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What Does Ectoine Do to DNA? A Molecular-Scale Picture of Compatible Solute−Biopolymer Interactions
(2020)
Compatible solutes are accumulated in the cytoplasm of halophilic microorganisms. These molecules enable their survival in a high salinity environment. Ectoine is such a compatible solute. It is a zwitterionic molecule which strongly interacts with surrounding water molecules and changes the dynamics of the local hydration shell. Ectoine interacts with biomolecules such as lipids, proteins and DNA. The molecular interaction between ectoine and biomolecules in particular the interaction between ectoine and DNA is far from being understood.
In this paper we describe molecular aspects of the interaction between ectoine and double stranded DNA(dsDNA). Two 20 base pairs long dsDNA fragments were immobilized on a Gold surface via a thiol-tether. The interaction between the dsDNA monolayers with diluted and concentrated ectoine solutions was examined by means of X-ray photoelectron and polarization modulation infrared reflection absorption spectroscopies (PM IRRAS). Experimental results indicate that the ability of ectoine to bind water reduces the strength of hydrogen bonds formed to the ribose-phosphate backbone in the dsDNA. In diluted (0.1 M) ectoine solution, DNA interacts predominantly with water molecules. The sugar-phosphate backbone is involved in the formation of strong hydrogen bonds to water, which with elapsing time leads to a reorientation of the planes of nucleic acid bases. This reorientation destabilizes the hydrogen bonds strength between the bases and leads to a partial dehybridizaiton of the dsDNA. In concentrated ectoine solution (2.5 M), almost all water molecules interact with ectoine. Under this condition ectoine is able to interact directly with DNA. Density functional theory (DFT) calculations demonstrate that the direct interaction involves the nitrogen atoms in ectoine and phosphate groups in the DNA molecule. The results of the quantum chemical calculations Show that rearrangements in the ribose-phosphate backbone, caused by a direct interaction with ectoine, facilitates contacts between O atom in the phosphate group and H atoms in a nucleic acid base. In the PM IRRA spectra, an increase in the number of the IR absorption modes in the base pair frequency region proves that the hydrogen bonds between bases become weaker.
Thus, a sequence of reorientations caused by interaction with ectoine leads to a breakdown of hydrogen bonds between bases in the double helix.
Water is generally considered to be an undesirable substance in fuel system, which may lead to microbial contamination. The antibacterial strategies that can turn water into things of value with high disinfection efficacy have been urgently needed for fuel system. Here, we reveal a water-fueled autocatalytic bactericidal pathway comprised by bi-metal micro-electrode system, which can spontaneously produce reactive oxygen species (mainly H2O2 and O2•–) by the electron Fenton-like reaction in water medium without external energy., The respiratory chain component of bacteria and the galvanic corrosion on the coated metals were two electron sources in the system. The specific model of Ag-Ru water-fueled autocatalytic (WFA) microelectrode particles presents extremely high disinfection efficiency (>99.9999%) in less than one hour for three aerobic bacteria (Escherichia coli, Pseudomonas aeruginosa and Bacillus subtilis) in LB media and high disinfection efficiency for the anaerobic bacteria (Desulfovibrio alaskensis) in Postgate E media without natural light irradiation. Overall, the novel WFA Ag-Ru antibacterial material explored in this study has a high potential for sterilizing applications in fuel system and this work provides the potential for the development of non-chemical and water-based antibacterial materials, such as WFA Ag-Ru antibacterial coating on stainless steel.
The potential release of hazardous substances from polymer-based products is currently in the focus of environmental policy. Environmental simulations are applied to expose such products to selected aging conditions and to investigate release processes. Commonly applied aging exposure types such as solar and UV radiation in combination with water contact, corrosive gases, and soil contact as well as expected general effects on polymers and additional ingredients of polymer-based products are described. The release of substances is based on mass-transfer processes to the material surfaces. Experimental approaches to investigate transport processes that are caused by water contact are presented. For tailoring the tests, relevant aging exposure types and release quantification methods must be combined appropriately. Several studies on the release of hazardous substances such as metals, polyaromatic hydrocarbons, flame retardants, antioxidants, and carbon nanotubes from polymers are summarized exemplarily. Differences between natural and artificial exposure tests are discussed and demonstrated for the release of flame retardants from several polymers and for biocides from paints. Requirements and limitations to apply results from short-term artificial environmental exposure tests to predict long-term environmental behavior of polymers are presented.
