Mass spectra of perfluoroalkyl and perfluoroalkylether nitriles and acyl halides

Electron impact fragmentation patterns were obtained for perfluoroalkylether nitriles, C,F,O[CF(CF₃)CFIO]ICF(CF₃)CN (x = 1 and 2), perfluoroalkylether acyl halides, CSF,OCF(CF,)-CF₂OCF(CF₃)COX (X = F and Cl), n-perfluorooctanonitrile and n-perfiuorooctanoyl chloride. The perfluoroalkyl and perfluoroalkylether nitriles afforded ions characteristic of the nitrile function. The major fragment from the acyl chlorides was the [COClJ]+ ion; the presence of chlorine was evidenced also by rearrangement ions of the general form [R_fCl] t. The perfluoroalkylether compounds appeared to undergo a typical fragmentation governed by the cleavage of the carbon-oxygen bond.     

Fitting tabulated current functions to linear-sweep voltammograms

A procedure is described for fitting tabulated theoretical current functions to linear-sweep voltammograms. The method, suitable for a small microcomputer, employs linear extrapolation between current function values, and non-linear regression for minimizing deviations between experimental and theoretical currents. Examples of its use for confirmation of simple electrode reaction mechanisms and estimation of electrochemical parameters are described.     

Guest sorption and desorption in the metal-organic framework [Co(INA)(2)] (INA=isonicotinate)--evidence of intermediate phases during desorption

The metal-organic framework [Co(INA)(2)]x0.5EtOH (INA = isonicotinate, NC(5)H(4)-4-CO(2)(-)), was synthesised under solvothermal conditions. Its X-ray crystal structure shows channels containing ethanol guests which are hydrogen-bonded to carboxylate oxygens of the framework. The pyridyl rings of the framework alternate between 'open' and 'closed' positions along the channels resulting in large variation in the channel cross-sectional area from ca. 1.4 by 2.3 A at the narrowest point to 4.9 by 5.3 A at the widest. Despite the very small windows, the ethanol guests (of van der Waals diameter ca. 4.2-6.1 A) may be reversibly desorbed and sorbed into the structure quantitatively, as shown by in situ variable-temperture IR spectroscopy and XRPD. The single-crystal structure of the desolvated form [Co(INA)(2)] shows that there is no change in the overall connectivity on desolvation, but the rotational positions of the pyridine rings are altered. This suggests that pyridyl rotation may occur to allow guests to pass in and out. When the synthesis was conducted in 1-propanol solvent [Co(INA)(2)]x0.5Pr(n)OHxH(2)O, was obtained, and a single-crystal X-ray structure revealed the same overall connectivity as in but with pyridine rings disordered over closed and open positions. There was no evidence of included guests from X-ray crystallography, suggesting that they are also highly disordered. Variable-temperature XRPD performed on bulk samples showed peaks which were unsymmetrical and exhibited shoulders, suggesting that for each pattern obtained the material actually consisted of several closely-related phases. The movements of the peaks during desolvation showed the presence of intermediate phases before the final desolvated product was formed. The peak positions of the intermediate phases matched more closely with the calculated pattern for than with or, suggesting that they may have disordered structures similar to. The results also suggest that the intermediate phase represents an initial increase in volume before a larger decrease in volume occurs to give the final desolvated material.     

Computational study on the ring-opening reaction of protonated oxirane and methylpropene

A computational study on the intermolecular reaction of protonated oxirane with methylpropene, as a model for initiation of oxidosqualene cyclisation, shows that the S_N2-like ring opening is strongly exothermic with a low barrier to reaction and establishes the geometry of the intermolecular reaction.     

Macroreticular ion-exchange resins: some analytical applications to petroleum products

Extraction and subsequent recovery, in four separate fractions, of naphthenic acids, alkylphenols, pyrrollic compounds and nitrogen bases can be made from petroleum products using macroporous ion-exchange resins. Distinctive features of the technique are the use of dissolved gases in polar solvents as eluants and the application of the carbonate form of anion-exchange resins. The transition metal form of a macroreticular cation exchanger is shown to extract ligands from non-aqueous systems and a specific application to petroleum analysis is given.     

Comparative studies of electron-impact (EI) and field ionization (FI) mass spectra of pentaerythritol derivatives

The EI Mass spectra of the polyfunctional pentaerythritol derivatives show that the molecular ions [M]⁺· exhibit extensive ion fragmentation. No Information about [M]⁺·. can be obtained. In Contrast to this, the FI Mass spectra of these compounds show intense [M]⁺· and/or [M + 1]⁺, and a characteristic ion at m/e 31, which is assumed to be the oxonium ion \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_2 = \mathop {\rm O}\limits^ + {\rm H} $\end{document}. Because of surface adsorption and field attraction, FI mass spectrometry presents a serious problem in quantitative analysis of a mixture containing compounds with quite different degrees of polarization.     

Amide-water interactions in cosolvent systems. I. Solubilities and apparent molar volumes of methyl paraben

Solubility and apparent molar volume data are used to demonstrate effects of amide alkylation on amide-water interactions at 25° C. Precise measurements were made of the apparent molar volumes of the amides in binary amide-water mixtures using a dilatometric technique. The results show that the apparent molar volumes of alkyl-substituted amides in water pass through a minimum at an amide concentration which varies inversely with the degree of alkylation. Further studies showed that the solubilities of methyl paraben (methyl-p-hydroxybenzoate) and naphthalene in various amide-water solvent systems increased in characteristic fashion with amide alkylation.     

Photon-induced dissociation with a four-sector tandem mass spectrometer

The feasibility of using photodissociation of protonated peptide molecules to sequence specific fragment ions with a 193-nm pulsed laser beam in a magnetic deflection tandem mass spectrometer of EBEB configuration was demonstrated. Although the short pulse (15 ns) and low repetition rate (100 Hz) of the excimer laser permitted the irradiation of only ～ 0.02% of the (M + H)⁺ ions exiting MS-1, a photon-induced decomposition spectrum of the heptapeptide angiotensio III (M _r 930.5) was produced that was practically the same (but with better signal-to-noise ratio) as that generated by collision-activated dissociation at the same low duty cycle. Because of the low and pulsed fragment ion currents, an array detector was used to record the spectra. A dependence between laser power and abundance of fragment ions was observed (increased power increases the relative abundance of ions of low mass). Laser power was varied from 6 to 80 mJ. Formation of fragment ions from a large peptide (melittin, M, 2844.75) was also observed. The results permit the design of modifications that may increase the fragment ion yield to 10% or higher, which would make photon-induced decomposition a useful method for magnetic deflection mass spectrometers.     

Tuning the band gap in hybrid tin iodide perovskite semiconductors using structural templating

Structural distortions within the extensive family of organic/inorganic hybrid tin iodide perovskite semiconductors are correlated with their experimental exciton energies and calculated band gaps. The extent of the in- and out-of-plane angular distortion of the SnI4(2-) perovskite sheets is largely determined by the relative charge density and steric requirements of the organic cations. Variation of the in-plane Sn-I-Sn bond angle was demonstrated to have the greatest impact on the tuning of the band gap, and the equatorial Sn-I bond distances have a significant secondary influence. Extended Hückel tight-binding band calculations are employed to decipher the crystal orbital origins of the structural effects that fine-tune the band structure. The calculations suggest that it may be possible to tune the band gap by as much as 1 eV using the templating influence of the organic cation.