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A compositionally tunable series of AuCu films is active for electrocatalytic urea generation from carbon dioxide and nitrate.
Existing methods for lignin deconstruction to aromatic monomers primarily cleave carbon–oxygen bonds within the polymer, resulting in sub-optimal monomer yields and formation of oligomers that retain intact carbon–carbon bonds. Here, we demonstrate that copper-catalyzed aerobic oxidation under aqueous alkaline conditions promotes oxidative cleavage of carbon–carbon bonds in lignin oligomers derived from reductive catalytic fractionation (RCF) of pine and poplar biomass. Fundamental insights are gained from reactions of model compounds that resemble subunits present in RCF oligomers. Optimal results are achieved in a flow reactor that provides precise control over O2 delivery, temperature, and reaction residence time. The Cu-catalyzed aerobic oxidation conditions access aromatic monomers in 19 and 34 wt% monomer yields, respectively, from pine- and poplar-derived RCF oligomers. Overall, the sequence consisting of biomass RCF into monomers and oligomers followed by oxidative deconstruction of the RCF oligomers generates substantially higher yields of aromatic monomers from lignin. Engineered strains of Pseudomonas putida support biological funneling of the oligomer-derived oxygenated aromatic compounds into cis,cis-muconic acid from pine or 2-pyrone-4,6-dicarboxylic acid from poplar.
Upcycling of waste polyolefins into higher-value functional polymers through chemical functionalization is a promising strategy to recover value and minimize their environmental impact. We report the hydrocarboxylation of polycyclooctene as a model for accessing ethylene acrylic acid copolymers (EAA) from waste polyethylene. The effects of various process parameters on the hydrocarboxylation were investigated. The relationship between carboxylic acid concentration and material properties, including crystallinity, melting temperature, glass transition temperature, adhesive properties, and wettability, was studied in comparison to an unfunctionalized polyethylene. Among the catalysts evaluated, Co 2 (CO) 8 exhibited relatively slow kinetics toward the hydrocarboxylation and was not compatible with 2,6-di-tert-butyl hydroxytoluene, a common additive present in commercial polyolefins. PdCl 2 (PPh 3 ) 2 exhibited a higher reactivity toward the hydrocarboxylation, though polymer gelation was observed with extended reaction times or high catalyst loadings. Carboxylic acid incorporation into the polymer was readily controlled by varying the reaction time. Altogether, the resultant COOH-functionalized polyolefins possessed properties analogous to commercial EAA.
We introduce cymyc, a high-performance Python library for numerical investigation of the geometry of a large class of string compactification manifolds and their associated moduli spaces. We develop a well-defined geometric ansatz to numerically model tensor fields of arbitrary degree on a large class of Calabi-Yau manifolds. cymyc includes a machine learning component which incorporates this ansatz to model tensor fields of interest on these spaces by finding an approximate solution to the system of partial differential equations they should satisfy.
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We discuss the modification of the properties of the tetraquark-like and its heavy quark spin partner, immersed in a hot bath of pions. We consider these exotic states as purely isoscalar DD* and D*D* S-wave bound states, respectively. Finite temperature effects are incorporated through the D and D* state-of-the-art thermal spectral functions calculated in [G. Montana et al., Phys. Rev. D, 102 (2020) 096020], using the imaginary-time formalism. We find important modifications of the DD* and D*D* scattering amplitudes already for MeV, and show that the hot-bath lineshapes of these tetraquark-like states strongly depend on their Weinberg molecular content. We find that the thermal and spectral functions change more rapidly with temperature for high molecular probabilities P0. For large values of P0, the widths significantly increase with temperature, leading to the melting of these exotic states for temperatures larger than 80 MeV. For small molecular components, the changes in the spectral functions of these states due to temperature become significantly less important. All these results show that any future experimental determination of the D(*)D* scattering amplitudes at finite temperature will provide valuable insights into the molecular content of the and exotics.
Reversible cyclopropane formation is examined in a chromium diamide–diimine chelate complex via reduction. Sites of electrophilicity incur similar and divergent chemistry; structural, electrochemical, and calculational studies afford their rationale.
We report a comprehensive study on the synthesis, reactivity, mechanism, and computation for the β-alkynyl eliminations of secondary and tertiary propargylic alkoxides of Cu( i ) complexes supported by N-heterocyclic carbenes and diphosphines.
Here, the utility of the sterically bulky terphenylthiolate ligand, (SAr iPr6 ) 1− in expanding uranium reductive chemistry has been explored. Reduction of U(SAr iPr6 ) 2 I forms the U(II) complex, U(SAr iPr6 ) 2 , in which the metal is protected by the flanking arene rings of the ligand, but they move out of the way to accommodate the four electron reduction of PhN=NPh to form the U(VI) bis(imido) product U(SAr iPr6 ) 2 (=NPh) 2 (THF) 2 . Here, the KC 8 reduction of U(SAr iPr6 ) 2 generates a more reduced complex, KU(μ-SAr iPr6 ) 2 , initially identified by a −2.55 V vs. Fc + /Fc electrochemical reduction event in THF.
