Multi-electron dissociative ionization of clusters under picosecond and femtosecond laser irradiation: the case of alkyl-halide clusters

The multi-electron dissociative ionization (MEDI) of alkyl-halide clusters induced by 35 ps (at 266, 532 and 1064 nm) and 20 fs (at 400 and 800 nm) laser pulses is reported. In most cases, the MEDI of clusters is observed at substantially lower laser intensities than those reported for the monomer molecules, while the fragment ions are released with higher kinetic energies. From the comparative analysis of the experimental data, is concluded that the increase of molecular chain and/or the presence of a lighter halogen (I, Br, Cl) in the molecular skeleton results in the increase of the laser intensity thresholds for the appearance of the singly and multiply charged fragment ions. As far as the angular distributions of the ejected ions are concerned, they are found to be dependent on the laser pulse duration. For the observed experimental data, a physical mechanism is proposed, based on the combined action of the laser and the electric field created within the clusters after their single ionization.     

Lateralization produced by interaural temporal and intensitive disparities of high-frequency, raised-sine stimuli: data and modeling

An acoustic pointing task was used to measure extents of laterality produced by combinations of ongoing envelope-based interaural temporal disparities (ITDs) and interaural intensitive disparities (IIDs) of 4-kHz-centered raised-sine stimuli [Bernstein and Trahiotis, J. Acoust. Soc. Am. 125, 3234-3242 (2009),] while varying, parametrically, their peakedness, depth of modulation, and frequency of modulation. The study was designed to assess whether IIDs act as "weights" within the putative "binaural display" at high spectral frequencies (where the envelopes convey ITD-information) as appears to be the case at low spectral frequencies (where the waveforms, i.e., fine-structure and envelopes, convey ITD-information). The data indicate that envelope-based IIDs do principally act as weights and that they appear to exert their influence on lateral position independently of the influence of ITDs. Quantitative analyses revealed that an augmented form of the cross-correlation-based "position-variable" model of Stern and Shear [J. Acoust. Soc. Am. 100, 2278-2288 (1996)] accounted for 94% of the variance in the data. This success notwithstanding, for a small subset of the data, predictions could be improved by assuming that the listeners utilized information within auditory filters having center frequencies above 4 kHz.     

Developments on chemometric approaches to optimize and evaluate microextraction

Chemometric experimental design in microextraction plays a crucial role in sustaining the highest quality of analytical data. Making use of the main significant points of chemometric experimental design and microextraction in analytical chemistry we formed the core of this review article. A step-by-step chemometric approach is provided to optimize and validate microextraction-based analytical processes. Significant applications are reported with developments related to microextraction combined with chemometric optimization processes. As it appears from the numerous examples provided in this review, a great number of researchers give credit to the combination of microextraction and chemometrics recognizing that it significantly streamlines sample processing. Moreover, the combination of microextraction with chemometrics addresses problems relating to improvement in detectability and method validation. A worked example on the microextraction of polychlorinated biphenyls is incorporated into the relevant sections of this article and comprehensively provides in a rational and integrated way guidance to people dealing with this subject.     

Resonance fluorescence spectrum of a three-level atom. II. Numerical results

Numerical computations are presented for the excitation spectra arising from the interaction between a three-level atom in the cascade configuration and a strong electromagnetic field whose frequency mode is initially populated. The excitation spectra are considered when the laser field is at resonance with the equally spaced levels of the atom as well as a function of the detunings. The physical process of optical amplification occurs without population inversion and it is more pronounced when the laser field is detuned than when it is at resonance. The shapes of the spectral lines for a number of side-bands are of the absorption-amplification type rather than that of the absorption one. In the presence of detunings as well as in the cooperative two-photon cascade process, the resulting spectra are far more complicated than those occuring at resonance. Results of numerical calculations for a wide range of Rabi frequencies and detunings are presented graphically.     

Simultaneous quantification of candesartan and irbesartan in rabbit eye tissues by liquid chromatography–tandem mass spectrometry

Diabetic retinopathy is a major cause of vision loss in adults. Novel eye-drop formulations of candesartan and irbesartan are being developed for its cure or treatment. To support a preclinical trial in rabbits, it was critical to develop and validate a new LC–MS/MS method for simultaneous quantification of candesartan and irbesartan in rabbit eye tissues (cornea, aqueous humor, vitreous body and retina/choroid). Eye tissue samples were first homogenized in H₂O-diluted rabbit plasma. The candesartan and irbesartan in the supernatants together with their respective internal standards (candesartan-d₄ and irbesartan-d₄) were extracted by solid-phase extraction. The extracted samples were injected onto a C₁₈ column for gradient separation. The MS detection was in the positive electrospray ionization mode using the multiple reaction monitoring transitions of m/z 441 → 263, 445 → 267, 429 → 207, and 433 → 211 for candesartan, candesartan-d₄, irbesartan and irbesartan-d₄, respectively. For the validated concentration ranges (2–2000 and 5–5000 ng/g for candesartan and irbesartan, respectively), the within-run and between-run accuracies (% bias) were within the range of −8.0–10.0. The percentage CV ranged from 0.6 to 7.3. There was no significant matrix interference nor matrix effect from different eye tissues and different rabbits. The validated method was successfully used in the Good Laboratory Practice (GLP) study of rabbits.     

Graph complexity and the laplacian matrix in blocked experiments

connections between the efficiency of statistical designs, the Laplacian matrix studied in algebra, and graphs of maximal complexity are being described. Up to a positive scalar multiple the Laplacian (or Kirchhoff) matrix concides with the information matrix that arises out of a statistical additive model with treatment and block effects. By way of the matrix-tree theorem design efficiency is shown to be closely related to graph complexity. Several open questions regarding graphs of maximal complexity are being brought to attention.     

Acylaminoacetyl derivatives of active methylene compounds. 4

Meldrum's acid has been found to be effectively acylated using the imidazolides of N-protected glycines, X-NHCH₂COOH (X = -COPh, -COMe, -Z, -Boc, -COOMe and -COOEt). The corresponding C-acylation compounds were isolated in high yields and were readily converted to the N-protected tetramic acids. It was shown by pmr spectroscopy that these acids exist as the enol tautomers in DMSO-d₆ solution, whereas in deuteriochloroform solution both the enol and keto tautomers can be observed.     

Assignment of stereochemistry to cyclohexenylidenecyanoacetates by 1H NMR spectroscopy

The stereochemistry of various pairs of isomeric 2-cyclohexen-1-ylidenecyanoacetates was assigned using ¹H NMR spectroscopy. The isomers with the γ-methylene or the γ-vinyl protons cis to the carbalkoxy group were found to have the signals of these protons at approximately 0.3 ppm and 1 ppm, respectively, downfield relative to their geometrical isomers or the corresponding 2-cyclohexen-1-ylidenemalononitriles. The observation regarding the γ-vinyl proton proved useful for the assignment of configuration to cyclohex-enylidenecyanoacetates derived form cholest-4-en-3-one. The large and constant downfield shift (c. 1 ppm) of the γ-vinyl proton when cis to the ester group results from the rigid cyclohexenylidenecyanoacetate system, in which the vinylic proton can approach more closely to the magnetically anisotropic ester carbonyl group.