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These results can help inform future efforts to conserve and bolster managed and wild pollinator populations to ensure sustainable production of key agricultural crops.Herein, the design and development of a new one-pot and metal-free oxidative C-H activation/aza-Prins type cyclization of alkynylamines is reported. The scope of this method was demonstrated by the preparation of ten new pyrido[2,1-a]isoquinolines in moderate to high yields (38-92%). Furthermore, a mechanistic proposal for the alkyne aza-Prins cyclization is described based on DFT calculations.Electrolyte screening is well known for its detrimental impact on the sensitivity of liquid-gated field-effect transistor (FET) molecular sensors and is mostly described by the linearized Debye-Hückel model. However, charged and pH-sensitive FET sensing surfaces can limit the FET molecular sensitivity beyond the Debye-Hückel screening formalism. Pre-existing surface charges can lead to the breakdown of Debye-Hückel screening and induce enhanced nonlinear Poisson-Boltzmann screening. Moreover, the charging of the pH-sensitive surface groups interferes with biomolecule sensing resulting in a pH interference mechanism. With analytical equations and TCAD simulations, we highlight that the Debye-Hückel approximation can underestimate screening and overestimate FET molecular sensitivity by more than an order of magnitude. Screening strengthens significantly beyond Debye-Hückel in the proximity of even moderately charged surfaces and biomolecule charge densities (≥1 × 1012 q/cm2). We experimentally show the strong impact of both nonlinear screening and the pH interference effect on charge-based biomolecular sensing using a model system based on the covalent binding of single-stranded DNA on silicon FET sensors. [https://www.selleckchem.com/peptide/tirzepatide-ly3298176.html Tirzepatide] The DNA signal increases from 24 mV at pH 7 to 96 mV at pH 3 in 1.5 mM PBS for a DNA density of 7 × 1012 DNA/cm2. Our model quantitatively explains the signal's pH dependence with roughly equal nonlinear screening and pH interference contributions. This work shows the importance of reducing the net charge and the pH sensitivity of the sensing surface to improve molecular sensing. Therefore, tailoring the gate dielectric and functional layer of FET sensors is a promising route to strong silicon FET molecular sensitivity boosts.Structural information is crucial for understanding catalytic mechanisms and to guide enzyme engineering efforts of biocatalysts, such as terpene cyclases. However, low sequence similarity can impede homology modeling, and inherent protein instability presents challenges for structural studies. We hypothesized that X-ray crystallography of engineered thermostable ancestral enzymes can enable access to reliable homology models of extant biocatalysts. We have applied this concept in concert with molecular modeling and enzymatic assays to understand the structure activity relationship of spiroviolene synthase, a class I terpene cyclase, aiming to engineer its specificity. Engineering a surface patch in the reconstructed ancestor afforded a template structure for generation of a high-confidence homology model of the extant enzyme. On the basis of structural considerations, we designed and crystallized ancestral variants with single residue exchanges that exhibited tailored substrate specificity and preserved thermostability. We show how the two single amino acid alterations identified in the ancestral scaffold can be transferred to the extant enzyme, conferring a specificity switch that impacts the extant enzyme's specificity for formation of the diterpene spiroviolene over formation of sesquiterpenes hedycaryol and farnesol by up to 25-fold. This study emphasizes the value of ancestral sequence reconstruction combined with enzyme engineering as a versatile tool in chemical biology.This study investigated the alleviative effects of l-arginine and l-lysine on the emulsifying properties and structural changes of myosin under hydroxyl radical (·OH) stress. The results showed that ·OH decreased the emulsifying activity index and emulsifying stability index but increased the creaming index and droplet size of a soybean oil-myosin emulsion (SOME). Confocal laser scanning microscopy demonstrated that ·OH caused larger and more inhomogeneous SOME droplets. l-Arginine and l-lysine effectively alleviated ·OH-induced destructive effects on the emulsifying properties of myosin. In addition, ·OH increased the extent of protein carbonylation and dityrosine formation, surface hydrophobicity, and β-sheet content, but decreased the tryptophan fluorescence intensity, solubility, total sulfhydryl, and α-helix content of myosin. Although l-lysine increased dityrosine fluorescence intensity, l-arginine and l-lysine effectively alleviated the aforementioned structural changes of myosin. Therefore, l-arginine and l-lysine could mitigate ·OH-induced structural changes of myosin, which enabled myosin to maintain its emulsifying capacity under oxidative stress.An implementation of the replica exchange with dynamical scaling (REDS) method in the commonly used molecular dynamics program GROMACS is presented. REDS is a replica exchange method that requires fewer replicas than conventional replica exchange while still providing data over a range of temperatures and can be used in either constant volume or constant pressure ensembles. Details for running REDS simulations are given, and an application to the human islet amyloid polypeptide (hIAPP) 11-25 fragment shows that the model efficiently samples conformational space.LCMS analysis of an extract of the New Zealand tunicate Synoicum kuranui showed evidence for numerous new rubrolides. Following a mass spectrometry-guided isolation procedure, new hydrated rubrolides V and W (5 and 6), along with previously reported rubrolide G (3), were isolated and characterized using MS and NMR. The anti-bacterial and cell cytotoxic activity of the compounds were compared to the potent anti-MRSA compound rubrolide A; hydration across the C-5/C-6 bond was shown to abrogate antibacterial activity.Polycyclic aromatic hydrocarbon (PAH) concentrations were measured in atmospheric samples collected at five sites near the shores of the North American Great Lakes once every 12 days from 1997 to 2018 (inclusive). These data were analyzed using multiple linear regression statistics to isolate the environmental variables controlling these PAH concentrations. About 74% of the variability is related to the number of people living and working within 25 km of the sampling site. Clearly, urban areas are major sources of PAH to the atmosphere. PAH concentrations at all sites lumped together are decreasing with halving times of about 25 years, and this factor represents about 1.5% of the variability. This is slower than the halving times for most banned compounds because PAH continue to be emitted directly into the atmosphere from many combustion sources. In the atmosphere, the concentrations of relatively volatile PAH maximize in July, but those of relatively nonvolatile PAH maximize in January. This seasonality factor represents about 2.