Notes

Unraveling the particular metabolic community regarding organic fatty acids in solid-state fermentation regarding Oriental breakfast cereal white vinegar.
Os(II) complexes showing singlet-to-triplet absorption are of growing interest as a new class of triplet sensitizers that circumvent energy loss during intersystem crossing, and they enable effective utilization of input photon energy in various applications, such as photoredox catalysis, photodynamic therapy, and photon upconversion. However, triplet excited-state lifetimes of Os(II) complexes are often too short (τ less then 1 μs) to transfer their energy to neighboring molecules. While the covalent conjugation of chromophores has been known to extend the net excited-state lifetimes through an intramolecular triplet energy transfer (IMET), heavy-atom effects of the central metals on the attached chromophore units have rarely been discussed. Here, we investigate the relationship between the spin-density contribution of the heavy metals and the net triplet excited-state lifetimes for a series of Os(II) and Ru(II) bis(terpyridine) complexes modified with perylene units. Phosphorescence lifetimes of these compounds strongly depend on the lifetimes of the perylenyl group-localized excited states that are shortened by the heavy-atom effect. The degree of heavy-atom effect can be largely circumvented by introducing meta-phenylene bridges, where the perylene unit retains its intrinsic long excited-state lifetime. The thermal activation to the short-lived excited states is suppressed, thanks to sufficient but still small energy losses during the IMET process. Involvement of the metal center was also confirmed by the prolonged lifetime by replacing Os(II) with Ru(II) that possesses a smaller spin-orbit coupling constant. These results indicate the importance of ligand structures that give a minimum heavy-atom effect as well as the sufficient energy gap among the excited states and fast IMET for elongating the triplet excited-state lifetime without sacrificing the excitation energy.Pollen is a source of nutrients for honeybees (Apis mellifera L.) and suitable for human consumption as well. In our research, a multiresidue method for pesticide determination was developed and validated for the bee pollen matrix. 247 components met the validation criteria for limit of detection, limit of quantification, linearity, and interday repeatability. Average recoveries varied between 70 and 120% except for 14 analytes, which were corrected during on-going validation. The matrix effect was strong for certain analytes, which required the use of matrix-matched calibration. The pesticide residue profiles of 21 pollen samples of different botanical origins were identified by the developed method. The most common active substances were chlorpyrifos, thiacloprid, and acetamiprid. Some products contained pesticides that are already banned. According to our estimates, the tested samples do not pose an acute risk on honeybees, although the combination of pesticides may cause synergistic toxicity.We analyze airborne measurements of atmospheric CO concentration from 70 flights conducted over six years (2015-2020) using an inverse model to quantify the CO emissions from the Washington, DC, and Baltimore metropolitan areas. We found that CO emissions have been declining in the area at a rate of ≈-4.5 % a-1 since 2015 or ≈-3.1 % a-1 since 2016. In addition, we found that CO emissions show a "Sunday" effect, with emissions being lower, on average, than for the rest of the week and that the seasonal cycle is no larger than 16 %. Our results also show that the trend derived from the NEI agrees well with the observed trend, but that NEI daytime-adjusted emissions are ≈50 % larger than our estimated emissions. In 2020, measurements collected during the shutdown in activity related to the COVID-19 pandemic indicate a significant drop in CO emissions of 16 % relative to the expected emissions trend from the previous years, or 23 % relative to the mean of 2016 to February 2020. Our results also indicate a larger reduction in April than in May. Last, we show that this reduction in CO emissions was driven mainly by a reduction in traffic.Metal-organic framework-808 has been functionalized with 11 amino acids (AA) to produce a series of MOF-808-AA structures. The adsorption of CO2 under flue gas conditions revealed that glycine- and dl-lysine-functionalized MOF-808 (MOF-808-Gly and -dl-Lys) have the highest uptake capacities. Enhanced CO2 capture performance in the presence of water was observed and studied by using single-component sorption isotherms, CO2/H2O binary isotherm, and dynamic breakthrough measurements. The key to the favorable performance was uncovered by deciphering the mechanism of CO2 capture in the pores and attributed to the formation of bicarbonate as evidenced by 13C and 15N solid-state nuclear magnetic resonance spectroscopy studies. On the basis of these results, we examined the performance of MOF-808-Gly in simulated coal flue gas conditions and found that it is possible to capture and release CO2 by vacuum swing adsorption. MOF-808-Gly was cycled at least 80 times with full retention of performance. This study significantly advances our understanding of CO2 chemistry in MOFs by revealing how strongly bound amine moieties to the MOF backbone create the chemistry and environment within the pores, leading to the binding and release of CO2 under mild conditions without application of heat.Approximately 75% of breast cancers are estrogen receptor alpha-positive (ERα+), and targeting ERα directly with ERα antagonists/degraders or indirectly with aromatase inhibitors is a successful therapeutic strategy. However, such treatments are rarely curative and development of resistance is universal. We recently reported ErSO, a compound that induces ERα-dependent cancer cell death through a mechanism distinct