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This study utilizes the FMN-dependent NADHquinone oxidoreductase from Pseudomonas aeruginosa PAO1 to investigate the effect of introducing an active site negative charge on the flavin absorption spectrum both in the absence and presence of a long-range electrostatic potential coming from solution ions. There were no observed changes in the flavin UV-visible spectrum when an active site tyrosine (Y277) becomes deprotonated in vitro. These results could only be reproduced computationally using average solvent electrostatic configuration (ASEC) QM/MM simulations that include both positive and negative solution ions. The same calculations performed with minimal ions to neutralize the total protein charge predicted that deprotonating Y277 would significantly alter the flavin absorption spectrum. https://www.selleckchem.com/products/azd7648.html Analyzing the distribution of solution ions indicated that the ions reorganize around the protein surface upon Y277 deprotonation to cancel the effect of the tyrosinate on the flavin absorption spectrum. Additional biochemical experiments were performed to test this hypothesis.We report a deep learning (DL) model that predicts various material properties while accepting directly accessible inputs from routine experimental platforms chemical compositions and diffraction data, which can be obtained from the X-ray or electron-beam diffraction and energy-dispersive spectroscopy, respectively. These heterogeneous forms of inputs are treated simultaneously in our DL model, where the novel chemical composition vector is proposed by developing element embedding with the normalized composition matrix. With 1524 binary samples available in the Materials Project database, the model predicts formation energies and band gaps with mean absolute errors of 0.29 eV/atom and 0.66 eV, respectively. According to the weighing test between these two inputs, the properties tend to be more influenced by the chemical composition than the crystal structure. This work intentionally avoids using inputs that are not directly accessible (e.g., atomic coordinates) in experimental platforms, and thus is expected to substantially improve the practical use of DL models.Owing to its high theoretical capacity, appropriate working potential, abundant resource, intrinsic safety, and low cost, zinc (Zn) metal is regarded as one of the most promising anode candidates for aqueous batteries. However, the hazards caused by dendrite growth and side reactions impede its practical applications. Herein, to solve these problems, a protective heterogeneous layer composed of electronic conductive sulfur-doped three-dimensional (3D) MXene and ionic conductive ZnS on Zn anode is designed and constructed. The sulfur doping and the creation of a 3D structure on MXene are simultaneously achieved during the generation of ZnS. The sulfur-doped 3D MXene can effectively homogenize distribution of electric field, decrease local current density, and alleviate volume change. The ZnS can inhibit side reactions, promote uniform Zn2+ distribution, and accelerate Zn2+ migration. Consequently, a stable and dendrite-free Zn anode is achieved with notable cycling stability up to 1600 h and rate performance. The relationship between structure of protective layer and performance of Zn anode is also probed. With the protected Zn anode and freestanding sulfur-doped 3D MXene@MnO2 cathode, a high-energy, long cycling life, and high-rate full cell is obtained. This work may provide a direction for the design of practical Zn anodes and other metal-based battery systems.Condiments such as spreads, dressings, or sauces are usually consumed together with carrier foods such as breads or vegetables. Dynamic interactions between condiments and carriers occur during consumption, which can influence aroma release and perception. This study investigated in vivo aroma release (PTR-MS) and dynamic sensory perception (time-intensity) of mayonnaises spiked with lemon aroma (limonene, citral). Mayonnaises were assessed without and with carrier foods (bread, potato). When different mayonnaises were consumed and assessed alone, aroma release and intensity perception were positively correlated. Interestingly, when mayonnaises were combined with carriers, aroma release and perception were no longer positively correlated. Addition of carriers increased release of limonene and citral into the nasal cavity during consumption but decreased perceived aroma intensity of condiments. The increase in aroma release induced by the carriers can be explained by differences in oral processing behaviors and by the increased surface area of mayonnaise-carrier combinations. Carrier addition is likely to modulate aroma perception of composite foods by cross-modal texture-aroma interactions. This work demonstrates that not only physicochemical characteristics of foods but also cross-modal interactions play a role in influencing flavor perception of composite foods.Ideal conductive hydrogels for flexible, wearable strain sensors should be tough, highly resilient, adhesive, and anti-freezing. However, such hydrogels are difficult to design. Herein, a multifunctional macromolecular cross-linker (MC) based on poly(hydroxyethyl-l-glutamine) was designed and used to synthesize the hydrogels. Cross-linking with the MC leads to a reduced inhomogeneity of the gel network. Therefore, the mechanical properties of the gels are significantly improved compared with the ordinary hydrogels cross-linked with the conventional cross-linker N,N-methylenebisacrylamide (BIS). The MC-cross-linked gels also exhibit high resilience. At the same time, replacing BIS with MC significantly improves the adhesive properties of the gel, which is attributed to the introduction of a large amount of adhesive groups with the MC. The gels can stick to various substrates including skin. The good tissue adhesiveness