Mooneystryhn9206

Due to their mountability, in situ LoC technologies provide ideal instrumentation for underwater analyzers, especially for miniaturized underwater observation platforms. Consequently, the appropriate combination of reliable LoC and underwater technologies is essential to realize practical in situ LoC analyzers suitable for underwater environments, including the deep sea. Moreover, the development of fundamental LoC technologies for underwater analyzers, which operate stably in extreme environments, should also contribute to in situ measurements for public or industrial purposes in harsh environments as well as the exploration of the extraterrestrial frontier.We herein present a case study on the templated, Pd-catalyzed polymerization reaction of methyl propiolate in the confined pore space of three different surface anchored metal-organic framework (SURMOF) systems in order to introduce electrical conductivity to MOF thin films and provide predictions for potential device integrations. To gain comprehensive insight into the influence of the template on polymerization, we chose Cu(bpdc), Cu2(bdc)2(dabco) and HKUST-1 because of their different types of pore channels, 1D, quasi-1D and 3D, and their free pore volumes. Well-defined MOF thin films were prepared using layer-by-layer deposition, which allows for the application of several characterization techniques not applicable for conventional powder MOFs. With SEM, AFM, XRD, MALDI-ToF/MS, ToF-SIMS and QCM, we were able to investigate the behaviour of the polymer formation. For lower dimensional pore channels, we find a depot-like release of monomeric units leading to top-layer formation determined by desorption kinetics, whereas for the 3D channels, quick release of an excess amount of monomers was observed and polymerization proceeds perfectly. Despite polymerization issues, control over the maximum chain lengths and the molecular weight distribution was achieved depending on the dimensionality of the pore systems. For the HKUST-1 system, polymerization was optimized and we were able to measure the electrical conductivity introduced by the conjugated polymer inside the channels.Correction for 'Cyclization of 5-alkynones with chromium alkylidene equivalents generated in situ from gem-dichromiomethanes' by Masahito Murai et al., Chem. Commun., 2020, 56, 9711-9714, DOI .Organic azides are an efficient source of nitrenes, which serve as vigorous intermediates in many useful organic reactions. In this work, the complete active space self-consistent field (CASSCF) and its second-order perturbation (CASPT2) methods were employed to study the photochemistry of 2-furoylazide 1 and 3-furoylazide 5, including the Curtius rearrangement to two furylisocyanates (3 and 7) and subsequent reactions to the final product cyanoacrolein 9. Our calculations show that the photoinduced Curtius rearrangement of the two furoylazides takes place through similar stepwise mechanisms via two bistable furoylnitrenes 2 and 6. However, the decarbonylation and ring-opening process of 7 to 9 prefers a stepwise mechanism involving the 3-furoylnitrene intermediate 8, while 3 to 9 goes in a concerted asynchronous way without the corresponding 2-furoylnitrene intermediate 4. Importantly, we revealed that several conical intersections play key roles in the photochemistry of furoylazides. Our results are not only consistent and also make clear the experimental observations (X. Zeng, et al., J. Am. Chem. Soc., 2018, 140, 10-13), but additionally provide important information on the chemistry of furoylazides and nitrenes.Coordination polymers (CPs) in recent times have emerged as active constituents in many semiconductor devices like light emitting diodes (LED), field effect transistors (FET), photovoltaic devices and Schottky barrier diodes. An intelligent choice of linkers, careful selection of metal ions and post synthetic modification (PSM) can provide a better pathway for charge transportation. However, a proper understanding of the charge transport mechanism in CPs is still inadequate due to the lack of considerable experimental and theoretical work. In this paper, we address the theoretical elucidation of semiconducting properties and a probable pathway for charge transportation in three of our previously published CPs using density functional theory (DFT). These results help us to recognize the orbitals that have major contributions in the formation of the valence band and also provide the most likely pathway for optimum electronic communication. In this regard, the role of hydrogen bonding and unpaired electrons of metal d-orbitals is also established.Metal-free boron- and carbon-based catalysts have shown both great fundamental and practical value in oxidative dehydrogenation (ODH) of light alkanes. In particular, boron-based catalysts show a superior selectivity toward olefins, excellent stability and atom-economy to valuable carbon-based products by minimizing CO2 emission, which are highly promising in future industrialization. The carbonaceous catalysts also exhibited impressive behavior in the ODH of light alkanes helped along by surface oxygen-containing functional groups. This review surveyed and compared the preparation methods of the boron- and carbon-based catalysts and their characterization, their performance in the ODH of light alkanes, and the mechanistic issues of the ODH including the identification of the possible active sites and the exploration of the underlying mechanisms. We discussed different boron-based materials and established versatile methodologies for the investigation of active sites and reaction mechanisms. We also elaborated on the similarities and differences in catalytic and kinetic behaviors, and reaction mechanisms between boron- and carbon-based metal-free materials. A perspective of the potential issues of metal-free ODH catalytic systems in terms of their rational design and their synergy with reactor engineering was sketched.Chemical doping engineering is an effective strategy to modify the hole transport layer (HTL) and achieve high-efficiency