Rapid Synthesis of Novel and Known Coumarin‐3‐carboxylic Acids Using Stannous Chloride Dihydrate under Solvent‐Free Conditions

Various coumarin‐3‐carboxylic acid (=2‐oxo‐2H‐1‐benzopyran‐3‐carboxylic acid; CcaH) derivatives have been synthesized in good yields using catalytic amounts of SnCl₂?2 H₂O under solvent‐free conditions. This inexpensive, nontoxic, and readily available catalytic system (10 mol‐%) efficiently catalyzes the Knoevenagel condensation and intramolecular cyclization of various 2‐hydroxybenzaldehydes or acetophenones with Meldrum's acid. High product yields, use of inexpensive and safe catalyst, and solvent‐free conditions display both economic and environmental advantages.     

Two Novel Push?Pull Series of Benzothiazole‐Based Dyes: Synthesis and Characterization

New dichromophoric cyanine dyes based on benzothiazol‐2‐amines as push? pull systems were synthesized in two series of disperse and cationic forms (see 4 in Scheme 1 and 5 in Scheme 2, resp.). Their thermal stabilities, UV/VIS, fluorescence, and solvatochromic behavior, which are important parameters in push? pull systems, were also studied.     

Analysis of trace amounts of chlorobenzenes in water samples: An approach towards the automation of dynamic hollow fiber liquid-phase microextraction

We have combined dynamic hollow fiber liquid-phase microextraction with GC and electron capture detection for the quantitative determination of five chlorobenzenes in water samples. Extraction is based on an automated dynamic extraction device called TT-tube extractor which consists of a polypropylene hollow fiber mounted inside a stainless steel tube. Toluene is used as the extraction solvent that fills the lumen and pores of the hydrophobic fiber and flows through the lumen of the fiber using a programmable syringe pump. The type of organic solvent, ionic strength, diameter of the TT-tube, sample volume, and the times for extraction and dwelling were optimized. Under optimum conditions, the method gives limits of detection as low as 10–100?ng?L^?1, a linear dynamic range of 0.05–100?μg?L^?1, and relative standard deviations of <7% (n?=?6). The preconcentration factor can be as large as 562–973. In an example for a practical application, the chlorobenzenes were successfully determined in environmental aqueous samples. The hollow fiber membrane can be used at least 20 times without any carry-over or loss in extraction efficiency. The system is inexpensive and convenient, and requires minimal manual handling.

A simple and expedient method for the stepwise synthesis of 2-ethoxy-(4H)-3,1-benzoxazine-4-ones

A simple and practical route is described for the synthesis of 2-efhoxy-(4H)-3,1 -benzoxazine-4-ones using the coupling reaction of anthranilic acid derivatives with diethyl dicarbonate following with fast cyclization of the carbamate adduct with a dehydrocyclization agent such as cyanuric chloride and N,N′-dicyclohexylcarbodiimide in PEG at room temperature.High yields of the products obtained under mild reaction conditions with simple work-up of the reaction mixture.     

Perceptually optimized gain function for cochlear implant signal-to-noise ratio based noise reduction

Noise reduction in cochlear implants has achieved significant speech perception improvements through spectral subtraction and signal-to-noise ratio based noise reduction techniques. Current methods use gain functions derived through mathematical optimization or motivated by normal listening psychoacoustic experiments. Although these gain functions have been able to improve speech perception, recent studies have indicated that they are not optimal for cochlear implant noise reduction. This study systematically investigates cochlear implant recipients' speech perception and listening preference of noise reduction with a range of gain functions. Results suggest an advantageous gain function and show that gain functions currently used for noise reduction are not optimal for cochlear implant recipients. Using the cochlear implant optimised gain function, a 27% improvement over the current advanced combination encoder (ACE) stimulation strategy in speech weighted noise and a 7% improvement over current noise reduction strategies were observed in babble noise conditions. The optimized gain function was also most preferred by cochlear implant recipients. The CI specific gain function derived from this study can be easily incorporated into existing noise reduction strategies, to further improve listening performance for CI recipients in challenging environments.     

Effect of staining reagent on peptide mass fingerprinting from in-gel trypsin digestions: a comparison of SyproRuby and DeepPurple

As the new fluorescent stains such as SyproRuby and DeepPurple are getting widespread recognition for proteome analyses by the traditional 2-D gel method, it becomes important to test the feasibility of these stains with respect to staining reproducibility, protein quantitation, and compatibility of the stain with downstream MS. The binding of epicocconone, active ingredient of DeepPurple, to one of the primary cleavage sites of trypsin (lysine residue) raises the possibility of incomplete cleavage and interference with PMF. However, the current study tests and concludes that the DeepPurple stain can result in increased peptide recovery compared to SyproRuby stain and can improve MS-based identification of lower intensity proteins spots.     

