Element-selective detection using capillary gas chromatography with atomic emission detection

Capillary GC coupled to an atomic emission detector (AED) provides a powerful new hyphenated technique for the separation and characterization of complex mixtures and compounds. The AED provides simultaneous and truly specific multi-element detection. The specificity of detection reduces the need for the complex sample pretreatment procedures which are necessary to reduce the interference from co-eluted substances which is experienced with detectors such as the FID and the ECD. A range of environmentally significant problems has been studied, including PCB analysis, the characterization of the reaction products of a novel waste treatment process, and the profiling of sulfur-containing species formed by the pyrolysis of various types of coal.     

Scaling laws in simple and complex proteins: size scaling effects associated with domain number and folding class

The native states of the most compact globular proteins have been described as being in the so-called “collapsed-polymer regime,” characterized by the scaling law R _g ~ n ^ν, where R _g is radius of gyration, n is the number of residues, and ν ≈ 1/3. However, the diversity of folds and the plasticity of native states suggest that this law may not be universal. In this work, we study the scaling regimes of: (i) one to four-domain protein chains, and (ii) their constituent domains, in terms of the four major folding classes. In the case of complete chains, we show that size scaling is influenced by the number of domains. For the set of domains belonging to the all-α, all-β, α/β, and α?+?β folding classes, we find that size-scaling exponents vary between 0.3?≤?ν?≤?0.4. Interestingly, even domains in the same folding class show scaling regimes that are sensitive to domain provenance, i.e., the number of domains present in the original intact chain. We demonstrate that the level of compactness, as measured by monomer density, decreases when domains originate from increasingly complex proteins.     

Aryl‐Phosphonate Lanthanide Complexes and Their Fluorinated Derivatives: Investigation of Their Unusual Relaxometric Behavior and Potential Application as Dual Frequency 1H/19F MRI Probes

A series of low molecular weight lanthanide complexes were developed that have high ¹H longitudinal relaxivities (r₁) and the potential to be used as dual frequency ¹H and ¹⁹F MR probes. Their behavior was investigated in more detail through relaxometry, pH‐potentiometry, luminescence, and multinuclear NMR spectroscopy. Fitting of the ¹H NMRD and ¹⁷O NMR profiles demonstrated a very short water residence lifetime (<10 ns) and an appreciable second sphere effect. At lower field strengths (20 MHz), two of the complexes displayed a peak in r₁ (21.7 and 16.3 mM ^?1 s^?1) caused by an agglomeration, that can be disrupted through the addition of phosphate anions. NMR spectroscopy revealed that at least two species are present in solution interconverting through an intramolecular binding process. Two complexes provided a suitable signal in ¹⁹F NMR spectroscopy and through the selection of optimized imaging parameters, phantom images were obtained in a MRI scanner at concentrations as low as 1 mM . The developed probes could be visualized through both ¹H and ¹⁹F MRI, showing their capability to function as dual frequency MRI contrast agents.     

The mass spectra of some naphthoquinones. Lapachol,isolapachol and related compounds

Several alkylhydroxynaphthoquinones and chemically related cyclic compounds were subjected to mass spectrometric investigation. Fragmentation pathways were elucidated by use of metastable ions, relative intensities of normal ions and accurate mass measurement. In these series, differences in the spectra of 1,2- and 1,4-naphthoquinones are slight. Evidence for ring expansion in ions from furans is suggested.     

Ionization equilibrium and radiative energy loss rates for C,N, and O ions in low-density plasmas

The results of calculations of the ionization equilibrium and radiative energy loss rates for C, N and O ions in low-density plasmas are presented for electron temperatures in the range 10⁴–10⁷ °K (～1–10³ eV). The ionization structure is determined using the steady-state corona model, in which electron impact ionization from the ground states is balanced by direct radiative and dielectronic recombination. Using an improved theory, detailed calculations are carried out for the dielectronic recombination rates in which account is taken of all radiative and autoionization processes involving a single-electron electricdipole transition of the recombining ion. The radiative energy loss processes considered are electron-impact excitation of resonance line emission, direct radiative recombination, dielectronic recombination, and electron-ion bremsstrahlung. For all three elements, resonance line emission resulting from 2s?2p transitions produces a broad maximum in the energy loss rate near 10⁵°K(～ 10 eV).     

