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Blankenship posted an update 7 months, 2 weeks ago
The simulations reproduce the spectral trends observed in the X-ray but also optical absorption experiments. Our results underscore the importance of solute-solvent interactions when aiming for an accurate description of the valence electronic structure of solvated transition metal complexes and demonstrate how L2,3-edge absorption spectroscopy can aid in understanding the impact of the solution environment on intramolecular covalency and the electronic charge distribution.To facilitate potential applications of water-in-supercritical CO2 microemulsions (W/CO2 μEs) efficient and environmentally responsible surfactants are required with low levels of fluorination. As well as being able to stabilize water-CO2 interfaces, these surfactants must also be economical, prevent bioaccumulation and strong adhesion, deactivation of enzymes, and be tolerant to high salt environments. Recently, an ion paired catanionic surfactant with environmentally acceptable fluorinated C6 tails was found to be very effective at stabilizing W/CO2 μEs with high water-to-surfactant molar ratios (W0) up to ∼50 (Sagisaka, M.; et al. Langmuir 2019, 35, 3445-3454). As the cationic and anionic constituent surfactants alone did not stabilize W/CO2 μEs, this was the first demonstration of surfactant synergistic effects in W/CO2 microemulsions. The aim of this new study is to understand the origin of these intriguing effects by detailed investigations of nanostructure in W/CO2 microemulsions using high-pressure small-angle neutron scattering (HP-SANS). These HP-SANS experiments have been used to determine the headgroup interfacial area and volume, aggregation number, and effective packing parameter (EPP). These SANS data suggest the effectiveness of this surfactant originates from increased EPP and decreased hydrophilic/CO2-philic balance, related to a reduced effective headgroup ionicity. This surfactant bears separate C6F13 tails and oppositely charged headgroups, and was found to have a EPP value similar to that of a double C4F9-tail anionic surfactant (4FG(EO)2), which was previously reported to be one of most efficient stabilizers for W/CO2 μEs (maximum W0 = 60-80). Catanionic surfactants based on this new design will be key for generating superefficient W/CO2 μEs with high stability and water solubilization.The g-factor shift of the g = 4.1 EPR signal was detected in spinach PsbO/P/Q-depleted PS II. The effective g-factor of the signal shifts up to ∼4.9, depending on the Ca2+ concentration. Hyperfine structure spacing with about 3 mT was detected in this g = 5 (4.9) signal. The shift to g = 5 (4.9) was related to the distortion of the manganese cluster, derived from the modification of the chemical bond or the crystalline field of the Mn4(III) in the manganese cluster. Based on the EPR analysis of the g = 5 (4.9) spin state, another molecular structure of the S2 state, a “distant Mn” structure, was discussed as an intermediate state between the S2 and S3 states.Soft tissue sarcomas (STS) are a rare group of mesenchymal solid tumors with heterogeneous genetic profiles and clinical features. read more Systemic chemotherapy is the backbone treatment for advanced STS; however, STS frequently acquire resistance to standard therapies, which highlights the need to improve treatments and identify novel therapeutic targets. Increases in the knowledge of the molecular pathways that drive sarcomas have brought to light different molecular alterations that cause tumor initiation and progression. These findings have triggered a breakthrough of targeted therapies that are being assessed in clinical trials. Cancer stem cells (CSCs) exhibit mesenchymal stem cell (MSC) features and represent a subpopulation of tumor cells that play an important role in tumor progression, chemotherapy resistance, recurrence and metastasis. In fact, CSCs phenotypes have been identified in sarcomas, allied to drug resistance and tumorigenesis. Herein, we will review the published evidence of CSCs in STS, discussing the molecular characteristic of CSCs, the commonly used isolation techniques and the new possibilities of targeting CSCs as a way to improve STS treatment and consequently patient outcome.Continuous monitoring of landslides is of basic importance for understanding their behavior, defining their 3D geometry, and providing a basis for early warning purposes. While a number of instrumentations can be used for tracking surface displacement, only automatic or fixed multi-module inclinometers can be used for continuous monitoring of displacement at depth, providing valuable information for landslide geometry reconstruction. Since these instruments are very expensive, thus rarely used, a low-cost and multi-module fixed inclinometer for continuous landslide monitoring has been developed. In this paper, the electronics of the system, including sensor characteristics and optimization, controlling software, and structure are presented. For system development, a single module prototype was first developed and tested in the field to ensure sufficient measuring performance. Subsequently, the multi-module system was designed, assembled, and tested in controlled conditions. Test results indicate the good performance of the system with a displacement measuring accuracy of 0.37% of the length of the inclinometer chain. The linearity test indicates the high linearity of the measures, especially in the range ±20°, which is the typical operating range of such kinds of instrumentations. The thermal efficiency test indicates the high efficiency of the system in preventing measuring errors caused by thermal drifting.Vaccinium myrtillus fruit (bilberry) is well known for its high richness in anthocyanins, which may be responsible for its preventive effects on several oxidative and carbonyl stress-related pathologies. However, limited data are available regarding the antioxidant and antiglycative contributions of its constituents. Spectrometric analyses were performed to evaluate anthocyanin content, radical scavenging and antiglycative properties of an anthocyanin-rich extract from bilberries. Additionally, original DPPH and methylglyoxal pre-column HPLC methods were instigated to allow straightforward identification of the main contributors to radical and carbonyl trapping effects. Finally, representative pure anthocyanins were evaluated using classical DPPH and antiglycation assays. Delphinidin, petunidin and cyanidin glycosides were identified as the most effective radical scavenging constituents in both HPLC and spectrometric DPPH evaluations. Potent antiglycative activities were also assessed for cyanidin, delphinidin and petunidin glucosides as attested by their respective IC50 values of 114.