Measurement of benzene concentration in urban air using passive sampling

The concentration of benzene in urban air in the Tri-City area of Poland (Gdańsk–Sopot–Gdynia, and Tczew) was assessed using diffusive passive samplers (Radiello). Samples were collected during a four-year monitoring campaign (2007–2010) at selected monitoring stations managed by the Agency of Regional Air Quality Monitoring in the Gdańsk Metropolitan Area (ARMAAG) Foundation. The performance of the passive samplers was investigated in a field study that measured the benzene concentration in urban air. The results obtained by the Radiello samplers were compared with the results obtained using an on-line monitor (Chrompack CP 7001). Statistical analysis of the results obtained by the two different techniques (passive and on-line) was performed by a linear regression method (Student’s t-test). The influence of temperature fluctuations on the uptake rate behavior of the passive samplers was also investigated.     

Antimicrobial,Cytotoxic and Mutagenic Activity of Gemini QAS Derivatives of 1,4:3,6-Dianhydro-l-iditol

A series of quaternary diammonium salts derivatives of 1,4:3,6-dianhydro-l-iditol were synthesized, using isommanide (1,4:3,6-dianhydro-d-mannitol) as a starting material. Both aromatic (pyridine, 4-(N,N-dimethylamino)pyridine (DMAP), (3-carboxamide)pyridine; N-methylimidazole) and aliphatic (trimethylamine, N,N-dimethylhexylamine, N,N-dimethyloctylamine, N,N-dimethyldecylamine) amines were used, giving eight gemini quaternary ammonium salts (QAS). All salts were tested for their antimicrobial activity against yeasts, Candida albicans and Candida glabrata, as well as bacterial Staphylococcus aureus and Escherichia coli reference strains. Moreover, antibacterial activity against 20 isolates of S. aureus collected from patients with skin and soft tissue infections (n = 8) and strains derived from subclinical bovine mastitis milk samples (n = 12) were evaluated. Two QAS with octyl and decyl residues exhibited antimicrobial activity, whereas those with two decyl residues proved to be the most active against the tested pathogens, with MIC of 16–32, 32, and 8 µg/mL for yeast, E. coli, and S. aureus reference and clinical strains, respectively. Only QAS with decyl residues proved to be cytotoxic in MTT assay against human keratinocytes (HaCaT), IC₅₀ 12.8 ± 1.2 μg/mL. Ames test was used to assess the mutagenic potential of QAS, and none of them showed mutagenic activity in the concentration range 4–2000 µg/plate.     

Natural and Conventional Cosmetics—Mercury Exposure Assessment

Mercury (Hg) can enter the human body through the respiratory tract and digestive system, but also through the skin. Sources of Hg in the environment can be natural processes, but also human activities, including agriculture, chemical, and pharmaceutical industries. Hg can also enter the body through food, but also with cosmetics that are used for a long time. Therefore, the aim of this study was to evaluate the Hg content in 268 randomly selected cosmetics: Natural and conventional, for face and body. Hg content was determined using an atomic absorption spectrometer (AMA 254, Leco, Prague, Czech Republic). It was shown that the face preparations were characterized by a significantly higher Hg content than the body preparations. No differences in the content of the tested element were found between natural and conventional preparations. Hg could be detected in all samples with concentrations measured from 0.348 to 37.768 µg/kg.     

Dissociative electron attachment to triflates

Gas phase studies of dissociative electron attachment to simple alkyl (CF(3)SO(3)CH(3)) and aryl (C(6)H(5)SO(3)CF(3) and CF(3)SO(3)C(6)H(4)CH(3)) triflates, model molecules of nonionic photoacid generators for modern lithographic applications, were performed. The fragmentation pathways under electron impact below 10 eV were identified by means of crossed electron-molecular beam mass spectrometry. Major dissociation channels involved C-O, S-O, or C-S bond scissions in the triflate moiety leading to the formation of triflate (OTf(-)), triflyl (Tf(-)), or sulfonate (RSO(3)(-)) anions, respectively. A resonance leading to C-O bond breakage and OTf(-) formation in alkyl triflates occurred at electron energies about 0.5 eV lower than the corresponding resonance in aryl triflates. A resonance leading to S-O bond breakage and Tf(-) formation in aryl triflates occurred surprisingly at the same electron energies as C-O bond breakage. In case of alkyl triflates S-O bond breakage required 1.4 eV higher electron energies to occur and proceeded with substantially lower yields than in aryl triflates. C-S bond scission occurred for all presently studied triflates at energies close to 3 eV.     

