Synthesis of Optically Active endo,endo Bicyclo[2.2.2]octane-2,5-diol, Bicyclo[2.2.2]octane-2,5-dione, and Related Compounds

Optically active C(2)-symmetric (1S,2S,4S,5S)-bicyclo[2.2.2]octane-2,5-diol ((+)-12; 98% ee) and several selectively protected optically active intermediates useful for synthetic transformations were synthesized via a 1,2-carbonyl transposition route starting from the easily available optically active (1R,4S,6S)-6-hydroxybicyclo[2.2.2]octan-2-one ((-)-2). The synthetic route also allowed the preparation of optically active (1S,4S)-bicyclo[2.2.2]octane-2,5-dione ((+)-14; 98% ee).     

Asymmetric Reduction of Ketones with Catecholborane Using 2,6-BODOL Complexes of Titanium(IV) as Catalysts

Reductions performed with Ti^IV complexes of ligands based on bicyclo[2.2.2]octane diols 5 and 6 are effective catalysts in the reduction of prochiral ketones to optically active alcohols, with catecholborane as the reducing agent. Methyl ketones are favored and enantiomeric excesses (ee) of ≤98 % have been achieved with acetophenone as the substrate. Several other substrates were tested, among them 2-octanone, which gave 2-octanol in 87 % ee. Further details of the method were examined, for example, temperature, solvent composition, amount of molecular sieves (4 Å), and catecholborane quality, as well as the sensitivity of the ligands towards acids. NMR spectroscopic methods were used to gain some insight into the complexes formed between the ligands and [Ti(OiPr)₄]. A dimeric structure is proposed for the pre-catalyst.     

Superpositioned dielectrophoresis for enhanced trapping efficiency

One of the major applications for dielectrophoresis is selective trapping and fractionation of particles. If the surrounding medium is of low conductivity, the trapping force is high, but if the conductivity increases, the attraction decreases and may even become negative. However, high-conductivity media are essential when working with biological material such as living cells. In this paper, some basic calculations have been performed, and a model has been developed which employs both positive and negative dielectrophoresis in a channel with interdigitated electrodes. The finite element method was utilized to predict the trajectories of Escherichia coli bacteria in the superpositioned electrical fields. It is shown that a drastic improvement of trapping efficiency can be obtained in this way, when a high conductivity medium is employed.     

Analysis of time-resolved PIV measurements of a confined turbulent jet using POD and Koopman modes

We present a comparative analysis of proper orthogonal decomposition (POD) and dynamic mode decomposition (DMD) computed from experimental data of a turbulent, quasi 2-D, confined jet with co-flow (Re?=?11,500, co-flow ratio inner-to-outer flow ≈2:1). The experimental data come from high-speed 2-D particle image velocimetry. The flow is fully turbulent, and it contains geometry-dependent large-scale coherent structures; thus, it provides an interesting benchmark case for the comparison between POD and DMD. In this work, we address issues related to snapshot selections (1), convergence (2) and the physical interpretation (3) of both POD and DMD modes. We found that the convergence of POD modes follows the criteria of statistical convergence of the autocovariance matrix. For the computation of DMD modes, we suggest a methodology based on two criteria: the analysis of the residuals to optimize the sampling parameters of the snapshots, and a time-shifting procedure that allows us to identify the spurious modes and retain the modes that consistently appear in the spectrum. These modes are found to be the ones with nearly null growth rate. We then present the selected modes, and we discuss the way POD and DMD rank them. POD analysis reveals that the most energetic spatial structures are related to the large-scale oscillation of the inner jet (flapping); from the temporal analysis emerges that these modes are associated with a low-frequency peak at St?=?0.02. At this frequency, DMD identifies a similar mode, where oblique structures from the walls appear together with the flapping mode. The second most energetic group of modes identified is associated with shear-layer oscillations, and to a recirculation zone near the inner jet. Temporal analysis of these modes shows that the flapping of the inner jet might be sustained by the recirculation. In the DMD, the shear-layer modes are separated from the recirculation modes. These have large amplitudes in the DMD. In conclusion, the DMD modes with eigenvalues on the unit circle are found to be similar to the most energetic POD modes, although differences appear due to the fact that DMD isolates structures associated with one frequency only.     

