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Purpose: To evaluate the shear bond strength (SBS) of resin composite to dentin contaminated with artificial saliva (AS) containing mucin and amylase using an experimental method controlling the volume of saliva and adhesive in a defined surface area., Methods: Flat bonding surfaces were prepared on extracted human molars (320 grit surface). Using adhesive tape, a 4.5 mm bonding window was prepared on the dentin surfaces. Groups (n= 12) were prepared using the etch & rinse (ER) or self-etch (SE) modes for Adhese Universal (ADH), Scotchbond Universal Plus (SBU), and Prime & Bond active (PBA) dental adhesives (DA). For the control (C) groups, the adhesives were applied per the manufacturers' instructions with 2.0 µl or 3.0 µl of the adhesive. For the saliva-contaminated groups, 1.0 µl of artificial saliva with mucin was applied in the bonding window either dried or allowed to remain wet before the application of either 2.0 µl or 3.0 µl of the adhesive. After the adhesive film was air dried and light cured using an Ultradent bonding fixture, Spectrum TPH3 was bonded to the prepared surfaces. After water storage for 24 hours at 37°C, the specimens were debonded and shear bond strength (SBS) was calculated (MPa). A Kruskal-Wallis test with Bonferroni correction was used to determine group differences (P< 0.05). Scanning electron microscopy (SEM) was performed to visualize the interfacial surfaces prepared using an ion-etching technique., Results: Mean SBS for the three adhesives were similar in both ER and SE modes to uncontaminated dentin surfaces for all the control groups. For dentin contaminated with dried or wet saliva, both the surface condition and the adhesive system were significant factors at a confidence level of 95%. For the dried saliva test groups, ADH and PBA with 3.0 µl of adhesive generated similar SBS values to controls while SBU generated lower values. Lower values were generated when using 2.0 µl of adhesive for the three adhesives in SE and ER modes except for PBA in the ER mode. Using wet saliva and 3.0 µl of adhesive ADH and SBU generated lower SBS values while PBA generated similar values to controls. Under SEM, morphology at the adhesive dentin interfaces was similar among the adhesives to uncontaminated dentin but notable differences were observed for SBU and ADH for both wet and dried saliva-contaminated surfaces., Clinical Significance: Salivary contamination differentially affects shear bond strength and the morphology of the bonded interface of universal adhesives to dentin. These differences are specific to the adhesive tested and are influenced by using the etch and rinse or self-etch strategies and the volume of adhesive used. When concerned about salivary contamination clinically, maximizing the volume of adhesive on the substrate may help mitigate the deleterious effects of saliva contamination., Competing Interests: The authors declared no conflict of interest. This study was supported through a research grant awarded to Creighton University School of Dentistry. Frank Pfefferkorn and Luisa Antunes are employees of Dentsply/Sirona. The research was conducted at Creighton University, Omaha Nebraska, Nihon University, Tokyo Japan, and the Center of Excellence for Polymer Development, Konstanz, Germany., (Copyright©American Journal of Dentistry.)

On 17 August 2017, gravitational waves (GWs) were detected from a binary neutron star merger, GW170817, along with a coincident short gamma-ray burst, GRB 170817A. An optical transient source, Swope Supernova Survey 17a (SSS17a), was subsequently identified as the counterpart of this event. We present ultraviolet, optical, and infrared light curves of SSS17a extending from 10.9 hours to 18 days postmerger. We constrain the radioactively powered transient resulting from the ejection of neutron-rich material. The fast rise of the light curves, subsequent decay, and rapid color evolution are consistent with multiple ejecta components of differing lanthanide abundance. The late-time light curve indicates that SSS17a produced at least ~0.05 solar masses of heavy elements, demonstrating that neutron star mergers play a role in rapid neutron capture (r-process) nucleosynthesis in the universe., (Copyright © 2017, American Association for the Advancement of Science.)

On 17 August 2017, the Laser Interferometer Gravitational-Wave Observatory (LIGO) and the Virgo interferometer detected gravitational waves (GWs) emanating from a binary neutron star merger, GW170817. Nearly simultaneously, the Fermi and INTEGRAL (INTErnational Gamma-Ray Astrophysics Laboratory) telescopes detected a gamma-ray transient, GRB 170817A. At 10.9 hours after the GW trigger, we discovered a transient and fading optical source, Swope Supernova Survey 2017a (SSS17a), coincident with GW170817. SSS17a is located in NGC 4993, an S0 galaxy at a distance of 40 megaparsecs. The precise location of GW170817 provides an opportunity to probe the nature of these cataclysmic events by combining electromagnetic and GW observations., (Copyright © 2017, American Association for the Advancement of Science.)

