Protecting the Last Line of Defense: Analytical Approaches for Sample Preparation and Determination of the Reserve Group of Antibiotics in the Environment.

Drug resistance in microorganisms is a serious threat to life and health due to the limited number of antibiotics that show efficacy in treating infections and the difficulty in discovering new compounds with antibacterial activity. To address this issue, the World Health Organization created the AWaRe classification, a tool to support global and national antimicrobial stewardship programs. The AWaRe list categorizes antimicrobials into three groups - Access, Watch, and Reserve - according to their intended use. The Reserve group comprises "last resort" medicines used solely for treating infections caused by bacterial strains that are resistant to other treatments. It is therefore necessary to protect them, not only by using them as prudently as possible in humans and animals, but also by monitoring their subsequent fate. Unmetabolized antibiotics enter the environment through hospital and municipal wastewater or from manure, subsequently contaminating bodies of water and soils, thus contributing to the emergence and spread of antibiotic resistance. This article presents a review of determination methods for the Reserve group of antimicrobials in water, wastewater, and manure. Procedures for extracting and determining these substances in environmental samples are described, showing the limited research available, which is typically on a local level.

Application of UHPLC-MS/MS method to monitor the occurrence of sulfonamides and their transformation products in soil in Silesia, Poland.

Sulfonamides circulating in the environment lead to disturbances in food chains and local ecosystems, but most importantly contribute to development of resistance genes, which generate problems with multidrug-resistant bacterial infections treatment. In urban areas, sources of sulfonamide distribution in soils have received comparatively less attention in contrast to rural regions, where animal-derived manure, used as a natural fertilizer, is considered the main source. The aim of this study was to determine eight sulfonamides (sulfadiazine, sulfamerazine, sulfamethazine, sulfamethizole, sulfamethoxazole, sulfapyridine, sulfathiazole, and sulfisoxazole) in environmental soil samples collected from urbanized regions in Silesian Voivodeship with increased animal activity. These soils were grouped according to the organic carbon content. It was necessary to develop versatile and efficient extraction and determination method to analyze selected sulfonamides in various soil types. The developed LC-MS/MS method for sulfonamides analyzing was validated. The obtained recoveries exceeded 45% for soil with medium organic carbon content and 88% for sample with a very low organic carbon content (arenaceous quartz). The obtained results show the high impact of organic matter on analytes adsorption in soil, which influences recovery. All eight sulfa drugs were determined in environmental samples in the concentration range 1.5-10.5 ng g-1. The transformation products of the analytes were also identified, and 29 transformation products were detected in 24 out of 27 extracts from soil samples.

Highly Substituted 10-RO-(hetero)acenes-Electric Properties of Vacuum-Deposited Molecular Films.

The functionalization of the aromatic backbone allows the improvement of the electrical properties of acene molecules in the amorphous layered structures of organic thin films. In the present work, we discuss the electric properties of the stable, amorphous, vacuum-deposited films prepared from five highly substituted 10-RO-acenes of various electronic properties, i.e., two extreme electron-donor (1,3-dioxa-cyclopenta[b]) anthracenes with all RO substituents, two anthracene carbaldehydes and one benzo[b]carbazole carbaldehyde possessing both electron-donor and acceptor substituents. The hole mobility data were obtained using subsequent steady state space charge limited currents (SCLC) and Time of Flight (TOF) measurements, performed on the same sample and these were then compared with the results of theoretical hole mobility calculations obtained using the Density Functional Theory (DFT) quantum-chemical calculations using the Marcus-Hush theory. The study shows a good agreement between the theoretical and experimental values which allows for the quick and quantitative estimation of Einstein's mobility values for highly substituted 10-RO anthracene and benzo[b]carbazole based on chemical calculations. This agreement also proves that the transport of holes follows the hopping mechanism. The theoretical calculations indicate that the reorganization energy plays a decisive role in the transport of holes in the amorphous layers of highly substituted hetero(acenes).

Mass/Heat Transfer Analogy Method in the Research on Convective Fluid Flow through a System of Long Square Mini-Channels.

The paper presents the results of experimental investigations of mass transfer processes with the use of the limiting current technique. This experimental work analyzed the not fully developed entrance laminar region. The tested case refers to the convective fluid flow through a system of nine long, square mini-channels that are 2 mm wide and 100 mm long. The method used in the measurements allows one to determine mass transfer coefficients during the electrolyte flow by utilizing electrochemical processes. The received mass transfer coefficients were applied to the analogous heat transfer case. The Chilton-Colburn analogy between mass and heat transfer was applied. The obtained results, in the form of the dependence of Nusselt number within the function of Reynolds and Prandtl numbers, can be a useful formula in the design and analysis of heat transfer processes in mini heat exchangers.