Photoelectron Spectroscopy of Nickel, Palladium, and Platinum Oxide Anions

The 364-nm negative ion photoelectron spectra of XO and OXO molecules (X=Ni, Pd, and Pt) are reported. The spectra yield the electron affinities (EAs): EA(NiO)=1.455±0.005 eV; EA(PdO)=1.672±0.005 eV; EA(PtO)=2.172±0.005 eV; EA(ONiO)=3.043±0.005 eV; EA(OPdO)=3.086±0.005 eV; EA(OPtO)=2.677±0.005 eV. In addition, for the diatomics, transitions from the anion X?²Π_3/2 and X?′²Π_1/2 states into neutral X?³Σ⁻, ³Π, and for NiO and PdO, ¹Π, are assigned. Several states have been reassigned from those in the existing literature. Anion ²Π_3/2-²Π_1/2 spin-orbit splittings are measured, as are neutral ³Π₂-³Π₁ spin-orbit splittings: the XO ³Π ₂-³Π₁ splittings increase from 405±30 cm⁻¹ (NiO) to 805±30 cm⁻¹ (PdO) to 3580±40 cm⁻¹ (PtO). A bond length shortening of 0.03±0.01 Å is measured upon electron detachment from NiO⁻, resulting in an anion bond length of 1.66±0.01 Å. The bond length does not change upon electron detachment from PdO⁻ using 3.4-eV photons. The Pt-O bond length decreases by 0.035±0.010 Å in the ³Π₁←²Π_3/2 transition. The spectrum of OPtO displays a significantly more extended vibrational progression than those of ONiO or OPdO, and the O-Pt bond length is found to decrease by 0.07±0.01 Å upon electron detachment. The spectra support the view that the Ni-O bond is largely ionic, the Pd-O bond is somewhat less so, and the Pt-O bond displays a substantial covalent character.     

Trace metal determinations in estuarine waters by electrothermal atomic absorption spectrometry after extraction of dithiocarbamate complexes into freon

Cadmium, copper, iron, lead, nickel and zinc are determined. The dithiocarbamate complexes of the metals are extracted into Freon-TF and back-extracted into dilute nitric acid solution. Portions of the back-extracts are injected into a graphite furnace. The method gives complete separation from the matrix irrespective of salinity. It is therefore useful throughout the full salinity range of an estuary, 0–35‰.The effect of high iron concentrations on the extraction is eliminated by using a mixed acetate buffercomplexing agent solution.     

Hydrogels from a water-soluble zwitterionic polythiophene: dynamics under pH change and biomolecular interactions observed using quartz crystal microbalance with dissipation monitoring

The water-soluble zwitterionic polythiophene, poly(3-((S)-5-amino-5-carboxyl-3-oxapentyl)-2,5-thiophene) hydrochloride (POWT), is a conjugated polyelectrolyte (CPE) with properties well suited for biochip applications. CPEs readily form hydrogels when exposed to water-based buffer solutions or biomolecule solutions. In this work, we used in situ quartz crystal microbalance with dissipation (QCM-D) monitoring to collect information on the interaction between POWT films exposed to buffers with different pH and POWT/DNA chains. Our data show that POWT swells significantly when exposed to low-pH buffers, such as pH 4 acetate, this is seen as an increase in thickness and decrease in viscosity obtained via a Voight-based modeling of combined f and D QCM-D measurements. The magnitude of thickness and viscosity change upon changing from a pH 10 carbonate buffer to pH 4 acetate is 100% increase in thickness and 50% decrease in viscosity. The response of the hydrogel under pH change is well correlated with fluorescence data from POWT films on glass. The state of the hydrogel is important during interaction with biomolecules; illustrated by the observation that a swollen CPE hydrogel adsorbs a higher amount of DNA than a compacted one. In agreement with previous results, the QCM-D data confirmed that the POWT/DNA hydrogel sense complementary DNA specifically and with negligible binding of noncomplementary DNA. These results are important for efficient constructions of biochips in water environments using this class of materials.     

Synthesis and characterisation of Gd2O3 nanocrystals functionalised by organic acids

Nanocrystals of Gd2O3 have been prepared by various methods, using, e.g., trioctylphosphine oxide (TOPO), diethylene glycol (DEG) or glycine. The crystalline particles were of sizes 5 to 15 nm. Different carboxylic acids, e.g., oleic acid or citric acid, were adsorbed onto the surface of the particles made with DEG. IR measurements show that the molecules coordinate to the Gd2O3 surface via the carboxylate group in a bidentate or bridging manner. The organic-acid/particle complexes were characterised by XRPD, TEM, FTIR, Raman, and XPS.     

Enzymatic degradation of model cellulose films

Enzymatic degradation of model cellulose films prepared by a spin-coating technique was investigated by ellipsometry. The cellulose films were prior to degradation characterized by ellipsometry, contact angle measurements, ESCA (electron spectroscopy for chemical analysis) and AFM (atomic force microscopy). At enzyme addition to preformed cellulose films an initial adsorption was observed, which was followed by a total interfacial mass decrease due to enzymatic degradation of the cellulose films. The degradation rate was found to be constant during an extended time of hours, whereafter the degradation leveled off. In parallel to the decreased interfacial mass, the cellulose degradation resulted in a thinner and more dilute interfacial film. At long degradation times, however, there was an expansion of the cellulose film. The enzyme concentration affected the degradation rate significantly, with a faster degradation at a higher enzyme concentration. The effects of pH, temperature, ionic strength and stirring rate in the cuvette were also investigated.     

Fast Laplace Transforms for the Exponential Radon Transform

The Fourier slice theorem for the standard Radon transform generalizes to a Laplace counterpart when considering the exponential Radon transform. We show how to use this fact in combination with algorithms for the unequally spaced fast Laplace transform to construct fast and accurate methods for computing both the forward exponential Radon transform and the corresponding back-projection operator.