Westrich3005

Two-dimensional (2D) intrinsic half-metallic materials with room-temperature ferromagnetism, sizable magnetic anisotropy energy (MAE), and wide half-metallic gap are excellent candidates for pure spin generation, injection, and transport in nanospintronic applications. However, until now, such 2D half metallicity has been rarely observed in experiment. In this work, by using first-principles calculations, we design a series of such materials, namely, Mn2X3 (X = S, Se, Te) nanosheets, which could be obtained by controlling the thickness of synthesized α-MnX(111) nanofilm to a quintuple X-Mn-X-Mn-X layer. All these nanosheets are dynamically and thermally stable. Electronic and magnetic studies reveal they are intrinsic half metals with high Curie temperatures between 718 and 820 K, sizable MAEs with -1.843 meV/Mn for Mn2Te3 nanosheet, and wide half-metallic gaps from 1.55 to 1.94 eV. Above all, the outstanding features of Mn2X3 nanosheets make them promising in fabricating nanospintronic devices working at room temperature.We report herein the development of α-borylmethyl-(Z)-crotylboronate reagent and the application in highly stereo- and enantioselective syntheses of (E)-δ-hydroxymethyl-syn-homoallylic alcohols. Starting from 1,4-pentadiene, α-borylmethyl-(Z)-crotylboronate was synthesized in two steps with high Z-selectivity and enantioselectivity. Subsequent aldehyde allylboration with the developed boron reagent gave highly enantioenriched (E)-δ-hydroxymethyl-syn-homoallylic alcohols upon oxidative workup.A series of 9-amino-10-halophenanthrenes were synthesized through a one-pot process, including dephosphinylative Sonogashira-Hagihara coupling of 2-bromobiphenyls with air-stable phosphinyl ynamines, followed by halonium-promoted [4 + 2] benzannulation of the resulting 2-(aminoethynyl)biphenyls. Nonsubstituted and methyl-substituted 2-bromobiphenyls rapidly underwent the Sonogashira-Hagihara aminoethynylation and the halogenative Friedel-Crafts benzannulation to provide the corresponding amino(halo)phenanthrenes in high yields, while electron-sufficient and -deficient substrates did slowly undergo the former and the latter to result in low yields, respectively. This protocol worked well for the syntheses of highly π-extended aminophenanthrenes and aminobenzonaphthothiophenes with different optical properties. Further application of this approach between 2,2″- and 2',5'-dibromo-p-terphenyls with phosphinyl ynamines led to the regioselective formation of 6,13-diamino-5,12-dihalo- and 5,12-diamino-6,13-dihalo-dibenz[a,h]anthracenes via dual aminoethynylation and [4 + 2] benzannulation. The obtained analogues showed different ultraviolet-visible absorption and photoluminescence spectra with different emission quantum yields in CH2Cl2 solution and the powder state.Supramolecular and covalent polymers share multiple structural effects such as chiral amplification, helical inversion, sergeants and soldiers, or majority rules, among others. These features are related to the axial helical structure found in both types of materials, which are responsible for their properties. Herein a novel material combining information and characteristics from both fields of helical polymers, supramolecular (oligo(p-phenyleneethynylene) (OPE)) and covalent (poly(acetylene) (PA)), is presented. To achieve this goal, the poly(acetylene) must adopt a dihedral angle between conjugated double bonds (ω1) higher than 165°. In such cases, the tilting degree (Θ) between the OPE units used as pendant groups is close to 11°, like that observed in supramolecular helical arrays of these molecules. Polymerization of oligo[(p-phenyleneethynylene)n]phenylacetylene monomers (n = 1, 2) bearing L-decyl alaninate as the pendant group yielded the desired scaffolds. These polymers adopt a stretched and almost planar polyene helix, where the OPE units are arranged describing a helical structure. As a result, a novel multihelix material was prepared, the ECD spectra of which are dominated by the OPE axial array.Recent experimental advances on investigating nanoparticle catalysts with multiple active sites provided a large amount of quantitative information on catalytic processes. These observations stimulated significant theoretical efforts, but the underlying molecular mechanisms are still not well-understood. We introduce a simple theoretical method to analyze the reaction dynamics on catalysts with multiple active sites based on a discrete-state stochastic description and obtain a comprehensive description of the dynamics of chemical reactions on such catalysts. We explicitly determine how the dynamics of catalyzed chemical reactions depend on the number of active sites, on the number of intermediate chemical transitions, and on the topology of underlying chemical reactions. It is argued that the theory provides quantitative bounds for realistic dynamic properties of catalytic processes that can be directly applied to analyze the experimental observations. In addition, this theoretical approach clarifies several important aspects of the molecular mechanisms of chemical reactions on catalysts.Ions are of central importance in nature, and a variety of potential models was proposed to model ions in different phases for an in-depth exploration of ion-related systems. Here, we developed point charge models of 14 monovalent ions with the traditional 12-6 Lennard-Jones (LJ) potential for use in conjunction with 11 water models of TIP3P, OPC3, SPC/E, SPC/Eb, TIP3P-FB, a99SB-disp, TIP4P-Ew, OPC, TIP4P/2005, TIP4P-D, and TIP4P-FB. The designed models reproduced the real hydration free energy (HFE) of ions and the ion-oxygen distance (IOD) in the first hydration shell accurately and simultaneously, a performance similar to the previously reported 12-6-4 LJ-type ion models (12-6 LJ plus an attractive C4 term for cations or a repulsive one for anions). This work, along with our previous work on di-, tri-, and tetravalent metal cations (J. Chem. Inf. Model. 2021, 61, 4031-4044; J. Chem. Inf. Model. 