Stereochemical assignment of the C1-C6 fragment of psymberin by synthesis and natural product degradation

[reaction: see text] Psymberin is a sponge-derived natural product that shows striking selectivity as a cytotoxic agent. Conformational mobility has precluded stereochemical assignment for the acyl fragment of this molecule (psymberic acid) by NMR. Herein we report stereoselective syntheses of all four stereoisomers of psymberic acid. A comparison of the acid-mediated cyclization products of these compounds to the product of psymberin's acidic methanolysis showed the stereochemical configuration of this fragment to be 4S,5S.     

Use of high-molecular-mass polyacrylamides as matrices for microchip electrophoresis of DNA fragments

DNA fragment analysis requires the use of polymer solutions as sieving matrices. Generally, such matrices are constituted of high-molar-weight polymers employed at a concentration higher than their entanglement threshold concentration. These polymer solutions are highly viscous and difficult to use in the narrow channels of a microchip. Ultralarge polyacrylamides synthesized via a nonconventional method, being the low-temperature plasma-induced polymerization (PIP), were used as DNA sieving matrices for microchip electrophoresis. The distinctive features of these polymers (ultralarge molecular mass and linearity) allow their use at a dilute concentration. Dilute PIP polyacrylamides revealed a constant value of resolution in a broad range of DNA fragment sizes (123 bp-1353 bp), thus proving to be effective in common genotyping applications. Moreover, the low viscosity of the dilute solutions enable it to be easier and faster in filling the channel between runs, thus enhancing the throughput of the microchip devices.     

Performance of a sound card as data acquisition system and a lock-in emulated by software in capillary electrophoresis

The performance of fluorescence detectors in capillary electrophoresis is maximized when the excitation light intensity is modulated in time with optimal frequencies. This is especially true when photomultiplier tubes are used to detect the fluorescent light. The photomultiplier tube amplified raw output signal can in principle be captured directly by a personal computer sound card (PCSC) and processed by a lock-in emulated by software. This possibility is demonstrated in the present work and the performance of this new setup is compared with a traditional data acquisition system. The results obtained with this “PCSC and lock-in emulated by software” were of the same quality or even better compared to that obtained by conventional time integrators (Boxcars) and data acquisition boards. With PCSC the limits of detection (LOD) found for both naphthalene-2,3-dicarboxaldehyde-derivatized tyrosine and alanine were 3.3 and 3.5 fmol (injection of 5 nL of samples at 0.66 and 0.70 μmol/L), respectively. This is at least three times better compared to conventional systems when light emitting diodes (LEDs) are used as the excitation source in fluorescence detectors. The PCSC linear response range was also larger compared to conventional data acquisition boards. This scheme showed to be a practical and convenient alternative of data acquisition and signal processing for detection systems used in capillary electrophoresis.     

Recombination and transport in microcrystalline pin solar cells studied with pulsed electrically detected magnetic resonance

An analysis of spin-dependent processes in microcrystalline silicon (μc-Si:H) pin solar cells is presented using pulsed electrically detected magnetic resonance (pEDMR). In this first study it is shown that by modulating the morphology of the n-type contact layer from amorphous to microcrystalline, pronounced changes in the pEDMR spectra may be observed. Due to the fact that pEDMR allows a deconvolution of the spin-dependent signals in time as well as in magnetic field domain, we were able to significantly reduce the complexity of the spectra compared to conventional EDMR. In the samples containing amorphous n-type contact layers we found signals from shallow localized conduction band tail states and phosphorous donor states. Upon replacement of this layer by its microcrystalline counterpart both signals disappeared. Possible spin-dependent transport mechanisms involving paramagnetic states in the various layers are discussed in view of sign and time evolution of the associated pEDMR signals.     

Lyapunov exponent diagrams of a 4-dimensional Chua system

We report numerical results on the existence of periodic structures embedded in chaotic and hyperchaotic regions on the Lyapunov exponent diagrams of a 4-dimensional Chua system. The model was obtained from the 3-dimensional Chua system by the introduction of a feedback controller. Both the largest and the second largest Lyapunov exponents were considered in our colorful Lyapunov exponent diagrams, and allowed us to characterize periodic structures and regions of chaos and hyperchaos. The shrimp-shaped periodic structures appear to be malformed on some of Lyapunov exponent diagrams, and they present two different bifurcation scenarios to chaos when passing the boundaries of itself, namely via period-doubling and crisis. Hyperchaos-chaos transition can also be observed on the Lyapunov exponent diagrams for the second largest exponent.