Fulvenallenyl Radical (C7H5·)-Mediated Gas-Phase Synthesis of Bicyclic Aromatic C10H8 Isomers: Can Fulvenallenyl Efficiently React with Closed-Shell Hydrocarbons?

To understand the reactivity of resonantly stabilized radicals, often found in relevant concentrations in gaseous environments, it is important to determine their main reaction pathways. Here, it is investigated whether the fulvenallenyl radical (C7H5·) reacts preferentially with closed-shell molecules or radicals. Electronic structure calculations on the C10H9 potential energy surface accessed by the reactions of C7H5· with methylacetylene (CH3CCH) and allene (H2CCCH2) were combined with RRKM-ME calculations of temperature- and pressure-dependent rate constants using the automated EStokTP software suite and kinetic modeling to assess the reactivity of C7H5· with closed-shell unsaturated hydrocarbons. Experimentally, the reactions were attempted in a chemical microreactor heated to 998 ± 10 K by preparing fulvenallenyl radicals via pyrolysis of trichloromethylbenzene (C7H5Cl3) and seeding the radicals in methylacetylene or allene carrier gas, with product identification by means of photoionization mass spectrometry. The measured photoionization efficiency curve of m/z = 128 was assigned to a linear combination of the reference curves of two C10H8 isomers, azulene (minor) and naphthalene (major), presumably resulting from the C7H5· plus C3H4 reactions. However, the calculations demonstrated that these reactions are too slow, and kinetic modeling of processes in the reactor allowed us to conclude that the observation of naphthalene and azulene is due to the C7H5· plus C3H3· reaction, where propargyl is produced by direct hydrogen atom abstraction by chlorine (Cl) atoms from allene or methylacetylene and Cl stem from the pyrolysis of C7H5Cl3. Modeling results under the copyrolysis conditions of toluene and methylacetylene in high-temperature shock tube experiments confirmed the prevalence of the fulvenallenyl reaction with propargyl over its reactions with C3H4 even when the concentrations of allene and methylacetylene largely exceed that of propargyl. Overall, the reactions of fulvenallenyl with both allene and methylacetylene were found to be noncompetitive in the formation of naphthalene and azulene thus attesting the inefficiency of the fulvenallenyl radical reactions with the prototype closed-shell hydrocarbon species. In the meantime, the new reaction pathways revealed, including H-assisted isomerizations between C10H8 isomers and decomposition reactions of various C10H9 isomers, emerge as relevant and are recommended for inclusion in combustion kinetic models for naphthalene formation.

Radical-Radical Reactions in Molecular Weight Growth: The Phenyl + Propargyl Reaction.

The mechanism for hydrocarbon ring growth in sooting environments is still the subject of considerable debate. The reaction of phenyl radical (C6H5) with propargyl radical (H2CCCH) provides an important prototype for radical-radical ring-growth pathways. We studied this reaction experimentally over the temperature range of 300-1000 K and pressure range of 4-10 Torr using time-resolved multiplexed photoionization mass spectrometry. We detect both the C9H8 and C9H7 + H product channels and report experimental isomer-resolved product branching fractions for the C9H8 product. We compare these experiments to theoretical kinetics predictions from a recently published study augmented by new calculations. These ab initio transition state theory-based master equation calculations employ high-quality potential energy surfaces, conventional transition state theory for the tight transition states, and direct CASPT2-based variable reaction coordinate transition state theory (VRC-TST) for the barrierless channels. At 300 K only the direct adducts from radical-radical addition are observed, with good agreement between experimental and theoretical branching fractions, supporting the VRC-TST calculations of the barrierless entrance channel. As the temperature is increased to 1000 K we observe two additional isomers, including indene, a two-ring polycyclic aromatic hydrocarbon, and a small amount of bimolecular products C9H7 + H. Our calculated branching fractions for the phenyl + propargyl reaction predict significantly less indene than observed experimentally. We present further calculations and experimental evidence that the most likely cause of this discrepancy is the contribution of H atom reactions, both H + indenyl (C9H7) recombination to indene and H-assisted isomerization that converts less stable C9H8 isomers into indene. Especially at low pressures typical of laboratory investigations, H-atom-assisted isomerization needs to be considered. Regardless, the experimental observation of indene demonstrates that the title reaction leads, either directly or indirectly, to the formation of the second ring in polycyclic aromatic hydrocarbons.