of the gel allows it to stick to skin by itself without using any straps or adhesive tapes when used as a flexible wearable strain sensor. Both large and subtle human movements were successfully monitored using the sensor. The signals are highly stable and reliable, thanks to the high resilience of the gel. The introduction of the polar groups also improved dramatically the anti-freezing properties of the gels. Even at -20 °C, the gels still remained highly flexible and stretchable, therefore allowing the gel-based sensor to work at sub-zero temperatures. The excellent toughness, resilience, tissue-adhesiveness, and anti-freezing properties of the gel make it a good choice for a flexible wearable sensor.Atypical myopathy (AM) is a severe rhabdomyolysis syndrome that occurs in grazing horses. Despite the presence of toxins in their blood, all horses from the same pasture are not prone to display clinical signs of AM. The objective of this study was to compare the blood metabolomic profiles of horses with AM clinical signs with those of healthy co-grazing (Co-G) horses. To do so, plasma samples from 5 AM horses and 11 Co-G horses were investigated using untargeted metabolomics. Metabolomic data were evaluated using unsupervised, supervised, and pathway analyses. Unsupervised principal component analysis performed with all detected features separated AM and healthy Co-G horses. Supervised analyses had identified 1276 features showing differential expression between both groups. Among them, 46 metabolites, belonging predominantly to the fatty acid, fatty ester, and amino acid chemical classes, were identified by standard comparison. Fatty acids, unsaturated fatty acids, organic dicarboxylic acids, and fatty esters were detected with higher intensities in AM horses in link with the toxins' pathological mechanism. The main relevant pathways were lipid metabolism; valine, leucine, and isoleucine metabolism; and glycine metabolism. This study revealed characteristic metabolite changes in the plasma of clinically affected horses, which might ultimately help scientists and field veterinarians to detect and manage AM. The raw data of metabolomics are available in the MetaboLights database with the access number MTBLS2579.Nanogaps between Au nanoparticles and Au substrates are the simplest systems that generate extremely high electric fields at hotspots for surface-enhanced Raman spectroscopy (SERS). However, the electric field cancellation at the hotspots in the systems can cause the reduction of Raman signal when two metallic materials are physically contacted due to the low concentration of analytes. Here, we propose an atomically thin hexagonal boron nitride (h-BN) shielding layer for Au substrates, which can be used as an insulating spacer to prevent electrical shorts at nanogaps. Experimental investigation of the SERS effect combined with theoretical studies by finite-difference time-domain simulations demonstrate that the Au NP/h-BN/Au substrate structure has excellent performance in electrical short prevention, thus facilitating ultrasensitive Raman detection. The outstanding chemical and thermal stability of h-BN allow the efficient recycling of the SERS substrate by protecting the Au surface during the removal of Au NPs and molecular analytes by chemical and thermal processes.Vaccines induce immunity by presenting disease antigens through several platforms ranging from individual protein subunits to whole viruses. Due to the large difference in antigen size, the analytical techniques employed for vaccine characterization are often platform-specific. A single, robust analytical technique capable of widespread, cross-platform use would be of great benefit and allow for comparisons across manufacturing processes. One method that spans the antigen mass range is charge detection mass spectrometry (CDMS). CDMS is a single-ion approach where the mass-to-charge ratio (m/z) and charge are measured simultaneously, allowing accurate mass distributions to be measured for heterogeneous analytes over a broad size range. In this work, CDMS was used to characterize the antigens from three classical multivalent vaccines, inactivated poliomyelitis vaccine (IPOL), RotaTeq, and Gardasil-9, directly from commercial samples. For each vaccine, the antigen purity was inspected, and in the whole virus vaccines, empty virus particles were detected. For IPOL, information on the extent of formaldehyde cross-linking was obtained. RotaTeq shows a narrow peak at 61.06 MDa. This is at a slightly lower mass than expected for the double-layer particle, suggesting that around 10 pentonal trimers are missing. For Gardasil-9, buffer exchange of the vaccine resulted in very broad mass distributions. However, removal of the virus-like particles from the aluminum adjuvant using a displacement reaction generated a spectrum with narrow peaks.The binding of adenosine 5'-triphosphate (ATP) and adenosine 5'-monophosphate (AMP) to adenylate kinase (AdK) drives closure of lids over the substrate adenosyl groups. We test the hypothesis that this conformational change activates AdK for catalysis. The rate constants for Homo sapiens adenylate kinase 1 (HsAdK1)-catalyzed phosphoryl group transfer to AMP, kcat/Km = 7.0 × 106 M-1 s-1, and phosphite dianion, (kHPi)obs ≤1 × 10-4 M-1 s-1, show that the binding energy of the adenosyl group effects a ≥7.0 × 1010-fold rate acceleration of phosphoryl transfer from ATP. The third-order rate constant of kcat/KHPiKEA = 260 M-2 s-1 for 1-(β-d-erythrofuranosyl)adenine (EA)-activated phosphoryl transfer to phosphite dianion was determined, and the isohypophosphate reaction product characterized by 31P NMR. The results demonstrate the following (i) a ≥14.7 kcal/mol stabilization of the transition state for phosphoryl transfer by the adenosyl group of AMP and a ≥2.6 × 106-fold rate acceleration from the EA-driven conformational change and (ii) the recovery of ≥8.