formylindolo[3,2‐b]carbazole (FICZ) is a Nanomolar Photosensitizer that Can be Harnessed for the Photodynamic Elimination of Skin Cancer Cells in Vitro and in Vivo

UV‐chromophores contained in human skin may act as endogenous sensitizers of photooxidative stress and can be employed therapeutically for the photodynamic elimination of malignant cells. Here, we report that 6‐formylindolo[3,2‐b]carbazole (FICZ), a tryptophan‐derived photoproduct and endogenous aryl hydrocarbon receptor agonist, displays activity as a nanomolar sensitizer of photooxidative stress, causing the photodynamic elimination of human melanoma and nonmelanoma skin cancer cells in vitro and in vivo. FICZ is an efficient UVA/Visible photosensitizer having absorbance maximum at 390 nm (ε = 9180 L mol^?1 cm^?1), and fluorescence and singlet oxygen quantum yields of 0.15 and 0.5, respectively, in methanol. In a panel of cultured human squamous cell carcinoma and melanoma skin cancer cells (SCC‐25, HaCaT‐ras II‐4, A375, G361, LOX), photodynamic induction of cell death was elicited by the combined action of solar simulated UVA (6.6 J cm^?2) and FICZ (≥10 nm ), preceded by the induction of oxidative stress as substantiated by MitoSOX Red fluorescence microscopy, comet detection of Fpg‐sensitive oxidative genomic lesions and upregulated stress response gene expression (HMOX1, HSPA1A, HSPA6). In SKH1 “high‐risk” mouse skin, an experimental FICZ/UVA photodynamic treatment regimen blocked the progression of UV‐induced tumorigenesis suggesting feasibility of harnessing FICZ for the photooxidative elimination of malignant cells in vivo.     

Mixed Organometallic–Organic Hybrid Assemblies Based on the Diarsene Complex [Cp2Mo2(CO)4(μ,η2-As2)], AgI Salts and N-Donor Organic Molecules

The reaction of the organometallic diarsene complex [Cp₂Mo₂(CO)₄(η²-As₂)] ( 1 ) with Ag[Al{OC(CF₃)₃}₄] (Ag[TEF]) yielded the Ag^I monomer [Ag(η²- 1 )₃][TEF] ( 2 ). This compound exhibits dynamic behavior in solution, which allows directed selective synthesis of unprecedented organometallic–organic hybrid assemblies upon its reaction with N-donor organic molecules by a stepwise pathway, which is supported by DFT calculations. Accordingly, the reaction of 2 with 2,2′-bipyrimidine ( L1 ) yielded the dicationic molecular compound [{(η²- 1 )₂Ag}₂(μ- L1 )][TEF]₂ ( 3 ) or the 1D polymer [{(η²- 1 )Ag}(μ- L1 )]_n[TEF]_n ( 4 ) depending on the ratio of the reactants. However, its reactions with the pyridine-based linkers 4,4′-bipyridine ( L2 ), 1,2-bis(4-pyridyl)ethylene ( L3 ) and 1,2-bis(4-pyridyl)ethyne ( L4 ) allowed the formation of the 2D polymers [{(η²- 1 )Ag}₂(μ- Lx )₃]_n[TEF]_2n [ Lx=L2 ( 5 ), L3 ( 6 ), L4 ( 7 ), respectively]. Additionally, this concept was extended to step-by-step one-pot reactions of 1 , [Ag(CH₃CN)₃][Al{OC(CF₃)₂(CCl₃)}₄] ([Ag(CH₃CN)₃][TEF^Cl]) and linkers L2 – L4 to produce the 2D polymers [{(η²- 1 )Ag}₂(μ, Lx )₃]_n[TEF^Cl]_2n [ Lx = L2 ( 8 ), L3 ( 9 ), L4 ( 10 ), respectively].     

Magnetic NiFe2O4 Nanoparticles Prepared via Non-Aqueous Microwave-Assisted Synthesis for Application in Electrocatalytic Water Oxidation

Phase-pure spinel-type magnetic nickel ferrite (NiFe₂O₄) nanocrystals in the size range of 4 to 11 nm were successfully synthesized by a fast and energy-saving microwave-assisted approach. Size and accessible surface areas can be tuned precisely by the reaction parameters. Our results highlight the correlation between size, degree of inversion, and magnetic characteristics of NiFe₂O₄ nanoparticles, which enables fine-tuning of these parameters for a particular application without changing the elemental composition. Moreover, the application potential of the synthesized powders for the electrocatalytic oxygen evolution reaction in alkaline media was demonstrated, showing that a low degree of inversion is beneficial for the overall performance. The most active sample reaches an overpotential of 380 mV for water oxidation at 10 mA cm⁻² and 38.8 mA cm⁻² at 1.7 V vs. RHE, combined with a low Tafel slope of 63 mV dec⁻¹.     

Allicin,the Odor of Freshly Crushed Garlic: A Review of Recent Progress in Understanding Allicin’s Effects on Cells

The volatile organic sulfur compound allicin (diallyl thiosulfinate) is produced as a defense substance when garlic (Allium sativum) tissues are damaged, for example by the activities of pathogens or pests. Allicin gives crushed garlic its characteristic odor, is membrane permeable and readily taken up by exposed cells. It is a reactive thiol-trapping sulfur compound that S-thioallylates accessible cysteine residues in proteins and low molecular weight thiols including the cellular redox buffer glutathione (GSH) in eukaryotes and Gram-negative bacteria, as well as bacillithiol (BSH) in Gram-positive firmicutes. Allicin shows dose-dependent antimicrobial activity. At higher doses in eukaryotes allicin can induce apoptosis or necrosis, whereas lower, biocompatible amounts can modulate the activity of redox-sensitive proteins and affect cellular signaling. This review summarizes our current knowledge of how bacterial and eukaryotic cells are specifically affected by, and respond to, allicin.