from clinically approved ERα drugs, via hyperactivation of the anticipatory unfolded protein response. ErSO has remarkable tumor-eradicative activity in multiple ERα+ tumor models. While ErSO has promise as a new drug, it has effects on ERα-negative (ERα-) cells in certain contexts. Herein, we construct modified versions of ErSO and identify variants with enhanced differential activity between ERα+ and ERα- cells. We report ErSO-DFP, a compound that maintains antitumor efficacy, has enhanced selectivity for ERα+ cancer cells, and is well tolerated in rodents. ErSO-DFP and related compounds represent an intriguing new class for the treatment of ERα+ cancers.Histamine-based imidazole alkaloids N-caprylhistamine (HmC8) and N-caprylhistamine-β-glucoside (HmC8-Glc) were recently identified as precursors for a tomato biomarker. As studies regarding metabolism and bioavailability are scarce, the present study aimed at the elucidation of intestinal absorption and metabolism using the Caco-2 model and the pig cecum model to mimic human intestinal conditions. The most abundant imidazole alkaloid HmC8-Glc was neither absorbed nor transferred across cellular barriers but extensively metabolized to HmC8 in the pig cecum model, whereas the aglycon HmC8 is subjected to transport and metabolic processes through the Caco-2 monolayer and metabolized to the bioactive neurotransmitter histamine by the intestinal microbiota. Deduced from the combined results of both methods, HmC8-Glc is not absorbed directly via the intestinal epithelium but requires a metabolic cleavage of the glycosidic bond by the gut microbiota. Because of the high bioavailability of the released HmC8 and histamine, HmC8 and its glucoside might also be involved in the intolerance to tomato products by histamine-intolerant consumers.Waterflooding is potentially a viable approach to enhance oil recovery, though its efficacy can profoundly be compromised due to formation damage as a result of inorganic scale deposition. In this study, a series of high-temperature core flooding experiments were conducted to evaluate two green scale inhibitors (SIs) of folic acid and inulin as alternative inhibitors to mitigate mineral deposition. The co-injection of two incompatible brines (with and without SIs) for two flow rates of 0.5 and 3 mL/min into two core samples of dolomite and sandstone was experimentally investigated. The results showed that folic acid would inhibit scale formation as much as 45-49%, at the lower flow rate, compared to inulin with an efficiency of 29-39%, at the higher flow rate. Moreover, computed tomography imaging technique showed that scale formation and fine migration would be dominant mechanisms for formation damage in dolomite and sandstone rocks, respectively. The theoretical study based on surface energy also confirmed the experimental results in terms of the work of adhesion which showed that folic acid would mitigate the calcite deposition on rock surfaces approximately 55%. Finally, a phosphonate-based commercial SI was compared with the green SIs which reaffirmed their potencies.Produced water (PW), a waste byproduct of oil and gas extraction, is a complex mixture containing numerous organic solubles and elemental species; these constituents range from polycyclic aromatic hydrocarbons to naturally occurring radioactive materials. Identification of these compounds is critical in developing reuse and disposal protocols to minimize environmental contamination and health risks. In this study, versatile extraction methodologies were investigated for the untargeted analysis of PW. Thin-film solid-phase microextraction with hydrophilic-lipophilic balance particles was utilized for the extraction of organic solubles from eight PW samples from the Permian Basin and Eagle Ford formation in Texas. Gas chromatography-mass spectrometry analysis found a total of 266 different organic constituents including 1,4-dioxane, atrazine, pyridine, and PAHs. The elemental composition of PW was evaluated using dispersive solid-phase extraction followed by inductively coupled plasma-mass spectrometry, utilizing a new coordinating sorbent, poly(pyrrole-1-carboxylic acid). This confirmed the presence of 29 elements including rare earth elements, as well as hazardous metals such as Cr, Cd, Pb, and U. selleck inhibitor Utilizing chemometric analysis, both approaches facilitated the discrimination of each PW sample based on their geochemical origin with a prediction accuracy above 90% using partial least-squares-discriminant analysis, paving the way for PW origin tracing in the environment.Mediating the redox kinetics of polysulfides is a promising strategy to mitigate the shuttling and sluggish conversion of polysulfides for practical application of lithium-sulfur (Li-S) batteries. Herein, novel TiH2 nanodots (THNDs) fabricated by sonication-assisted liquid-phase exfoliation are used as bifunctional electrocatalysts for Li-S batteries. Both experimental and theoretical results reveal that THNDs can not only provide a strong chemical affinity to polysulfides but also bidirectionally promote the precipitation/decomposition of Li2S from/to polysulfides during the discharge/charge process, thus effectively suppressing the shuttle effect and improving the redox kinetics of polysulfides. Owing to these advantages accompanied by the abundant catalytically active sites of THNDs, the assembled Li-S batteries deliver a low capacity fading rate of 0.055% per cycle over 1000 cycles at 1C and a high areal capacity of 5.38 mAh cm-2 after 50 cycles with a high sulfur loading of 8.5 mg cm-2. This work demonstrates the great potential of utilizing functional metal hydrides as effective electrocatalysts for Li-S batteries, which will incite more investigation into the specific selection of metal compounds to boost the redox kinetics of polysulfides.
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