Epitaxial lattice matching is an important condition for the formation of coherent interfaces with low defect densities. However, lattice-matched substrates with the same crystal structure as the active layer are often not available, suggesting opportunities for utilizing heterostructural interfaces. For example, at high Al contents that are interesting for ultrawide-gap applications in power electronics, Al x Ga 1-x N semiconductor alloys in the (0001) orientation of the wurtzite (wz) structure become lattice-matched to (111)-oriented rocksalt (rs) TaC substrates. To predict the expected interface atomic structures under different synthesis conditions, we perform high-throughput density-functional-theory calculations, using an algorithm for systematic sampling of the possible stacking sequences of the atomic layers on the in-plane hexagonal lattice. The approach considers octahedral, tetrahedral, and prismatic coordination motifs, and is generally applicable for the modeling of commensurate rs/wz heterostructural interfaces. Our results provide guidance for synthesis control of substrate-film bonding and the polarity of ultrawide-gap Al x Ga 1-x N alloys on TaC substrates.
Abstract Usinge + e − annihilation data sets corresponding to an integrated luminosity of 4.5 fb −1 , collected with the BESIII detector at center-of-mass energies between 4.600 and 4.699 GeV, we report the first measurements of the absolute branching fractions$$ \mathcal{B}\left({\Lambda}_c^{+}\to p{K}_L^0\right) $$ B Λ c + → p K L 0 = (1.67±0.06±0.04)%,$$ \mathcal{B}\left({\Lambda}_c^{+}\to p{K}_L^0{\pi}^{+}{\pi}^{-}\right) $$ B Λ c + → p K L 0 π + π − = (1.69±0.10±0.05)%, and$$ \mathcal{B}\left({\Lambda}_c^{+}\to p{K}_L^0{\pi}^0\right) $$ B Λ c + → p K L 0 π 0 = (2.02±0.13±0.05)%, where the first uncertainties are statistical and the second systematic. Combining with the known branching fractions of$$ {\Lambda}_c^{+}\to p{K}_S^0 $$ Λ c + → p K S 0 ,$$ {\Lambda}_c^{+}\to p{K}_S^0{\pi}^{+}{\pi}^{-} $$ Λ c + → p K S 0 π + π − , and$$ {\Lambda}_c^{+}\to p{K}_S^0{\pi}^0 $$ Λ c + → p K S 0 π 0 , we present the first measurements of the$$ {K}_S^0 $$ K S 0 -$$ {K}_L^0 $$ K L 0 asymmetries$$ R\left({\Lambda}_c^{+},{K}_{S,L}^0X\right)=\frac{\mathcal{B}\left({\Lambda}_c^{+}\to {K}_S^0X\right)-\mathcal{B}\left({\Lambda}_c^{+}\to {K}_L^0X\right)}{\mathcal{B}\left({\Lambda}_c^{+}\to {K}_S^0X\right)+\mathcal{B}\left({\Lambda}_c^{+}\to {K}_L^0X\right)} $$ R Λ c + K S , L 0 X = B Λ c + → K S 0 X − B Λ c + → K L 0 X B Λ c + → K S 0 X + B Λ c + → K L 0 X in charmed baryon decays:$$ R\left({\Lambda}_c^{+},p{K}_{S,L}^0\right)=-0.025\pm 0.031 $$ R Λ c + p K S , L 0 = − 0.025 ± 0.031 ,$$ R\left({\Lambda}_c^{+},p{K}_{S,L}^0{\pi}^{+}{\pi}^{-}\right)=-0.027\pm 0.048 $$ R Λ c + p K S , L 0 π + π − = − 0.027 ± 0.048 and$$ R\left({\Lambda}_c^{+},p{K}_{S,L}^0{\pi}^0\right)=-0.015\pm 0.046 $$ R Λ c + p K S , L 0 π 0 = − 0.015 ± 0.046 . No significant asymmetries with statistical significance are observed.
Ring size effects on geometries and electronic structures were investigated for the (C n H n )M(C m H m ) (n = 4, 5, or 6; m = 8, 7, or 6; m + n = 12; M = Ti–Ni) systems using density functional theory. The lowest-energy C 12 H 12 M structures for the early transition metals titanium, vanadium, and chromium are the experimentally known singlet (η 5 -C 5 H 5 )Ti(η 7 -C 7 H 7 ), doublet (η 5 -C 5 H 5 )V(η 7 -C 7 H 7 ), and singlet (η 6 -C 6 H 6 ) 2 Cr, respectively. The likewise experimentally known singlet (η 6 -C 6 H 6 ) 2 Ti, doublet (η 6 -C 6 H 6 ) 2 V, and singlet (η 5 -C 5 H 5 )Cr(η 7 -C 7 H 7 ) are the secondlowest- energy structures with only a small energy difference between the two vanadium structures. For the later transition metals, dibenzenemetal complexes are the lowest-energy C 12 H 12 M species with two fully bonded hexahapto benzene rings in the lowest-energy manganese and iron derivatives and one hexahapto and one dihapto benzene ring in the lowest-energy cobalt and nickel derivatives. The lowest-energy (C 5 H 5 )M(C 7 H 7 ) structures for the later transition metals iron, cobalt, and nickel have partially bonded nonplanar C 7 H 7 rings with one or two uncomplexed C=C bonds. The (C 4 H 4 )M(C 8 H 8 ) (M = Ti–Ni) structures with the metal sandwiched between four- and eight-membered rings were found to be much higher in energy than their (C 5 H 5 )M(C 7 H 7 ) and (C 6 H 6 ) 2 M isomers.