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As a potential multifunctional phase transition material, the organic-inorganic hybrid perovskite has attracted extensive attention in recent years. Here, we report the single-crystal to single-crystal phase transition and excitation-wavelength-dependent emission (EDE) of layered perovskite (COOH(CH2)3NH3)2PbI4. Single-crystal X-ray diffraction indicated that the crystal structure changes from layered Ruddlesden-Popper (RP) at 302 K to "X" network composed of face-sharing and corner-sharing [PbX6]4- octahedra at 425 K. The material exhibits thermochromic change from orange to yellow at higher temperature. Considering the thermochromism of the material, we apply it for anticounterfeiting and information encryption. The material exhibits EDE properties with a fluorescence color changing from green to red upon 420 and 546 nm excitation, respectively. Time-dependent density functional theory indicated that this phenomenon is mainly related to the laser-induced crystal structural transfer. Our research shows that the (COOH(CH2)3NH3)2PbI4 crystal has a potential application for multifunctional devices.Interleukin-4 (IL-4) is a potentially interesting anti-inflammatory therapeutic, which is rapidly excreted. Therefore, serum half-life extension by polymer conjugation is desirable, which may be done by PEGylation. Here, we use PEtOx as an alternative to PEG for bioconjugate engineering. We genetically extended murine IL-4 (mIL-4) with the d-domain of insulin-like growth factor I (IGF-I), a previously identified substrate of transglutaminase (TG) Factor XIIIa (FXIIIa). Thereby, engineered mIL-4 (mIL-4-TG) became an educt for TG catalyzed C-terminal, site-directed conjugation. This was deployed to enzymatically couple an azide group containing peptide sequence to mIL-4, allowing C-terminal bioconjugation of polyethylene glycol or poly(2-ethyl-2-oxazoline). Both bioconjugates had wild-type potency and alternatively polarized macrophages.Eu2+,Pb2+-doped core-shell-structured CaS@CaZnOS phosphors were synthesized by a two-step high-temperature solid-phase method. The as-synthesized CaSEu2+,Pb2+@CaZnOSPb2+ phosphors possess excellent dual-excitation and dual-emission (DE2) luminescent properties, which give rise to red emission peaking at 650 nm under green excitation, derived from the core CaSEu2+,Pb2+, and blue emission peaking at 424 nm, originating from the shell CaZnOSPb2+, under ultraviolet (UV) excitation. In addition, tunable red/blue emission can be achieved by changing the doping concentration of Pb2+ in the CaZnOS shell. The red/blue dual emission of core-shell DE2 phosphors under excitation of UV and green light significantly matches with the absorption spectrum of chlorophyll (a, b); hence, the as-prepared phosphors are excellent solar spectral conversion (SSC) auxiliaries of plastic films or laminated glass for greenhouses and provide ideas for creating more efficient and practically valuable SSC auxiliaries. The DE2 properties are described, and the energy transfer mechanism from Pb2+ to Eu2+ in the core is proposed and discussed in detail.The leucine-rich repeat kinase 2 (LRRK2) protein has been genetically and functionally linked to Parkinson's disease (PD), a disabling and progressive neurodegenerative disorder whose current therapies are limited in scope and efficacy. In this report, we describe a rigorous hit-to-lead optimization campaign supported by structural enablement, which culminated in the discovery of brain-penetrant, candidate-quality molecules as represented by compounds 22 and 24. These compounds exhibit remarkable selectivity against the kinome and offer good oral bioavailability and low projected human doses. Furthermore, they showcase the implementation of stereochemical design elements that serve to enable a potency- and selectivity-enhancing increase in polarity and hydrogen bond donor (HBD) count while maintaining a central nervous system-friendly profile typified by low levels of transporter-mediated efflux and encouraging brain penetration in preclinical models.Stable hydrogen isotope compositions (2H/1H ratios) have been an invaluable tool for studying biogeochemical processes in nature, but the diversity of molecular targets amenable to such analysis is limited. Here, we demonstrate a new technique for measuring δ2H of biomolecules via Orbitrap mass spectrometry (MS) using acetate as a model analyte. Acetate was chosen as a target molecule because its production and consumption are central to microbial carbon cycling, yet the mechanisms behind acetate turnover remain poorly understood. δ2H of acetate could provide a useful constraint on these processes; however, it remains uncharacterized in nature due to analytical challenges. Electrospray ionization (ESI)-Orbitrap MS circumvents these challenges and delivers methyl-specific H-isotope compositions of acetate with nanomole sensitivity, enough to enable analyses of environmental samples. This approach quantifies the methyl-specific δ2H and molecular-average δ13C of acetate simultaneously while achieving 310‰ depletion) associated with the Wood-Ljungdahl pathway, while fermentation expressed a muted (∼80‰) fractionation. With its high precision and sensitivity, Orbitrap MS is a promising tool for investigating these signals in nature after offline purification. Furthermore, the ESI-Orbitrap method presented here could be applied to other molecules amenable to ESI, including central metabolites and sugars, greatly expanding the molecular targets used in hydrogen isotope biogeochemistry.The hybrid quadrupole ion trap/time-of-flight mass spectrometry (QIT/TOFMS) device is popular because of its advantages of high sensitivity, high resolution, and MS/MS capability. However, the analytical performance of QIT/TOFMS