Facile Ozonation of Light Alkanes to Oxygenates with High Atom Economy in Tunable Condensed Phase at Ambient Temperature

We have demonstrated the oxidation of mixed alkanes (propane, n-butane, and isobutane) by ozone in a condensed phase at ambient temperature and mild pressures (up to 1.3 MPa). Oxygenated products such as alcohols and ketones are formed with a combined molar selectivity of >90%. The ozone and dioxygen partial pressures are controlled such that the gas phase is always outside the flammability envelope. Because the alkane–ozone reaction predominantly occurs in the condensed phase, we are able to harness the unique tunability of ozone concentrations in hydrocarbon-rich liquid phases for facile activation of the light alkanes while also avoiding over-oxidation of the products. Further, adding isobutane and water to the mixed alkane feed significantly enhances ozone utilization and the oxygenate yields. The ability to tune the composition of the condensed media by incorporating liquid additives to direct selectivity is a key to achieving high carbon atom economy, which cannot be achieved in gas-phase ozonations. Even in the liquid phase, without added isobutane and water, combustion products dominate during neat propane ozonation, with CO2 selectivity being >60%. In contrast, ozonation of a propane+isobutane+water mixture suppresses CO2 formation to 15% and nearly doubles the yield of isopropanol. A kinetic model based on the formation of a hydrotrioxide intermediate can adequately explain the yields of the observed isobutane ozonation products. Estimated rate constants for the formation of oxygenates suggest that the demonstrated concept has promise for facile and atom-economic conversion of natural gas liquids to valuable oxygenates and broader applications associated with C–H functionalization

Mimicking Elementary Reactions of Manganese Lipoxygenase Using Mn-hydroxo and Mn-alkylperoxo Complexes

Manganese lipoxygenase (MnLOX) is an enzyme that converts polyunsaturated fatty acids to alkyl hydroperoxides. In proposed mechanisms for this enzyme, the transfer of a hydrogen atom from a substrate C-H bond to an active-site MnIII-hydroxo center initiates substrate oxidation. In some proposed mechanisms, the active-site MnIII-hydroxo complex is regenerated by the reaction of a MnIII-alkylperoxo intermediate with water by a ligand substitution reaction. In a recent study, we described a pair of MnIII-hydroxo and MnIII-alkylperoxo complexes supported by the same amide-containing pentadentate ligand (6Medpaq). In this present work, we describe the reaction of the MnIII-hydroxo unit in C-H and O-H bond oxidation processes, thus mimicking one of the elementary reactions of the MnLOX enzyme. An analysis of kinetic data shows that the MnIII-hydroxo complex [MnIII(OH)(6Medpaq)]+ oxidizes TEMPOH (2,2′-6,6′-tetramethylpiperidine-1-ol) faster than the majority of previously reported MnIII-hydroxo complexes. Using a combination of cyclic voltammetry and electronic structure computations, we demonstrate that the weak MnIII-N(pyridine) bonds lead to a higher MnIII/II reduction potential, increasing the driving force for substrate oxidation reactions and accounting for the faster reaction rate. In addition, we demonstrate that the MnIII-alkylperoxo complex [MnIII(OOtBu)(6Medpaq)]+ reacts with water to obtain the corresponding MnIII-hydroxo species, thus mimicking the ligand substitution step proposed for MnLOX

Scaling Symmetries of Scatterers of Classical Zero-Point Radiation

Classical radiation equilibrium (the blackbody problem) is investigated by the use of an analogy. Scaling symmetries are noted for systems of classical charged particles moving in circular orbits in central potentials V(r)=-k/r^n when the particles are held in uniform circular motion against radiative collapse by a circularly polarized incident plane wave. Only in the case of a Coulomb potential n=1 with fixed charge e is there a unique scale-invariant spectrum of radiation versus frequency (analogous to zero-point radiation) obtained from the stable scattering arrangement. These results suggest that non-electromagnetic potentials are not appropriate for discussions of classical radiation equilibrium.Comment: 13 page

Reverse-engineering the cortical architecture for controlled semantic cognition.

