Modeling the acoustic radiation force in microfluidic chambers

A procedure is demonstrated to quantitatively evaluate the acoustic radiation forces in microfluidic particle manipulation chambers. Typical estimates of the acoustic pressure and the acoustic radiation force are based on an analytical solution for a simple one-dimensional standing wave pattern. The complexities of a typical microfluidic channel limit the usefulness of this approach. By leveraging finite elements, and a generalized equation for the acoustic radiation force, channel designs can be investigated in two and three dimensions. Calculations and experimental observations in this report and the literature, confirm these claims.     

Total Synthesis of (6R,10R,13R,14R,16R,17R,19S,20R,21R,24S, 25S,28S,30S,32R,33R,34R,36S,37S,39R)‐Azaspiracid‐3 Reveals Non‐Identity with the Natural Product

A convergent and stereoselective total synthesis of the previously assigned structure of azaspiracid‐3 has been achieved by a late‐stage Nozaki–Hiyama–Kishi coupling to form the C21?C22 bond with the C20 configuration unambiguously established from l ‐(+)‐tartaric acid. Postcoupling steps involved oxidation to an ynone, modified Stryker reduction of the alkyne, global deprotection, and oxidation of the resulting C1 primary alcohol to the carboxylic acid. The synthetic product matched naturally occurring azaspiracid‐3 by mass spectrometry, but differed both chromatographically and spectroscopically.     

Narrow-linewidth passband filter for ultraviolet rotational Raman imaging

We present a narrow-passband spectral filter capable of frequency-resolved imaging of rotational Raman light scattering with strong spectral rejection of out-of-band Raman, Rayleigh, and Mie scattering. The filter is based on mercury-vapor absorption, and subsequent resonant fluorescence and has a passband of less than 1 cm(-1). It is paired with an injection-seeded, cavity-locked, frequency-tripled Ti:sapphire laser that produces >30 mJ/pulse of single-mode, tunable light in the vicinity of 253.7 nm. The laser and filter are combined to spectrally resolve scattering from individual rotational Raman lines of nitrogen and oxygen.     

Osmotic Pressure and Phase Boundary Determination of Multiphase Systems by Analytical Ultracentrifugation

We show that analytical ultracentrifugation can be applied to derive full equations of state of colloids in a single sedimentation equilibrium experiment, by determination of single‐phase boundaries as well as of osmotic pressure versus concentration at fixed temperatures. A continuous dependence of the osmotic pressure, over orders of magnitude between at least ～10¹ and 10⁴ Pa, and a wide concentration range, are determined in agreement with standard theoretical considerations. Two model experimental colloidal systems are investigated: For a well‐known synthetic clay system (laponite), it is shown that two regimes—counter‐ion ideal gas and interacting double layers—can easily be identified in the equation of state, whereas metastable glass‐ or microphase‐separated gel states previously encountered in osmotic stress measurements of laponite are circumvented. For the case of rigid, crystallized catanionic bilayers, single phase domains can be identified. Osmotic pressure results in this case disagree with results obtained using the classical osmotic stress technique, as a result of sample adhesion to the ultracentrifuge cell windows and uncertainty due to possible micromolar ion contamination.     

Charge-transfer transitions in the vacuum-ultraviolet of protein circular dichroism spectra

Circular dichroism (CD) is widely used in the structural characterization and secondary structure determination of proteins. The vacuum UV region (below 190 nm), where charge-transfer transitions have an influence on the CD spectra, can be accessed using synchrotron radiation circular dichroism (SRCD) spectroscopy. Recently, charge-transfer transitions in a conformationally diverse set of dipeptides have been characterized ab initio using complete active space self-consistent field calculations, and the relevant charge distributions have been parametrized for use in the matrix method for calculations of protein CD. Here, we present calculations of the vacuum UV CD spectra of 71 proteins, for which experimental SRCD spectra and X-ray crystal structures are available. The theoretical spectra are calculated considering charge-transfer and side chain transitions. This significantly improves the agreement with experiment, raising the Spearman correlation coefficient between the calculated and the experimental intensity at 175 nm from 0.12 to 0.79. The influence of the conformation on charge-transfer transitions is analyzed in detail, showing that the n --> pi* charge-transfer transitions are most important in alpha-helical proteins, whereas in beta strand proteins the pi --> pi* charge-transfer transition along the chain in the amino- to carboxy-end direction is most dominant.     

One-pot enol silane formation-Mukaiyama aldol-type addition to dimethyl acetals mediated by TMSOTf

Various ketones, esters, amides, and thioesters add in high yield to dimethyl acetals in the presence of silyl trifluoromethanesulfonates and an amine base. Acetals derived from aryl, unsaturated, and aliphatic aldehydes are all effective substrates. The reaction proceeds in a single reaction flask, with no purification of the intermediate enol silane necessary.     

Uniform periodic point growth in entropy rank one

We show that algebraic dynamical systems with entropy rank one have uniformly exponentially many periodic points in all directions.

     

Stable carbon and nitrogen isotope discrimination and turnover in a small-bodied insectivorous lizard

Laboratory experiments are useful for estimating the carbon and nitrogen isotope discrimination factors and turnover rates that are critical for drawing field-based inferences on consumer diets using stable isotopes. Although the utility of these discrimination factors is widely recognized, work in terrestrial systems has largely been limited to studies involving mammals and birds. In contrast, scant attention has been paid to the application of isotopic techniques to reptiles, despite their broad diversity in terms of numbers of species as well as their trophic roles. Here we estimate carbon and nitrogen isotope discrimination factors and turnover for the tree lizard (Urosaurus ornatus) using a diet-switch experiment. Lizards were collected from a C₄-dominated grassland and then switched to C₃-based diet (crickets) in the laboratory. We estimated discrimination by lizard claw tissue as Δ¹³C?=?1.2?±?0.1?‰ for carbon and Δ¹⁵N?=?0.7?±?0.1?‰ (mean?±?1 SE) for nitrogen, with 95?% turnover occurring after ～15.5 days. These estimates should be appropriate for use in trophic studies of U. ornatus, and possibly other related small-bodied insectivorous lizards.     

Total syntheses of conformationally locked difluorinated pentopyranose analogues and a pentopyranosyl phosphate mimetic

Trifluoroethanol has been elaborated, via a telescoped sequence involving a metalated difluoroenol, a difluoroallylic alcohol, [2,3]-Wittig rearrangement, and ultimately an RCM reaction and requiring minimal intermediate purification, to a number of cyclooctenone intermediates. Epoxidation of these intermediates followed by transannular ring opening or dihydroxylation, then transannular hemiacetalization delivers novel bicyclic analogues of pentopyranoses, which were elaborated (in one case) to an analogue of a glycosyl phosphate.