Enhancement of activity of platinum towards oxidation of ethanol by supporting on titanium dioxide containing phosphomolybdate-modified gold nanoparticles

A new concept of utilization of titanium dioxide matrix in electrocatalysis by admixing it with polyoxometallate modified gold nanoparticles is described here. The approach utilizes Keggin-type phosphododecamolybdate (PMo₁₂O₄₀³⁻) adsorbates capable of modifying, activating and stabilizing Au nanoparticles of the sizes of 30-40 nm. Ultra-thin films of phosphomolybdates on nanostructured gold are characterized by well-defined fast (reversible) multi-electron electrochemical reactions. By dispersing platinum black over the Au-containing TiO₂, the electrocatalytic activity of Pt nanoparticles towards oxidation of ethanol has been enhanced. Remarkable increases of electrocatalytic currents measured under voltammetric and chronoamperometric conditions have been observed. The most likely explanation takes into account improvement of overall conductivity (due to the presence of nanostructured gold) at the electrocatalytic interface (including TiO₂-support), as well as and possibility of specific Pt-TiO₂ or Pt-Au electronic interactions and existence of active hydroxyl groups (on titanium dioxide or polyoxometallate surfaces) in the vicinity of catalytic Pt sites.     

Electrocatalytic properties of platinum nanocenters electrogenerated at ultra-trace levels within zeolitic phosphododecatungstate cesium salt matrices

A unique preparation method of obtaining stable composite film (with ultra-low platinum content) highly active towards oxygen reduction and hydrogen oxidation is presented here. The matrix for platinum centers consists of high-surface-area zeolite-type acidic salt of cesium phosphododecatungstate (Cs_2.5H_0.5PW₁₂O₄₀) admixed with carbon (Vulcan XC-72) carriers. Platinum nanoparticles were deposited on the working electrode modified with matrix via corrosion of platinum counter electrode during cyclic voltammetry experiment conducted in acid electrolyte containing chloride ions. The results obtained from rotating disk voltammetry revealed that the composite film containing Pt nanoparticles at very low loadings (on the level of 2–5 μg cm^?2) demonstrated remarkable electrocatalytic activity towards both oxygen reduction and hydrogen oxidation, particularly, when compared to the performance of the Cs_2.5H_0.5PW₁₂O₄₀-free system (i.e., containing only Vulcan support) prepared and examined under analogous conditions. The phenomenon should be primarily ascribed to the mesoporous nature of the matrix enabling immobilization and stabilization of small catalytic nanoparticles (1–2 nm diameters) inside the pores as well as to high surface acidity of the polyoxometalate-based salt providing proton-rich environment at the electrocatalytic interface.     

Effectiveness of Volatile Natural Deep Eutectic Solvents (VNADESs) for the Green Extraction of Chelidonium majus Isoquinoline Alkaloids

The Chelidonium majus plant is rich in biologically active isoquinoline alkaloids. These alkaline polar compounds are isolated from raw materials with the use of acidified water or methanol; next, after alkalisation of the extract, they are extracted using chloroform or dichloromethane. This procedure requires the use of toxic solvents. The present study assessed the possibility of using volatile natural deep eutectic solvents (VNADESs) for the efficient and environmentally friendly extraction of Chelidonium alkaloids. The roots and herb of the plant were subjected three times to extraction with various menthol, thymol, and camphor mixtures and with water and methanol (acidified and nonacidified). It has been shown that alkaloids can be efficiently isolated using menthol–camphor and menthol–thymol mixtures. In comparison with the extraction with acidified methanol, the use of appropriate VNADESs formulations yielded higher amounts of protopine (by 16%), chelidonine (35%), berberine (76%), chelerythrine (12%), and coptisine (180%). Sanguinarine extraction efficiency was at the same level. Additionally, the values of the contact angles of the raw materials treated with the tested solvents were assessed, and higher wetting dynamics were observed in the case of VNADESs when compared with water. These results suggest that VNADESs can be used for the efficient and environmentally friendly extraction of Chelidonium alkaloids.     

Parallel imaging of coagulation pathway proteases activated protein C,thrombin, and factor Xa in human plasma

Activated protein C (APC), thrombin, and factor (f) Xa are vitamin K-dependent serine proteases that are key factors in blood coagulation. Moreover, they play important roles in inflammation, apoptosis, fibrosis, angiogenesis, and viral infections. Abnormal activity of these coagulation factors has been related to multiple conditions, such as bleeding and thrombosis, Alzheimer''s disease, sepsis, multiple sclerosis, and COVID-19. The individual activities of APC, thrombin, and fXa in coagulation and in various diseases are difficult to establish since these proteases are related and have similar substrate preferences. Therefore, the development of selective chemical tools that enable imaging and discrimination between coagulation factors in biological samples may provide better insight into their roles in various conditions and potentially aid in the establishment of novel diagnostic tests. In our study, we used a large collection of unnatural amino acids, and this enabled us to extensively explore the binding pockets of the enzymes'' active sites. Based on the specificity profiles obtained, we designed highly selective substrates, inhibitors, and fluorescent activity-based probes (ABPs) that were used for fast, direct, and simultaneous detection of APC, thrombin, and fXa in human plasma.

Using a collection of natural and unnatural amino acids, we synthesized a set of fluorescent activity-based probes for the fast, direct, and simultaneous detection of coagulation factors in human plasma.