Especially added on many industrial and domestic products as flame retardants (FRs), polybrominated diphenyl ethers (PBDEs) are among the chemicals of high environmental concern because of their ...potential harmfulness for environmental and human health. Seafood consumption is considered the main source of PBDEs and their methoxylated congeners (MeO-BDEs) for humans. The present study aims to investigate the seasonal occurrence of six PBDEs and eight MeO-BDEs congeners using Douro river biota (different trophic levels) as sentinels, as well as to evaluate the human exposure risk to PBDEs through seafood consumption. Biota samples (n = 273) were collected from one of the most important Portuguese estuaries in the north-western coast of Portugal at four different seasons (2019–2020). The analyses were performed by an environmental-friendly extraction procedure followed by Gas Chromatography coupled to a triple quadrupole detector (GC–MS/MS). PBDEs were detected in all seafood samples analysed, with means ranging from 0.02 ng g−1 ww (flounder in autumn) to 3.75 ng g−1 ww (mussel in winter). Levels of lower-brominated PBDE congeners were significantly higher than higher-brominated ones in all seasons (p < 0.01). MeO-BDEs ranged from 0.001 ng g−1 ww (grey mullet in summer) to 5.66 ng g−1 ww (green crab in spring). Crabs and mussels presented the highest means of PBDEs and MeO-BDEs. Regarding the health risk assessment of the studied PBDE congeners (47, 99, and 153), consumption of Douro river fish is not a case of concern for consumers.
Display omitted
•PBDEs and their metabolites were found in Douro river biota.•Higher levels of MeO-BDEs were found in both invertebrate and macroalgae species.•PBDEs and MeO-BDEs levels varied among seasons.•Low risk through fish consumption according to the MOE threshold for PBDEs.
Laser spectroscopy of muonic deuterium Pohl, Randolf; Nez, François; Fernandes, Luis M. P. ...
Science (American Association for the Advancement of Science),
08/2016, Letnik:
353, Številka:
6300
Journal Article
Recenzirano
Odprti dostop
The deuteron is the simplest compound nucleus, composed of one proton and one neutron. Deuteron properties such as the root-mean-square charge radius rd and the polarizability serve as important ...benchmarks for understanding the nuclear forces and structure. Muonic deuterium μd is the exotic atom formed by a deuteron and a negative muon μ⁻. We measured three 2S-2P transitions in μd and obtain rd = 2.12562(78) fm, which is 2.7 times more accurate but 7.5σ smaller than the CODATA-2010 value rd = 2.1424(21) fm. The μd value is also 3.5σ smaller than the rd value from electronic deuterium spectroscopy. The smaller rd, when combined with the electronic isotope shift, yields a "small" proton radius rp, similar to the one from muonic hydrogen, amplifying the proton radius puzzle.
The unstoppable growth of human population that occurs in parallel with all manufacturing activities leads to a relentless increase in the demand for resources, cultivation land, and energy. In ...response, currently, there is significant interest in developing strategies to optimize any available resources and their biowaste. While solutions initially focused on recovering biomolecules with applications in food, energy, or materials, the feasibility of synthetic biology in this field has been demonstrated in recent years. For instance, it is possible to genetically modify Saccharomyces cerevisiae to produce terpenes for commercial applications (i.e., against malaria or as biodiesel). But the production process, similar to any industrial activity, generates biowastes containing promising biomolecules (from fermentation) that if recovered may have applications in different areas. To test this hypothesis, in the present study, the lipid composition of by-products from the industrial production of β-farnesene by genetically modified Saccharomyces cerevisiae are studied to identify potentially bioactive compounds, their recovery, and finally, their stability and in vitro bioactivity. The assayed biowaste showed the presence of triterpenes, phytosterols, and 1-octacosanol which were recovered through molecular distillation into a single fraction. During the assayed stability test, compositional modifications were observed, mainly for the phytosterols and 1-octacosanol, probably due to oxidative reactions. However, such changes did not affect the in vitro bioactivity in macrophages, where it was found that the obtained fraction decreased the production of TNF-α and IL-6 in lipopolysaccharide (LPS)-induced inflammation.
A geochemical investigation was carried out on the bottom sediments of a riverine reservoir, located in a mountainous rural region (NE Portugal), with the aim of evaluating the contents of As, metals ...and P and their potential availability. The elements contents were detected in the following ranges (µg g−1): As (18–64); Cr (32–128); Cu (39–93); Ni (18–80); Pb (49–160); Zn (207–334); P (1705–2681). The reducible fraction is the most significant in the retention of the elements. Based on their potential relative mobility, the detected metals could be classed as follows: Zn > As, Pb > Cu > Cr, Ni. The results on geochemical partitioning were revealed to be important when the Sediment Quality Guidelines (SQGs) were considered. Arsenic, Cr, Ni, Pb and Zn showed total contents exceeding the values of Probable Effect Level (PEL), but only As occurred in the most potentially available form; Cr and Ni can be considered relatively unavailable, since these are mainly associated with the residual phase. Locally, oxygen depletion could release P into the water column due to the higher concentrations in Fe-P and CDB-P fractions. The potential availability of As, metals and P in sediments indicates that the quality of sediments accumulated in small reservoirs should be considered in management policies.
Display omitted
The major challenge of the pharmaceutical industry is to find potential solvents for poorly water-soluble drug molecules. Ionic liquids (ILs) have attracted this industry as (co-) ...solvents due to their unique physicochemical and biological properties. Herein, a straightforward approach for the enhancement of the water solubility of paracetamol and sodium diclofenac is presented, using new biocompatible N-acetyl amino acid N-alkyl cholinium-based ionic liquids as co-solvents (0.2–1 mol%). These new ionic liquids were able to increase the water solubility of these drugs up to four times that in pure water or in an inorganic salt solution. In the presence of these ILs, the drugs lipophilicity (log P was not significantly changed for paracetamol, but for sodium diclofenac it was possible to decrease significantly its lipophilicity. Concerning cytotoxicity in human dermal fibroblasts it was observed that ILs did not show a significant toxicity, and were able to improve cell viability compared with the respective precursors.
