Liquid chromatographic analysis of cinchona alkaloids in beverages

A method for the determination of Cinchona extract (whose main components are the alkaloids cinchonine, cinchonidine, quinidine, and quinine) in beverages by liquid chromatography was developed. A beverage with an alcohol content of more than 10% was loaded onto an OASIS HLB solid-phase extraction cartridge, after it was adjusted to pH 10 with 28% ammonium hydroxide. Other beverages were centrifuged at 4000 rpm for 5 min, and the supernatant was loaded onto the cartridge. The cartridge was washed with water followed by 15% methanol, and the Cinchona alkaloids were eluted with methanol. The Cinchona alkaloids in the eluate were chromatographed on an L-column ODS (4.6 mm id x 150 mm) with methanol and 20 mmol/L potassium dihydrogen phosphate (3 + 7) as the mobile phase. Cinchona alkaloids were monitored with an ultraviolet (UV) detector at 230 nm, and with a fluorescence detector at 405 nm for cinchonine and cinchonidine and 450 nm for quinidine and quinine (excitation at 235 nm). The calibration curves for Cinchona alkaloids with the UV detector showed good linearity in the range of 2-400 microg/mL. The detection limit of each Cinchona alkaloid, taken to be the concentration at which the absorption spectrum could be identified, was 2 microg/mL. The recovery of Cinchona alkaloids added at a level of 100 microg/g to various kinds of beverages was 87.6-96.5%, and the coefficients of variation were less than 3.3%. A number of beverage samples, some labeled to contain bitter substances, were analyzed by the proposed method. Quinine was detected in 2 samples of carbonated beverage.     

Synthesis and evaluation of fluorogenic reagents for simultaneous detection of peptides and proteins by HPLC in two different samples

To find the pairs of fluorogenic reagents having similar retention times in HPLC but with different fluorescent characteristics, six fluorogenic reagents bearing benzoxadiazole or benzoselenadiazole skeletons were synthesized. The resultant derivatives obtained from the reaction of peptides and proteins with reagents which have a benzoselenadiazole skeleton showed different fluorescence characteristics from those with a benzoxadiazole skeleton. Since each corresponding derivatives of trypsin inhibitor and BSA with DAABD-Cl and 7-fluoro-N-[2-(diethylamino)ethyl]-2,1,3-benzoselenadiazole-4-sulfonamide (DEAEABSeD-F) have similar retention times, the pair of reagents was adopted for the sensitive simultaneous detection of proteins in two different samples. When the soluble fraction of mouse hippocampus was divided into the two samples (A and B), each was reacted with DEAEABSeD-F for A and DAABD-Cl for B, respectively. The two reaction solutions were combined and subjected to HPLC analysis with two fluorescent detectors in series (excitation and emission at different wavelengths for A and B, respectively). The resultant two chromatograms had quite similar patterns for each other. The new pair of fluorogenic reagents (DAABD-Cl and DEAEABSeD-F) would be applicable to proteomics studies using the previously reported FD-LC-MS/MS method.     

Multibubble sonoluminescence enhancement by fluid flow

Forced fluid flow can cause the enhancement of multibubble sonoluminescence (SL) under suitable conditions. The effect of directional flow with a circulator is similar to that of rotating flow with a stirrer. The mechanism of the enhancement is that both flows prevent cavitation bubbles from coalescing and clustering, which are responsible for the quenching of SL. The intensity of sonochemiluminescence (SCL) in an aqueous luminol solution increases with flow speed at higher ultrasonic powers more significantly than that of SL in distilled water. However, in the range of low ultrasonic power, the intensities of SL and SCL decrease with flow speed. Therefore, an optimum flow speed exists in relation to ultrasonic power and frequency.     

Combination of LFP‐TRIR spectroscopy and DFT computation as a tool to determine the intermediate during the photooxidation of triarylphosphine

Laser flash photolysis‐time‐resolved infrared spectroscopy (LFP‐TRIR) was performed on an acetonitrile or dichloromethane solution of triarylphosphines, Ar₃P, in air. A transient spectrum consisting of several absorption bands appeared in the region of 1050–1300 cm^?1 on the TRIR on a microsecond timescale, which disappeared on a millisecond timescale. To identify the observed transient intermediate, the IR spectra of possible intermediates of the photoreaction were simulated by theoretical calculations based on density functional theory (DFT). The IR spectrum simulated for the phosphine peroxidic radical cation, Ar₃P⁺OO^?, well predicted the observed IR spectrum, showing that Ar₃P⁺OO^? is formed as a transient intermediate upon the LFP of Ar₃P in air. Copyright © 2014 John Wiley & Sons, Ltd.     

