Clean synthesis of 1,8-dioxooctahydroxanthenes promoted by DABCO-bromine in aqueous media

<正>An efficient procedure is reported for the synthesis of 3,3,6,6-tetramethyl-9-aryl-1,8-dioxooctahydroxanthenes using a one-pot condensation of arylaldehydes and 5,5-dimethyl-1,3-cyclohexandione in the presence of DABCO-bromine(TDB) as an acid catalyst.To the best of our knowledge this is the first time that DABCO-bromine is used as an acid catalyst in aqueous media for this type of reaction.This method provides several advantages such as use of water as solvent,easy and clean synthesis,simple work up and versatility.     

Microfluidic channel with embedded SERS 2D platform for the aptamer detection of ochratoxin A

A selective aptameric sequence is adsorbed on a two-dimensional nanostructured metallic platform optimized for surface-enhanced Raman spectroscopy (SERS) measurements. Using nanofabrication methods, a metallic nanostructure was prepared by electron-beam lithography onto a glass coverslip surface and embedded within a microfluidic channel made of polydimethylsiloxane, allowing one to monitor in situ SERS fingerprint spectra from the adsorbed molecules on the metallic nanostructures. The gold structure was designed so that its localized surface plasmon resonance matches the excitation wavelength used for the Raman measurement. This optofluidic device is then used to detect the presence of a toxin, namely ochratoxin-A (OTA), in a confined environment, using very small amounts of chemicals, and short data acquisition times, by taking advantage of the optical properties of a SERS platform to magnify the Raman signals of the aptameric monolayer system and avoiding chemical labeling of the aptamer or the OTA target.

Optimal synchronization of two different in‐commensurate fractional‐order chaotic systems with fractional cost function

This article investigates the optimal synchronization of two different fractional‐order chaotic systems with two kinds of cost function. We use calculus of variations for minimizing cost function subject to synchronization error dynamics. We introduce optimal control problem to solve fractional Euler–Lagrange equations. Optimal control signal and minimum time of synchronization are obtained by proposed method. Examples show the optimal synchronization of two different systems with two different cost functions. First, we use an ordinary integer cost function then we use a fractional‐order cost function and comparing the results. Finally, we suggest a cost function which has the optimal solution of this problem, and we can extend this solution to solve other synchronization problems. © 2016 Wiley Periodicals, Inc. Complexity 21: 401–416, 2016     

Breakdown limits of optical multimode fibers for the application of nanosecond laser pulses at 532 nm and 1064 nm wavelength

For many applications, optical multimode fibers are used for the transmission of powerful laser radiation. High light throughput and damage resistance are desirable. Laser-induced breakdown at the end faces of fibers can limit their performance. Therefore, the determination of laser-induced damage thresholds (LIDT) at the surface of fibers is essential.Nanosecond (1064 nm and 532 nm wavelength) single-shot LIDT were measured according to the relevant standard on SiO₂ glass preforms (Suprasil F300) as basic materials of the corresponding fibers. For 10 kinds of fused silica fibers (FiberTech) with core diameters between 180 μm and 600 μm, an illumination approach utilizing a stepwise increase of the laser fluence on a single spot was used. For both wavelengths, the LIDT values (0% damage probability) obtained by means of the two methods were compared. The influence of surface preparation (polishing) on damage resistance was investigated. For equal surface finishing, a correlation between drawing speed of the fibers and their surface LIDT values was found. In addition to the surface measurements, bulk LIDT were determined for the preform material.     

Nanosecond laser-induced surface damage of optical multimode fibers and their preforms

High-power optical multimode fibers are essential components for materials processing and surgery and can limit the performance of expensive systems due to breakdown at the end faces. The aim of this paper is the determination of laser-induced damage thresholds (LIDT) of fibers (FiberTech) and preforms (Heraeus Suprasil F300). Preforms served as models. They were heated up to maximum temperatures of 1100, 1300 and 1500°C and cooled down to room temperature at rates of 10 K min⁻¹ (oven) and ∼10⁵ K min⁻¹ (quenched in air) to freeze in various structural states simulating different conditions similar to a drawing process during the production of fibers. Single- and multi-pulse LIDT measurements were done in accordance with the relevant ISO standards. Nd:YAG laser pulses with durations of 15 ns (1064 nm wavelength) and 8.5 ns (532 nm) at a repetition rate of 10 Hz were used. For the preforms, LIDT values (1-on-1) ranged from 220 to 350 J/cm² (1064 nm) and from 80 to 110 J/cm² (532 nm), respectively. A multi-pulse impact changed the thresholds to lower values. The LIDT (1064 nm wavelength) of the preforms can be regarded as a lower limit for those of the fibers.     

Flaws in foldamers: conformational uniformity and signal decay in achiral helical peptide oligomers

Although foldamers, by definition, are extended molecular structures with a well-defined conformation, minor conformers must be populated at least to some extent in solution. We present a quantitative analysis of these minor conformers for a series of helical oligomers built from achiral but helicogenic α-amino acids. By measuring the chain length dependence or chain position dependence of NMR or CD quantities that measure screw-sense preference in a helical oligomer, we quantify values for the decay constant of a conformational signal as it passes through the molecular structure. This conformational signal is a perturbation of the racemic mixture of M and P helices that such oligomers typically adopt by the inclusion of an N or C terminal chiral inducer. We show that decay constants may be very low (<1% signal loss per residue) in non-polar solvents, and we evaluate the increase in decay constant that results in polar solvents, at higher temperatures, and with more conformationally flexible residues such as Gly. Decay constants are independent of whether the signal originates from the N or the C terminus. By interpreting the decay constant in terms of the probability with which conformations containing a screw-sense reversal are populated, we quantify the populations of these alternative minor conformers within the overall ensemble of secondary structures adopted by the foldamer. We deduce helical persistence lengths for Aib polymers that allow us to show that in a non-polar solvent a peptide helix, even in the absence of chiral residues, may continue with the same screw sense for approximately 200 residues.     

Ultrahigh‐Resolution Diffusion‐Ordered Spectroscopy

Diffusion‐ordered spectroscopy (DOSY) is an effective method for the analysis of intact mixtures, but the quality of results is critically limited by resolution in the NMR dimension. A new experiment integrating diffusion weighting into the PSYCHE method for pure shift NMR spectroscopy allows DOSY spectra to be measured with ultrahigh NMR resolution at improved sensitivity.