A combined rheometry and imaging study of viscosity reduction in bacterial suspensions.

Suspending self-propelled "pushers" in a liquid lowers its viscosity. We study how this phenomenon depends on system size in bacterial suspensions using bulk rheometry and particle-tracking rheoimaging. Above the critical bacterial volume fraction needed to decrease the viscosity to zero, [Formula: see text], large-scale collective motion emerges in the quiescent state, and the flow becomes nonlinear. We confirm a theoretical prediction that such instability should be suppressed by confinement. Our results also show that a recent application of active liquid-crystal theory to such systems is untenable.

The Reaction of o-Benzyne with Vinylacetylene: An Unexplored Way to Produce Naphthalene.

The mechanism and kinetics of the reaction of ortho-benzyne with vinylacetylene have been studied by ab initio and density functional CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G(d,p) calculations of the pertinent potential energy surface combined with Rice-Ramsperger-Kassel-Marcus - Master Equation calculations of reaction rate constants at various temperatures and pressures. Under prevailing combustion conditions, the reaction has been shown to predominantly proceed by the biradical acetylenic mechanism initiated by the addition of C4 H4 to one of the C atoms of the triple bond in ortho-benzyne by the acetylenic end, with a significant contribution of the concerted addition mechanism. Following the initial reaction steps, an extra six-membered ring is produced and the rearrangement of H atoms in this new ring leads to the formation of naphthalene, which can further dissociate to 1- or 2-naphthyl radicals. The o-C6 H4 +C4 H4 reaction is highly exothermic, by ∼143 kcal/mol to form naphthalene and by 31-32 kcal mol-1 to produce naphthyl radicals plus H, but features relatively high entrance barriers of 9-11 kcal mol-1 . Although the reaction is rather slow, much slower than the reaction of phenyl radical with vinylacetylene, it forms naphthalene and 1- and 2-naphthyl radicals directly, with their relative yields controlled by the temperature and pressure, and thus represents a viable source of the naphthalene core under conditions where ortho-benzyne and vinylacetylene are available.

Direct and Water-Mediated Adsorption of Stabilizers on SERS-Active Colloidal Bimetallic Plasmonic Nanomaterials: Insight into Citrate-AuAg Interactions from DFT Calculations.

In previous studies, AuAg colloidal nanostar formulations were developed with the two-fold aim of producing optimized surface-enhanced Raman spectroscopy (SERS) substrates and investigating the nature of the capping process itself. Findings demonstrated that the nanoparticle metals are alloyed and neutral, and capping by stabilizers occurs via chemisorption. This study utilizes citrate as the model stabilizer and investigates the mechanistic aspects of its interaction with mono- (Au20) and bimetallic (Au19Ag) surfaces by density functional theory (DFT) calculations. Citrate was modeled according to the colloid's pH and surrounded by a water and sodium first solvation shell. A population of stable cluster-citrate structures was obtained, and energies were refined at the uB3LYP//LANL2TZ(f)/cc-pVTZ level of theory. Solvation was accounted for both explicitly and implicitly by the application of the continuum model SMD. Results indicate that both direct binding and binding by water proxy through the charge-transfer complex formation are thermodynamically favorable. Water participation in citrate adsorption is supported by the adsorption behavior observed experimentally and the comparison between experimental and DFT-simulated IR spectra. Vibrational mode analysis suggests the possible presence of water within a crystal in dried nanostar residues. All ΔGads(aq) indicate a weak chemisorptive process, leading to the hypothesis that citrate could be displaced by analytes during SERS measurements.

Gas-phase synthesis of corannulene - a molecular building block of fullerenes.