Organosulfur Materials with High Photo- and Photo-Oxidation Stability: 10-Anthryl Sulfoxides and Sulfones and Their Photophysical Properties Dependent on the Sulfur Oxidation State.

While few studies show only symmetrical and poorly mono-SOn (n = 0-2) substituted acenes, in this study, we present a synthesis of a new group of unsymmetrical, significantly substituted derivatives, which revealed unique photophysical properties. Both sulfides (S), sulfoxides (SO) and sulfones (SO2) showed very high photochemical stabilities, unusual for these groups, during UV-irradiation at 254/365 nm (air O2 and Ar), which was higher than any found in the literature. For the (S)/(SO) series (254 nm), the stabilities of 80-519 min. (air O2 and Ar) were found. At 365 nm, stabilities of 124-812 min./(air O2) for (S)/(SO) and higher for (SO2) were observed. Photoluminescence lifetimes of (SOn) of the lower anthryl symmetry remained in the following order: (SO2) < (S) < (SO); those with full symmetry were in the following order: (S) < (SO) < (SO2). The enhanced photostability was explained with DFT/MS/Hammett's constants, which showed the leading role of the SOn groups in stabilization of HOMO/LUMO frontier orbitals. The SOn (n = 0-2) substituted acenes turned out to be tunable violet/blue/green emitters by oxidation of S atoms and the introduction of rich substitution.

Application of UHPLC-MS/MS method to study occurrence and fate of sulfonamide antibiotics and their transformation products in surface water in highly urbanized areas.

Sulfonamide antibiotics (SAs) are used on a large scale in human and veterinary medicine. The main goal of this study was to develop a method for the detection of selected SAs (sulfamethoxazole, sulfadiazine, sulfamethazine, sulfathiazole, sulfapyridine, sulfamerazine, sulfamethiazole, and sulfisoxazole) in aqueous samples (targeted analysis), and then conduct a non-targeted analysis to determine the transformation products to elucidate their degradation pathways. These analyses were performed using ultra-high-performance liquid chromatography coupled to tandem mass spectrometry. The procedure was used to detect selected antibiotics in water samples collected throughout a highly urbanized area. Among the studied compounds, sulfamethoxazole (max. 78.88 ng L-1) and sulfapyridine (max. 38.88 ng L -1) were the most common pollutants identified in surface waters. Trace amounts of sulfadiazine (below LOQ = 0.40 ng L-1) were also detected. Next, the samples were screened to detect the transformation products. Several sulfadiazine and sulfamethoxazole transformation products were detected and confirmed in the environmental samples.

Experimental investigations on graphene oxide/rubber composite thermal conductivity.

Graphene oxide/rubber composites were experimentally investigated for obtaining their thermal properties. Three kinds of the composite matrix material have been used: NBR, HNBR and FKM. The reduced graphene oxide in the form of crumped flakes has been applied as the filler influencing on thermal conductivity of the composites. Two values of graphene oxide weight concentration have been taken into account in the investigation. Thermal conductivity of the composites and basic matrix has been measured by the professional apparatus with the use of the guarded heat plate method. Before measurements the preliminary tests using the simplified comparative method have been performed. The results obtained, both from preliminary tests and using the guarded heat plate method, show an increase in thermal conductivity with increasing the reduced graphene oxide content in the composite. The experimental investigation allowed to determine not only the increase in thermal properties of graphene oxide/rubber composites compared to the basic matrix, but also the absolute values of thermal conductivities. Additionally, the SEM analysis showed that the tested composite samples contain agglomerates of the rGO nanoparticles. The occurrence of agglomerates could affect the composite thermal properties. This was noticed in the comparatively measurements of the temperature of different composites during the heating of samples tested. The maximum enhancement of thermal conductivity obtained was about 11% compared to the basis matrix of the composites tested.

Optically Active Cubic Liquid Crystalline Phase Made of Achiral Polycatenar Stilbene Derivatives.

Achiral stilbene polycatenars forming smectic, columnar or cubic phase depending on the terminal chains length, were studied. The cubic Im3m phase exhibited optical activity originating in twisted face-to-face molecular aggregates. The optical activity of the phase is preserved upon sample crystallization, providing evidence of a transfer of chirality on a molecular level.