Crossdalgaard2561

The ability of a compound to broadly absorb light across the incident solar spectrum is an important design target in the development of molecular photosensitizers. The 'HOMO inversion' model predicts that for [(tpy)2Fe]2+ (tpy = 2,2'6',2″-terpyridine) compounds, adjusting the character of the highest occupied molecular orbital (HOMO) from metal-centered to ligand-centered can drastically improve photophysical properties by broadening absorption in the visible and increasing molar extinction coefficients. In an effort to experimentally realize strong, panchromatic absorption, a tridentate N^N - ^N diarylamido ligand bearing flanking benzannulated N-heterocyclic donors ( tBu L) was used to prepare deeply colored, pseudo-octahedral coordination complexes of a range of first-row transition and main-group metals [( tBu L)2M0/+; M = Fe, Co, Ni, Zn, Ga]. While the Fe(II) congener exhibits the sought-after broad absorption, isostructural and isoelectronic complexes of other first-row transition and main-group metals show vastly different absorption and redox properties. Density functional theory (DFT) calculations point toward the relative energies of the metal d orbitals and ligand orbitals as the source of major changes in electronic structure, confirming aspects and limitations of the predictive 'HOMO inversion' model in experimentally realized systems with implications for the design of abundant transition-metal sensitizers with broad, panchromatic absorptive properties.Diamagnetic H2 phthalocyanine molecules are probed on superconducting Pb(100) using a low-temperature scanning tunneling micoscope (STM). In supramolecular arrays made with the STM, the molecules acquire a spin as detected via the emergence of Yu-Shiba-Rusinov resonances. The spin moments vary among the molecules and are determined by the electrostatic field that results from polar bonds in the surrounding Pc molecules. The moments are further finely tuned by repositioning the hydrogen atoms of the inner macrocycle of the surrounding molecules.Monoethylhexyl phthalate (MEHP) is one of the main active metabolites of the plasticizer di(2-ethylhexyl) phthalate. It has been known that MEHP has an impact on lipolysis; however, its mechanism on the cellular lipid metabolism remains largely unclear. Here, we first utilized global lipid profiling to fully characterize the lipid synthesis and degradation pathways upon MEHP treatment on hepatic cells. Meanwhile, we further identified the possible MEHP-targeted proteins in living cells using the cellular thermal shift assay (CETSA) method. The lipidomics results showed that there was a significant accumulation of fatty acids and other lipids in the cell. The CETSA identified 18 proteins and fatty acid β-oxidation inhibition pathways that were significantly perturbed. MEHP's binding with selected proteins HADH and HSD17B10 was further evaluated using molecule docking, and results showed that MEHP has higher affinities as compared to endogenous substrates, which was further experimentally confirmed in the surface plasma resonance interaction assay. In summary, we found a novel mechanism for MEHP-induced lipid accumulation, which was probably due to its inhibitive effects on the enzymes in fatty acid β-oxidation. This mechanism substantiates the public concerns on the high exposure level to plasticizers and their possible role as an obesogen.The cannabis analysis has gained new importance worldwide due to the rapid expansion of the hemp global market. Many reverse phase high performance liquid chromatography (HPLC) methods have been developed to analyze cannabidiol (CBD) and its analogues due to the nice fit with their log P values at around 6. However, when CBD was blended with hemp seed oil in consumer, cosmetic, and food industries, the high content of triacylglycerides (TAGs) from hemp seed oil were retained and accumulated inside C18 columns with the common mobile phases and caused a column pressure increase and ghost peaks after continuous sample injections. Selleckchem Belinostat Coupled with the chemical profile from high resolution mass spectrometry (HRMS) detection, a novel hydrophilic interaction liquid chromatography (HILIC) CBD quantitation method was developed, specifically for CBD blended hemp seed oil materials, which can overcome the matrix buildup in reverse phase columns. The zwitterionic (ZIC)-cHILIC column containing a dense water layer on the stationary phase surface provided a stable partitioning separation mechanism to separate the CBD from TAGs in hemp seed oil. This water layer favors the sustaining NH4F buffer ions, which can maximize the salting-out action and help reduce the adsorptive interaction between TAGs and stationary phase sulfobetaine materials. The high percentage of acetonitrile (99%) contributed to method sensitivity and reduced instrument maintenance time. The method was developed and validated for the first time. It has been successfully applied to quantify CBD content in hemp seed oil samples, thus demonstrating it to be a useful tool for both quality control and safety assurance in CBD hemp seed oil raw materials and related products.Iron phosphorus triselenide (FePSe3) is attractive for energy applications owing to its interesting layered geometry, electronic structure, and physiochemical property, while it is limited in actual application because of a very long fabrication time of over 7 days. Herein, we report a new synthetic route to a high-quality sheetlike hybrid of iron phosphorus triselenide nanocrystals coated with graphitic carbon (FePSe3/C) as an alternative kind of van der Waals heterostructures for the first time via a pyrolytic process at 600 °C from the precursors of ferrocene, red phosphorus, and selenium in a quartz tube with a significantly shortened reaction time of 24 h and even down