Fullerenes (C60, C70) detected in planetary nebulae and carbonaceous chondrites have been implicated to play a key role in the astrochemical evolution of the interstellar medium. However, the formation mechanism of even their simplest molecular building block-the corannulene molecule (C20H10)-has remained elusive. Here we demonstrate via a combined molecular beams and ab initio investigation that corannulene can be synthesized in the gas phase through the reactions of 7-fluoranthenyl (C16H9˙) and benzo[ghi]fluoranthen-5-yl (C18H9˙) radicals with acetylene (C2H2) mimicking conditions in carbon-rich circumstellar envelopes. This reaction sequence reveals a reaction class in which a polycyclic aromatic hydrocarbon (PAH) radical undergoes ring expansion while simultaneously forming an out-of-plane carbon backbone central to 3D nanostructures such as buckybowls and buckyballs. These fundamental reaction mechanisms are critical in facilitating an intimate understanding of the origin and evolution of the molecular universe and, in particular, of carbon in our galaxy.

Theoretical Study of the Phenoxy Radical Recombination with the O(3P) Atom, Phenyl plus Molecular Oxygen Revisited.

Quantum chemical calculations of the C6H5O2 potential energy surface (PES) were carried out to study the mechanism of the phenoxy + O(3P) and phenyl + O2 reactions. CASPT2(15e,13o)/CBS//CASSCF(15e,13o)/DZP multireference calculations were utilized to map out the minimum energy path for the entrance channels of the phenoxy + O(3P) reaction. Stationary points on the C6H5O2 PES were explored at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311++G** level for the species with a single-reference character of the wave function and at the CASPT2(15e,13o)/CBS//B3LYP/6-311++G** level of theory for the species with a multireference character of the wave function. Conventional, variational, and variable reaction coordinate transition-state theories were employed in Rice-Ramsperger-Kassel-Marcus master equation calculations to assess temperature- and pressure-dependent phenomenological rate constants and product branching ratios. The main bimolecular product channels of the phenoxy + O(3P) reaction are concluded to be para/ortho-benzoquinone + H, 2,4-cyclopentadienone + HCO and, at high temperatures, also phenyl + O2. The main bimolecular product channels of the phenyl + O2 reaction include 2,4-cyclopentadienone + HCO at lower temperatures and phenoxy + O(3P) at higher temperatures. For both the phenoxy + O(3P) and phenyl + O2 reactions, the collisional stabilization of peroxybenzene at low temperatures and high pressures competes with the bimolecular product channels.

Gas-Phase Formation of Fulvenallene (C7H6) via the Jahn-Teller Distorted Tropyl (C7H7) Radical Intermediate under Single-Collision Conditions.

The fulvenallene molecule (C7H6) has been synthesized via the elementary gas-phase reaction of the methylidyne radical (CH) with the benzene molecule (C6H6) on the doublet C7H7 surface under single collision conditions. The barrier-less route to the cyclic fulvenallene molecule involves the addition of the methylidyne radical to the π-electron density of benzene leading eventually to a Jahn-Teller distorted tropyl (C7H7) radical intermediate and exotic ring opening-ring contraction sequences terminated by atomic hydrogen elimination. The methylidyne-benzene system represents a benchmark to probe the outcome of the elementary reaction of the simplest hydrocarbon radical-methylidyne-with the prototype of a closed-shell aromatic molecule-benzene-yielding nonbenzenoid fulvenallene. Combined with electronic structure and statistical calculations, this bimolecular reaction sheds light on the unusual reaction dynamics of Hückel aromatic systems and remarkable (polycyclic) reaction intermediates, which cannot be studied via classical organic, synthetic methods, thus opening up a versatile path to access this previously largely obscure class of fulvenallenes.

Spectroscopic and Theoretical Insights into Surprisingly Effective Sm(III) Extraction from Alkaline Aqueous Media by o-Phenylenediamine-Derived Sulfonamides.