On 17 August 2017, Swope Supernova Survey 2017a (SSS17a) was discovered as the optical counterpart of the binary neutron star gravitational wave event GW170817. We report time-series spectroscopy of SSS17a from 11.75 hours until 8.5 days after the merger. Over the first hour of observations, the ejecta rapidly expanded and cooled. Applying blackbody fits to the spectra, we measured the photosphere cooling from [Formula: see text] to [Formula: see text] kelvin, and determined a photospheric velocity of roughly 30% of the speed of light. The spectra of SSS17a began displaying broad features after 1.46 days and evolved qualitatively over each subsequent day, with distinct blue (early-time) and red (late-time) components. The late-time component is consistent with theoretical models of r-process-enriched neutron star ejecta, whereas the blue component requires high-velocity, lanthanide-free material., (Copyright © 2017, American Association for the Advancement of Science.)

Eleven hours after the detection of gravitational wave source GW170817 by the Laser Interferometer Gravitational-Wave Observatory and Virgo Interferometers, an associated optical transient, SSS17a, was identified in the galaxy NGC 4993. Although the gravitational wave data indicate that GW170817 is consistent with the merger of two compact objects, the electromagnetic observations provide independent constraints on the nature of that system. We synthesize the optical to near-infrared photometry and spectroscopy of SSS17a collected by the One-Meter Two-Hemisphere collaboration, finding that SSS17a is unlike other known transients. The source is best described by theoretical models of a kilonova consisting of radioactive elements produced by rapid neutron capture (the r-process). We conclude that SSS17a was the result of a binary neutron star merger, reinforcing the gravitational wave result., (Copyright © 2017, American Association for the Advancement of Science.)

Compounds of the rotenoid class are naturally occurring in the Leguminosae and Nyctaginacae families. Rotenoids have found a myriad of uses, for example, in the agricultural industry as an insecticide and piscicide, and as an anticancer therapeutic. The scientific literature questions whether cyclization of the rotenoid B-ring occurs via a pathway containing either cationic or free-radical intermediates. In this work, both propositions are analyzed using DFT (B3LYP and M06-2X) and the G3 composite method in gas- and (implicit) solution-phase. The accuracy of these methods is compared to several experimental C-H bond dissociation energies (BDEs). We find that of the methods surveyed M06-2X provides the most accurate BDEs. Further, there is a clear thermodynamic preference for the free-radical pathway.

Herein we describe our exploration, using density functional theory calculations, of a conjugate addition-rearrangement sequence that leads to medium-ring cyclic amines. On the basis of the results of our calculations, we conclude that the rearrangement step is rate determining. In addition, we analyze the role of a carbanion lone pair in the rearrangement step, concluding that it functions as a substituent on a [3,3] sigmatropic shift, rather than a nucleophile; thus, the Woodward-Hoffmann rules are not circumvented in this reaction via involvement of orthogonal orbitals on an atom involved in the rearrangement.

Certain room-temperature ionic liquids exhibit hypergolic activity as liquid bipropellants. Understanding the chemical pathways and reaction mechanisms associated with hypergolic ignition is important for designing new fuels. It has been proposed (J. Phys. Chem. A 2008, 112, 7816) that an important ignition step for the hypergolic ionic liquid bipropellant system of dicyanamide/nitric acid is the activation and dissociation of the 1,5-dinitrobiuret anion DNB(-). For the work reported here, a quasiclassical direct dynamics simulation, at the DFT/M05-2X level of theory, was performed to model H(+) + DNB(-) association and the ensuing unimolecular decomposition of HDNB. This association step is 324 kcal/mol exothermic, and the most probable collision event is for H(+) to directly scatter off of DNB(-), without sufficient energy transfer to DNB(-) for H(+) to associate and form a highly vibrationally excited HDNB molecule. Approximately 1/3 of the trajectories do form HDNB, which decomposes by eight different reaction paths and whose unimolecular dynamics is highly nonstatistical. Some of these paths are the same as those found in a direct dynamics simulation of the high-temperature thermal decomposition of HDNB (J. Phys. Chem. A 2011, 115, 8064), for a similar total energy.

