GC–MS analysis of phenolic compounds in fuels after conversion to trifluoroacetate esters

The GC–MS characteristics of trifluoroacetate esters of phenolic compounds are discussed. Linear temperature programmed retention indices and total ion current MS response factors of over 120 phenolic esters are reported. The main GC advantages from analysis of trifluoroacetate esters as compared to plain phenols are enhanced volatility and improved resolution. For example, the elution temperature of a given phenol is typically 50 °C greater than that of the corresponding trifluoroacetate ester. Also, while retention of compounds with two trifluoroacetate groups is only moderately greater than mono esters, underivatized dihydroxy compounds are very difficult to elute from any GC column. Complete resolution of isomeric C₀-, C₁- and C₂-alkylphenol esters is readily achieved on conventional fused silica GC columns; resolution of the corresponding underivatized compounds requires specialized GC columns with low temperature limits. In general, mass spectra of trifluoroacetate esters are more characteristic of a given structure than those of the corresponding phenols and may be more rigorously interpreted towards structural elucidation. A table in the report summarizes some of the more important spectral features used in compound identification. Example applications in analysis of coal-, shale- and petroleum-derived materials are presented. Selected ion monitoring is used to determine individual phenolic components in whole distillates; reconstructed ion chromatograms are used to illustrate distributions of selected species as a function of fuel storage and thermal stress.     

The number of components in profile analysis tasks.

The central issue of this paper is how detection of a change in spectral shape depends on the number of components m that define the spectrum. First, a channel theory is reviewed and the predictions relating the detectability of such a change as a function of the number of components are derived. Second, the existing literature is reviewed. Most of it concerns the detection of an increment in a single tone of an m-component, equal-amplitude complex. The data are close (+/- 2 dB) to the predictions of the theory, which suggests that there is a relatively small change in threshold as the number of components increases. The consistency of the data is also discussed and hypotheses for discrepancies are presented. Finally, the results of an experiment measuring the detectability of a special spectral shape change is explored. In this case, all the changes are equal in size but some are opposite in sign, so that the summed change is zero. The results using this "balanced" spectral change are also consistent with the predictions of the theory and show that for this special kind of spectral change thresholds improve by nearly 7 dB as m increases from 4 to 24 components.     

Abbau von Palustrin zu (−)-Dihydropalustraminsäure ((2R, 6S, 1′S)-[6-(1′-Hydroxypropyl)-2-piperidyl]essigsäure) und Struktur von Palustrin und Palustridin. Mitteilung über Schachtelhalmalkaloide

Degradation of palustrin to (?)-dihydropalustramic acid ((2R,6S,1′S)-[6-(1′-hydroxypropyl)-2-piperidyl]acetic acid), and the structure of palustrin and palustridin The structure of the macrocyclic alkaloid palustrin is shown to be 1a . Its piperidine unit can be obtained as (?)-dihydropalustramic acid ( 6a ) by the following sequence of degradation reactions (Scheme 1): catalytic hydrogenation of 1a followed by methylation and Hofmann degradation provides the allyl base 4 . the regioselectivity of the Hofmann elimination is explained by intramolecular proton abstraction at C(3) by C(18)-O^?. Catalytic reduction of 4 and subsequent acidic hydrolysis yielded 6a and N, N-dimethylputrescine (?N,N-dimethyl-1,4-butanediamine; 7 ). Loss of the N-alkyl group in the formation of 6a occurs during the catalytic hydrogenation step. This interpretation is supported by the results of model experiments. The position of the double bond in 1a is deduced from the IR. spectrum of the bromo-δ-lactone 19 prepared by treatment of 1a with N-bromosuccinimide at pH 4 (Scheme 3). Some of our previously published results on the degradation of dihydropalustrin ( 2a ) are obviously at variance with the newly proposed structure for palustrin ( 1a ). They can easily be explained by assuming a partial hydrogenolysis of the C(17)-N(1) bond during the preparation of dihydropalustrin from palustrin. Periodate cleavage of dihydropalustramic acid methyl ester ( 6b ) liberates propionaldehyde, which can be trapped by working at pH 7.5 (Scheme 2); at lower pH values it condenses rapidly with the simultaneously generated 3,4,5,6-tetrahydropyridine derivative 15 . The structure of the condensation product is proposed to be 16 on the basis of the isolation of its hydrogenation product, an isomeric dihydropalustramic acid ( 17 ).     

