Kaplanmunro4107

The search for new nanostructural topologies composed of elemental carbon is driven by technological opportunities as well as the need to understand the structure and evolution of carbon materials formed by planetary shock impact events and in laboratory syntheses. We describe two new families of diamond-graphene (diaphite) phases constructed from layered and bonded sp3 and sp2 nanostructural units and provide a framework for classifying the members of this new class of materials. The nanocomposite structures are identified within both natural impact diamonds and laboratory-shocked samples and possess diffraction features that have previously been assigned to lonsdaleite and postgraphite phases. The diaphite nanocomposites represent a new class of high-performance carbon materials that are predicted to combine the superhard qualities of diamond with high fracture toughness and ductility enabled by the graphitic units and the atomically defined interfaces between the sp3- and sp2-bonded nanodomains.Alpha-amylase/trypsin inhibitors (ATIs) may have a role in non-coeliac wheat sensitivity (NCWS); but the ATI content and diversity across a range of wheat cultivars is not well characterised. Discovery proteomics was used to detect ATIs across two wheat cultivars Chara and Magenta. PH-797804 cost Comprehensive mapping of detected ATIs with the ATIs from the recently published wheat genome RefSeq v1.0 shows the presence of three major subclasses monomeric (9%), dimeric (61%) and CM-type (30%). Subsequently, the level of 18 ATI isoforms (63 peptides) grouped into four subtypes were monitored across 15 commercial wheat cultivars and the 8 parental lines from a multiparent advanced generation intercross (MAGIC) population using LC-MRM-MS. The ATI content of wheat cultivars Janz, Sunvale, Diamond Bird and Longreach Scout was significantly lower than other wheat cultivars. The MAGIC parental cultivars Baxter and Xiaoyan contain higher levels (~115% relative to the average wheat ATI content), whereas cultivar Pastor contained the lowest levels (~87%). Comprehensive sequence analysis, annotation, chromosomal locations and epitope mapping enabled us to build a LC-MRM-MS method to monitor and quantify the immunostimulatory ATI proteins potentially related to NCWS, autoimmune diseases and metabolic disorders. This provides an opportunity to select wheat cultivars with significantly lower level of ATIs.Stimuli-responsive mesoporous silica films were prepared by evaporation-induced self-assembly through the physical entrapment of a functional metalloblock copolymer structuring agent, which simultaneously served to functionalize the mesopore. After end-functionalization with a silane group, the applied functional metalloblock copolymers were covalently integrated into the silica mesopore wall. In addition, they were partly degraded after the formation of the mesoporous film, which enabled the precise design of accessible mesopores. These polymer-silica hybrid materials exhibited remarkable and gating ionic permselectivity and offer the potential for highly precise pore filling design and combination with high-throughput printing techniques. This in situ functionalization strategy of mesoporous silica using responsive metalloblock copolymers has the potential to improve how we approach the design of complex architectures at the nanoscale for tailored transport. This functionalization strategy paves the way for a variety of technologies based on molecular transport in nanoscale pores, including separation, sensing, catalysis, and energy conversion.Binding between protein and DNA is an essential process to regulate different biological activities. Two puzzling questions in protein-DNA recognition are (i) how the protein's binding domain identifies the DNA sequence in an aqueous solution and (ii) how the formation of the complex alters the dynamical environment around it. In this work, we present results obtained from molecular dynamics simulations of the N-terminal α-helical domain of the λ-repressor protein (in dimeric form) bound to the corresponding operator DNA. Effects of formation of the complex in modifying the microscopic dynamics of water as well as the kinetics of hydrogen bonds at the interface have been explored. Locally heterogeneous restricted water motions at the complex interface have been observed, the extent of restriction being more significant around the directly bound residues of the protein and the DNA. In particular, the calculation revealed the existence of significantly constrained motionally restricted water layer that can form either bridges around the directly bound residues of the protein and DNA or are engaged in forming water-mediated contacts between a fraction of the unbound residues. More importantly, it is observed that the restricted water motion around the complex is correlated with the hydrogen bond relaxation time scale at the interface. It is further demonstrated that the kinetics of water-water hydrogen bonds involving the bridged water are influenced more due to complex formation.New derivatives of α-phenyl-N-tert-butyl nitrone (PBN) bearing a hydroxyl, an acetate, or an acetamide substituent on the N-tert-butyl moiety and para-substituted phenyl or naphthlyl moieties were synthesized. Their ability to trap hydroxymethyl radical was evaluated by electron paramagnetic resonance spectroscopy. The presence of two electron-withdrawing substituents on both sides of the nitronyl function improves the spin-trapping properties, with 4-HOOC-PBN-CH2OAc and 4-HOOC-PBN-CH2NHAc being ∼4× more reactive than PBN. The electrochemical properties of the derivatives were further investigated by cyclic voltammetry and showed that the redox potentials of the nitrones are largely influenced by the nature of the substituents both on the aromatic ring and on the N-tert-butyl function. The acetamide derivatives PBN-CH2NHAc, 4-AcNHCH2-PBN-CH2NHAc, and 4-MeO-PBN-CH2NHAc were the easiest to oxidize. A computational approach was used to rationalize the effect of functionalization on the free energies of nitrone reactivity with hydroxymethyl radical as well as on the electron affinity and ionization potential. Finally, the neuroprotection of the derivatives was evaluated in an in vitro model of cellular injury on cortical neurons. Five derivatives showed good protection at very low concentrations (0.1-10 μM), with PBN-CH2NHAc and 4-HOOC-PBN being the two most promising agents.