perovskite solar cells (PSCs). In this work, we synthesize an infrequent trilacunary Keggin type polyoxometalate Na10[Zn2(H2O)6(WO2)2(BiW9O33)2] (BiW9-Zn) and apply it as an additive to enhance the hole mobility and electrical conductivity of Spiro-OMeTAD based HTLs. Thanks to the strong electron-accepting properties of polyoxometalate molecules, the as-synthesized BiW9-Zn can directly oxidize Spiro-OMeTAD under an inert atmosphere and avoid the tedious long-term oxidation process. Therefore, the power conversion efficiency (PCE) of optimal PSCs with BiW9-Zn doping is enhanced from 17.58% (without doping) to 19.56% with a significantly improved fill factor and open-circuit voltage. In addition, the assembly repeatability and long-term stability of PSCs are also improved. This work demonstrates the potential of using polyoxometalates (POMs) as low-cost, efficient and highly flexible chemical dopants for HTLs, and more importantly paves a new route to enhance the performance of PSCs.Emerging evidence shows that amino acids can modulate lipid metabolism. Aromatic amino acids (AAAs) serve as important precursors of several neurotransmitters and metabolic regulators that play a vital role in regulating nutrient metabolism. But whether AAAs have a lipid-lowering function remains unknown. Here mice were fed amino acid-defined diets containing AAAs at 1.82% and 3.64% for 3 weeks. We demonstrated that double AAA intake significantly decreased the serum and hepatic triglycerides and serum low-density lipoprotein cholesterol, but increased the high-density lipoprotein cholesterol as well as insulin tolerance. Combined metabolomic and transcriptomic analysis showed that the hepatic acidic pathway of bile acid synthesis was responsible for the improvement in lipid metabolism by AAA treatment. This study suggests that AAAs have the potential to ameliorate steatosis and provides a new alternative to improve lipid metabolism.Despite widespread development and use of ionic liquids (ILs) in both academic and industrial research, computational force fields (FFs) for most of those are not available for a precise description of inter-species interactions in aqueous environments. In the scope of this study, by means of molecular simulations, the osmotic coefficient of an aqueous solution of an IL is calculated and used as a basis to reparameterize popular IL-FFs existing in the literature. We first calculate the osmotic coefficients (at 298.15 K and 1 atm pressure) of aqueous solutions of 1-butyl-3-methylimidazolium chloride (BMIMCl), a generic IL, popularly used in biomass processing and the subsequent conversion to value-added intermediates. The performance of two popular atomic, nonpolarizable FFs developed for BMIMCl, one by Lopes, Pádua, and coworkers (FF-LP) and the other by Sambasivarao, Acevedo, and coworkers (FF-SA), when mixed with the SPC/E water model, is tested with respect to their ability to reproduce the experimental osexperimental solution properties, such as density, viscosity, association/dissociation, etc. We report that excessive dissociation of BMIMCl in water is responsible for the shortcomings observed in the original FFs and improved prediction of physicochemical properties could be achieved using the modified FFs.Here, we synthesized a valence tautomeric cobalt-dioxolene complex featuring a protected anchoring group. At room temperature, the complex reveals a nearly pure low-spin-Co(iii)-catecholate state in the solid state, but a nearly pure high-spin-Co(ii)-semiquinonate state in toluene solution. GSK3 inhibitor Thermal switchability of the complex in solution and in the solid state is investigated.At present, cancer is obviously a major threat to human health worldwide. Accurate diagnosis and treatment are in great demand and have become an effective method to alleviate the development of cancer and improve the survival rate of patients. A large number of theranostic probes that combine diagnosis and treatment methods have been developed as promising tools for tumor precision medicine. Among them, fluorescent theranostic probes have developed rapidly in the frontier research field of precision medicine with their real time, low toxicity, and high-resolution merit. Therefore, this review focuses on recent advances in the development of fluorescent theranostic probes, as well as their applications for cancer diagnosis and treatment. Initially, small-molecule fluorescent theranostic probes mainly including tumor microenvironment-responsive fluorescent prodrugs and phototherapeutic probes were introduced. Subsequently, nanocomposite probes are expounded based on four types of nano-fluorescent particles combining different therapies (chemotherapy, photothermal therapy, photodynamic therapy, gene therapy, etc.). Then, the capsule-type "all in one" probes, which occupy an important position in theranostic probes, are summarized according to the surface carrier type. This review aims to present a comprehensive guide for researchers in the field of tumor-related theranostic probe design and development.Mitochondrial dysfunction, oxidative stress and inflammation are crucial contributors to liver damage and nonalcoholic fatty liver disease (NAFLD) in adulthood in offspring affected by intrauterine growth retardation (IUGR). Resveratrol (RSV) has been reported to treat and/or prevent hepatic diseases under various pathological conditions. However, the therapeutic and/or preventive effects of RSV on hepatic abnormality in IUGR adults have not been investigated until now. The effects of IUGR and RSV on the hepatic metabolic status, mitochondrial function, redox homeostasis and inflammation in pigs in adulthood were investigated. A total of 36 pairs of IUGR and normal birth weight piglets were orally fed with 80 mg RSV per kg body weight per d or vehicle (0.5% carboxymethylcellulose) for 7-21 d after birth. And then the offspring were fed with a basal diet supplemented with 300 mg RSV per kg feed or a basal diet from weaning to slaughter at 150 d. The plasma and liver samples were collected for subsequent analysis.