Electronic structure and direct dynamics calculations were used to study the potential energy surface and atomic-level dynamics for the OH(-) + CH3I reactions. The results are compared with crossed molecular beam, ion imaging experiments. The DFT/B97-1/ECP/d level of theory gives reaction energetics in good agreement with experiment and higher level calculations, and it was used for the direct dynamics simulations that were performed for reactant collision energies of 2.0, 1.0, 0.5, and 0.05 eV. Five different pathways are observed in the simulations, forming CH3OH + I(-), CH2I(-) + H2O, CH2 + I(-) + H2O, IOH(-) + CH3, and [CH3--I--OH](-). The SN2 first pathway and the proton-transfer second pathway dominate the reaction dynamics. Though the reaction energetics favor the SN2 pathway, the proton-transfer pathway is more important except for the lowest collision energy. The relative ion yield determined from the simulations is in overall good agreement with experiment. Both the SN2 and proton-transfer pathways occur via direct rebound, direct stripping, and indirect mechanisms. Except for the highest collision energy, 70-90% of the indirect reaction for the SN2 pathway occurs via formation of the hydrogen-bonded OH(-)---HCH2I prereaction complex. For the proton-transfer pathway the indirect reaction is more complex with the roundabout mechanism and formation of the OH(-)---HCH2I and CH2I(-)---HOH complexes contributing to the reaction. The majority of the SN2 reaction is direct at 2.0, 1.0, and 0.5 eV, dominated by stripping. At 0.05 eV the two direct mechanisms and the indirect mechanisms have nearly equal contributions. The majority of the proton-transfer pathway is direct stripping at 2.0, 1.0, and 0.5 eV, but the majority of the reaction is indirect at 0.05 eV. The product relative translational energy distributions are in good agreement with experiment for both the SN2 and proton-transfer pathways. For both, direct reaction preferentially transfers the product energy to relative translation, whereas transfer to product vibration is more important for the indirect reactions. For the proton-transfer reactions the velocity scattering angle distribution is peaked in the forward direction and in quite good agreement with experiment. However, for the SN2 reaction, the experimental scattering is isotropic in nature whereas forward scattering dominates the simulation distributions. The implication is that the simulations give too much stripping, which leads to forward scattering. The dynamics for the OH(-) + CH3I SN2 pathway are similar to those found previously for the F(-) + CH3I SN2 reaction.

Direct dynamics simulations are a very useful and general approach for studying the atomistic properties of complex chemical systems, since an electronic structure theory representation of a system's potential energy surface is possible without the need for fitting an analytic potential energy function. In this paper, recently introduced compact finite difference (CFD) schemes for approximating the Hessian [J. Chem. Phys.2010, 133, 074101] are tested by employing the monodromy matrix equations of motion. Several systems, including carbon dioxide and benzene, are simulated, using both analytic potential energy surfaces and on-the-fly direct dynamics. The results show, depending on the molecular system, that electronic structure theory Hessian direct dynamics can be accelerated up to 2 orders of magnitude. The CFD approximation is found to be robust enough to deal with chaotic motion, concomitant with floppy and stiff mode dynamics, Fermi resonances, and other kinds of molecular couplings. Finally, the CFD approximations allow parametrical tuning of different CFD parameters to attain the best possible accuracy for different molecular systems. Thus, a direct dynamics simulation requiring the Hessian at every integration step may be replaced with an approximate Hessian updating by tuning the appropriate accuracy.

Direct dynamics trajectory simulations were performed for two examples of the thiolate-disulfide exchange reaction, that is, HS(-) + HSSH and CH(3)S(-) + CH(3)SSCH(3). The trajectories were computed for the PBE0/6-31+G(d) potential energy surface using both classical microcanonical sampling at the ion-dipole complex and quasi-classical Boltzmann sampling (T = 300 K) at the central transition state. The potential energy surface for these reactions involves a hypercoordinate sulfur intermediate. Despite the fact that the intermediate resides in a shallow well (less than 5 kcal/mol), very few trajectories follow a direct substitution path (the S(N)2 pathway). Rather, the mechanism is addition-elimination, with several trajectories sampling the intermediate for long times, up to 15 ps or longer.

The biosynthesis of abietadiene is the first biosynthetically relevant process shown to involve a potential energy surface with a bifurcating reaction pathway. Herein, we use gas-phase, enzyme-free direct dynamics simulations to study the behavior of the key reaction (bifurcating) step, which is conversion of the C20 pimaradienyl cation to the abietadienyl cation. In a previous study (J. Am. Chem. Soc.2011, 133, 8335), a truncated C10 model was used to investigate this reaction. The current work finds that the complete C20 pimaradienyl cation gives reaction dynamics similar to that reported for the truncated C10 model. We find that in the absence of the enzyme, the C20 abietadienyl cation is generated in almost equal quantity (1.3:1) as an unobserved (in nature) seven-membered ring product. These simulations allude to a need for abietadiene synthase to steer the reaction to avoid generation of the seven-membered ring product. The methodology of post-transition state chemical dynamics simulations is also considered. The trajectories are initiated at the rate-controlling transition state (TS) separating the pimaradienyl and abietadienyl cations. Accurate results are expected for the short-time direct motion from this TS toward the abietadienyl cation. However, the dynamics may be less accurate for describing the unimolecular reactions that occur in moving toward the pimaradienyl cation, due to the unphysical flow of zero-point energy.

