Templemckinney4745

The excellent activity, stability, and economics of the Pt0.7Ru0.3/ZrO2 catalyst allow for its application in toluene removal.Mesoporous-structure perovskite solar cells (meso-PVKSCs) have been widely utilized due to the achieved high efficiency for which the TiO2 layer usually suffers from sufficient electron trap states, low electron mobility, and inavoidable catalytic activity. Herein, a mesoporous TiO2 (m-TiO2) layer is modified by tetraethylammonium p-toluenesulfonate (abbreviated as TEATS) for the first time, leading to a significant photoelectric conversion efficiency enhancement from 19.14 to 20.69% for Cs0.05MA0.12FA0.83PbI2.55Br0.45 (abbreviated as CsMAFA) meso-PVKSCs. In particular, the obtained champion open-circuit voltage (Voc) is 1.18 V, which is a record high value for meso-PVKSCs with CsMAFA triple cation mixed perovskite. A series of measurements were employed to investigate the influences of TEATS modification on the energy band structures of TiO2 as well as the CsMAFA perovskite layer atop, unveiling that TEATS modification benefits defect passivation of the TiO2 film along with a decrease in the work function of TiO2. TTNPB nmr Besides, TEATS modification helps to improve the wettability of perovskite precursors on the m-TiO2 substrate, affording improved film quality of perovskite with enhanced crystallinity and grain size. Consequently, the trap states existed in the perovskite film can be passivated, and the interfacial charge recombination is suppressed. This further benefits the improvement of the ambient stability of devices.Post-translational modification of proteins can form electrophilic cofactors that serve as a catalytic center. The derived electrophilic cofactors greatly expand protein activities and functions. However, there are few studies concerning how to profile the electrophiles in bacteria. Herein, we utilized a clickable probe called propargyl hydrazine to profile the protein-derived electrophilic cofactors in Escherichia coli (E. coli) cells. Since the cofactors are mostly carbonyl groups, the hydrazine-based probe can specifically react with the cofactors to form a Schiff base. The labeled proteins were then pulled down for mass spectrometry (MS) analysis. Fourteen proteins were shown to undergo enrichment by the probe and competitive binding by its analogue, propyl hydrazine. The identified proteins were further analyzed with targeted proteomics based on parallel reaction monitoring (PRM). Using this strategy, we obtained a global portrait of protein electrophiles in bacterial cells, among which the proteins of speD and panD were previously reported to derive pyruvoyl group as an electrophilic center while lpp can retain N-terminal formyl methionine. This quantitative chemical proteomics strategy can be used to find out protein electrophiles in bacteria and holds great potential to further characterize the protein functions.To date, there has been limited information on phytoestrogen (PE) exposure and metabolism in breastfed infants. In the present work, 50 sample pairs of Chinese breastfed infants' urine and the corresponding breast milk were collected. The contents of the relevant PE metabolites in the biosamples were detected via liquid chromatography-tandem mass spectrometry. The correlations between the PE metabolite contents in breastfed infants' urine and those in the corresponding breast milk were analyzed. The average concentrations of total PE metabolites in breast milk and urine were 0.27 and 0.23 nmol/mL, respectively. Genistein and enterolactone levels in the infant urine were positively correlated with their concentrations in the corresponding breast milk samples, which implies that urine excretion can be utilized as a noninvasive parameter for precise genistein and enterolactone intake assessment. Additionally, the efficiency of PE urine excretion showed significant differences across infants with different ages, genders, and durations of pregnancy.Fluoride ion detection in water focuses much attention due to the serious healthy impact in human pathologies. For fluoride recognition, the chemical affinity between fluoride and silicon has been developed on the basis of the degradation mechanism. However, most fluorescent probes are the "turn off" type due to the aggregation of the degradational products. Herein, we first developed an "off-on" hydrophilic luminescent polymer composed of amino-functionalized polyhedral oligomeric silsesquioxane (AE-POSS) and perylene diimides (PDIs) for fluoride ion in water. The AE-PDI polymer was "turned off" because of the photoinduced electron transfer (PET) between PDI and AE-POSS, and then after reaction with F-, the fluorescent emission could "turn on" obviously because the PET was blocked by the degradation of the cage. The PET from amino-POSS to PDI was proved by FL spectrum and energies of HOMO and LUMO orbitals. 