Boronic acids (BAs) are a promising bioconjugation function to design dynamic materials as they can establish reversible covalent bonds with oxygen/nitrogen nucleophiles that respond to different pH, ...ROS, carbohydrates and glutathione levels. However, the dynamic nature of these bonds also limits the control over the stability and site‐selectivity of the bioconjugation, which ultimately leads to heterogeneous conjugates with poor stability under physiological conditions. Here we disclose a new strategy to install BAs on peptide chains. In this study, a “boron hot spot“ based on the 3‐hydroxyquinolin‐2(1H)‐one scaffold was developed and upon installation on a peptide N‐terminal cysteine, enables the site‐selective formation of iminoboronates with 2‐formyl‐phenyl boronic acids (Ka of 58128±2 m−1). The reaction is selective in the presence of competing lysine ϵ‐amino groups, and the resulting iminoboronates, displayed improved stability in buffers solutions and a cleavable profile in the presence of glutathione. Once developed, the methodology was used to prepare cleavable fluorescent conjugates with a laminin fragment, which enabled the validation of the 67LR receptor as a target to deliver cargo to cancer HT29 cells.
Boron hot spot: Site‐selective installation of iminoboronates on N‐terminal cysteines using a 3‐hydroxyquinolin‐2(1H)‐one scaffold as a directing unit and the use of this boron hot spot in the synthesis of a cleavable fluorescent laminin conjugate targeting the 67LR receptor in HT29 cancer cells.
Myogenin (myog) encodes a highly conserved myogenic regulatory factor that is involved in terminal muscle differentiation. It has been shown in mammals that methylation of cytosines within the myog ...promoter plays a major role in regulating its transcription. In the present study, the Senegalese sole (Solea senegalensis) myog putative proximal promoter was identified and found to be highly conserved among teleosts. Therefore, it is plausible that it plays a similar role in controlling myog expression. Cytosine methylation of the myog promoter in skeletal muscle of Senegalese sole larvae undergoing metamorphosis was influenced by rearing temperature. A lower temperature (15°C) significantly increased myog promoter methylation in skeletal muscle, particularly at specific CpG sites, relatively to higher rearing temperatures (18 and 21°C). Myog transcription was downregulated at 15°C, whereas expression of dnmt1 and dnmt3b was upregulated, consistently with the higher myog methylation observed at this temperature. Rearing temperature also affected growth and fast muscle cellularity, producing larger fibers at 21°C. Taken together, our data provide the first evidence of an epigenetic mechanism that may be underlying the temperature-induced phenotypic plasticity of muscle growth in teleosts.
Hardwood and softwood lignins obtained from industrial sulphite and kraft and laboratory oxygen-organosolv pulping processes were employed in co-polymerization with tolylene 2,4-diisocyanate ...terminated poly(propylene glycol). The obtained lignin-based polyurethanes were doped with 0.72 w/w% of multiwall carbon nanotubes (MWCNTs) with the aim of increasing their electrical conductivity to the levels suitable for sensor applications. Effects of the polymer doping with MWCNTs were assessed using electrical impedance (EIS) and UV-Resonance Raman (UV-RR) spectroscopy. Potentiometric sensors were prepared by drop casting of liquid polymer on the surface of carbon glass or platinum electrodes. Lignin-based sensors displayed a very low or no sensitivity to all alkali, alkali-earth and transition metal cations ions except Cr(
vi
) at pH 2. Response to Cr(
vi
) values of 39, 50 and 53 mV pX
−1
for the sensors based on kraft, organosolv and lignosulphonate lignins, respectively, were observed. Redox sensitivity values close to the theoretical values of 20 and 21 mV pX
−1
for organosolv and lignosulphonate based sensors respectively were detected in the Cr(
iii
)/Cr(
vi
) solutions while a very low response was observed in the solutions containing Fe(CN)
6
3−/4−
. Conducting composite lignin-based polyurethanes doped with MWCNTs were suggested as being promising materials for Cr(
vi
)-sensitive potentiometric sensors.
Lignin co-polymerized with poly(propylene oxide) and doped with carbon nanotubes is suggested as a sensing material for Cr(
vi
) detection.
Accurate knowledge of the charge and Zemach radii of the proton is essential, not only for understanding its structure but also as input for tests of bound-state quantum electrodynamics and its ...predictions for the energy levels of hydrogen. These radii may be extracted from the laser spectroscopy of muonic hydrogen (μp, that is, a proton orbited by a muon). We measured the $2{\mathrm{S}}_{1/2}^{\mathrm{F}=0}-2{\mathrm{P}}_{3/2}^{\mathrm{F}=1}$ transition frequency in μp to be 54611.16(1.05) gigahertz (numbers in parentheses indicate one standard deviation of uncertainty) and reevaluated the $2{\mathrm{S}}_{1/2}^{\mathrm{F}=1}-2{\mathrm{P}}_{3/2}^{\mathrm{F}=1}$ transition frequency, yielding 49881.35(65) gigahertz. From the measurements, we determined the Zemach radius, r Z = 1.082(37) femtometers, and the magnetic radius, r M = 0.87(6) femtometer, of the proton. We also extracted the charge radius, r E = 0.84087(39) femtometer, with an order of magnitude more precision than the 2010-CODATA value and at 7σ variance with respect to it, thus reinforcing the proton radius puzzle.
PDF