to 30 min. Investigations demonstrated that the component phase of FePSe3 in the layered FePSe3/C hybrid nanosheets is the rhombohedral phase, and the hybrid nanosheets other than bulk crystals are about 15 nm in thickness. Acting as a cathode in fabricating half-cell sodium-ion batteries, the layered FePSe3/C hybrid nanosheets exhibited remarkable performance. Typically, when current density was set as 50 mA g-1, the hybrid nanosheet-assembled battery exhibited a capacity of 182.7 mA h g-1 after performing over 50 cycles, and the nanosheet battery exhibited a capacity of 142 mA h g-1 after performing for 200 cycling trials at 1 A g-1 in the 0.8-2.2 V voltage window. Meanwhile, the layered FePSe3/C hybrid nanosheets also exhibited very high rate capabilities at a relatively large current density in the present study, that is, 172 and 95 mA h g-1 under typical performing conditions at 0.5 and 5 A g-1, respectively.One-pot Julia olefination using ribofuranosyl sulfones is described. The α-anomers of the ribofuranosyl sulfones were synthesized with complete α-selectivity via the glycosylation of heteroarylthiols using ribofuranosyl iodides as glycosyl donors and the subsequent oxidation of the resulting heteroaryl 1-thioribofuranosides with magnesium monoperphthalate (MMPP). The Julia olefination of the α-ribofuranosyl sulfones with aldehydes proceeded smoothly in one pot to afford the thermodynamically less stable (E)-exo-glycals with modest-to-excellent stereoselectivity (up to E/Z = 946) under the optimized conditions. The E selectivity was especially high for aromatic aldehydes. In contrast, the (Z)-exo-glycal was obtained as the main product with low stereoselectivity when the corresponding β-ribofuranosyl sulfone was used (E/Z = 4159). The remarkable impact of the anomeric configuration of the ribofuranosyl sulfones on the stereoselectivity of the Julia olefination has been rationalized using density functional theory (DFT) calculations. The protected ribose moiety of the resulting exo-glycals induced completely α-selective cyclopropanation on the exocyclic carbon-carbon double bond via the Simmons-Smith-Furukawa reaction. The 2-cyanoethyl group was found to be useful for the protection of the exo-glycals, as it could be removed without affecting the exocyclic C═C bond.This study evaluates the potential circularity of PET, PE, and PP flows in Europe based on dynamic material flow analysis (MFA), considering product lifetimes, demand growth rates, and quality reductions of recycled plastic (downcycling). The circularity was evaluated on a baseline scenario, representing 2016 conditions, and on prospective scenarios representing key circularity enhancing initiatives, including (i) maintaining constant plastic consumption, (ii) managing waste plastic exports in the EU, (iii) design-for-recycling initiatives, (iv) improved collection, and (v) improved recovery and reprocessing. Low recycling rates (RR, 13-20%) and dependence on virgin plastic, representing 85-90% of the annual plastic demand, were demonstrated after 50 years in the baseline. Limited improvements were related to the individual scenarios, insufficient to meet existing recycling targets. However, by combining initiatives, RRs above 55%, where 75-90% was recycled in a closed loop, were demonstrated. Moreover, 40-65% of the annual demand could potentially be covered by recycled plastic. Maintaining a constant plastic demand over time was crucial in order to reduce the absolute dependence on virgin plastic, which was not reflected by the RR. Thus, focusing strictly on RRs and even whether and to which extent virgin material is substituted, is insufficient for evaluating the transition toward circularity, which cannot be achieved by technology improvements alone-the demand must also be stabilized.Flavor chemicals in electronic cigarette (EC) fluids, which may negatively impact human health, have been studied in a limited number of countries/locations. To gain an understanding of how the composition and concentrations of flavor chemicals in ECs are influenced by product sale location, we evaluated refill fluids manufactured by one company (Ritchy LTD) and purchased worldwide. Flavor chemicals were identified and quantified using gas chromatography/mass spectrometry (GC/MS). We then screened the fluids for their effects on cytotoxicity (MTT assay) and proliferation (live-cell imaging) and tested authentic standards of specific flavor chemicals to identify those that were cytotoxic at concentrations found in refill fluids. A total of 126 flavor chemicals were detected in 103 bottles of refill fluid, and their number per/bottle ranged from 1-50 based on our target list. Two products had none of the flavor chemicals on our target list, nor did they have any nontargeted flavor chemicals. A total of 28 flavor chemicals were present at concentrations ≥1 mg/mL in at least one product, and 6 of these were present at concentrations ≥10 mg/mL. The total flavor chemical concentration was ≥1 mg/mL in 70% of the refill fluids and ≥10 mg/mL in 26%. For sub-brand duplicate bottles purchased in different countries, flavor chemical concentrations were similar and induced similar responses in the in vitro assays (cytotoxicity and cell growth inhibition). The levels of furaneol, benzyl alcohol, ethyl maltol, ethyl vanillin, corylone, and vanillin were significantly correlated with cytotoxicity. The margin of exposure calculations showed that pulegone and estragole levels were high enough in some products to present a nontrivial calculated risk for cancer. Flavor chemical concentrations in refill fluids often exceeded concentrations permitted in other consumer products. These data support the regulation of flavor chemicals in EC products to reduce their potential for producing both cancer and noncancer toxicological effects.