An Improved HPLC Post-Column Methodology for the Identification of Free Radical Scavenging Phytochemicals in Complex Mixtures

The importance of natural antioxidants principally relates to their health-promoting properties. The discovery of new sources of established compounds or more potent compounds is a costly exercise and any technique capable of aiding this procedure would be highly significant. An approach combining chromatographic separation, component analysis and post-column identification of free radical scavenging has been reported. However, its effectiveness is dependent upon various factors and the number of samples analyzed without operator intervention is restricted. A more applicable technique using a 10% to 100% methanol with 2% acetic acid mobile phase and a citric acid-sodium citrate buffered methanolic 1,1-diphenyl-2-picrylhydrazyl free radical reagent is presented, whereby free radical scavengers can be detected within crude extracts of variable polarity without special considerations. As an illustration, acetone, 70% (aq.) methanol and acetonitrile-soluble extracts were prepared from sage (Salvia officinalis L.) for extraction of polar and non-polar radical scavengers and analyzed. Radical scavenging components were identified as carnosic, caffeic and rosmarinic acids and luteolin-7-O-glycoside. Others radical scavengers were tentatively identified as benzoic and hydroxycinnamic acid derivatives, flavonoids and diterpenoids. Through the application of this technique, carnosic acid and rosmarinic acid were identified as the principal free radical scavengers.     

Measurement of PCDDs, PCDFs, and non-ortho-PCBs by comprehensive two-dimensional gas chromatography-isotope dilution time-of-flight mass spectrometry (GC x GC-IDTOFMS)

Comprehensive two-dimensional gas chromatography with isotope-dilution time-of-flight mass spectrometry (GC × GC-IDTOFMS) was used to measure polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF), and coplanar polychlorinated biphenyl (cPCB) concentrations in ash, sediment, vegetation, and fish samples. The GC × GC capability was achieved by using a quad jet, dual stage, thermal modulator. Zone compression of the GC peaks from modulation resulted in a significant increase of the signal intensity over classical GC-IDTOFMS. The GC × GC column set used an Rtx-Dioxin 2 phase as the first dimension (¹D) and an Rtx-500 as the second dimension (²D). The chromatographic separation of the 17 PCDD/Fs and the 4 cPCBs was attained in ¹D except for 2,3,7,8-TCDD and CB126 for which deconvoluted ion currents (DIC) were required to be reported separately. The Rtx-500 phase separated the bulk matrix interfering compounds from the target analytes in ²D. The instrumental limit of detection (iLODs) was 0.5 pg for 2,3,7,8-TCDD. The calibration curves showed good correlation coefficients for all the compounds investigated in the concentration range of 0.5–200 pg. GC × GC-IDTOFMS results compared favorably to those from conventional isotope-dilution one-dimensional gas chromatography-high resolution mass spectrometry (GC-IDHRMS). The comprehensive mass analysis of the TOFMS further permitted the identification of other contaminants of concern in the samples.     

Comparison of model predictions with measured proton-induced production of nickel and iridium isotopes

Journal of Radioanalytical and Nuclear Chemistry - Calculations were performed to support method development for simultaneous production of Ni and Ir isotopes. The work scope included development...     

The effect of parametric variations of cochlear implant processors on speech understanding

This study investigated the effect of five speech processing parameters, currently employed in cochlear implant processors, on speech understanding. Experiment 1 examined speech recognition as a function of stimulation rate in six Med-E1/CIS-Link cochlear implant listeners. Results showed that higher stimulation rates (2100 pulses/s) produced a significantly higher performance on word and consonant recognition than lower stimulation rates (<800 pulses/s). The effect of stimulation rate on consonant recognition was highly dependent on the vowel context. The largest benefit was noted for consonants in the /uCu/ and /iCi/ contexts, while the smallest benefit was noted for consonants in the /aCa/ context. This finding suggests that the /aCa/ consonant test, which is widely used today, is not sensitive enough to parametric variations of implant processors. Experiment 2 examined vowel and consonant recognition as a function of pulse width for low-rate (400 and 800 pps) implementations of the CIS strategy. For the 400-pps condition, wider pulse widths (208 micros/phase) produced significantly higher performance on consonant recognition than shorter pulse widths (40 micros/phase). Experiments 3-5 examined vowel and consonant recognition as a function of the filter overlap in the analysis filters, shape of the amplitude mapping function, and signal bandwidth. Results showed that the amount of filter overlap (ranging from -20 to -60 dB/oct) and the signal bandwidth (ranging from 6.7 to 9.9 kHz) had no effect on phoneme recognition. The shape of the amplitude mapping functions (ranging from strongly compressive to weakly compressive) had only a minor effect on performance, with the lowest performance obtained for nearly linear mapping functions. Of the five speech processing parameters examined in this study, the pulse rate and the pulse width had the largest (positive) effect on speech recognition. For a fixed pulse width, higher rates (2100 pps) of stimulation provided a significantly better performance on word recognition than lower rates (<800 pps) of stimulation. High performance was also achieved by jointly varying the pulse rate and pulse width. The above results indicate that audiologists can optimize the implant listener's performance either by increasing the pulse rate or by jointly varying the pulse rate and pulse width.     