is severely limited by the parameters of the ion trap, as QIT is typically used as a TOF pulser because the ion initial distributions of space, velocity, and angle change dynamically with the phase angle of rf voltage. In this work, a square waveform phase modulation strategy was proposed to eliminate the influence of the rf phase angle, and the dependence of QIT/TOFMS performance on the phase angle was studied. It was found that the mass resolution and signal intensity showed a "W" trend with the increase of the ion extraction phase angle from 0° to 360°, where the best resolution and sensitivity were obtained at 0°, 180°, and 360° while the worst resolution and sensitivity were obtained at 90° and 270°. Moreover, the optimum phase angle was independent of m/z. As a result, the mass resolution for m/z 106, 164, and 258 was improved by 162%, 160%, and 210% respectively, while the signal intensities for m/z 106, 164, and 258 were enhanced by 25 ± 1, 10 ± 1, and 21 ± 1 fold, respectively, and a limit of detection down to 0.015 ppbv for m/z 164 was obtained. The experiment results indicated that the square waveform phase modulation strategy could be used to simultaneously improve the resolution and sensitivity of QIT/TOFMS.The targeted delivery of phytochemicals that promote energy expenditure for obesity therapy remains a challenge. [https://www.selleckchem.com/products/vx-561.html find more] This study assembled a functionalized adipo-8 aptamer loaded with allicin using isothermal rolling-circle techniques to form a synergistic adipocyte-targeted binary-drug delivery system for treating obesity. The functionalized adipo-8 aptamer efficiently protected allicin from adsorption, showing significant potential to encapsulate, transport, and release molecular cargos into white adipose tissue. Introducing the negatively charged allicin, a phytochemical able to induce adipose tissue browning, reduced the diameters of DNA-nanoflower from 770 to 380 nm and increased cellular uptake efficiency up to 118.7%. The intracellular distribution observed via confocal microscopy confirmed the successful receptor recognition mediated by aptamers in the DNA-nanoflower-allicin (NFA) framework as well as its excellent stability to escape from lysosomes. In vivo results demonstrated that subcutaneous administration of NFA effectively promoted adipocyte browning and systematic energy expenditure with minimal side effects. Furthermore, the G-quadruplex in the mitochondrial uncoupling protein-1 promoter was found to be an interactive allicin target for regulating thermogenesis to combat obesity.In organometallic complexes containing π-conjugated macrocyclic chelate ligands, conformational change significantly affects metal-ligand electronic interactions, hence tuning properties of the complexes. In this regard, we investigated the metal-ligand interactions in hexaphyrin mono-Pd(II) complexes Pd[28]M and Pd[26]H, which exhibit a redox-induced switching of Hückel-Möbius aromaticity and subsequent molecular conformation, and their effect on the electronic structure and photophysical behaviors. In Möbius aromatic Pd[28]M, the weak metal-ligand interaction leads to the π electronic structure of the hexaphyrin ligand remaining almost intact, which undergoes efficient intersystem crossing (ISC) assisted by the heavy-atom effect of the Pd metal. In Hückel aromatic Pd[26]H, the significant metal-ligand interaction results in ligand-to-metal charge-transfer (LMCT) in the excited-state dynamics. These contrasting metal-ligand electronic interactions have been revealed by time-resolved electronic and vibrational spectroscopies and time-dependent DFT calculations. This work indicates that the conspicuous modulation of metal-ligand interaction by Hückel-Möbius aromaticity switching is an appealing approach to manipulate molecular properties of metal complexes, further enabling the fine-tuning of metal-ligand interactions and the novel design of functional organometallic materials.Understanding the dynamical motions and ligand recognition motifs of heptosyltransferase I (HepI) can be critical to discerning the behavior of other glycosyltransferase (GT) enzymes. Prior studies in our lab have demonstrated that GTs in the GT-B structural class, which are characterized by their connection of two Rossman-like domains by a linker region, have conserved structural fold and dynamical motions, despite low sequence homology, therefore making discoveries found in HepI transferable to other GT-B enzymes. Through molecular dynamics simulations and ligand binding free energy analysis of HepI in the apo and bound complexes (for all kinetically relevant combinations of the native substrates/products), we have determined the energetically favored enzymatic pathway for ligand binding and release. Our principal component, dynamic cross correlation, and network analyses of the simulations have revealed correlated motions involving residues within the N-terminal domain communicating with C-terminal domain residues via both proximal amino acid residues and also functional groups of the bound substrates. Analyses of the structural changes, energetics of substrate/product binding, and changes in pKa have elucidated a variety of inter and intradomain interactions that are critical for enzyme catalysis. These data corroborate our experimental observations of protein conformational changes observed in both presteady state kinetic and circular dichroism analyses of HepI. These simulations provided invaluable structural insights into the regions involved in HepI conformational rearrangement upon ligand binding. Understanding the specific interactions governing conformational changes is likely to enhance our efforts to develop novel dynamics disrupting inhibitors against GT-B structural enzymes in the future.