Alkaline high-level waste (HLW) generated as a result of years of nuclear weapons production has complicated composition and requires comprehensive treatment methods, which would allow concentrating its most radiotoxic components in a small volume for geological disposal. We have investigated six alkyl-substituted o-phenylenediamine-derived sulfonamides for extraction and consecutive stripping of Sm(III) from alkaline aqueous media. Up to 81% of Sm(III) recovery at pH 13.0-13.5 was achieved by disulfonamide (dsa) or dsa/Et3N in CH2Cl2, measured after contact with organic phases and subsequent stripping with 0.1 M HNO3. The use of Et3N dramatically enhances Sm(III) extraction at lower pH ranges (10.5-11.5) but decreases extraction at pH 13.0-13.5, while control experiments with Et3N and no dsa showed no extraction. Analysis of the extraction equilibria gave a 1:1 sulfonamide-Sm(III) complexation ratio, with the extracted species also presumed to contain coordinated H2O or OH-, as also shown by DFT calculations. Titration experiments of sulfonamides with Sm(III) in CH3CN were consistent with a 1:1 complexation ratio of dsa-6 to Sm(III) with a K11 = 6.6 × 107 M-1 derived from nonlinear regression analysis of the 1:1 binding isotherm. Theoretical DFT calculations determined the structures of possible species formed during extraction and the thermodynamics of extraction processes based on several initial [Sm(OH)y(NO3)z(H2O)x]3-y-z species and 1:1 Sm(III)/dsa-32- complexes formed in the organic phase, in which dsa complexes to Sm(III) in its bis-deprotonated form (denoted below as dsa-32-). Organization of close ion pairs of type {Na[Sm(dsa-32-)(OH)2]·2H2O} was shown to be thermodynamically favorable for extraction from alkaline aqueous media with pH = 13.0-13.5. Theoretical calculations also demonstrated thermodynamically favorable coordination to Am(III).

Theoretical study of the reaction mechanism and kinetics of the phenyl + propargyl association.

Potential energy surface for the phenyl + propargyl radical recombination reaction has been studied at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G** level of theory for the closed-shell singlet species and at the triplet-singlet gap CASPT2/cc-pVTZ-CCSD(T)-F12/cc-pVTZ-f12//CASSCF/cc-pVTZ level of theory for the diradical species. High-pressure limit rate constants for the barrierless channels were evaluated with variable reaction coordinate transition state theory (VRC-TST). Rice-Ramsperger-Kassel-Marcus Master Equation (RRKM-ME) calculations have been performed to assess temperature- and pressure-dependent phenomenological rate constants and product branching ratios. The entrance channels of the radical association reaction produce 3-phenyl-1-propyne and phenylallene which can further dissociate/isomerize into a variety of unimolecular and bimolecular products. Theoretical evidence is presented that, at combustion relevant conditions, the phenyl + propargyl recombination provides a feasible mechanism for the addition of a second five-member ring to the first six-member aromatic ring producing the prototype two-ring species indene and indenyl. Rate expressions for all important reaction channels in a broad range of temperatures and pressures have been generated for kinetic modeling.

Theoretical Study of the Reaction Mechanism and Kinetics of the Phenyl + Allyl and Related Benzyl + Vinyl Associations.

Potential energy surfaces for the allyl + phenyl and benzyl + vinyl barrierless radical association reactions have been studied at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G** level of theory. Variable reaction coordinate transition state theory (VRC-TST) has been employed to evaluate high-pressure limit rate constants for the barrierless channels. Then, Rice-Ramsperger-Kassel-Marcus master equation (RRKM-ME) calculations have been performed to assess phenomenological rate constants and product branching ratios of various reaction channels at different temperatures and pressures. The initial step of both radical association reactions produces 3-phenylpropene which can further dissociate into a variety of bimolecular products including the indene precursor 1-phenylallyl + H. The results showed that at typical combustion conditions the collisional stabilization of 3-phenylpropene dominates both the phenyl + allyl and benzyl + vinyl reactions at temperatures below 1000 K and remains important at high pressures up to 2500 K. The main bimolecular products of the two reactions at high temperatures are predicted to be benzyl + vinyl and phenyl + allyl, respectively. The well-skipping mechanism to form 1-phenylallyl directly in the allyl + phenyl and benzyl + vinyl reactions appeared to be not significant, however, the reactions can provide some contributions into the formation of the indene precursor via the 3-phenylpropene stabilization/dissociation sequence and most of all, via the formation of 3-phenylpropene itself, which then can undergo H-abstraction by available radicals to produce 1-phenylallyl. The allyl + phenyl reaction can also contribute to the formation of two-ring PAH by producing benzyl radical at high temperatures, either by the well-skipping or stabilization/dissociation mechanisms; in turn, benzyl can readily react with acetylene or propargyl radical to form indene or naphthalene precursors, respectively. Rate expressions for all important reaction channels in a broad range of temperatures and pressures have been generated for kinetic modeling.

