Ion mobility spectrometry as flow-injection detector and continuous flow monitor for aniline in hexane and water

Ion mobility spectrometry (IMS) was used as a flow-injection detector to quantitatively examine the ionization chemistry of aniline in hexane. A 5-microl sample was vaporized at 15-90-sec intervals in a flowing air stream and analyzed with an IMS equipped with acetone reactant ion chemistry, ambient temperature drift tube and membrane-based inlet. Precision was 3-11% relative standard deviation for 1-100 ppm aniline in hexane with 90-sec injection intervals and detection limits were ca. 0.5 ppm with 5-microl injections. Matrix effects with amine and organic solvent mixtures were observed and corrected for low and medium proton affinity interferences with standard addition methods. Pronounced fouling of the IMS occurred when a continuous water flow was introduced for aqueous flow injection-IMS. Continuous water monitoring without degraded IMS performance was possible by sampling air flow through a Silastic tube immersed in an aqueous sample.     

Quinazolines and 1,4-benzodiazepines. XLVI. Photochemistry of nitrones and oxaziridines

The cyclic nitrones 7-chloro-1,3-dihydro-5-phenyl-2H-1,4-benzodiazepin-2-one 4-oxide ( 5a ) and 1,3-dihydro-7-methylthio-5-phenyl-2H-1,4-benzodiazepin-2-one 4-oxide ( 5b ) are photoisomerized to readily isolable oxaziridines, 7-chloro-4,5-epoxy-5-phenyl-1,3,4–5-tetrahydro-2H-1,4-benzodiazepin-2-one ( 6a ) and 4,5-epoxy-5-phenyl-1,3,4,5-tetrahydro-7-methylthio-2H-1,4-benzo-diazepin-2-one ( 6b ). Oxaziridine 6b upon further irradiation gave ring expansion and ring contraction products, 4,6-dihydro-2-phenyl-9-methylthio-5H-1,3,6-benzoxadiazocin-5-one ( 7b ) and 4-benzoyl-3,4-dihydro-6-methylthioquinoxalin-2(1H)-one ( 8b ) respectively. The ring contraction product, 4-benzoyl-6-chloro-3,4-dihydroquinoxalin-2(1H)-one ( 8a ), was obtained from irradiation of oxaziridine 6a .     

Solvent extraction and photometric determination of a microgram of cerium with N-p-tolyl-p-chlorobenzohydroxamic acid

A spectrophotometric method for determination of a microgram quantity of cerium with N-p-tolyl-p-chlorobenzohydroxamic acid is described. The orange-red-colored complex is extracted from chloroform at pH 9 which absorbs between 460 and 465 nm. Beer's law is obeyed at this wavelength. A clean-cut separation from many commonly occurring metal ions is easily accomplished. The system obeys Beer's law within the range of 0.5–28 ppm of cerium(IV). The molar absorptivity of cerium-N-p-tolyl-p-chlorobenzohydroxamic acid complex is 4.5 × 10³ liters mol^?1 cm^?1.     

Compactification of a myelin mimetic Langmuir monolayer upon adsorption and unfolding of myelin basic protein

The surface shear viscosity of a myelin mimetic Langmuir monolayer is investigated upon adsorption of myelin basic protein (MBP). We measure an increase of the surface shear viscosity at picomolar concentrations of the protein, suggesting that the globular conformation of MBP changes upon adsorption at the monolayer. The conformational change enables hydrodynamic interactions of the proteins, with a typical separation of hundreds of nanometers. This unfolding is essential for the compactification of the myelin sheath, serving an enhanced saltatory signal transduction in vertebrates. The viscometry used extends the sensitivity of standard surface viscometers toward lower viscosities.     

Influences of hydration force and elastic strain energy on the stability of solid film in a very thin solid-on-liquid structure

Since hydration forces become very strong at short range and are particularly important for determining the magnitude of the adhesion between two surfaces or interaction energy, the influences of the hydration force and elastic strain energy due to hydration-induced layering of liquid molecules close to a solid film surface on the stability of a solid film in a solid-on-liquid (SOL) nanostructure are studied in this paper. The liquid of this thin SOL structure is a kind of water solution. Since the surface forces play an important role in the structure, the total free energy change of SOL structures consists of the changes in the bulk elastic energy within the solid film, the surface energy at the solid-liquid interface and the solid-air interface, and highly nonlinear volumetric component associated with interfacial forces. The critical wavelength of one-dimensional undulation, the critical thickness of the solid film, and the critical thickness of the liquid layer are studied, and the stability regions of the solid film have been determined. Emphasis is placed on calculation of critical values, which are the basis of analyzing the stability of the very thin solid film.     

Delivery of Benzoporphyrin Derivative, a Photosensitizer, into Atherosclerotic Plaque of Watanabe Heritable Hyperlipidemic Rabbits and Balloon-Injured New Zealand Rabbits

