ACS Publications最新文献

The 13th Wartburg Symposium on Flavor Chemistry & Biology was held from October 3 to 6, 2023, in Eisenach, Germany. The scientific program that consisted of seven keynote lectures, 26 talks, 13 flash poster presentations, and 72 posters focused on the current hot spots in flavor research, including “functional flavor genomics & biotechnology”, “flavor systems: molecular decoding, interactions and perception”, “chemosensory perception and signal processing”, and “next-generation technologies in molecule discovery and analytics”. This editorial summarizes selected highlights from all of the scientific sections mentioned above and thus provides an overview of the progress in flavor research as presented and discussed during the 2023 edition of the Wartburg Symposium.

Despite extensive research on the sequence-determined self-assembly of both pathogenic and nonpathogenic proteins, the question of how the sequence identity would influence the coassembly or cross-seeding of diverse proteins without distinct sequence similarity remains largely unanswered. Here, we demonstrate that the rapid coaggregation of proteins with negligible sequence similarity is fundamentally governed by preferred heteromeric interactions between their partially unfolded states via the gain of additional charge complementarity and hydrophobic interactions. The partial loss of intramolecular interactions and concurrent gain of non-native intrinsically disordered regions with sticky groups become crucial for both aggressive heteromeric primary nucleation and secondary nucleation events. The results signify the direct relevance of sequence-independent conformational cross-talk between diverse proteins to the foundational events required for the growth of biological multiprotein amyloid deposits.

Ceramic matrix composites (CMCs) have played a significant role in increasing the efficiency of gas turbine engines. CMCs combine the high temperature resistance of ceramics with the high mechanical strength of ceramic fibers into a single unit. Interphase layers are a crucial component in CMCs, as they prevent ceramic fibers from oxidation and introduce strengthening mechanisms into the composite. Hexagonal boron nitride and pyrolytic carbon are the most commonly used interphase layers in the aerospace industry. Other than that, very few materials have been evaluated as interphase layers. In this study, we explore the possibilities of using titanium nitride as an interphase layer in single-tow CMCs (mini composite) representative of a unidirectional composite at a smaller scale. T-300 carbon fibers were coated with TiN by atmospheric pressure chemical vapor infiltration using TiCl₄, N₂, and H₂. The deposition temperature, precursor flow rate ratio, total precursor flow rate, and deposition time were optimized to obtain high-quality coatings. The best coating was produced at 800 °C, 4:1 H₂ [TiCl₄]/N₂ ratio, 125 standard cubic centimeters per minute (N₂ + H₂ [TiCl₄]) total flow precursor flow rate, and 2 h of deposition time. At these conditions, the coatings displayed good fiber coverage, good fiber adhesion, minimum fiber linkage, and minimum surface roughness. There was minimum fiber degradation after TiN coating, with a retention of 95% of the initial Young's modulus and 26% of the ultimate tensile strength of the carbon fiber. Adding the TiN interphase coating to the Cf/SiC CMC increased the ultimate tensile strength of the composite by 1122% and Young's modulus by 150%.

Efficient thermal insulators that can maintain their efficacy at extreme temperatures are in pressing demand, particularly in fields such as energy saving, aerospace, and sophisticated equipment. Herein, a novel and facile polymerization-regulated optimal strategy is adapted to realize the comprehensive performance of polyimide (PI) aerogel membranes with mechanical robustness, high flexibility, hydrophobicity, light transmittance, and efficient thermal insulation. Benefiting from the hydrolysis of monomers and chemical imidization reaction process verified by a thermo-chemo-mechanically coupled theoretical model, the viscosity of precursors, shrinkage rate, and microstructure of aerogels are precisely controlled, leading to a low thermal conductivity range of 0.023-0.044 W/(m·K). The fabricated PI aerogel membranes, which undergo a remarkable transformation from their initial brittle and opaque nature to a state of high flexibility and transparency, exhibit a 3.0 times increase in tensile strength (4.6 MPa) and a 8.4 times improvement in elongation at break (20.6%) over previous studies while demonstrating an exceptional light transmittance of 92.5% across a wide spectral range from 500 to 2500 nm. Additionally, the PI aerogel membranes possess superior mechanical properties and a wide temperature resistance range extending from -196 to 300 °C. These flexible PI aerogel membranes can be effectively adjusted to meet the practical application of a circular ring solar thermal collector, which displayed a high solar heat collection temperature of 135 °C at a thickness of 0.5 mm. The coordination between the thermophysical properties and mechanical properties of the PI aerogel membranes in this work holds great promise for application requirements of thermal insulators in optical elements under harsh environments.