Elucidating the Chemical Dynamics of the Elementary Reactions of the 1-Propynyl Radical (CH3CC; X2A1) with Methylacetylene (H3CCCH; X1A1) and Allene (H2CCCH2; X1A1).

The reactions of the 1-propynyl radical (CH3CC; X2A1) with two C3H4 isomers, methylacetylene (H3CCCH; X1A1) and allene (H2CCCH2; X1A1), along with their (partially) deuterated counterparts were explored at collision energies of 37 kJ mol-1, exploiting crossed molecular beams to unravel the chemical reaction dynamics to synthesize distinct C6H6 isomers under single collision conditions. The forward convolution fitting of the laboratory data along with ab initio and statistical calculations revealed that both reactions have no entrance barrier, proceed via indirect (complex-forming) reaction dynamics involving C6H7 intermediates with life times longer than their rotation period(s), and are initiated by the addition of the 1-propynyl radical with its radical center to the π-electron density of the unsaturated hydrocarbon at the terminal carbon atoms of methylacetylene (C1) and allene (C1/C3). In the methylacetylene system, the initial collision complexes undergo unimolecular decomposition via tight exit transition states by atomic hydrogen loss, forming dimethyldiacetylene (CH3CCCCCH3) and 1-propynylallene (H3CCCHCCCH2) in overall exoergic reactions (123 and 98 kJ mol-1) with a branching ratio of 9.4 ± 0.1; the methyl group of the 1-propynyl reactant acts solely as a spectator. On the other hand, in the allene system, our experimental data exhibit the formation of the fulvene (c-C5H4CH2) isomer via a six-step reaction sequence with two higher energy isomers-hexa-1,2-dien-4-yne (H2CCCHCCCH3) and hexa-1,4-diyne (HCCCH2CCCH3)-also predicted to be formed based on our statistical calculations. The pathway to fulvene advocates that, in the allene-1-propynyl system, the methyl group of the 1-propynyl reactant is actively engaged in the reaction mechanism to form fulvene. Because both reactions are barrierless and exoergic and all transition states are located below the energy of the separated reactants, the hydrogen-deficient C6H6 isomers identified in our investigation are predicted to be synthesized in low-temperature environments, such as in hydrocarbon-rich atmospheres of planets and their moons such as Titan along with cold molecular clouds such as Taurus Molecular Cloud-1.

Halobacterium salinarum storage and rehydration after spray drying and optimization of the processes for preservation of carotenoids.

Spray drying is appropriate for the preservation of halophilic microorganisms due to the nature of these microorganisms, as they survive in adverse environmental conditions by being encapsulated in salt crystals. Artificial neural networks were in this study used to optimize practically significant spray-drying regimes of the C50-carotenoids producer Halobacterium salinarum. Immediately after drying, the samples contained up to 54% halobacterial biomass and less than 5% moisture, and the level of preservation of carotenoids was 95-97%. The storage of biomass at 4 °C resulted in the gradual degradation of the carotenoids, which reached 58-64% in the best samples after 1 year. A comprehensive study of changes in halobacteria biomass after spray drying and the nature of the damage provided new data on the survival and preservation of cells and biologically active substances in the various spray-drying regimes and at different storage times.

A Theoretical Study of Pyrolysis of exo-Tetrahydrodicyclopentadiene and Its Primary and Secondary Unimolecular Decomposition Products.