We employ a reverse-engineering approach to illuminate the neurocomputational building blocks that combine to support controlled semantic cognition: the storage and context-appropriate use of conceptual knowledge. By systematically varying the structure of a computational model and assessing the functional consequences, we identified the architectural properties that best promote some core functions of the semantic system. Semantic cognition presents a challenging test case, as the brain must achieve two seemingly contradictory functions: abstracting context-invariant conceptual representations across time and modalities, while producing specific context-sensitive behaviours appropriate for the immediate task. These functions were best achieved in models possessing a single, deep multimodal hub with sparse connections from modality-specific regions, and control systems acting on peripheral rather than deep network layers. The reverse-engineered model provides a unifying account of core findings in the cognitive neuroscience of controlled semantic cognition, including evidence from anatomy, neuropsychology and functional brain imaging

Reaction Landscape of a Pentadentate N5-Ligated MnII Complex with O2•− and H2O2 Includes Conversion of a Peroxomanganese(III) Adduct to a Bis(μ-oxo)dimanganese(III,IV) Species

Herein we describe the chemical reactivity of the mononuclear [MnII(N4py)(OTf)](OTf) (1) complex with hydrogen peroxide and superoxide. Treatment of 1 with one equivalent superoxide at −40 °C in MeCN formed the peroxomanganese(III) adduct, [MnIII(O2)(N4py)]+ (2) in ~30% yield. Complex 2 decayed over time and the formation of the bis(μ-oxo)dimanganese(III,IV) complex, [MnIIIMnIV(μ-O)2(N4py)2]3+ (3) was observed. When 2 was formed in higher yields (~60%) using excess superoxide, the [MnIII(O2)(N4py)]+ species thermally decayed to MnII species and 3 was formed in no greater than 10% yield. Treatment of [MnIII(O2)(N4py)]+ with 1 resulted in the formation of 3 in ~90% yield, relative to the concentration of [MnIII(O2)(N4py)]+. This reaction mimics the observed chemistry of Mn-ribonucleotide reductase, as it features the conversion of two MnII species to an oxo-bridged MnIIIMnIV compound using O2− as oxidant. Complex 3 was independently prepared through treatment of 1 with H2O2 and base at −40 °C. The geometric and electronic structures of 3 were probed using electronic absorption, electron paramagnetic resonance (EPR), magnetic circular dichroism (MCD), variable-temperature, variable-field MCD (VTVH-MCD), and X-ray absorption (XAS) spectroscopies. Complex 3 was structurally characterized by X-ray diffraction (XRD), which revealed the N4py ligand bound in an unusual tetradentate fashion

MAPping the Chiral Inversion and Structural Transformation of a Metal-Tripeptide Complex having Ni-SOD Activity

This document is the Accepted Manuscript version of a Published Work that appeared in final form in the Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/ic102295s.The metal abstraction peptide (MAP) tag is a tripeptide sequence capable of abstracting a metal ion from a chelator and binding it with extremely high affinity at neutral pH. Initial studies on the nickel-bound form of the complex demonstrate that the tripeptide asparagine-cysteine-cysteine (NCC) binds metal with 2N:2S, square planar geometry and behaves as both a structural and functional mimic of Ni superoxide dismutase (Ni-SOD). Electronic absorption, circular dichroism (CD), and magnetic CD (MCD) data collected for Ni-NCC are consistent with a diamagnetic NiII center. It is apparent from the CD signal of Ni-NCC that the optical activity of the complex changes over time. Mass spectrometry data show that the mass of the complex is unchanged. Combined with the CD data, this suggests that chiral rearrangement of the complex occurs. Following incubation of the nickel-containing peptide in D2O and back-exchange into H2O, incorporation of deuterium into non-exchangeable positions is observed, indicating chiral inversion occurs at two of the alpha carbon atoms in the peptide. Control peptides were used to further characterize the chirality of the final nickel-peptide complex, and DFT calculations were performed to validate the hypothesized position of the chiral inversions. In total, these data indicate Ni-SOD activity is increased proportionally to the degree of structural change in the complex over time, as cross-correlation between the change in CD signal and change in SOD activity reveals a linear relationship

Controlling the Chiral Inversion Reaction of the Metallopeptide Ni-Asparagine-Cysteine-Cysteine with Dioxygen

