Investigation of the quantitative properties of the quadrupole orthogonal acceleration time-of-flight mass spectrometer with electrospray ionisation using 3,4-methylenedioxymethamphetamine

This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time-of-flight mass spectrometer (Q-TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4-methylenedioxymethamphetamine standards and 3,4-methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4-methylenedioxymethamphetamine and its metabolite 3,4-methylenedioxyamphetamine was prepared in each of these matrices again using 3,4-methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q-TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2-10 000 pg on-column, r(2) = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC-fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q-TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright 1999 John Wiley & Sons, Ltd.     

Crystallization kinetics study on higher homologues of benzylidene aniline compounds: impact of phase variant on nucleation process

A systematic kinetic study leading to the crystallization process from the kinetophases (which occur prior to crystal phase) smectic B, crystal G and smectic F is performed on representative compounds of the homologous series p-phenylbenzylidene-p'-alkylanilines (PBnA) and p-n-alkoxybenzylidene-p'-alkylanilines (nO.m) these compounds are p-phenylbenzylidene-p'-nonylaniline (PB9A), p-phenylbenzylidene-p'-tetradecylaniline (PB14A), p-n-pentadecyloxybenzylidene p'-tetradecylaniline (15O.14) and p-n-octadecyloxybenzylidene-p'-nonylaniline (18O.9). The molecular mechanism and dimensionality in crystal growth from the kineto phases are computed from the Avrami equation, while the characteristic crystalline time (t*) at each crystallization temperature is deduced from the individual plots of log t vs. ΔH. The low magnitudes of the dimensionality parameter n infers the occurrence of diffusion-controlled transformations leading to the formation of plates or needles of finite size possessing impinged edges. The degree of variation in the value of n at each crystallization temperature also reveals the existence of an independent nucleation mechanism for any individual member of the series. The influence of the terminal alkyl chain lengths on the rate of crystallization is determined from a comparative study with the reported analogous compounds.     

Magnetic moments of (νi132)−n isomers in neutron-deficient lead isotopes

The magnetic moments of the 12⁺ isomers in ^{192, 196, 198, 200, 206}Pb and of the $\text{33}\text{2}{}^{\mathrm{+}}$ isomer in ²⁰⁵Pb have been measured using the PAD technique. The results for the g-factors are: g(192) = ?0.173(2), g(196) = ?0.1600(15), g(198) = ?0.1552(15), g(200) = ?0.1512(15), g(206) = ?0.1496(18), and g(205) = ?0.148(5). As all states have a rather pure $\text{(νi}{}_{\mathrm{<mtext>13</mtext><mtext>2</mtext>}}\text{)}{}^{\mathrm{?n}}$ configuration, the values reflect directly the $\text{νi}{}_{\mathrm{<mtext>13</mtext><mtext>2</mtext>}}$ orbital. They show a decrease towards the more neutron-deficient isotopes attributed to the reduced core polarisation as a result of decreasing occupation of the $\text{i}{}_{\mathrm{<mtext>13</mtext><mtext>2</mtext>}}$ neutron shell. The measured systematics are discussed regarding core polarisation, mesonic corrections, and small admixtures of core-excited states to the $\text{i}{}_{\mathrm{<mtext>13</mtext><mtext>2</mtext>}}$ wave function.     

Radiative strength functions in odd-A spherical nuclei

The radiative strength functions for the partial γ-transitions from neutron resonances to the ground and low-lying states of odd-A spherical nuclei are calculated within the quasiparticle-phonon nuclear model. The fragmentation of one-quasiparticle and quasiparticle-plus-phonon states is calculated. This allowed one to calculate γ-transitions between the one-quasi-particle components (valence transitions) and γ-transitions between the quasiparticle-plus-phonon and one-quasiparticle components of the wave functions. The energy dependence of the strength functions $\text{C}$(E1, η) and $\text{C}$(M1, η) is calculated near the neutron binding energy B_n for ⁵⁵Fe and ^{59, 61}Ni. The corresponding experimental data are described qualitatively. The contribution of the valence E1 transitions to the strength function is shown to be from 20% to 90%, and M1 transitions about 1%. The influence of the M1 giant resonance is important for M1 transition probabilities.     

Reabsorption in a neodymium fibre laser

Resonance absorption, the reabsorption of laser light by the laser transition of the dopant material itself, is found to be the limiting factor for fibre lasers when extremely long fibres are used. We report on measurements of the temperature dependence of the losses in a 8.5 m long commercial Nd³⁺ doped fibre (York, ND 95020/E). To determine the reabsorption losses, the threshold power has been measured as a function of temperature between 243 K and 413 K. The results are compared with theory assuming a ⁴l level energy of 2110 cm^-1 and an absorption cross-section of δ = 1.15 x 10^-20cm². The comparison shows that reabsorption from the thermally populated ⁴l level is the dominant contribution to the measured losses.     

Lower Rim Substituted tert-Butyl calix[4]arenes (I). The Structure and Complexing Properties in Ion-Selective PVC Membrane Electrodes

Some di- and tetraamide tert-butylcalix[4]areneswere synthesized and described. Their ionophoric properties were studied in liquid membrane ion-selective electrodes. The correlation between thechemical structure (conformation in solution determined by ¹H NMR) and potentiometric ion-selectivity and complex formation constant havebeen studied. The PVC membrane electrodes based on tetraamides 8–11 show high sodium selectivity, are stable and long lasting. Disubstituted amides 1–7 are selective for larger and more lipophilic ions, as for exampleguanidinium ion. The crystal structure of the diamide 4 was determined by single crystal X-ray analysis. Crystals of 4 are triclinic, spacegroup P-1, with: a = 16,669(8), b = 17.795(10), c = 20.984(8) Å, =91.08(4)°, = 91.60(3)°, = 90.73(4)° and Z = 4. Ionophore 4 posseses a distorted cone conformation and is substituted at the proximal phenol rings.     

Surface species in the direct amination of methanol over Brønsted acidic mordenite catalysts

Quantitative in situ infrared spectroscopy in combination with kinetic analysis is utilized to derive mechanistic aspects for the reaction of methanol with ammonia on Brønsted acidic mordenite. Under non-reactive conditions, a coadsorption complex between methanol and ammonia is found, in which only ammonia is in direct interaction with the Brønsted acid sites of the zeolite. This complex is proposed to be the precursor for the formation of protonated methylamines in the zeolite pores which are formed in sequential order up to tetramethylammonium ions. These methylamines are unable to desorb under reaction conditions in the absence of ammonia. They leave the surface either by ammonia adsorption assisted desorption or by scavenging of methyl groups from protonated methylamines by ammonia. Both steps are concluded to be potentially rate determining.     

Cole-Cole Analysis of the Superspin Glass System Co 80 Fe 20 /Al 2 O 3

Ac susceptibility measurements were performed on discontinuous magnetic multilayers [Co 80 Fe 20 ( t )/Al 2 O 3 (3 nm)] 10 , t = 0.9 and 1.0 nm, by Superconducting Quantum Interference Device (SQUID) magnetometry. The CoFe forms nearly spherical ferromagnetic single-domain nanoparticles in the diamagnetic Al 2 O 3 matrix. Due to dipolar interactions and random distribution of anisotropy axes the system exhibits a spin-glass phase. We measured the ac susceptibility as a function of temperature 20 h T h 100 K at different dc fields and as a function of frequency 0.01 h f h 1000 Hz. The spectral data were successfully analyzed by use of the phenomenological Cole-Cole model, giving a power-law temperature dependence of the characteristic relaxation time c and a high value for the polydispersivity exponent, f , 0.8, typical of spin glass systems.