Theoretical calculations of the rate constants and product branching ratios in the pyrolysis of exo-tetrahydrodicyclopentadiene (JP-10) and its initial decomposition products at combustion-relevant pressures and temperatures were performed and compared to the experimental results from the recently reported molecular beam photoionization mass spectrometry study of the pyrolysis of JP-10 ( Zhao et al. Phys. Chem. Chem. Phys. 2017 , 19 , 15780 - 15807 ). The results allow us to quantitatively assess the decomposition mechanisms of JP-10 by a direct comparison with the nascent product distribution-including radicals and thermally labile closed-shell species-detected in the short-residence-time molecular beam photoionization mass spectrometry experiment. In accord with the experimental data, the major products predicted by the theoretical modeling include methyl radical (CH3), acetylene (C2H2), vinyl radical (C2H3), ethyl radical (C2H5), ethylene (C2H4), allyl radical (C3H5), 1,3-butadiene (C4H6), cyclopentadienyl radical (C5H5), cyclopentadiene (C5H6), cyclopentenyl radical (C5H7), cyclopentene (C5H8), fulvene (C6H6), benzene (C6H6), toluene (C7H8), and 5-methylene-1,3-cyclohexadiene (C7H8). We found that ethylene, allyl radical, cyclopentadiene, and cyclopentenyl radical are significant products at all combustion-relevant conditions, whereas the relative yields of the other products depend on temperature. The most significant temperature trends predicted are increasing yields of the C2 and C4 species and decreasing yields of the C1, C6, and C7 groups with increasing temperature. The calculated pressure effect on the rate constant for the decomposition of JP-10 via initial C-H bond cleavages becomes significant at temperatures above 1500 K. The initially produced radicals will react away to form closed-shell molecules, such as ethylene, propene, cyclopentadiene, cyclopentene, fulvene, and benzene, which were observed as the predominant fragments in the long-residence-time experiment. The calculated rate constants and product branching ratios should prove useful to improve the existing kinetic models for the JP-10 pyrolysis.

Flagellated bacterial motility in polymer solutions.

It is widely believed that the swimming speed, v, of many flagellated bacteria is a nonmonotonic function of the concentration, c, of high-molecular-weight linear polymers in aqueous solution, showing peaked v(c) curves. Pores in the polymer solution were suggested as the explanation. Quantifying this picture led to a theory that predicted peaked v(c) curves. Using high-throughput methods for characterizing motility, we measured v and the angular frequency of cell body rotation, Ω, of motile Escherichia coli as a function of polymer concentration in polyvinylpyrrolidone (PVP) and Ficoll solutions of different molecular weights. We find that nonmonotonic v(c) curves are typically due to low-molecular-weight impurities. After purification by dialysis, the measured v(c) and Ω(c) relations for all but the highest-molecular-weight PVP can be described in detail by Newtonian hydrodynamics. There is clear evidence for non-Newtonian effects in the highest-molecular-weight PVP solution. Calculations suggest that this is due to the fast-rotating flagella seeing a lower viscosity than the cell body, so that flagella can be seen as nano-rheometers for probing the non-Newtonian behavior of high polymer solutions on a molecular scale.

Elasto-inertial turbulence.

Turbulence is ubiquitous in nature, yet even for the case of ordinary Newtonian fluids like water, our understanding of this phenomenon is limited. Many liquids of practical importance are more complicated (e.g., blood, polymer melts, paints), however; they exhibit elastic as well as viscous characteristics, and the relation between stress and strain is nonlinear. We demonstrate here for a model system of such complex fluids that at high shear rates, turbulence is not simply modified as previously believed but is suppressed and replaced by a different type of disordered motion, elasto-inertial turbulence. Elasto-inertial turbulence is found to occur at much lower Reynolds numbers than Newtonian turbulence, and the dynamical properties differ significantly. The friction scaling observed coincides with the so-called "maximum drag reduction" asymptote, which is exhibited by a wide range of viscoelastic fluids.

How the Proximal Pocket May Influence the Enantiospecificities of Chloroperoxidase-Catalyzed Epoxidations of Olefins.