Understanding Stimulation of Conjugal Gene Transfer by Nonantibiotic Compounds: How Far Are We?
(2024)
A myriad of nonantibiotic compounds is released into the environment, some of which may contribute to the dissemination of antimicrobial resistance by stimulating conjugation. Here, we analyzed a collection of studies to (i) identify patterns of transfer stimulation across groups and concentrations of chemicals, (ii) evaluate the strength of evidence for the proposed mechanisms behind conjugal stimulation, and (iii) examine the plausibility of alternative mechanisms. We show that stimulatory nonantibiotic compounds act at concentrations from 1/1000 to 1/10 of the minimal inhibitory concentration for the donor strain but that stimulation is always modest (less than 8-fold). The main proposed mechanisms for stimulation via the reactive oxygen species/SOS cascade and/or an increase in cell membrane permeability are not unequivocally supported by the literature. However, we identify the reactive oxygen species/SOS cascade as the most likely mechanism. This remains to be confirmed by firm molecular evidence. Such evidence and more standardized and high-throughput conjugation assays are needed to create technologies and solutions to limit the stimulation of conjugal gene transfer and contribute to mitigating global antibiotic resistance.
Microplastics are small plastic fragments that are widely distributed in marine and terrestrial environments. While the soil ecosystem represents a large reservoir for plastic, research so far has focused mainly on the impact on aquatic ecosystems and there is a lack of information on the potentially adverse effects of microplastics on soil biota. Earthworms are key organisms of the soil ecosystem and are due to their crucial role in soil quality and fertility a suitable and popular model organism in soil ecotoxicology.
Therefore, the aim of this study was to gain insight into the effects of environmentally relevant concentrations of microplastics on the earthworm Eisenia andrei on multiple levels of biological organization after different exposure periods. Earthworms were exposed to two types of microplastics: (1) polystyrene-HBCD and (2) car tire abrasion in natural soil for 2, 7, 14 and 28 d. Acute and chronic toxicity and all subcellular investigations were conducted for all exposure times, avoidance behavior assessed after 48 h and reproduction after 28 d. Subcellular endpoints included enzymatic biomarker responses, namely, carboxylesterase, glutathione peroxidase, acetylcholinesterase, glutathione reductase, glutathione S-transferase and catalase activities, as well as fluorescence-based measurements of oxidative stress-related markers and multixenobiotic resistance activity. Multiple biomarkers showed significant changes in activity, but a recovery of most enzymatic activities could be observed after 28 d. Overall, only minor effects could be observed on a subcellular level, showing that in this exposure scenario with environmentally relevant concentrations based on German pollution levels the threat to soil biota is minimal. However, in areas with higher concentrations of microplastics in the environment, these results can be interpreted as an early warning signal for more adverse effects. In conclusion, these findings provide new insights regarding the ecotoxicological effects of environmentally relevant concentrations of microplastics on soil organisms.
Various microlevel circular economy indicators for assessing sustainability and, partly, additional sustainability characteristics have been developed, but an integrated solution considering the environmental, social, and economic pillars remains a research gap. Method: Based on a multimethod approach, including surveys and the analysis of existing sustainability assessment methodologies and standards, this paper proposes a concept for a multidimensional circular economy indicator tailored to public procurers. It relies on attractive existing building blocks including: the ecological scarcity method, European and international sustainability standards and indicators,and the STAR-ProBio-IAT concept. Results: This article presents the concept of the composite indicator Triple-C, consisting of 20 elements and aimed at facilitating sustainable circular public procurement. It is intended to be incorporated into software that facilitates sustainable product decisions among public procurers in Germany. Conclusions: We propose a generic indicator concept covering all three (environmental, social, and economic) sustainability pillars. More research and additional standards are needed to develop the Triple-C concept further into product-specific applications.
