Application of the slurry technique to biological materials: a survey of literature

Summary The literature on the application of the slurry technique to biological materials is reviewed. It is obvious from the various applications that the most frequently employed atomization method for slurry analysis in biological materials is electrothermal atomization using either graphite tube or platform atomizers. The slurry technique is particularly useful when certified reference materials are not available and when the standard addition method is to be avoided. The literature survey revealed that this technique compares favourably with other methods for the determination of trace metals in biological materials.     

Enantioselective synthesis of (+)-gossonorol and related systems using organozinc reagents

The sesquiterpene (+)-gossonorol is prepared in only three synthetic steps in 60% overall yield and 82% ee from commercially available reagents. The key asymmetric step is the catalytic enantioselective addition of dimethylzinc to 5-methyl-1-(2-methylphenyl)hex-4-en-1-one catalyzed by chiral isoborneolsulfonamide ligands in the presence of titanium tetraisopropoxide. The modular approach allows the synthesis not only of the aforementioned natural product but also other products arising from the corresponding processes of ethylation, phenylation, and ethynylation, just by changing the final nucleophilic reagent and using the same isoborneol type ligand.     

Determination of Paint Solvents by Vapour Phase Fourier Transform Infrared Spectrometry.

A fast procedure has been developed for the direct determination of paint solvents. The method is based on the injection of small volumes of untreated solvent mixtures into a heated Pyrex glass reactor in which the sample is volatilized and introduced by means of a flow of nitrogen into an IR multiple pass gas cell and the spectrum in the mid-IR region is registered as a function of time. Data found for samples are interpolated in calibration graphs obtained by injecting different volumes of pure compounds which constitute the solvent mixture. A methylisobutylketone (MIBK) toluene mixture was used as test system to develop the proposed procedure. The method provides a limit of detection of the order of 1–4 μg, a relative standard deviation of the order of 0.4 to 2% for five independent measurements, and recovery percentage values from 99.8 till 103.6 %. A commercial sample of polyurethane paint solvent has been analysed by the developed procedure.     

Unexpected reactivity of pyridinium salts toward alkynyl Fischer complexes to produce oxo‐heterocycles

The unprecedented reaction of ketone‐containing aromatic pyridinium salts 3a ‐ e and alkynyl Fischer complexes 1a ‐ f proceeds via a mild domino process to provide 4,6‐disubstituted pyran‐2‐ones 5a ‐ k and 2,3,5‐trisubstituted furans 6a ‐ h (45‐97%). According of the results of isotopic labeling experiments, a mechanism involving an initial Michael addition appears to be the key step, obtaining a mesomeric structure responsible for the formation of both products.     

Quantum modified Regge–Teitelboim cosmology

In this paper we study the late evolution of Relic Gravitational Waves in coupled dark energy models, where dark energy interacts with cold dark matter. Relic Gravitational Waves are second tensorial order perturbations of the Lemaitre–Friedman–Robertson–Walker metric and experiment an evolution ruled by the scale factor of the metric. We find that the amplitude of Relic Gravitational Waves is smaller in coupled dark energy models than in models with non interacting dark energy. We also find that the amplitude of the waves predicted by the models with coupling term proportional to the dark energy density is smaller than those of the models with coupling term proportional to dark matter density.     

Dynamical Bifurcation in Gas‐Phase XH− + CH3Y SN2 Reactions: The Role of Energy Flow and Redistribution in Avoiding the Minimum Energy Path

The gas‐phase reactions of XH^? (X=O, S) + CH₃Y (Y=F, Cl, Br) span nearly the whole range of S_N2 pathways, and show an intrinsic reaction coordinate (IRC) (minimum energy path) with a deep well owing to the CH₃XH???Y^? (or CH₃S^????HF) hydrogen‐bonded postreaction complex. MP2 quasiclassical‐type direct dynamics starting at the [HX???CH₃???Y]^? transition‐state (TS) structure reveal distinct mechanistic behaviors. Trajectories that yield the separated CH₃XH+Y^? (or CH₃S^?+HF) products directly are non‐IRC, whereas those that sample the CH₃XH???Y^? (or CH₃S^????HF) complex are IRC. The IRCIRC/non‐IRC ratios of 90:10, 40:60, 25:75, 2:98, 0:100, and 0:100 are obtained for (X, Y)=(S, F), (O, F), (S, Cl), (S, Br), (O, Cl), and (O, Br), respectively. The properties of the energy profiles after the TS cannot provide a rationalization of these results. Analysis of the energy flow in dynamics shows that the trajectories cross a dynamical bifurcation, and that the inability to follow the minimum energy path arises from long vibration periods of the X?C???Y bending mode. The partition of the available energy to the products into vibrational, rotational, and translational energies reveals that if the vibrational contribution is more than 80 %, non‐IRC behavior dominates, unless the relative fraction of the rotational and translational components is similar, in which case a richer dynamical mechanism is shown, with an IRC/non‐IRC ratio that correlates to this relative fraction.