High-power diode-pumped Yb3+:CaF2 femtosecond laser

We report what is believed to be the first demonstration of a high-power passively mode-locked diode-pumped femtosecond laser based on an Yb3+:CaF2 single crystal, directly pumped by a 15-W fiber-coupled laser diode. With a 5-at. % Yb3+ -doped sample and prisms for dispersion compensation we obtained pulses as short as 150 fs, with 880 mW of average power and up to 1.4-W average output power, with a pulse duration of 220 fs, centered at 1049 nm. The laser wavelength could be tuned from 1040 to 1053 nm in the femtosecond regime. Using chirped mirrors for dispersion compensation, the oscillator provided up to 1.74 W of average power, with a pulse duration of 230 fs, corresponding to a pulse energy of 20 nJ and a peak power of 85 kW.     

(19)F-(19)F and (19)F-(1)H spin-spin coupling constants in cyclic FH polymers (FH)(n), n=2-6

Spin-spin coupling constants (2h)J(F-F), (1)J(F-H), and (1h)J(H-F) have been obtained for cyclic complexes (FH)(n), with n=2-6, from ab initio equation-of-motion coupled cluster singles and doubles (EOM-CCSD) calculations. Although both the Fermi-contact (FC) term and (2h)J(F-F) increase and become positive as the cluster size increases, the FC term is not a good quantitative approximation to (2h)J(F-F). The paramagnetic spin-orbit (PSO) and spin-dipole (SD) terms which contribute to (2h)J(F-F) appear to be sensitive to the orientation of the hydrogen-bonded pair. However, the large increase in the FC term and (2h)J(F-F) as the size of the cluster increases is due primarily to the reorganization of sigma electron densities in both ground and excited states, and is another manifestation of cooperativity effects in hydrogen-bonded cyclic polymers. The FC term and (1)J(F-H) always increase upon complex formation, but (1)J(F-H) increases only slightly as the size of the cluster increases due to a concurrent decrease in the PSO term. The changes in (1)J(F-H) as a function of polymer size reflect the polarization of electron density away from H and toward F in the ground state, and the electron reorganization which occurs in the excited states which couple to the ground states through the FC and PSO operators. The FC term is a good approximation to (1h)J(H-F), and is always negative, indicating that the hydrogen bonds in the FH clusters are traditional hydrogen bonds.     

A Practical General Method for the Preparation of Long Acenes

The field of long acenes, the narrowest of the zig-zag graphene nanoribbons, has been an area of significant interest in the past decade because of its potential applications in organic electronics, spintronics and plasmonics. However the low solubility and high reactivity of these compounds has so far hindered their preparation on large scales. We report here a concise strategy for the synthesis of higher acenes through Diels–Alder condensation of arynes with a protected tetraene ketone. After deprotection by cleavage of the ketal, the obtained monoketone precursors cleanly yield the corresponding acenes through quantitative cheletropic thermal decarbonylation in the solid state, at moderate temperatures of 155 to 205 °C. This approach allows the preparation of heptacene, benzo[a]hexacene, cis- and trans-dibenzopentacene and offers a valuable new method for the synthesis of even larger acenes.     

Prototropic tautomerism of the addition products of N-heterocyclic carbenes to CO2, CS2, and COS

Structural Chemistry - The energies of 62 minima and 6 transition states have been calculated with the M06-2x functional and the aug-cc-pVDZ basis set. They correspond to carbenes and neutral...     

Determination of cocaine adulterants in human urine by dispersive liquid-liquid microextraction and high-performance liquid chromatography

Analytical and Bioanalytical Chemistry - This study aimed to determine simultaneously five major street cocaine adulterants (caffeine, lidocaine, phenacetin, diltiazem, and hydroxyzine) in human...     

