Lysgaardcollins9580

Gold/titanium dioxide (Au/TiO2) nanohybrid materials have been widely applied in various fields because of their outstanding optical and photocatalytic performance. By state-of-the-art polymer templating, it is possible to make uniform nanostructured TiO2 layers with potentially large-scale processing methods. We use customized polymer templating to achieve TiO2 nanostructures with different morphologies. Au/TiO2 hybrid thin films are fabricated by sputter deposition. An in-depth understanding of the Au morphology on the TiO2 templates is achieved with in situ grazing-incidence small-angle X-ray scattering (GISAXS) during the sputter deposition. The resulting Au nanostructure is largely influenced by the TiO2 template morphology. Based on the detailed understanding of the Au growth process, characteristic distances can be selected to achieve tailored Au nanostructures at different Au loadings. For selected sputter-deposited Au/TiO2 hybrid thin films, the optical response with a tailored localized surface plasmon resonance is demonstrated.Mirabilis multiflora is an acclaimed hallucinogen consumed traditionally by the Hopi Indians to induce diagnostic visions. Its root extract afforded a new (3) and four known (2, 5, 6, and 7) 12a-hydroxyrotenoids, a known rotenoid (4), and two known secondary metabolites (1 and 8). The structures of the compounds were elucidated based on spectroscopic and spectrometric data analysis. Electronic circular dichroism data were used to define the (6aS,12aR) absolute configuration of the 12a-hydroxyrotenoids. Compounds 2-7 were screened for their radioligand binding affinities toward the opioid (δ, κ, and μ) and cannabinoid (CB1 and CB2) receptor subtypes. The 6-methoxy-substituted rotenoids 3, 4, and 7 showed the highest receptor binding affinity with moderate selectivity toward the δ-opioid receptor subtype, with negligible binding affinities for CB1 and CB2. Their binding affinities toward the δ-opioid receptor were 64.5% (4), 58.7% (7), and 55.3% (3) at 10 μM, respectively.The ability of density functional theory (DFT) and time-dependent DFT (TDDFT) methods for the accurate prediction of the energies and oscillator strengths of the excited states in a series of fully conjugated meso-meso β-β β-β triple-linked porphyrin oligomers (porphyrin tapes 2-12) was probed in the gas phase and solution using several exchange-correlation functionals. It was demonstrated that the use of the hybrid B3LYP functional provides a good compromise for the accurate prediction of the localized π-π* and intramolecular charge-transfer transitions, thus allowing confident interpretation of the UV-vis-NIR spectra of porphyrin oligomers. The TDDFT-based sum-over-state (SOS) calculations for the porphyrin tape dimer 2 and trimer 3 as well as parent monomer 1 correctly predicted the signs and shapes of the magnetic circular dichroism (MCD) signals in the low-energy region of the spectra.Improved methods of convergent synthesis for peptidomimetic utilizing a chloroalkene dipeptide isostere (CADI) are reported. In this synthesis, Fmoc- or Boc-protected carboxylic acids can be produced from N- and C-terminal analogues corresponding to each amino acid starting material via an Evans syn aldol reaction, followed by a [3.3] sigmatropic rearrangement utilizing the Ichikawa allylcyanate rearrangement reaction. With this strategy, an Fmoc-protected CADI can be directly applied for solid-phase peptide synthesis. Using this approach, we have also identified the CADI-containing cyclo[-Lys-Leu-Val-Phe-Phe-] peptidomimetic, which is a superior inhibitor of amyloid-β aggregation than the parent peptide.The heme-dependent l-tyrosine hydroxylases (TyrHs) in natural product biosynthesis constitute a new enzyme family in contrast to the nonheme iron enzymes for DOPA production. A representative TyrH exhibits dual reactivity of C-H and C-F bond cleavage when challenged with 3-fluoro-l-tyrosine (3-F-Tyr) as a substrate. However, little is known about how the enzyme mediates two distinct reactions. Herein, a new TyrH from the thermophilic bacterium Streptomyces sclerotialus (SsTyrH) was functionally and structurally characterized. A de novo crystal structure of the enzyme-substrate complex at 1.89-Å resolution provides the first comprehensive structural study of this hydroxylase. Ibrutinib The binding conformation of l-tyrosine indicates that C-H bond hydroxylation is initiated by electron transfer. Mutagenesis studies confirmed that an active site histidine, His88, participates in catalysis. We also obtained a 1.68-Å resolution crystal structure in complex with the monofluorinated substrate, 3-F-Tyr, which shows one binding conformation but two orientations of the fluorine atom with a ratio of 73, revealing that the primary factor of product distribution is the substrate orientation. During in crystallo reaction, a ferric-hydroperoxo intermediate (compound 0, Fe3+-OOH) was observed with 3-F-Tyr as a substrate based on characteristic spectroscopic features. We determined the crystal structure of this compound 0-type intermediate and refined it to 1.58-Å resolution. Collectively, this study provided the first molecular details of the heme-dependent TyrH and determined the primary factor that dictates the partitioning between the dual reactivities of C-H and C-F bond activation.Agricultural soil is the main source of nitrous oxide (N2O) emissions which contribute to global warming and stratospheric ozone depletion. In recent decades, atmospheric nitrogen (N) deposition has increased dramatically as an important agricultural soil N input, while its effect on soil N2O emissions in the current and future climate change remains unknown. Here, we conducted a thorough analysis of the effect of N deposition and climate change on soil N2O emissions as well as their trends. Soil N2O emissions induced by N deposition accounted for 25% of global cropland soil N2O emissions. Global soil N2O emissions over croplands