Influence of dipolar interactions on radical pair recombination reactions subject to weak magnetic fields

Monte Carlo simulations of the effects of weak magnetic fields on the recombination of interacting radical pairs undergoing free diffusion in solution have been performed, with the aim of determining the influence on the low field effect of the magnetic dipolar coupling between the radicals. The suppression of singlet-triplet interconversion in the radical pair by the dipolar interaction is found to be pronounced at magnetic field strengths comparable to the hyperfine interactions in the radicals, to the extent that the low field effect is completely abolished. The averaging of the dipolar coupling by the translational diffusion of the radicals around one another is relatively efficient in the presence of strong magnetic fields but becomes ineffective in weak applied fields where the strength of the dipolar interaction is independent of the orientation of the inter-radical vector. Low field effects are only likely to be observed if the motion of the radical pair is restricted in some way so as to increase the likelihood that, having separated to the large distance required for the dipolar interaction to have a negligible effect, the radicals subsequently encounter and have the opportunity to recombine.     

Effect of scale and surface chemistry on the mechanical properties of carbon nanotubes‐based composites

In this article, Multi‐Walled Carbon Nanotubes (MWCNTs) of varying diameters, both untreated and polycarboxylated, were dispersed at constant weight percentage in an epoxy matrix, and resulting fracture toughnesses (K_Ic) were measured in each case. We show that changing the MWCNT diameter has two effects on the composite fracture toughness: (i) a small MWCNT diameter enables larger interfacial surface for adhesion maximization, which increases toughness; (ii) at the same time, it limits the available pull‐out energy and reduces the MWCNT ability to homogeneously disperse in the matrix due to this same large active surface: this decreases toughness. Most commercially available MWCNTs have a length range of several μm, thus an optimal diameter exists which depends on MWCNT wall thickness and surface treatment. Such optimal diameter maximizes pull‐out energy and thus composite fracture toughness. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Automated chemical resonance generation and structure filtration for kinetic modeling

This work discusses efficient and automated methods for constructing a set of representative resonance structures for arbitrary chemical species, including radicals and biradicals, consisting of the elements H, C, O, N, and S. Determining the representative reactive structures of chemical species is crucial for identification of reactive sites and consequently applying the correct reaction templates to generate the set of important reactions during automated chemical kinetic model generation. We describe a fundamental set of resonance pathway types, accounting for simple resonating structures, as well as global approaches for polycyclic aromatic species. Automatically discovering potential localized structures along with filtration to identify the representative structures was shown to be robust and relatively fast. The algorithms discussed here were recently implemented in the Reaction Mechanism Generator (RMG) software. The final structures proposed by this method were found to be in reasonable agreement with quantum chemical computation results of localized structure contributions to the resonance hybrid.     

Weak closure and Oliver’s p-group conjecture

To date almost all verifications of Oliver’s p-group conjecture have proceeded by verifying a stronger conjecture about weakly closed quadratic subgroups. We construct a group of order 3⁴⁹ which refutes the weakly closed conjecture but satisfies Oliver’s conjecture.     

Rigid Support Materials for the Immobilization of Enzymes

The purpose of the work presented here was to prepare a support material for enzymes and “affinity ligands” with the following characteristics: low cost, durability, rigidity, and high capacity. Our study encompassed conjugates of porous and nonporous silicas with organic polymers and macroporous ion-exchange resins. Poly-ethyleneimine (PEI), polyacrylic acid (PAA), poly (methyl vinyl ether/maleic anhydride) were attached to porous glass and silica in various combinations. The composite of silica beads with PEI and PAA is a good support for the enzyme trypsin as judged by the activity against N-α-benzoyl-L-arginine ethyl ester.

Amberlyst (macroporous, sulfonated polystyrene) was activated by treatment with thionyl chloride; the resulting resin was either used directly or reacted with a diamine. The diamine derivative was used for enzyme coupling or transformed further to the succinyl or p-aminobenzoyl derivative. None of these derivatives were particularly good as supports for the enzyme trypsin. Duolite converted to a PAA, succinyl, or succinimide derivative was a good support. The enzyme-resin adduct has good activity and stability.

The resin is quite durable and of low cost. The Duolite-trypsin has good activity against protein. In addition, this derivative was active in 7 M urea. The proteolytic activity was nearly doubled by urea, presumably as a result of substrate (casein) denaturation. The michaelis constants and pH dependences are compared for trypsin conjugates with Duolite A-7, Silica-PEI-PAA, agarose, and porous glass. A cost comparison reveals that the Duolite and silica derivatives are much less expensive than agarose and glass.