Abstract— In this study we compared the plasma distribution and arterial accumulation of a photosensitizer, benzoporphyrin derivative (BPD), in two models of atherosclerosis: the spontaneous lesions of the Watanabe heritable hyperlipidemic (WHHL) rabbit and induced lesions of the balloon-injured, cholesterol-fed New Zealand white (NZW) rabbit. Selective uptake and retention of a photosensitizer by the abnormal portion of a vessel is a necessity in order for photodynamic therapy to become a successful modality for inhibition of intimal hyperplasia, selective removal of atherosclerotic tissue or imaging of diseased arteries. Liposome-based formulations were compared to freshly isolated native low density lipoprotein (LDL) and acetylated-LDL (Ac-LDL) as delivery vehicles for BPD. Plasma distribution of the photosensitizer was analyzed by KBr density gradient ultracentrifuga-tion. Although the delivery vehicle influenced plasma distribution immediately postinjection, BPD subsequently partitioned according to the plasma concentration of the lipoproteins. Photosensitizer level in plaque and normal artery specimens was determined by ethyl acetate extraction and spectrofluorometric measurement. The measurement of BPD in normal and atherosclerotic arterial tissue demonstrated a selective accumulation in atherosclerotic tissue. Preassociation with LDL and Ac-LDL enhanced accumulation of BPD in atherosclerotic tissue when compared with normal artery (mean ratios of 2.8 and 4.1 were achieved, respectively). These results indicate that the preferential uptake of BPD by atherosclerotic plaque can be enhanced by preassociation with plasma lipoproteins, suggesting that light activation could lead to a highly selective destruction of diseased vascular tissue.     

Mössbauer study on the photochemical reactions of pentacarbonyliron with ethene in low temperature nitrogen matrix

The UV-induced photochemical reactions of pentacarbonyliron with ethene in a low temperature nitrogen matrix were studied by means of the Mössbauer technique. Fe/CO/₄/C₂H₄/ was produced by UV-irradiation of penfacarbonyliron in close proximity to ethene molecules in a pure ethene matrix, or a homogeneous cocondensed matrix. The other products were obtained via thermal reactions with ethene of Fe/CO/₄ trapped in stratified matrices.     

Polarography as a tool in organic analysis

Summary Rapid indirect polarographic and visual micromethods have been developed for the determination of the quinone and azoxy groups by reduction with titanium(III) at pH values of 3 and 5.5, respectively. The excess of reductant is first determined polarographically followed by visual back-titration of the same solution with iron(III) using thiocyanate as indicator a drop of neutral red is added in case of the quinone function. Although the results obtained by the two finishes are of approximately the same order of accuracy (±0.46%), yet the polarographic finish proved to be of more general applicability particularly for quinones that give rise, after reduction, to a variety of colours on adding the iron(III) solution.

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Anwendung der Polarographie in der organischen AnalyseIV. Bestimmung von Chinon- und Azoxygruppen durch Reduktion mit Titan(III)

Zusammenfassung Zur schnellen Bestimmung von Chinon- und Azoxygruppen durch Reduktion mit Titan(III) bei pH 3 bzw. 5,5 werden indirekte polarographische und visuelle Mikromethoden beschrieben. Der Überschuß an Reduktionsmittel wird zunächst polarographisch und anschließend volumetrisch durch Rücktitration mit Eisen(III)-lösung bestimmt, wobei Thiocyanat (bei der Chinongruppe noch zusätzlich Neutralrot) als Indicator dient. Beide Ergebnisse weisen etwa dieselbe Genauigkeit auf (±0,46%); doch ist die polarographische Methode allgemeiner anwendbar, besonders bei Chinonen, die nach der Reduktion auf Zusatz Eisen(III) verschiedenartige Färbungen hervorrufen.

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Part III: Mikrochim. Acta 1969, 44.     

Determination of stability constants of fixed-site complexes of copper(II) ions and of sorbed copper-l-proline complexes with an asymmetric resin containing l-proline groups

By study of the distribution of copper(II) and l-proline (Pro) ions between an aqueous phase and a resin phase with l-proline groupings on a polystyrene matrix (R ), the conditional stability constants of fixed-site R (2) Cu and sorbed R CuPro complexes have been determined and a method for calculation of the constants for alkaline and neutral media is proposed. The values obtained reflect the actual behaviour of the system, and strongly depend on the ph and the ionic strength of the solution in equilibrium with the resin phase. It was established that this dependence and the high values of the conditional constants of complex formation in comparison with the stability constants of low molecular-weight model compounds are due to the donnan distribution of the low molecular-weight participants and to the effect of the electrostatic field of the polyanion. The distribution of the fixed-site ligands on the resin causes considerable differences in the stability of individual fixed-site R Cu complexes and their capacity to enter into reactions with ligands in the aqueous phase.     

9(11)-Secoestra-11,17-dioic acids and related compounds

While hydrogenations of 2b furnished a mixture in which the rac 14α isomer 8b predominated, the rac lactone 6 was hydrogenolyzed to give the rac 14β diacid 9a. Clemmensen reduction of 6 gave the rac 14α tetrahydro compound 7a. Another route to 8 involved conversion of the d-ketoacid 11b into 23b via the cyanolactone 20b or the amidolactone 21b. Base-catalyzed elimination at 206° yielded the Δ¹⁶ diester 27 which was hydrogenated to 8c. An analogous conversion was also carried out in the ring B reduced series 13 → 20a + 21a → 23a → 25a → 26. In the 14β series, using the same sequence of reactions, the rac ketoacid 10a was transformed into the rac lactone ester 29. In distinction from the 14α series, treatment with alkali at 206° gave only partial elimination, the double bond migrating to the 14,15 position to furnish 2. Evidence is presented that amides of the ketoacid 13a exist in the hydroxylactam form 30 and can be readily O-alkylated to furnish 22. Attempts to aromatize ring B of 13a with DDQ led to lactones 15 and 16, while reaction of the ester 13b with DDQ gave the pentaene 17 and the hexaene 18, establishing that dehydrogenation proceeded stepwise in the sequence Δ⁸, Δ¹⁴ and finally Δ⁶.