CO cross-coupling of activated aryl and heteroaryl halides with aliphatic alcohols

A robust and general catalyst system facilitates the alkoxylation of activated heteroaryl halides with primary, secondary, and select tertiary alcohols without the need for an excess of either coupling partner. This catalyst system displays broad functional-group tolerance and excellent regioselectivity, and is insensitive to the order of reagent addition.     

ONIOM approach for non-adiabatic on-the-fly molecular dynamics demonstrated for the backbone controlled Dewar valence isomerization

Non-adiabatic on-the-fly molecular dynamics (NA-O-MD) simulations require the electronic wavefunction, energy gradients, and derivative coupling vectors in every timestep. Thus, they are commonly restricted to the excited state dynamics of molecules with up to ≈20 atoms. We discuss an approximation that combines the ONIOM(QM:QM) method with NA-O-MD simulations to allow calculations for larger molecules. As a proof of principle we present the excited state dynamics of a (6-4)-lesion containing dinucleotide (63 atoms), and especially the importance to include the confinement effects of the DNA backbone. The method is able to include electron correlation on a high level of theory and offers an attractive alternative to QM:MM approaches for moderate sized systems with unknown force fields.     

Controlling the spontaneous emission of a superconducting transmon qubit

We present a detailed characterization of coherence in seven transmon qubits in a circuit QED architecture. We find that spontaneous emission rates are strongly influenced by far off-resonant modes of the cavity and can be understood within a semiclassical circuit model. A careful analysis of the spontaneous qubit decay into a microwave transmission-line cavity can accurately predict the qubit lifetimes over 2 orders of magnitude in time and more than an octave in frequency. Coherence times T1 and T_{2};{*} of more than a microsecond are reproducibly demonstrated.     

A direct synthesis of α-keto five- and six-membered cyclic ethers

A simple synthesis of tetrahydro-2H-pyran-2-yl and tetrahydrofuran-2-yl ketones from their corresponding carboxylic acids was studied. A comparison was made of organolithium and Grignard alkylating reagents as a means of reducing the formation of byproducts and improving the yields.     

Origin assessment of green coffee (Coffea arabica) by multi-element stable isotope analysis of caffeine

The delta(13)C(VPDB), delta(2)H(VSMOW) and delta(18)O(VSMOW) values of caffeine isolated from Arabica green coffee beans of different geographical origin have been determined by isotope ratio mass spectrometry (IRMS) using elemental analysis (EA) in the "combustion" (C) and "pyrolysis" (P) modes (EA-C/P-IRMS). In total, 45 coffee samples (20 from Central and South America, 16 from Africa, six from Indonesia, and three from Jamaica and Hawaii) were analysed, as well as three reference samples of synthetic caffeine. Validation was performed by excluding isotope discrimination in the course of sample preparation and determining linear dynamic ranges for EA-P-IRMS measurements. The values for caffeine from green coffee ranged from -25.1 to - 29.9 per thousand, -109 to -198 per thousand, and +2.0 to -12.0 per thousand for delta(13)C(VPDB), delta(2)H(VSMOW), and delta(18)O(VSMOW), respectively. Data evaluation by linear discrimination analysis (LDA) and by classification and regression tree (CART) analysis revealed the delta(18)O(VSMOW) values to be highly significant. Use of LDA on the delta(2)H(VSMOW) and delta(18)O(VSMOW) data from coffee of African and Central/South American provenance led to error rates of 5.7% and 7.7% for adaption and cross validation, respectively.     

Evaluation of a method for determining concentrations of isoeugenol, an AQUI-S residue, in fillet tissue from freshwater fish species

AQUI-S is a fish anesthetic/sedative that is approved for use in a number of countries throughout the world and has the potential for use in the United States. The active ingredient in AQUI-S is isoeugenol. A method for determining isoeugenol concentrations in edible fillet tissue is needed for regulatory purposes, including surveillance and potential use in studies fulfilling human food safety data requirements if U.S. Food and Drug Administration approval is pursued. A method was developed and evaluated for determining isoeugenol concentrations in fillet tissue using relatively common procedures and equipment. The method produced accurate and precise results with fillet tissue from 10 freshwater fish species. The percentage of isoeugenol recovered from samples fortified with isoeugenol at nominal concentrations of 1, 50, and 100 microg/g for all species was always >80 and <97%. Within-day precision for samples fortified at those same concentrations was < or =10%, and day-to-day precision was < or =4.0%. Method precision with fillet tissue containing biologically incurred isoeugenol was < or =8.1%. There were no or minimal chromatographic interferences in control fillet tissue extracts from 9 of the 10 species. The method detection limits for all but one species ranged from 0.004 to 0.014 microg/g, and the quantitation limits ranged from 0.012 to 0.048 microg/g.