Carbon-13 chemical shifts of bicyclic compounds

¹³C NMR absorption spectra of 50 bicyclic hydrocarbons, alcohols and ketones have been measured, in addition to some terpenes. The ¹³C chemical shifts are approximately additive for similar compounds and can be used for the determination of molecular structure; they differ for endo- and exo-isomers, just as in proton spectra. These quite regular and predictable ¹³C shift differences are much larger and are caused by the 1,4-nonbonded interaction between atoms heavier than hydrogen, not by magnetic anisotropy effects.     

Modification of Lignins. I. Reaction of Lignins with Chlorophosphazenes

Lignin is a potential raw material for several applications. The immediate future should result in the development of lignin modifications yielding new polymers with special properties such as flame and/or thermal resistance. In this report a new reaction of lignins with chlorophosphazenes is discussed. The effect of different types of lignin and chlorophosphazene oligomers on the properties of the reaction product was investigated. The reactions were found to result in products with flame as well as with a base and acid hydrolitic resistance.     

Stability considerations of a high-temperature superconductor tape at different operating temperatures

Stability of a Bi-2223/Ag multifilamentary composite conductor against fast transport current ramps was studied by using a numerical model. The model was based on the two-dimensional magnetic diffusion and heat conduction equations. Calculations were carried out both in an adiabatic mode and pool boiling modes in liquid helium, hydrogen and nitrogen. When estimating the heat load (AC losses), real temperature dependent current density–electric field characteristics were used. The results computed by the finite element method are presented and discussed with special emphasis on differences of the stability considerations between high-temperature and low-temperature superconductors.     

Density functional studies of the hydrolysis of aluminum (chloro)hydroxide in water with CPMD and COSMO

Car-Parrinello molecular dynamics (CPMD) and the static density functional method (DFT) with a conductor-like screening model (COSMO) were used to investigate the chemistry of aluminum (chloro)hydroxide in water. With these methods, the stability, reactivity, and acidic nature of the chosen chlorohydrate were able to be determined. Constrained molecular dynamics simulations were used to investigate the binding of chlorine in an aquatic environment. According to the results, aluminum preferred to be 5-fold-coordinated. In addition, the activation energy barriers for the dissociation of chlorine atoms from the original chlorohydrate structure were able to be determined. The actual values for the barriers were 14 +/- 3 and 40 +/- 5 kJ mol (-1). The results also revealed the acidity of the original cationic dimer. DFT with COSMO was used to determine free energy differences for the reactions detected in the molecular dynamic simulations. In conclusion, new results and insight into the aquatic chemistry of the aluminum (chloro)hydroxides are provided.     

High-energy sub-nanosecond optical pulse generation with a semiconductor laser diode for pulsed TOF laser ranging utilizing the single photon detection approach

Bulk and quantum well laser diodes with a large equivalent spot size of d _a /Γ _a  ≈ 3 µm and stripe width/cavity length of 30 µm/3 mm were realized and tested. They achieved a pulse energy and pulse length of the order of ~1 nJ and ~100 ps, respectively, with a peak pulse current of 6–8 A and a current pulse width of 1 ns. The 2D characteristics of the optical output power versus wavelength and time were also analyzed with a monochromator/streak camera set-up. The far-field characteristics were studied with respect to the time-homogeneity and energy distribution. The feasibility of a laser diode with a large equivalent spot size in single photon detection based laser ranging was demonstrated to a non-cooperative target at a distance of a few tens of meters.     

Determination of Stoichiometric Dissociation Constants of Benzoic Acid in Aqueous Sodium or Potassium Chloride Solutions at 25°C

Equations were determined for the calculation of the stoichiometric (molality scale) dissociation constant K_m of benzoic acid in dilute aqueous NaCl and KCl solutions at 25°C from the thermodynamic dissociation constant K_a of this acid and from the ionic strength I_m of the solution. The salt alone determines mostly the ionic strength of the solutions considered in this study and the equations for K_m were based on the single-ion activity coefficient equations of the Hückel type. The existing literature data obtained by conductance measurements and by electromotive force (EMF) measurements on Harned cells were first used to revise the thermodynamic value of the dissociation constant of benzoic acid. A value of K_a = (6.326 ± 0.005) × 10^-5 was obtained from the most precise conductivity set [Brockman and Kilpatrick] and this value is supported within their precisions by the less precise conductivity set of Dippy and Williams and by the EMF data set measured by Jones and Parton with quinhydrone electrodes. The new data measured by potentiometric titrations in a glass electrode cell were then used for the estimation of the parameters of the Hückel equations of benzoate ions. The resulting parameters were also tested with the existing literature data measured by cells with and without a liquid junction. The Hückel parameters suggested here are close to those determined previously for anions resulting from aromatic and aliphatic carboxylic acids. By means of the calculation method based on the Hückel equations, K_m can be obtained almost within experimental error at least up to I_m of about 0.5 mol-kg_-1 for benzoic acid in NaCl and KCl solutions.     

A study of 1,5-hydrogen shift and cyclization reactions of an alkali isomerized methyl linolenoate

Heating a mixture formed by alkali isomerization of methyl linolenoate (1) produces a complex mixture with the bicyclic hexahydroindenoic esters 4β-(7-methoxycarbonylheptyl)-5α-methyl-2,3,3aα,4,5,7aαhexahydroindene (CL5) and 4β-ethyl-5α-(6-methoxycarbonylhexyl)-2,3,3aα,4,5,7aα-hexahydroindene (CL6) as main components. Similar isomerization reactions of three synthetic model compounds, methyl 9Z,13E,15Z-octadecatrienoate (2), 9Z,14E,16E-octadecatrienoate (4) and 9Z,11E,15Z-octadecatrienoate (5) corroborated the results obtained with alkali isomerized methyl linolenoate.     

Sterically hindered phenols in negative ion mobility spectrometry–mass spectrometry

Negative corona discharge atmospheric pressure chemical ionization (APCI) was used to investigate phenols with varying numbers of tert‐butyl groups using ion mobility spectrometry–mass spectrometry (IMS‐MS). The main characteristic ion observed for all the phenolic compounds was the deprotonated molecule [M–H]⁻. 2‐tert‐Butylphenol showed one main mobility peak in the mass‐selected mobility spectrum of the [M–H]⁻ ion measured under nitrogen atmosphere. When air was used as a nebulizer gas an oxygen addition ion was seen in the mass spectrum and, interestingly, this new species [M–H+O]⁻ had a shorter drift time than the lighter [M–H]⁻ ion. Other phenolic compounds primarily produced two IMS peaks in the mass‐selected mobility spectra measured using the [M–H]⁻ ion. It was also observed that two isomeric compounds, 2,4‐di‐tert‐butylphenol and 2,6‐di‐tert‐butylphenol, could be separated with IMS. In addition, mobilities of various characteristic ions of 2,4,6‐trinitrotoluene were measured, since this compound was previously used as a mobility standard. The possibility of using phenolic compounds as mobility standards is also discussed. Copyright © 2009 John Wiley & Sons, Ltd.