This document is the Accepted Manuscript version of a Published Work that appeared in final form in the Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/ic301717q.Synthetically generated metallopeptides have the potential to serve a variety of roles in biotechnology applications, but the use of such systems is often hampered by the inability to control secondary reactions. We have previously reported that the NiII complex of the tripeptide LLL-asparagine-cysteine-cysteine, LLL-NiII-NCC, undergoes metal-facilitated chiral inversion to DLD-NiII-NCC, which increases the observed superoxide scavenging activity. However, the mechanism for this process remained unexplored. Electronic absorption and circular dichroism studies of the chiral inversion reaction of NiII-NCC reveal a unique dependence on dioxygen. Specifically, in the absence of dioxygen, the chiral inversion is not observed, even at elevated pH, whereas the addition of O2 initiates this reactivity and concomitantly generates superoxide. Scavenging experiments using acetaldehyde are indicative of the formation of carbanion intermediates, demonstrating that inversion takes place by deprotonation of the alpha carbons of Asn1 and Cys3. Together, these data are consistent with the chiral inversion being dependent on the formation of a NiIII-NCC intermediate from NiII-NCC and O2. The data further suggest that the anionic thiolate and amide ligands in NiII-NCC inhibit Cα–H deprotonation for the NiII oxidation state, leading to a stable complex in the absence of O2. Together, these results offer insights into the factors controlling reactivity in synthetic metallopeptides

A novel tripeptide model of nickel superoxide dismutase

This document is the Accepted Manuscript version of a Published Work that appeared in final form in the Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/ic901828m.Nickel superoxide dismutase (Ni-SOD) catalyzes the disproportionation of superoxide to molecular oxygen and hydrogen peroxide, but the overall reaction mechanism has yet to be determined. Peptide-based models of the 2N:2S nickel coordination sphere of Ni-SOD have provided some insight into the mechanism of this enzyme. Here we show that the coordination sphere of Ni-SOD can be mimicked using the tripeptide asparagine-cysteine-cysteine (NCC). NCC binds nickel with extremely high affinity at physiological pH with 2N:2S geometry, as demonstrated by electronic absorption and circular dichroism (CD) data. Like Ni-SOD, Ni-NCC has mixed amine/amide ligation that favors metal-based oxidation over ligand-based oxidation. Electronic absorption, CD, and magnetic CD data (MCD) collected for Ni-NCC are consistent with a diamagnetic Ni(II) center bound in square planar geometry. Ni-NCC is quasi-reversibly oxidized with a midpoint potential of 0.72(2) V (versus Ag/AgCl) and breaks down superoxide in an enzyme-based assay, supporting its potential use as a model for Ni-SOD chemistry

The Structure, Kinematics and Physical Properties of the Molecular Gas in the Starburst Nucleus of NGC 253

We present 5.2" x 2.6" resolution interferometry of CO J=1-0 emission from the starburst galaxy NGC 253. The high spatial resolution of these new data, in combination with recent high resolution maps of 13CO, HCN and near-infrared emission, allow us for the first time to link unambiguously the gas properties in the central starburst of NGC 253 with its bar dynamics. We confirm that the star formation results from bar-driven gas flows as seen in "twin peaks" galaxies. Two distinct kinematic features are evident from the CO map and position-velocity diagram: a group of clouds rotating as a solid body about the kinematic center of the galaxy, and a more extended gas component associated with the near-infrared bar. We model the line intensities of CO, HCN and 13CO to infer the physical conditions of the gas in the nucleus of NGC 253. The results indicate increased volume densities around the radio nucleus in a twin-peaks morphology. Compared with the CO kinematics, the gas densities appear highest near the radius of a likely inner Linblad resonance, and slightly lead the bar minor axis. This result is similar to observations of the face-on, twin-peaks galaxy NGC 6951, and is consistent with models of starburst generation due to gas inflow along a bar.Comment: To appear in the ApJ, 28 pages, 12 figure file

Statistical description of inhomogeneous samples by scanning microwave microscopy

A quantitative analysis of the dielectric properties of a multiphase sample using a scanning microwave microscope (SMM) is proposed. The method is demonstrated using inhomogeneous samples composed of a resin containing micrometric inclusions of a known ceramic material. The SMM suitable for this task employs relatively large tips (tens of micrometers in diameter). Additionally, in order to make the instrument more suitable for high-throughput analysis, an original design for rapid tip changes is implemented. Single-point measurements of dielectric constant at random locations on the sample were performed, leading to histograms of dielectric constant values. These are related to the dielectric constants of the two phases using Maxwell–Garnett effective medium theory, taking into account the volume-of-interaction in the sample beneath the tip