A practical comparison of MQMAS techniques

A systematic experimental evaluation of several approaches to multiple-quantum MAS NMR was performed for spin-5/2 nuclei using (27)Al NMR of the aluminosilicate andalusite and the porous aluminum phosphate AlPO(4)-14 as model. Experiments were conducted in the fields of 9.4 and 17.6T using magic-angle spinning frequencies up to 30kHz and rf-field strengths of 250 and 120kHz. Numerical SIMPSON optimizations of the NMR parameters were performed alongside the experimental evaluations. Both theory and experiment show that the optimization is most critical for the species in the sample that have the largest quadrupolar coupling constant. For 5QMAS experiments it could be confirmed that the highest available rf-field strength and rotation frequency are favorable for the efficiency of the experiments. For 3QMAS experiments of sites with moderate quadrupolar coupling constants optimum results were obtained at less stringent conditions. The comparison of a FAM II-modification and DFS gave the expected improvement by a factor of about two with respect to a rectangular pulse. No significant difference between these techniques concerning the signal-to-noise ratios was obtained. An actual improvement of the isotropic resolution by a factor of about two was obtained going from 3QMAS to 5QMAS. In addition the resolution of the spectra increases by a factor of about two going from 9.4 to 17.6T.     

Cycloaddition reactions of 2H-benzo[b]thiete and conjugated cyclic dienes

2H-Benzo[b]thiete 1 reacts with cyclopentadiene 3 in consecutive [8π + 2π]cycloadditions yielding the condensed heterocycles 6–8 . Tetracyclone 9 on the other hand gives only the monoadduct 10 . An [8π + 8π]cycloaddition can be observed for 1 and diphenylisobenzofuran 11 . The related π system 13 shows again consecutive [477π + 27π]processes ( 1 + 13 ← 14, 15 ).     

In-line Particle Size Analysis in the fines outlet of an air classifier

Laser diffraction (LD), with reference to the analysis time, is highly advantageous for the automation of particle size analysis. The high measuring frequencies alloy quasi-continous measuring operation. The fineness values obtained form the particle size distribution (PSD) can be transformed into electrical signals for automatic process control. For industrial purposes, an encapsulated measuring cell was developed where the laser beam penetrates the dispersed fines stream via two optical windows. Thus, hazardous materials can also be measured, specifically pharmaceutical or chemical products, or applications requiring explosion-proof plant design are possible. Great efforts had to be made to keep the inner side of the windows clean form product dust. Ultimately, batches running for more than 8 h could be analysed continuously without any contamination of the windows. For the PSD measurements, a standard LD instrument was used with a measuring range of 0.5/0.9–175 μm. As product fineness is monitored continuously in-stream, and virtually without delay, any changes in the fineness during classifier operation can be detected immediately. On the one hand, this opens up a new field for studies of classifier performance. On the other, immediate quality control of even very small batches is possible during the micronization process. The results demonstrate very clearly, for example, the importance of controlling the feed rate to the classifier. Therefore, fineness control by means of this in-line technique gives superior advantages for direct adjustment of the classifier speed.     

Pyrolysis-gas chromatography/fourier-transform infrared spectrometry of poly(ester urethane) elastomers

Three types of industrial poly (ester urethane) elastomers were studied by Curie–point pyrolysis–gas chromatography/Fourier–Transform infrared spectrometry (Py–GC/FTIR) with a maximum pyrolysis temperature of 973 K. The samples chosen were the Urepans 600 and 641 from Bayer and Elastollan C 78 A from BASF/Elastogran. The poly(ester urethane) elastomers are composed of three units: a polyesterdiol, a short chain diol and a diisocyanate. Py–GC/FTIR allows a rapid and unambiguous identification of the polymer chains by key fragments.     

Dynamic mechanical investigations of different substituted cellulose o-silyl ethers

In contrast to many cellulose derivatives, the cellulose O-silyl ethers with bulky side groups exhibit scarcely a change in glass transition temperature by a variation of the degree of substitution (DS) or degree of polymerization (DP) or by introducing phenyl carbamate groups for the remaining hydroxyls along the main chain. However, a substitution of these hydroxyls by flexible acetate groups lowers the glass transition temperature considerably. The secondary dispersion (relaxation) behavior is strongly influenced by the various substituents and can be correlated to specific motions of the molecules. The dynamic mechanical properties are also dependent on the kind of preconditioning of the samples.     

Hindered organoboron groups in organic synthesis. 17 [1]. Synthesis of 2,4,6-triisopropylphenylborane (TripBH2)2, a useful alternative to thexylborane

2,4,6-Triisopropylphenylborane (tripylborane, TripBH₂) resembles thexylborane in having a single, bulky organic group attached to boron, but the group is aromatic rather than aliphatic. The compound has been synthesized by two alternative routes, one involving direct reduction of dimethoxytripylborane and the other involving redistribution between ditripylborane and borane. It is a solid which is considerably more stable than thexylborane.     

Formation of polymer - polymer complexes in the system poly(methacrylic acid) - hydroxyethylcellulose

An interpolymer complex was prepared by mixing aqueous solutions of poly(methacrylic acid) and hydroxyethylcellulose (molar substitution 2.5) and studied by using viscometric method. The hydrogen bonding is primarily involved in these complexations, but the hydrophobic interaction plays also an important role. The complex composition is not changing with the solvents used and is stable in the temperature range 25 °C - 65 °C.