Absorption spectra and photochemistry of the toluene cation and benzyl radical in solid argon

Toluene diluted in argon subjected to continuous argon discharge radiation during condensation at 21 K revealed absorptions at 310.5 and 449.6 nm due to benzyl radical, and 317 nm due to a C₇7H₉ radical. A photosensitive 430 nm band, in agreement with photodissociation spectra of the toluene parent cation, is assigned to this species.     

Graphical Representations of Speed: Obstacles Preservice K‐8 Teachers Experience

This study examines the difficulties college students experience when creating and interpreting graphs in which speed is one of the variables. Nineteen students, all preservice elementary or middle school teachers, completed an upper‐level course exploring algebraic concepts. Although all of these preservice teachers had previously completed several mathematics courses, including calculus, they demonstrated widespread misconceptions about the variable speed. This study identifies four cognitive obstacles held by the students, provides excerpts of their graphical constructions and verbal interpretations, and discusses potential causes for the confusion. In particular, misconceptions arose when students interpreted the behavior and nature of speed within a graphical context, as well as in situations where they were required to construct a graph involving speed as a variable. The study concludes by offering implications for the teaching and learning of speed and its interpretation within a graphical setting.     

Copper and iron interactions with angiotensin-converting enzyme inhibitors. A study by fast-atom bombardment tandem mass spectrometry

Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd.     

Sigma/pi Bonding Preferences of Solvated Alkali-Metal Cations to Ditopic Arylmethyl Anions

Arylmethyl anions allow alkali-metals to bind in a σ-fashion to the lateral carbanionic centre or a π-fashion to the aryl ring or in between these extremities, with the trend towards π bonding increasing on descending group 1. Here we review known alkali metal structures of diphenylmethane, fluorene, 2-benzylpyridine and 4-benzylpyridine. Next, we synthesise Li, Na, K monomers of these diarylmethyls using polydentate donors PMDETA or Me₆TREN to remove competing oligomerizing interactions, studying the effect that two aromatic rings has on negative charge (de)localisation via NMR, X-ray crystallographic and DFT studies. Diphenylmethyl and fluorenyl anions maintain C(H)−M interactions regardless of alkali-metal, although the adjacent arene carbons engage in interactions with larger alkali-metals. Introducing a nitrogen atom into the ring (at the 2- or 4-position) encourages relocalisation of negative charge away from the deprotonated carbon and onto nitrogen. Phenyl(2-pyridyl)methyl moves from an enamide formation at one extremity (lithium) to an aza-allyl formation at the other extremity (potassium), while C- or N-coordination modes become energetically viable for Na and K phenyl(4-pyridyl)methyl complexes.     

A rapid technique to determine the internal area function of finite-length ducts using maximum length sequence analysis

This paper describes a rapid technique for reconstruction of the internal area function of a duct using blockage-induced eigenvalue shifts determined from eigenfrequencies measured under two sets of duct termination boundary conditions. A single broad band maximum length sequence (MLS) measurement of short duration is utilized to obtain the transfer function of the duct, which in turn can be utilized to determine its eigenvalue shifts and subsequently its internal area function using an inverse perturbation technique. The reconstruction results display the same order of accuracy as those obtained previously using swept sine measurements of extended duration. An expression for the determination of the area function is presented utilizing resonant frequency information alone, thus rendering duct length determination unnecessary. A computational routine further simplifies the process such that the accuracy of the technique could be ascertained for a range of configurations including longer ducts and ducts that initially have nonuniform internal cross section over their length. Development of a relationship between obstacle length and wavelength of the lowest eigenfrequency required for successful reconstruction is also described. This is an important result for longer ducts where measurement of lower eigenfrequencies may present problems using standard measurement equipment.     

Liquid–liquid extraction of neodymium (III) and europium (III) using synergic mixture of furosemide and tribenzylamine in benzyl alcohol

The extraction behavior of Nd(III) and Eu(III) with 0.05 mol dm⁻³ furosemide in benzyl alcohol as single acidic extractant and then with equimolar (0.05 mol dm⁻³) synergic mixture of furosemide as acidic extractant and tribenzylamine as neutral donor in benzyl alcohol has been studied from aqueous solutions of pH 1 to 6. The effect of various parameters and of various cations and anions on the extraction of these metal ions was investigated. The composition of the extracted adducts was determined by slope analysis method that came out to be [(M(FS)₂)⁺ (CH₃COO)⁻] and [M(FS)₃·3TBA] where M = Nd(III) and Eu(III).

