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.  https://www.selleckchem.com/products/Temsirolimus.html  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.