Method validation by interlaboratory studies of improved hydrophilic oxygen radical absorbance capacity methods for the determination of antioxidant capacities of antioxidant solutions and food extracts

Hydrophilic oxygen radical absorbance capacity (H-ORAC) is a method for evaluating antioxidant capacities of solutions of hydrophilic compounds. In this study, we improved the original method for H-ORAC determination, and evaluated the precision of the two improved methods (methods A and B) by interlaboratory studies using 5 antioxidant solutions and 5 food extracts as test samples. An interlaboratory study of method A, in accordance with the harmonized protocol, demonstrated satisfactory performance (intermediate precision relative standard deviations (RSD(int)) ranging from 4.6 to 18.8%; the reproducibility relative standard deviations (RSD(R)) ranging from 7.0 to 21.1%, and the HorRat values ranging from 0.40 to 1.93). However, methodological problems remained, and a further improved method, method B, was thus developed. An interlaboratory study of method B by 5 participating laboratories showed better intermediate precision and reproducibility (RSD(int) and RSD(R) ranging from 1.8 to 9.4%, and from 4.4 to 13.8%, respectively), and all HorRat values for the test samples were less than 1.3, suggesting good performance for the H-ORAC measurement.     

Crystal Structure of Zinc(II) Complexes with 2-Ethyl-3-hydroxy-4H-pyran-4-thione and 2-Ethyl-3-hydroxy-4H-pyran-4-selenone

Crystallography Reports - Zn(II) complexes with 2-ethyl-3-hydroxy-4H-pyran-4-thione, [Zn(ehpt)2], and 2-ethyl-3-hydroxy-4H-pyran-4-selenone, [Zn(ehps)2], were synthesized and characterized by...     

A compact AMORS (atomic magneto-optical rotation spectrometer) usable on a motorcar for in-situ field analysis of trace amounts of elements by direct atomization, utilizing the atomic Faraday effect

Summary A compact spectrometer usable on a motorcar was constructed for in-situ field analysis of trace amounts of elements by direct atomization, utilizing the atomic Faraday effect. Two fully charged car batteries, which supplied all the power required for the spectrometer, served for more than 100 atomizations. The basic performance of the constructed spectrometer, involving the capability to remove background signals, was evaluated in the direct determination of Mn and/or Cu in juices of tomato and mandarin orange, in oyster mantle and in volcanic ashes. Rapid analysis in max. 5 min could be performed with freedom from background signals caused by non-atomic species resulting from sample matrix.

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Kompaktes magneto-optisches Atomrotations-Spektrometer (AMORS) zur Benutzung in einem Kraftfahrzeug für die In-situ-Feldanalyse von Elementspuren durch direkte Atomisierung, unter Ausnutzung des Faraday-Effektes

Zusammenfassung Das kompakte Spektrometer, das in einem Kraftfahrzeug leicht untergebracht werden kann, wurde zur Elementspurenbestimmung vor Ort konstruiert. Zwei voll geladene Autobatterien, die die benötigte Energie liefern, reichen für mehr als 100 Atomisierungen aus. Die Leistungsfähigkeit des Gerätes, das auch Untergrundsignale eliminieren kann, wurde an Hand der direkten Bestimmung von Cu und/oder Mn in Tomaten- und Orangensaft, in Austernschalen sowie in Vulkanasche demonstriert. Eine Analyse läßt sich in 5 min ohne Beeinflussung durch Untergrundsignale aus der Matrix durchführen.

     

Influences of serum magnesium on measurements of serum parathyroid hormone

The amino sequence recognizable parathyroid hormones (PTH) in lower and non-lower magnesemic groups in randomized samples were measured by using various kinds of the well established PTH kits. The levels of carboxy terminal, mid-region and intact PTH in lower magnesemic group were more decreased than these in non-lower magnesemic group. It is likely that the shortage of magnesium in serum makes a suppression of PTH secretion.     

Correlation in spatial intensity distribution between volumetric bubble oscillations and sonochemiluminescence in a multibubble system

The correlation in spatial intensity distribution between volumetric oscillation of multibubble and sonochemiluminescence in an ultrasonic standing-wave field is investigated through the measurements of scattered light from bubbles by changing the measuring position in the direction of sound propagation and sonochemiluminescence with luminol. When a thin light sheet, finer than half the wavelength of sound, is introduced into the cavitation bubbles at the anti-node of the sound pressure, the scattered light intensity oscillates temporally. The peak-to-peak light intensity corresponds to the number of the bubbles which contribute to the sonochemical reaction because the radius for oscillating bubbles at pressure antinode is restrictive in a certain range due to the shape instability and the action of Bjerknes force that expels from anti-node bubbles larger than the resonant size. The experimental results show that at the side near the water surface, the peak-to-peak light intensity is larger in comparison with the intensity near the sound source, and this tendency becomes apparent at higher input power. These light scattering results correspond with the spatial intensity distribution of the sonochemiluminescence with luminol. Therefore, it is interpreted that most of the cavitation bubbles contributing to the sonochemical reactions in the standing wave field exist near liquid surface. Present method of light scattering in reference with the image of the sonochemiluminescence is promising for evaluating spatial distribution of violently oscillating cavitation bubbles effective for sonochemical reactions.     

Total synthesis of (+/-)-mycoepoxydiene,a novel fungal metabolite having an oxygen-bridged cyclooctadiene skeleton

[reaction: see text] The first total synthesis of (+/-)-mycoepoxydiene has been accomplished. A ring-closing olefin metathesis (RCM) approach was employed for the construction of the oxygen-bridged eight-membered bicyclic skeleton. The RCM product was converted to the target natural product featuring the oxidative rearrangement of a furfuryl alcohol introduced as the side chain and the stereoselective 1,2-reduction of a delta-keto-beta,gamma-unsaturated alpha-lactol intermediate.