Palladium-Catalyzed Coupling of L-Proline Acid Chloride with Vinylstannanes

Vinylstannanes were found to undergo a palladium-catalyzed coupling with L-N-protected proline acid chloride to produce the corresponding N-protected α'-amino-α,β-unsaturated ketones in moderate to good yield.     

Kuhn and the Chemical Revolution: a re-assessment

A recent paper by Hoyningen-Huene argues that the Chemical Revolution is an excellent example of the success of Kuhn’s theory. This paper gives a succinct account of some counter-arguments and briefly refers to some further existing counter-arguments. While Kuhn’s theory does have a small number of more or less successful elements, it has been widely recognised that in general Kuhn’s theory is a “preformed and relatively inflexible framework” (1962, p. 24) which does not fit particular historical examples well; this paper clarifies that those examples include the Chemical Revolution.     

Development and validation of a multiplex real-time PCR method to simultaneously detect 47 targets for the identification of genetically modified organisms

Considering the increase of the total cultivated land area dedicated to genetically modified organisms (GMO), the consumers’ perception toward GMO and the need to comply with various local GMO legislations, efficient and accurate analytical methods are needed for their detection and identification. Considered as the gold standard for GMO analysis, the real-time polymerase chain reaction (RTi-PCR) technology was optimised to produce a high-throughput GMO screening method. Based on simultaneous 24 multiplex RTi-PCR running on a ready-to-use 384-well plate, this new procedure allows the detection and identification of 47 targets on seven samples in duplicate. To comply with GMO analytical quality requirements, a negative and a positive control were analysed in parallel. In addition, an internal positive control was also included in each reaction well for the detection of potential PCR inhibition. Tested on non-GM materials, on different GM events and on proficiency test samples, the method offered high specificity and sensitivity with an absolute limit of detection between 1 and 16 copies depending on the target. Easy to use, fast and cost efficient, this multiplex approach fits the purpose of GMO testing laboratories.

The Reduction of Aromatic Aldehydes and Benzils by Sodium Formaldehyde Sulphoxylate

Sodium formaldehyde sulphoxylate is shown to be an effective reagent for the reduction of some aromatic aldehydes to alcohols. Benzils are also reduced under neutral or basic conditions to give mainly benzoins. Ketones are reduced only slowly.     

Palladium-Catalysed Couplings of Halofurans with Activated Alkenes and Terminal Alkynes. A Short Synthesis of Dihydrowyerone

The palladium-catalysed coupling of bromofurans with activated alkenes and of furanoyl chlorides with either terminal alkynes or alkynyl stannanes gave good yields of the corresponding vinyl furans and alkynyl ketones. These studies culminated in a short synthesis of the antifungal agent dihydrowyerone.     

Rapid Aqueous Borohydride Reduction of Carbonyls Under Sealed-Tube Microwave Conditions

Ketones and aldehydes are conveniently and rapidly reduced to the corresponding alcohols in good yields using sodium borohydride under sealed-tube microwave conditions in either 95% ethanol or water. In purely aqueous systems, highly aliphatic substrates are sluggish, but this can be overcome by introducing sodium dodecyl sulfate (SDS) at the critical micelle concentration. With a 2:1 substrate/borohydride ratio and a reaction temperature of 100 °C, reduction is typically complete within 1 min in 95% ethanol and 5 min in water/SDS. The methodology is well suited for parallel and combinatorial synthetic approaches.     

Effect of ionic liquid on polyaniline chemically synthesised under falling-pH conditions

This study investigates the effect of the ionic liquid 1-butyl-3-methyl imidazolium chloride ([bmim]Cl) on the morphological, structural, and electronic properties of polyaniline (PANI) products synthesised by the falling-pH method. Products were characterised by SEM, FT-IR, UVVIS, N₂-physisorption, and conductivity measurements. The [bmim]Cl addition strongly influenced the PANI morphology, specific surface area, porosity, and conductivity. Depending on the [bmim]Cl: ANI ratio and the synthesis pH, a wide range of PANI nanostructures could be prepared, with rod-like, and fibre-like elongated structures being the dominant morphology under most experimental conditions. Samples prepared in the presence of [bmim]Cl exhibit specific areas of ca 22–35 m² g^?1. The conductivity of the final products depends on the [bmim]Cl: ANI ratio. Temperature dependence of conductivity in the temperature range from 77 K to 300 K was also studied.     

Efficient calculation of SAMPL4 hydration free energies using OMEGA,SZYBKI, QUACPAC,and Zap TK

Several submissions for the SAMPL4 hydration free energy set were calculated using OpenEye tools, including many that were among the top performing submissions. All of our best submissions used AM1BCC charges and Poisson–Boltzmann solvation. Three submissions used a single conformer for calculating the hydration free energy and all performed very well with mean unsigned errors ranging from 0.94 to 1.08 kcal/mol. These calculations were very fast, only requiring 0.5–2.0 s per molecule. We observed that our two single-conformer methodologies have different types of failure cases and that these differences could be exploited for determining when the methods are likely to have substantial errors.