     

Comparison of mouse brain DTI maps using K-space average,image-space average,or no average approach

Diffusion tensor imaging (DTI) is achieved by collecting a series of diffusion-weighted images (DWIs). Signal averaging of multiple repetitions can be performed in the k-space (k-avg) or in the image space (m-avg) to improve the image quality. Alternatively, one can treat each acquisition as an independent image and use all of the data to reconstruct the DTI without doing any signal averaging (no-avg). To compare these three approaches, in this study, in vivo DTI data were collected from five normal mice. Noisy data with signal-to-noise ratios (SNR) that varied between five and 30 (before averaging) were then simulated. The DTI indices, including relative anisotropy (RA), trace of diffusion tensor (TR), axial diffusivity (λ║), and radial diffusivity (λ ⊥), derived from the k-avg, m-avg, and no-avg, were then compared in the corpus callosum white matter, cortex gray matter, and the ventricles. We found that k-avg and m-avg enhanced the SNR of DWI with no significant differences. However, k-avg produced lower RA in the white matter and higher RA in the gray matter, compared to the m-avg and no-avg, regardless of SNR. The latter two produced similar DTI quantifications. We concluded that k-avg is less preferred for DTI brain imaging.     

Photoactivation of vascular iNOS and elevation of cGMP in vivo: possible mechanism for photovasorelaxation and inhibition of restenosis in an atherosclerotic rabbit models

Recently, intravascular low-power red laser light (LPRLL) therapy has been proposed for the prevention of postangioplasty restenosis due to the observed inhibition of experimental neointimal formation. The objective of this study was to determine the impact of endoluminal LPRLL on vascular levels of inducible nitric oxide synthase (iNOS) and cyclic guanosine monophosphate (cGMP) to help define the mechanism of this effect. Eight atherosclerotic male adult New Zealand White rabbits weighing 4-6 kg were used in these studies. The iliac arteries were treated in separate zones with: (1) balloon inflation only; (2) laser illumination only; and (3) balloon inflation + laser illumination. An uninjured zone of the iliac artery served as a control. Laser irradiation (630 nm) was delivered to the vessel wall via a Cold laser Illuminator (Cook, Inc., Bloomington, IN), with a 3 mm-diameter balloon. Experiments demonstrated that vascular cGMP levels obtained immediately following treatment in the balloon only group was the lowest (0.29 +/- 0.05 pmol/mg protein) and significantly lower compared with the uninjured controls (1.01 +/- 0.07 pmol/ mg protein) (P < 0.001). In the laser only treated group cGMP levels were significantly increased (2.87 +/- 0.12 pmol/mg protein) compared with the uninjured control (P < 0.001) and the balloon only group (P < 0.001). Vascular cGMP levels in the balloon + laser group (2.09 +/0.07 pmol/mg protein) was also increased compared to the balloon only (P < 0.001) and control (P < 0.001) groups. Qualitative analysis of Western blot demonstrated that laser illumination induces iNOS. In contrast balloon dilatation did not induce iNOS. Balloon + laser treatment, however, tended to restore the expression of iNOS. Our study demonstrated that intravascular low dose laser irradiation induces iNOS and elevates vascular cGMP in an in vivo atherosclerotic rabbit model.     

The analysis of alkyl-capped alcohol ethoxylates and alcohol ethoxycarboxylates from alcohol ethoxylates by atmospheric pressure chemical ionization mass spectrometry

Alcohol ethoxylates (AEs) are nonionic surfactants. They are industrially important compounds that have historically been difficult to analyze, with the best results to date achieved through derivatization (e.g., silylation) followed by analysis by gas chromatography/mass spectrometry (GC/MS). Recently, mass spectrometric techniques such as field desorption (FD), time-of-flight secondary ion mass spectrometry (TOF-SIMS), fast atom bombardment (FAB), electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) have been employed to analyze surfynol(R) 4xx. In an effort to produce low-cost alkyl-capped AEs and anionic detergents from AEs, a fast and reliable measure of the product yields and conversions from AEs is required in research. We found that the product yields and conversions from reactions of AEs, obtained by the employment of atmospheric pressure chemical ionization (APCI), were in good agreement with those obtained from proton nuclear magnetic resonance spectroscopy ((1)H-NMR). Therefore, APCI can be used as a validated tool for studying AE reactions. Mixtures that contain either silylated or unsilylated ethoxylates and/or carboxylates yield the same APCI mass spectra. Copyright -Copyright 1999 John Wiley & Sons, Ltd.