Multivariate calibration for the improvement of the quantification of cadmium in the presence of potassium as interferent by total reflection X-ray fluorescence

A multivariate calibration method was applied to improve the accuracy of the determination of cadmium in the presence of potassium by total reflection X-ray fluorescence (TXRF). Due to TXRF's relatively low resolution, a particular interference caused by potassium at line Kα 3.31 keV as interference can compromise the cadmium determination at line Lα 3.13 keV, respectively. The method is based on the hypothesis that the application of a multivariate calibration method, for example, partial least squares, could reduce variations due to interference and, consequently, improve the selectivity and accuracy in Cd determination. In this work, this strategy was evaluated on the X-ray fluorescence emission signals between 2.50 and 3.90 keV for a set of 26 different synthetic calibration mixtures and eight different mixtures for external calibration. Based on a certified reference material (Clay 2—CRM051) with high potassium levels, a significant improvement of accuracy for cadmium determination was observed, overcoming the problems associated with spectral interferences by potassium.     

Diagram,valence-to-core,and hypersatellite Kβ X-ray transitions in metallic chromium

We report on measurements of the Kβ diagram, valence-to-core (VtC), and hypersatellite X-ray spectra induced in metallic Cr by photon single and double K-shell ionization. The experiment was carried out at the Stanford Synchrotron Radiation Lightsource using the seven-crystal Johann-type hard X-ray spectrometer of the beamline 6-2. For the Kβ diagram and VtC transitions, the present study confirms the line shape features observed in previous works, whereas the K^hβ hypersatellite transition was found to exhibit a complex spectral line shape and a characteristic low-energy shoulder. The energy shift of the hypersatellite relative to the parent diagram line was deduced from the measurements and compared with the result of extensive multiconfiguration Dirac–Fock (MCDF) calculations. A very good agreement between experiment and theory was found. The MCDF calculations were also used to compute the theoretical line shape of the hypersatellite. A satisfactory agreement was obtained between the overall shapes of the experimental and theoretical spectra, but deviations were observed on the low- and high-energy flanks of the hypersatellite line. The discrepancies were explained by chemical effects, which were not considered in the MCDF calculations performed for isolated atoms.     

AuI-Catalyzed Haloalkynylation of Alkenes

The formal insertion of alkenes into aromatic chloro- and bromoalkynes takes place under cationic gold catalysis. This haloalkynylation reaction can be performed with cyclic, gem-disubstituted and monosubstituted alkenes, using BINAP, triazolo[4,3-b]isoquinolin-3-ylidene ligands or SPhos, respectively. The products were isolated in moderate to excellent yields and with complete diastereo- and regioselectivity; the halogen atom bonding the more substituted carbon of the alkene. Preliminary experiments showed that the enantioselective haloalkynylation of cyclopentene can be performed with (S)-BINAP to afford the insertion products with moderate to good enantioselectivities.     

Versatile anisotropic mesh adaptation methodology applied to pure quantity of interest error estimator. Steady,laminar incompressible flow

We introduce a new flexible mesh adaptation approach to efficiently compute a quantity of interest by the finite element method. Efficiently, we mean that the method provides an evaluation of that quantity up to a predetermined accuracy at a lower computational cost than other classical methods. The central pillar of the method is our scalar error estimator based on sensitivities of the quantity of interest to the residuals. These sensitivities result from the computation of a continuous adjoint problem. The mesh adaptation strategy can drive anisotropic mesh adaptation from a general scalar error contribution of each element. The full potential of our error estimator is then reached. The proposed method is validated by evaluating the lift, the drag, and the hydraulic losses on a 2D benchmark case: the flow around a cylinder at a Reynolds number of 20.     

Freeze–Thaw-Promoted Fabrication of Clean and Hierarchically Structured Noble-Metal Aerogels for Electrocatalysis and Photoelectrocatalysis

Noble-metal aerogels (NMAs) have drawn increasing attention because of their self-supported conductive networks, high surface areas, and numerous optically/catalytically active sites, enabling their impressive performance in diverse fields. However, the fabrication methods suffer from tedious procedures, long preparation times, unavoidable impurities, and uncontrolled multiscale structures, discouraging their developments. By utilizing the self-healing properties of noble-metal aggregates, the freezing-promoted salting-out behavior, and the ice-templating effect, a freeze–thaw method is crafted that is capable of preparing various hierarchically structured noble-metal gels within one day without extra additives. In light of their cleanliness, the multi-scale structures, and combined catalytic/optical properties, the electrocatalytic and photoelectrocatalytic performance of NMAs are demonstrated, which surpasses that of commercial noble-metal catalysts.