Characterization of individual airborne particles - methods used and their limitations

The characterization of individual airborne particles plays an important role in assessing environmental contamination. The morphology, elemental composition and surface properties of these particles must be determined for complete characterization.     

Discoloration of cellulose solutions in <Emphasis Type="Italic">N</Emphasis>-methylmorpholine-<Emphasis Type="Italic">N</Emphasis>-oxide (Lyocell). Part 2: Isolation and identification of chromophores

The Lyocell process is a modern green industrial fiber-making technology, which employs N-methylmorpholine-N-oxide monohydrate (NMMO) to directly dissolve cellulose. One problem in Lyocell processing is the discoloration of the spinning dope due to chemical side reactions. Two different methods were elaborated to isolate chromophores, which are present in minute amounts only, from Lyocell fibers, the first one using hydrogen chloride in alcoholic solution, the second one employing boron trifluoride – acetic acid complex. Several chromophores were unambiguously identified by a combination of analytical techniques and comparison to authentic samples. Carbohydrate condensation products, such as catechols, were shown to dominate in early phases of chromophore formation. In later stages, these initial chromophores undergo further condensation reactions with degradation products of NMMO and NMMO itself, leading to nitrogen-containing heterocycles and quinoid products, among others. The incorporation of nitrogen into the chromophores and thus the participation of the solvent in chromophore formation were proven.     

Trifluoromethanesulfenyl acetate, CF3S-OC(O)CH3, and trifluoromethanesulfenyl trifluoroacetate, CF3S-OC(O)CF3: unexpected conformational properties

Structural and conformational properties of two sulfenyl derivatives, trifluoromethanesulfenyl acetate, CF3S-OC(O)CH3 (1), and trifluoromethanesulfenyl trifluoroacetate, CF3S-OC(O)CF3 (2), were determined by gas electron diffraction, vibrational spectroscopy, in particular with IR (matrix) spectroscopy, which includes photochemical studies, and by quantum chemical calculations. Both compounds exist in the gas phase as a mixture of two conformers, with the prevailing component possessing a gauche structure around the S-O bond. The minor form, 15(5)% in 1 and 11(5)% in 2 according to IR(matrix) spectra, possesses an unexpected trans structure around the S-O bond. The C=O bond of the acetyl group is oriented syn with respect to the S-O bond in both conformers. UV-visible broad band irradiation of 1 and 2 isolated in inert gas matrixes causes various changes to occur. Conformational randomization clearly takes place in 2 with simultaneous formation of CF3SCF3. For 1 the only reaction channel detected leads to the formation of CH3SCF3 with the consequent extrusion of CO2. Quantum chemical calculations (B3LYP/6-31G and MP2 with 6-31G and 6-311G(2df,pd) basis sets) confirm the existence of a stable trans conformer. The calculations reproduce the conformational properties for both compounds qualitatively correct with the exception of the B3LYP method for compound 2 which predicts the trans form to be prevailing, in contrast to the experiment.     

A novel approach to determination of carbonyl groups in DMAc/LiCl-insoluble pulps by fluorescence labeling

The CCOA method for profiling of carbonyl groups by fluorescence labeling has meanwhile become an established procedure for dissolving pulps and rag papers. High molecular weight pulps, such as certain paper pulps, could not be analyzed so far due to their limited solubility in DMAc/LiCl. The new approach presented in this paper is based on the heterogeneous carbonyl-selective fluorescence labeling with CCOA (2), which is subsequently released with triflic acid from the labeled pulp in a quantitative manner, and the concentration of CCOA and CCOA-derived products is determined by HPLC. The procedure requires material in the mg range only. Calibration was performed against DMAc/LiCl-soluble standard pulps. Comparison of the data obtained by the novel approach correlated well with data from the established CCOA procedure.     

On the Nature of Carbonyl Groups in Cellulosic Pulps

Apart from the reducing end groups, most celluloses contain small amounts of carbonyl groups in the mol/g range, which are introduced into the material by a variety of preparation, processing and purification steps. By a combination of carbonyl-selective fluorescence labeling (CCOA method) and UV resonance Raman spectroscopy it was demonstrated that carbonyls in celluloses are not only present as a C=O structure with an sp²-hybridized carbon, but also to a significant extent in sp³-hybridized form as hydrates or hemiacetals.     

A general, selective, high-yield N-demethylation procedure for tertiary amines by solid reagents in a convenient column chromatography-like setup

[reaction: see text] A traditional preparative chromatographic column can be used to achieve quantitative N-demethylation of tertiary N-methylamines and alkaloids. The filling is the crucial part and is loaded with different solid reagents in three reaction zones. The parent compound is charged on the column, and the neat N-demethylated secondary amine leaves the column some minutes later.