increased by 2% yr-1 during 1996-2013, of which N deposition could explain 15% of the increase. The emission factor of N deposition was ∼7 times that of N fertilizer plus manure (∼1%) through a more direct way, since N deposition including nitrate (NO3-) and ammonium (NH4+) could be directly used for nitrification and denitrification. By 2100, N deposition will increase by 80% and cropland soil N2O emissions will increase by 241% under the RCP8.5 scenario in comparison with the 2010 baseline. These results suggest that, under the background of increasing global N deposition, it is essential to consider its effects on soil N2O emissions in climatic change studies.By using commercially available 1,4-pentadiene as a pronucleophile, a copper(I)-catalyzed regioselective asymmetric allylation of ketones is achieved. A variety of chiral tertiary alcohols bearing a terminal (Z)-1,3-diene unit are generated in high (Z)/(E) ratio and high enantioselectivity. Both aromatic ketones and aliphatic ketones serve as suitable substrates. Furthermore, the reactions with (E)-C1(alkyl)-1,4-dienes proceed in moderate yields with acceptable enantioselectivity but with low (Z,E)/others ratio, which demonstrates the partial isomerization of (E)-allylcopper(I) species to (Z)-allylcopper(I) species through 1,3-migration. Subsequent Heck reaction and olefin metathesis compensate for the low efficiency with C1-1,4-dienes. The synthetic utility of the product is further demonstrated by a copper(I)-catalyzed regioselective borylation of the 1,3-diene group.ConspectusLike singlet carbenes and silylenes, transient electrophilic terminal phosphinidene complexes enabled highly selective synthetic transformations, but the required multistep synthetic protocols precluded widespread use of these P1 building blocks. By contrast, nucleophilic M/Cl phosphinidenoid complexes can be easily accessed in one step from [M(CO)n(RPCl2)] complexes. This advantage and the mild reaction conditions opened broad synthetic applicability that enabled access to a variety of novel compounds. The chemistry will be described in this Account, including bonding and mechanistic considerations derived from high-level density functional theory calculations.In 2007, we gained the first strong evidence for the formation of these thermally labile complexes using two different synthetic approaches P-H deprotonation and Cl/Li exchange; the latter has become the preferred method. Intense studies revealed that steric demand of the P substituents in combination with metal complexation, a donor solvent,trophilic phosphinidene complexes via chloride elimination. The latter is clearly restricted to P-amino derivatives because of their enhanced π-donation capability, as evidenced in a recent study on umpolung of these reactive intermediates. While our efforts to expand M/X phosphinidenoid complex chemistry are ongoing, we want to emphasize that the development of new reactive intermediates not only improves our understanding of bonding and reactivity but also opens new perspectives in organoelement chemistry.To fabricate high efficiency photoanodes for water oxidation, it is highly required to engineer their nanoporous architecture and interface to improve the charge separation and transport efficiency. By focusing on this aspect, we developed hierarchical nanoporous BiVO4 (BV) from solution processed two-dimensional BiOI (BI) crystals. The orientation of the BI crystals was controlled by changing the solvent volume ratios of ethylene glycol (EG) to ethanol (ET), which resulted in different hierarchical and planar BV morphologies through a chemical treatment followed by thermal heating. The morphology with optimal particle dimension, connectivity, and porosity can offer a highly enhanced electrochemically active surface area (ECSA). The hierarchical BV owning a maximum ECSA showed the best photoelectrochemical (PEC) performance in terms of the highest photocurrent density and charge separation efficiency. However, to further improve the performance of the electrode, conformal and ultrathin SnO2 underlayers were deposited by a powerful atomic layer deposition technique at the interface to effectively block the defect density, which significantly improved the photocurrents as high as 3.25 mA/cm2 for sulfite oxidation and 2.55 mA/cm2 for water oxidation at 0.6 V versus the reversible hydrogen electrode (RHE). The electrode possessed record charge separation efficiency of 97.1% and charge transfer efficiency of 90.1% at 1.23 VRHE among to-date reported BiVO4-based photoanodes for water oxidation. Furthermore, a maximum applied bias photon-to-current efficiency (ABPE) of 1.61% was found at a potential as low as 0.6 VRHE, which is highly promising to make a tandem cell. These results indicate that the construction of the hierarchical nanoporous photoanode with an enhanced ECSA and its proper interface engineering can significantly improve the PEC performance.Optofluidic biolasers have emerged as promising tools for biomedical analysis due to their strong light-matter interactions and miniaturized size. Recent developments in optofluidic lasers have opened a new Frontier in monitoring biological processes. However, most biolasers require precise recording of the lasing spectrum at the single cavity level, which limits its application in high-throughput applications. Herein, a microdroplet laser array encapsulated with living Escherichia coli was printed on highly reflective mirrors, where laser emission images were employed to reflect the dynamic changes in living organisms. The concept of image-based lasing analysis was proposed by quantifying the integrated pixel intensity of the lasing image from whispering-gallery modes. Finally, dynamic interactions between E. coli and antibiotic drugs were compared under fluorescence and laser emission images. The amplification that occurred during laser generation enabled the quantification of tiny biological changes in the gain medium.