29Si, 19F NMR, and 1H NMR titration, XRD, FTIR, size analysis, and ion chromatography were applied to demonstrate the degradation mechanism. These results indicated that the higher quantum yield could be obtained by introducing the amide group in the PDI and the products of AE-PDI polymer might exist in the form of complex compounds with partial condensation of organosiloxane. With high selectivity and sensitivity (detection limit of 16.2 ppb), this probe was successfully applied for F- detection in actual water samples.Titania (TiO2) has wide applications in the realm of perovskite solar cells (PSCs). Because high-temperature processing severely limits the application of flexible and tandem devices, it is significant to develop a high-quality electron-transport layer (ETL) by low-temperature processing. Here, we design a new strategy by introducing a bifunctional molecule (thioacetamide, TAA) in the TiO2 ETL. During the low-temperature annealing, the N and S atoms in TAA can bond with the Ti atom in the ETL and the Pb atom in the perovskite (PVK) layer, respectively. The formation of coordinate bonds is beneficial to increase the crystallinity and reduce the roughness of TiO2 ETLs and PVK layers, which effectively passivate the defects. Meanwhile, the energy level matching between the ETL and PVK is optimized. The structure characterization and electrochemical measurement demonstrate the design. Compared with precursor doping, surface spin-coating is a more effective method for introducing TAA into TiO2. Significantly, the PSC based on the surface spin-coated TAA TiO2 ETL achieves the best power conversion efficiency (PCE) of 21.17%. Nevertheless, the PSC fabricated with the pristine TiO2 ETL offers a PCE of 19.52% under the same conditions. The results demonstrate a novel method for optimizing the properties of PSCs.An asymmetric approach for the first total synthesis of (-)-rhodomollanol A, a highly oxidized diterpenoid, is described. The efficient synthetic strategy features three key transformations (1) an oxidative dearomatization-induced (5 + 2) cycloaddition/pinacol-type 1,2-acyl migration cascade to build up the bicyclo[3.2.1]octane skeleton; (2) a retro-Dieckmann fragmentation/vinylogous Dieckmann cyclization cascade to assemble the bicyclo[3.3.0]octane subunit; and (3) a photo-Nazarov cyclization/intramolecular cycloetherification cascade to forge the 7-oxabicyclo[4.2.1]nonane core structure of the natural product.Expanded porphyrins provide a versatile route to molecular switching devices due to their ability to shift between several π-conjugation topologies encoding distinct properties. DFT remains the workhorse for modeling such extended macrocycles, when taking into account their size and huge conformational flexibility. Nevertheless, the stability of Hückel and Möbius conformers depends on a complex interplay of different factors, such as hydrogen bonding, π···π stacking, steric effects, ring strain, and electron delocalization. As a consequence, the selection of an exchange-correlation functional for describing the energy profile of topological switches is very difficult. For these reasons, we have examined the performance of a variety of wave function methods and density functionals for describing the thermochemistry and kinetics of topology interconversions across a wide range of macrocycles. Especially for hexa- and heptaphyrins, the Möbius structures have a stronger degree of static correlation than the HückeYP, outperform other functionals with RMSDs of 0.6 and 0.8 kcal mol-1, respectively. While the original DSD-PBEP86 double hybrid performs fairly poorly for these extended π-systems, the errors drop down to 1.9 kcal mol-1 for the revised revDOD-PBEP86-NL, which eliminates the same-spin correlation energy. Minnesota meta-GGA functionals with high fractions of exact exchange (M06-2X and M08-HX) also perform reasonably well, outperforming more robust and significantly less empirically parametrized functionals like SCAN0-D3.Oxidative coupling (OC) through o-quinone intermediates has been established as an efficient and site-selective way to modify protein N-termini and the unnatural amino acid p-aminophenylalanine (paF). Recently, we reported that the tyrosinase-mediated oxidation of phenol-tagged cargo molecules is a particularly convenient method of generating o-quinones in situ. The coupling partners can be easily prepared and stored, the reaction takes place under mild conditions (phosphate buffer, pH 6.5, 4 to 23 °C), and dissolved oxygen is the only oxidant required. Here, we show an important extension of this chemistry for the activation of tyrosine residues that project into solution from the N or C-termini of peptide and protein substrates. Generating the o-quinone electrophiles from tyrosine allows greater flexibility in choosing the nucleophilic coupling partner and expands the scope of the reaction to include C-terminal positions. We also introduce a new bacterial tyrosinase enzyme that shows improved activation for some tyrosine substrates. The efficacy of several secondary amines and aniline derivatives was evaluated in the coupling reactions, providing important information for coupling partner design. This strategy was used to modify the C-termini of an antibody scFv construct and of Protein L, a human IgG kappa light chain binding protein. The use of the modified proteins as immunolabeling agents was also demonstrated.Diseases are multifactorial, with redundancies and synergies between various pathways. However, most of the antibody-based therapeutics on the market interact with only one target, thus limiting their efficacy. The targeting of multiple epitopes could improve the therapeutic index of treatment and counteract mechanisms of resistance. To this effect, a new class of therapeutics has emerged bispecific antibodies. Bispecific formation using chemical methods is rare and low-yielding and/or requires a large excess of one of the two proteins to avoid homodimerization and heterogeneity. In order for chemically prepared bispecifics to deliver their full potential, high-yielding, modular, and reliable cross-linking technologies are required. Herein, we describe a novel approach not only for the rapid and high-yielding chemical generation of bispecific antibodies from native antibody fragments, but also for the site-specific dual functionalization of the resulting bioconjugates. Based on orthogonal clickable functional groups, this strategy enables the assembly of functionalized bispecifics with controlled loading in a modular and convergent manner.