2021, 61, 4613-4629), demonstrates the feasibility of the simple 12-6 LJ potential in ion modeling. In order for the 12-6 LJ potential to reproduce both the HFE and IOD, the LJ R parameters need to be close to Shannon's ionic radii for the highly charged cations and to the Stokes's van der Waals (vdW) radii for the monovalent ions. With an additional C4 term, the R parameters of 12-6-4 LJ ion models agree well with the Stokes's vdW radii and have a more physical meaning. It appears that the C4 term can be merged into the 12-6 LJ potential by a rational tuning of R and the LJ well depth. Simulations of the osmotic coefficients of alkali chloride solutions and the properties of gaseous and solid alkali halides indicate the necessity of further optimizing ion-ion interactions via, for instance, targeting more properties or using a more physical (polarizable) model.The rising prevalence of multidrug-resistant bacteria is an urgent health crisis that can only be countered through renewed investment in the discovery and development of antibiotics. There is no panacea for the antibacterial resistance crisis; instead, a multifaceted approach is called for. In this Perspective we make the case that, in the face of evolving clinical needs and enabling technologies, numerous validated antibacterial targets and associated lead molecules deserve a second look. At the same time, many worthy targets lack good leads despite harboring druggable active sites. Tanespimycin Creative and inspired techniques buoy discovery efforts; while soil screening efforts frequently lead to antibiotic rediscovery, researchers have found success searching for new antibiotic leads by studying underexplored ecological niches or by leveraging the abundance of available data from genome mining efforts. The judicious use of "polypharmacology" (i.e., the ability of a drug to alter the activities of multiple targets) can also provide new opportunities, as can the continued search for inhibitors of resistance enzymes with the capacity to breathe new life into old antibiotics. We conclude by highlighting available pharmacoeconomic models for antibacterial discovery and development while making the case for new ones.Multimodal mass spectrometry imaging (MSI) is a critical technique used for deeply investigating biological systems by combining multiple MSI platforms in order to gain the maximum molecular information about a sample that would otherwise be limited by a single analytical technique. The aim of this work was to create a multimodal MSI approach that measures metabolomic and proteomic data from a single biological organ by combining infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) for metabolomic MSI and nanodroplet processing in one pot for trace samples (nanoPOTS) LC-MS/MS for spatially resolved proteome profiling. Adjacent tissue sections of rat brain were analyzed by each platform, and each data set was individually analyzed using previously optimized workflows. IR-MALDESI data sets were annotated by accurate mass and spectral accuracy using HMDB, METLIN, and LipidMaps databases, while nanoPOTS-LC-MS/MS data sets were searched against the rat proteome using the Sequest HT algorithm and filtered with a 1% FDR. The combined data revealed complementary molecular profiles distinguishing the corpus callosum against other sampled regions of the brain. A multiomic pathway integration showed a strong correlation between the two data sets when comparing average abundances of metabolites and corresponding enzymes in each brain region. This work demonstrates the first steps in the creation of a multimodal MSI technique that combines two highly sensitive and complementary imaging platforms. Raw data files are available in METASPACE (https//metaspace2020.eu/project/pace-2021) and MassIVE (identifier MSV000088211).The lack of an appropriate analytical approach characterizing metabolites from dietary proteins may prevent further studies that could clarify their health benefits. In this study, we attempted to establish a novel analytical assay of peptide metabolites from glycinin using matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS), in combination with the amine derivatization technique with coumarin (Cou). Cou (30 mmol/L) derivatization of peptides under rapid (30 min) and mild (25 °C, pH 8.5) conditions caused higher MS detection of the peptides as compared to nonderivatized peptides. In addition, an MS shift of the target by Cou derivatization (+202.0 m/z) can help to easily discriminate peptide metabolites in glycinin-administered blood, by comparing the MALDI-MS spectra of Cou-derivatized plasma with those of preadministered blood. After the oral administration of glycinin (100 mg/kg) to Sprague-Dawley rats, 15 di- to tetrapeptides were successfully characterized as glycinin-derived metabolites, demonstrating that the proposed Cou-tagged MALDI-MS is an appropriate characterization technique for peptide metabolites.Peptide hydrogels are widely used for biomedical applications owing to their good biocompatibility and unique advantages in terms of amino acid-based structures and functions. However, the exploration of the peptide/saccharide composite hydrogels as potential biomaterials for chronic diabetic wound healing is still limited. Herein, hyaluronic acid (HA) was incorporated into diphenylalanine (FF) conjugated with different aromatic moieties by a one-pot reaction. Our results showed that the dipeptide derivatives modified by benzene (B), naphthalene (N), and pyrene (P) self-assembled into composite hydrogels with uniform distribution and good mechanical properties in the presence of HA. The obtained N-FF/HA composite hydrogel exhibited greatly improved self-healing properties via injection syringe needle operation and good biocompatibility on human skin fibroblast (HSF) cells. Besides, the structure of thinner nanofibers and honeycomb networks inside the composite hydrogel allowed for a longer sustained release of curcumin, a hydrophobic drug for anti-inflammation and wound healing.