Under the guidance of genome mining combined with bioassay-coupled metabolomic analyses, an unprecedented macrodiolide sanyensin (1), with two flexible macrolides fused by the rigid oxabicyclo[3.3.1]nonane core, was isolated from the deep-sea-derived Streptomyces sp. OUCT16-30. The stereochemistry of 1 was established by NOEs (nuclear Overhauser effects), J-based configuration analysis, Marfey's analysis, and together with a newly introduced stereochemical study workflow, which greatly shortens the time to obtain correct conformations of flexible structures based on the NMR constraints, thus leading to reliable quantum chemical calculations to establish the absolute configurations. This workflow is expected to have broad applicability for elucidating the stereochemistry of flexible natural products. The macrodiolide framework of 1 is proposed to be formed through a biocatalytic cyclodimerization, followed by a series of nonenzymatic reactions. This work leads to new insights into the unexplored biosynthetic potential of deep-sea microbes and also provides a practical streamline for efficient mining of novel natural products, from discovery to stereochemical finalization.

Nondestructive detection methods based on vibrational spectroscopy have been widely used in many critical applications in a variety of fields such as the chemical industry, pharmacy, national defense, security, and so on. As these methods/applications rely on machine learning models for data analysis, studying the threats associated with adversarial examples in vibrational spectroscopy and defenses against them is of great importance. In this paper, we propose a novel adversarial method to attack vibrational spectroscopy, named SynPat, where synthetic peaks produced by a physical model are placed at key locations to form adversarial perturbations. Our new attack generates perturbations that successfully deceive machine learning models for Raman and infrared spectrum analysis while they blend much better into the spectra and hence are unnoticeable to human operators, unlike the existing state-of-the-art adversarial attacking methods, e.g., images and audio. We verified the superiority of the proposed SynPat by an imperceptibility test conducted by human experts and of defense experiments by an AI detector. To the best of our knowledge, this is a first thorough study on the robustness of vibrational spectroscopic techniques against adversarial samples and defense mechanisms. Our extensive experiments show that machine learning models for vibrational spectroscopy, including conventional and deep models for Raman or infrared classification and regression, are all vulnerable to adversarial perturbations and thus may pose serious security threats to our society.

Polyoxometalates (POMs) are esteemed for their remarkable stability and exceptionally high proton conductivity, rendering them ripe for extensive exploration owing to their research significance. Herein, we synthesized two bimolybdenum-capped {AlMo^VI₈Mo^V₆O₄₄} cluster-based coordination polymers through a solvothermal method. Single-crystal X-ray diffraction analysis elucidates that H[(H₂bimb)₃(AlMo^VI₈Mo^V₆O₄₄)] [bimb = 1,4-bis(imidazole-1-ylmethyl)benzene, compound 1] is the POMs-organic supramolecular structure. The introduction of zinc ions into the reaction environment facilitated the connection of initially dispersed ligands, which yielded the well-ordered structure H₃[Zn₂(bimb)₄(AlMo^VI₈Mo^V₆O₄₄)]·4H₂O (compound 2) with a layer distance of 11.8 Å. The proton conductivities (σ) of two compounds were measured under conditions of 85 °C and 98% relative humidity (RH), resulting in values of 3.89 × 10^-2 and 4.76 × 10^-2 S·cm^-1, respectively. This study presents a novel approach to fabricating POMs as proton conductors through structural design and manufacturing adjustments.