We present a study of the different product channels in the reactions of OH and OH-(H2O) with methyl iodide over a range of collision energies. Direct dynamics classical trajectory simulations are employed to obtain an atomistic comparison with the experimental results. For the experiments we have combined a crossed beam ion imaging setup with a multipole rf ion trap. The trap allows us to prepare the molecular and cluster ions with a controlled internal temperature and thus provides well-defined initial conditions for reaction experiments at low collision energy. Changing the internal temperature of the cluster ions was found to have a profound effect on their reactivity.

Abietic acid, a constituent of pine resin, is naturally derived from abietadiene --a process that requires four enzymes: one (abietadiene synthase) for conversion of the acyclic, achiral geranylgeranyl diphosphate to the polycyclic, chiral abietadiene (a complex process involving the copalyl diphosphate intermediate) and then three to oxidize a single methyl group of abietadiene to the corresponding carboxylic acid. In previous work (Nature Chem.2009, 1, 384), electronic structure calculations on carbocation rearrangements leading to abietadienyl cation revealed an interesting potential energy surface with a bifurcating reaction pathway (two transition-state structures connected directly with no intervening minimum), which links two products--one natural and one not yet isolated from Nature. Herein we describe direct dynamics simulations of the key step in the formation of abietadiene (in the gas phase and in the absence of the enzyme). The simulations reveal that abietadiene synthase must intervene in order to produce abietadiene selectively, in essence steering this reaction to avoid the generation of byproducts with different molecular architectures., (© 2011 American Chemical Society)

Intramolecular [2 + 2] cycloaddition reactions of allene-ynes offer a quick and efficient route to fused bicyclic ring structures. Insights into the mechanism and regiochemical preferences of this reaction are provided herein on the basis of the results of quantum chemical calculations (B3LYP/6-31+G(d,p)) and select experiments; both indicate that the reaction likely proceeds through a stepwise diradical pathway where one radical center is stabilized through allylic delocalization. The influences of the length of the tether connecting the alkyne and allene and substituent effects are also discussed.

A series of sandwich compounds of transition metals (M=Ni, Fe, Cr) with cyclic hydrocarbon (M(CH)(n)) and borane (M(BH(2))(n)), ligands (including mixed hydrocarbon/borane sandwiches) has been studied using density functional theory (B3LYP/6-311+G(df,p)). Multicenter bonding between the central metal atom and basal cycloborane rings provides stabilization to planar cycloborane species. Large negative NICS values allude to aromatic character in the cycloboranes similar to the analogous cyclic hydrocarbons. The ability of cycloborane sandwiches to stabilize attached carbocations, radicals and carbanions is also assessed.

N-Allylhydrazones are reported to undergo an elaborate [3,3]-sigmatropic shift/N2 extrusion sequence. Both concerted and radical cation pathways for the [3,3]-sigmatropic shift of several N-allylhydrazones were investigated using B3LYP/6-31+G(d,p) calculations. It was discovered that, assuming facile formation of the N-allylhydrazone radical cation, the rearrangement takes place through a series of low barrier steps energetically preferred to the concerted alternative available to neutral N-allylhydrazones. Subsequent N2 extrusions forming corresponding homoallyl radicals were found to be extremely facile.

The cycloaddition of (Z)-7-(prop-1-enyl)-7-azabicyclo[4.1.0]heptane with dimethyl acetylene dicarboxylate (DMAD) was reported previously to proceed with complete stereoselectivity. Quantum chemical calculations (B3LYP) were used to evaluate the mechanism of the cyclization process, and it was discovered that a stepwise pathway is preferred. The subsequent electrocyclic ring opening reaction of the cyclobutene was also studied, and it was found that ring opening to the "methyl-in" dienamine is preferred to the "methyl-out" product by some 4-5 kcal/mol.

[structure: see text] Quantum chemical calculations (B3LYP and Moeller-Plesset second-order perturbation theory) on carbonium ions containing hypercoordinated carbon atoms in distorted square-pyramidal geometries are described. The importance of overall charge (in addition to the delocalization of a certain number of electrons) for the stability of such structures is explored through calculations on isoelectronic systems containing boron atoms. The effects of alkyl substitution as well as variations in the structure of the linker attached to the C(5) core substructure are explored systematically for a variety of structures that do not have severe geometric constraints that rigidly enforce unusual geometries. In addition, transition structures for reactions involving the intramolecular attack of tetracoordinate carbons on carbenium ion centers were located; in some cases, such carbenium-to-carbonium rearrangement processes (in which tetracoordinate carbon centers act as nucleophiles) are actually both exothermic and accompanied by low activation barriers.