Wave reflection in slightly compressible, finitely deformed elastic media

Summary  In this paper, the reflection of a plane wave at an incrementally traction-free boundary of a half-space composed of nearly incompressible elastic material is considered. It is shown that two distinct cases exist, these being dependent on the underlying primary deformation. In the first case, the appropriate slowness sections are each approximately elliptical, and the corresponding reflection phenomena closely mirrors that associated with the corresponding linear isotropic theory. Specifically, an angular range of direction of incident wave exists, for which both a quasi-longitudinal and quasi-shear wave are reflected, the former being replaced by a surface wave outside this angular range. In the second case, the outer slowness section is re-enrant and, in addition to the scenarios previously mentioned, it is possible for two quasi-shear waves to be reflected. Numerical illustrations of reflection coefficients are presented in respect of a modified Varga material and the case of increasing bulk modulus is investigated. Received 17 January 2000; accepted for publication 22 February 2000     

Abnormal long wave dispersion phenomena in a slightly compressible elastic plate with non-classical boundary conditions

A two parameter asymptotic analysis is employed to investigate some unusual long wave dispersion phenomena in respect of symmetric motion in a nearly incompressible elastic plate. The plate is not subject to the usual classical traction free boundary conditions, but rather has its faces fixed, precluding any displacement on the boundary. The abnormal long wave behaviour results in the derivation of non-local approximations for symmetric motion, giving frequency as a function of wave number. Motivated by these approximations, the asymptotic forms of displacement components established and long wave asymptotic integration is carried out.     

Is There an Effect of Dysphonic Teachers' Voices on Children's Processing of Spoken Language?

There is a vast body of literature on the causes, prevalence, implications, and issues of vocal dysfunction in teachers. However, the educational effect of teacher vocal impairment is largely unknown. The purpose of this study was to investigate the effect of impaired voice quality on children's processing of spoken language. One hundred and seven children (age range, 9.2 to 10.6, mean 9.8, SD 3.76 months) listened to three video passages, one read in a control voice, one in a mild dysphonic voice, and one in a severe dysphonic voice. After each video passage, children were asked to answer six questions, with multiple-choice answers. The results indicated that children's perceptions of speech across the three voice qualities differed, regardless of gender, IQ, and school attended. Performance in the control voice passages was better than performance in the mild and severe dysphonic voice passages. No difference was found between performance in the mild and severe dysphonic voice passages, highlighting that any form of vocal impairment is detrimental to children's speech processing and is therefore likely to have a negative educational effect. These findings, in light of the high rate of vocal dysfunction in teachers, further support the implementation of specific voice care education for those in the teaching profession.     

Localized vibration in elastic structures with slowly varying thickness

High frequency localized vibration modes for linear isotropicelastic plates and rods of slowly varying thickness are shownto occur within the vicinity of maximal or minimal cross-sections.Long wave asymptotic integration close to the eigenmodes ofsuch cross-sections is provided. The cases of a one integerparameter of thickness resonances (for a plate in plane stress)and two integer parameters (for a rod of circular cross-section)are fully investigated. One-dimensional Hermite-type equationsfor the eigenmodes are derived and associated frequency shiftsfrom those of the thickness resonances of the maximal or minimalcross-section obtained. It is established that the existenceof this type of localization phenomena is strongly dependenton the sign of the group velocity of the associated uniformthickness structure this being the same as that of the localgroup velocity calculated at the maximal or minimal cross-section.It is confirmed that positive group velocity allows localizationfor elevated structures with negative group velocity allowinglocalization only for ligaments. In each case intervals of thePoisson's ratio providing localization are given for the firstfew modes.