Chloroperoxidase-catalyzed enantiospecific epoxidations of olefins are of significant biotechnological interest. Typical enantiomeric excesses are in the range of 66%-97% and translate into free energy differences on the order of 1 kcal/mol. These differences are generally attributed to the effect of the distal pocket. In this paper, we show that the influence of the proximal pocket on the electron transfer mechanism in the rate-limiting event may be just as significant for a quantitatively accurate account of the experimentally-measured enantiospecificities.

A possible mechanism for redox control of human neuroglobin activity.

Neuroglobin (Ngb) promotes neuron survival under hypoxic/ischemic conditions. In vivo and in vitro assays provide evidence for redox-regulated functioning of Ngb. On the basis of X-ray crystal structures and our MD simulations, a mechanism for redox control of human Ngb (hNgb) activity via the influence of the CD loop on the active site is proposed. We provide evidence that the CD loop undergoes a strand-to-helix transition when the external environment becomes sufficiently oxidizing, and that this CD loop conformational transition causes critical restructuring of the active site. We postulate that the strand-to-helix mechanics of the CD loop allows hNgb to utilize the lability of Cys46/Cys55 disulfide bonding and of the Tyr44/His64/heme propionate interaction network for redox-controlled functioning of hNgb.

Theoretical study of HOCl-catalyzed keto-enol tautomerization of ß-cyclopentanedione in an explicit water environment.

The mechanism of acid-catalyzed keto-enol tautomerization of ß-cyclopentanedione (CPD) in solution is studied computationally. Reaction profiles are first calculated for a limited solvation environment using ab initio and density functional methods. Barrier heights for systems including up to one hydration shell of explicit water molecules depend strongly on the number of waters involved in proton transfer and to a lesser but significant extent on the number of waters forming hydrogen bonds with waters in the proton-transfer chain (each such water reduces the barrier by 4.4 kcal/mol on average). Barriers of 8-13 kcal/mol were obtained when a full or nearly full hydration shell was present, consistent with calculations for nonacid-catalyzed keto-enol tautomerization of related molecules. The presence of HOCl reduced the barrier by 4.5 kcal/mol in relation to the gas phase, consistent with the well-known principle that keto-enol tautomerization can be acid- or base-catalyzed. The reaction was also modeled beginning with snapshots of reactant conformations taken from a 300 K molecular dynamics simulation of CPD, HOCl, and 324 explicit waters. Reaction profiles were calculated at a QM/MM level with waters in the first hydration shell either fixed or energy-minimized at each step along the reaction coordinate. A substantial variation in barrier height was observed in both cases, depending primarily on electrostatic interactions (hydrogen bonding) with first-hydration-shell waters and, to a lesser extent, on electrostatic interactions with more distant waters and geometric distortion effects. For the lowest barriers, the extent of barrier reduction by waters involved in proton transfer is consistent with the limited solvation results, but further barrier reduction due to hydrogen bonding to waters involved in proton transfer is not observed. It is postulated that this is because highly flexible structures such as extensive hydrogen bonding networks optimal for reaction are entropically disfavored and so may not contribute significantly to the observed reaction rate.

Gas-phase preparation of azulene (C10H8) and naphthalene (C10H8) via the reaction of the resonantly stabilized fulvenallenyl and propargyl radicals.

Synthetic routes to the 10π Hückel aromatic azulene (C10H8) molecule, the simplest polycyclic aromatic hydrocarbon carrying an adjacent five- and seven-membered ring, have been of fundamental importance due to the role of azulene - a structural isomer of naphthalene - as an essential molecular building block of saddle-shaped carbonaceous nanostructures such as curved nanographenes and nanoribbons. Here, we report on the very first gas phase preparation of azulene by probing the gas-phase reaction between two resonantly stabilized radicals, fulvenallenyl and propargyl , in a molecular beam through isomer-resolved vacuum ultraviolet photoionization mass spectrometry. Augmented by electronic structure calculations, the novel Fulvenallenyl Addition Cyclization Aromatization (FACA) reaction mechanism affords a versatile concept for introducing the azulene moiety into polycyclic aromatic systems thus facilitating an understanding of barrierless molecular mass growth processes of saddle-shaped aromatics and eventually carbonaceous nanoparticles (soot, interstellar grains) in our universe.