Tracking sperm whales with a towed acoustic vector sensor

Passive acoustic towed linear arrays are increasingly used to detect marine mammal sounds during mobile anthropogenic activities. However, these arrays cannot resolve between signals arriving from the port or starboard without vessel course changes or multiple cable deployments, and their performance is degraded by vessel self-noise and non-acoustic mechanical vibration. In principle acoustic vector sensors can resolve these directional ambiguities, as well as flag the presence of non-acoustic contamination, provided that the vibration-sensitive sensors can be successfully integrated into compact tow modules. Here a vector sensor module attached to the end of a 800 m towed array is used to detect and localize 1813 sperm whale "clicks" off the coast of Sitka, AK. Three methods were used to identify frequency regimes relatively free of non-acoustic noise contamination, and then the active intensity (propagating energy) of the signal was computed between 4-10 kHz along three orthogonal directions, providing unambiguous bearing estimates of two sperm whales over time. These bearing estimates are consistent with those obtained via conventional methods, but the standard deviations of the vector sensor bearing estimates are twice those of the conventionally-derived bearings. The resolved ambiguities of the bearings deduced from vessel course changes match the vector sensor predictions.     

Analysis of Paraben Preservatives in Cosmetic Samples: Comparison of Three Different Dynamic Hollow Fiber Liquid-Phase Microextraction Methods

This study focused on a comparison of three different dynamic hollow fiber-based liquid-phase microextraction (DHF-LPME) methods for extraction and preconcentration of parabens from wastewater, toothpaste, cream, and shampoo samples. The first method is two-phase DHF-LPME, in which n-octanol was used as the extraction solvent. The second is three-phase DHF-LPME, in which n-octanol and basic aqueous solution were used as the extraction solvent and acceptor phase, respectively. High-performance liquid chromatography with UV detection (HPLC–UV) was applied for determination of the parabens in both methods. The third method is a recently introduced method; three-phase DHF-LPME based on two immiscible organic solvents (n-dodecane as organic solvent and acetonitrile as an acceptor phase). The quantitative analyses were performed by the use of gas chromatography-mass spectrometry (GC–MS) after injection port derivatization. The effect of different extraction conditions (i.e., extraction solvent, pH, ionic strength, stirring rate, and dynamic and extraction times) on the extraction efficiency of the parabens was investigated and optimized. All the three procedures provide similar working parameters characterized by high repeatability (3.9–6.3 %) and good linearity (correlation coefficient ranging from 0.989 to 0.998). Results of real sample analyses obtained by these three methods were highly correlated. Although all methods provide compatible alternatives for paraben analysis, the three-phase DHF-LPME based on two immiscible organic solvents may be a more appropriate technique due to its higher extraction efficiency and thus lower limits of detection (LODs). LODs for all the parabens ranged from 0.2 to 5.0 μg L^?1 using the two first methods combined with HPLC–UV. An improvement in sensitivity of several orders of magnitude was achieved using three-phase DHF-LPME based on two immiscible organic solvents followed by single-ion monitoring GC–MS analyses (0.01–0.2 μg L^?1) due to compatibility of this technique with GC instrument.     

An efficient and facile regioselective synthesis of new substituted (E)-1-(3-aryl-7,8-dihydrocinnoline-5(6H)-ylidene)hydrazines and (1E,2E)-1,2-bis(3-aryl-7,8-dihydrocinnoline-5(6H)-ylidene)hydrazines

A study concerning the new substituted cinnoline synthesis is described. The use of a one-pot three-component method allows a simple regioselective and efficient synthesis of cinnoline derivatives via reaction of arylglyoxals with 1,3-cyclohexanedione and dimedone in the presence of hydrazine hydrate.     

A New Solvated Phosphoric Triamide, [(C6H4(3-CH3)NH)3P(O)] · (C2H5OH): A Database Analysis of N Atom Geometry in Compounds with an [N]3P(O) Fragment

Abstract

In the crystal structure of the title compound C₂₁H₂₄N₃OP · C₂H₅OH, there are three crystallographically independent phosphoric triamide molecules and three ethanol molecules. The environments of the nitrogen atoms are practically planar. The phosphorus atoms display a distorted tetrahedral environment; the maximum and minimum values of angles are observed for one O?P?N and one N?P?N angles, respectively. In this structure, the phosphoramide and ethanol molecules are linked by some different intermolecular O?H···O and N?H···O hydrogen bonds to form chains. The title solvated compound has been further characterized by IR and ³¹P{¹H}, ¹H and ¹³C NMR spectroscopy. The geometry of the nitrogen atoms in this compound is analyzed and compared with those of analogous structures deposited in the Cambridge Structural Database (CSD; Allen, Acta Cryst. 2002, B58, 380-388).