Transparent polycarbonate coated with CeO2 nanozymes repel Pseudomonas aeruginosa PA14 biofilms
(2022)
Highly transparent CeO2/polycarbonate surfaces were fabricated that prevent adhesion, proliferation, and the spread of bacteria. CeO2 nanoparticles with diameters of 10–15 nm and lengths of 100–200 nm for this application were prepared by oxidizing aqueous dispersions of Ce(OH)3 with H2O2 in the presence of nitrilotriacetic acid (NTA) as the capping agent. The surface-functionalized water-dispersible CeO2 nanorods showed high catalytic activity in the halogenation reactions, which makes them highly efficient functional mimics of haloperoxidases. These enzymes are used in nature to prevent the formation of biofilms through the halogenation of signaling compounds that interfere with bacterial cell–cell communication (“quorum sensing”). Bacteria-repellent CeO2/polycarbonate plates were prepared by dip-coating plasma-treated polycarbonate plates in aqueous CeO2 particle dispersions. The quasi-enzymatic activity of the CeO2 coating was demonstrated using phenol red enzyme assays. The monolayer coating of CeO2 nanorods (1.6 µg cm−2) and the bacteria repellent properties were demonstrated by atomic force microscopy, biofilm assays, and fluorescence measurements. The engineered polymer surfaces have the ability to repel biofilms as green antimicrobials on plastics, where H2O2 is present in humid environments such as automotive parts, greenhouses, or plastic containers for rainwater.
The formation of transformation products (TPs) from contaminants and residues is becoming an increasing focus of scientific community. All organic compounds can form different TPs, thus demonstrating the complexity and interdisciplinarity of this topic. The properties of TPs could stand in relation to the unchanged substance or be more harmful and persistent. To get important information about the generated TPs, methods are needed to simulate natural and manmade transformation processes. Current tools are based on metabolism studies, photochemical methods, electrochemical methods, and Fenton's reagent. Finally, most transformation processes are based on redox reactions. This review aims to compare these methods for structurally different compounds. The groups of pesticides, pharmaceuticals, brominated flame retardants, and mycotoxins were selected as important residues/contaminants relating to their worldwide occurrence and impact to health, food, and environmental safety issues. Thus, there is an increasing need for investigation of transformation processes and identification of TPs by fast and reliable methods.
Bifunctional fluorescent molecular oxoanion probes based on the benzoxadiazole (BD) chromophore are described which integrate a thiourea binding motif and a polymerizable 2-aminoethyl methacrylate unit in the 4,7-positions of the BD core. Concerted charge transfer in this electron donor-acceptor-donor architecture endows the dyes with strongly Stokes shifted (up to >250 nm) absorption and fluorescence. Binding of electron-rich carboxylate guests at the thiourea receptor leads to further analyte-induced red-shifts of the emission, shifting the fluorescence maximum of the complexes to ≥700 nm. Association constants for acetate are ranging from 1–5×105 M−1 in acetonitrile. Integration of one of the fluorescent probes through its polymerizable moiety into molecularly imprinted polymers (MIPs) grafted from the surface of submicron silica cores yielded fluorescent MIP-coated particle probes for the selective detection of antibiotics containing aliphatic carboxylate groups such as enoxacin (ENOX) at micromolar concentrations in highly polar solvents like acetonitrile.
ABSTRACT: A collection of thioimidazolium salts were synthesized and used as a new class of nonvolatile alkylating agents. Their nonvolatility prevents exposure during use or handling and are thus drastically safer than conventional alkylating agents. We discovered that thioimidazolium Iodide salts cannot release volatile compounds in the solid state, but instead only decompose when molten. Since decomposition proceeds via alkyl iodide elimination, SN2 of iodide on the thioimidazolium cation is constrained in the solid state, and instead can occur only upon melting when ions are mobile. By smart design of these alkylators, the melting point and thus the decomposition temperature of these salts can be increased from 106 to 169 °C and release negligible volatile organic compounds prior to melting. Thioimidazolium-bis(trifluoromethanesulfonyl)imide (TFSI) ionic liquids act as a completely nonvolatile and air-stable TFSI-based alkylating agent and can be used for high-throughput Synthesis of TFSI ionic liquids without solvent. Alkyl groups from methyl to dodecyl can be transferred to a nucleophile and the product purified by sublimation of the thione byproduct, which can then be recycled. We also found that thioimidazolium salts with a dodecyl chain are bactericidal, yet can hydrolyze in water to form benign neutral products, and thus wont accumulate in the environment. These results demonstrate that thioimidazolium salts are a designable platform for the pursuit of safer and more environmentally friendly alkylating and antiseptic agents.