Effects of spectral flattening on vowel identification

The identification of front vowels was studied in normal-hearing listeners using stimuli whose spectra had been altered to approximate the spectrum of vowels processed by auditory filters similar to those that might accompany sensorineural hearing loss. In the first experiment, front vowels were identified with greater than 95% accuracy when the first formant was specified in a normal manner and the higher frequency formants were represented by a broad, flat spectral plateau ranging from approximately 1600 to 3500 Hz. In the second experiment, the bandwidth of the first formant was systematically widened for stimuli with already flattened higher frequency formants. Normal vowel identification was preserved until the first formant was widened to six times its normal bandwidth. These results may account for the coexistence of abnormal vowel masking patterns (indicating flattened auditory spectra) and normal vowel recognition.     

Active to sterile neutrino mixing limits from neutral-current interactions in MINOS

Results are reported from a search for active to sterile neutrino oscillations in the MINOS long-baseline experiment, based on the observation of neutral-current neutrino interactions, from an exposure to the NuMI neutrino beam of 7.07×10(20) protons on target. A total of 802 neutral-current event candidates is observed in the Far Detector, compared to an expected number of 754 ± 28(stat) ± 37(syst) for oscillations among three active flavors. The fraction f(s) of disappearing ν(μ) that may transition to ν(s) is found to be less than 22% at the 90% C.L.     

Measurement of the neutrino mass splitting and flavor mixing by MINOS

Measurements of neutrino oscillations using the disappearance of muon neutrinos from the Fermilab NuMI neutrino beam as observed by the two MINOS detectors are reported. New analysis methods have been applied to an enlarged data sample from an exposure of 7.25×10(20) protons on target. A fit to neutrino oscillations yields values of |Δm(2)|=(2.32(-0.08)(+0.12))×10(-3) eV(2) for the atmospheric mass splitting and sin(2)(2θ)>0.90 (90% C.L.) for the mixing angle. Pure neutrino decay and quantum decoherence hypotheses are excluded at 7 and 9 standard deviations, respectively.     

Determination of pKa values using 15N and 13C nuclear magnetic resonance spectroscopy. The case of apramycin

By comparison of pK^a values derived from ¹⁵N and ¹³C nuclear magnetic resonance (NMR) spectroscopies, the assignment of the ¹⁵N resonances of apramycin is completed. ¹³C NMR spectra appear to provide accurate pK_a determinations with this aminoglycoside. Hydroxylation adjacent to one of the basic nitrogens of apramycin appears to change the pK_a values of all five amines of the molecule.     

13C n.m.r. spectroscopy: Comparison of the spectra of some dimeric Catharanthus alkaloids and their derivatives

The ¹³C n.m.r. spectra of some dimeric Catharanthus alkaloids are reported and assigned. Methods devised to aid in the assignment of resonances in complex molecules are described. The ¹³C n.m.r. spectra of several derivatives of vinblastine are discussed.     

Susceptibility to intraspeech spread of masking in listeners with sensorineural hearing loss

Previous research with speechlike signals has suggested that upward spread of masking from the first formant (F 1) may interfere with the identification of place of articulation information signaled by changes in the upper formants. This suggestion was tested by presenting two-formant stop consonant--vowel syllables varying along a/ba--/da/--/ga/ continuum to hearing-impaired listeners grouped according to etiological basis of the disorder. The syllables were presented monaurally at 80 dB and 100 dB SPL when formant amplitudes were equal and when F 1 amplitude was reduced by 6, 12, and 18 dB. Noise-on-tone masking patterns were also generated using narrow bands of noise at 80 and 100 dB SPL to assess the extent of upward spread of masking. Upward spread of masking could be demonstrated in both speech and nonspeech tasks, irrespective of the subject's age, audiometric configuration, or etiology of hearing impairment. Attenuation of F 1 had different effects on phonetic identification in different subject groups: While listeners with noise-induced hearing loss showed substantial improvement in identifying place of articulation, upward spread of masking did not consistently account for poor place identification in other types of sensorineural hearing impairment.