Group mass spectroscopy

The preparation and spectroscopic properties (infrared, ultraviolet, NMR) of iV-alkoxycarbonyl-N -(2-thiazolyl)thioureas (268) have been studied by the Nagano group (78, 264). These compounds react with bromine in acetic acid or chloroform to give 2--alkoxycarbonylimino-thiazolo[3,2-h]thiadiazolines (Scheme 162), whose structures were established by mass spectroscopy, infrared, NMR, and reactivity patterns (481). 

Polyester composition can be determined by hydrolytic depolymerization followed by gas chromatography (28) to analyze for monomers, comonomers, oligomers, and other components including side-reaction products (ie, DEG, vinyl groups, aldehydes), plasticizers, and finishes. Mass spectroscopy and infrared spectroscopy can provide valuable composition information, including end group analysis (47,101,102). X-ray fluorescence is commonly used to determine metals content of polymers, from sources including catalysts, delusterants, or tracer materials added for fiber identification purposes (28,102,103). 

An important breakthrough in HTS ee assays came from the group of Reetz in late 1990, with the introduction of mass spectroscopy (MS)-based procedures [90]. These methods use special asymmetrically isotope-labeled compounds. Enzymatic transformations of these compounds usually lead to two pseudoenantiomeric compounds whose relative concentration can be estimated using MS techniques. 

Computational methods including both metabolism databases and predictive metabolism software can be used to aid bioanalytical groups in suggesting all possible potential metabolite masses before identification by mass spectroscopy (MS) [116,117]. This approach can also combine specialized MS spectra feature prediction software that will use the outputs from databases and prediction software and make comparisons with the molecular masses observed... 

Perhaps the most revolutionary development has been the application of on-line mass spectroscopic detection for compositional analysis. Polymer composition can be inferred from column retention time or from viscometric and other indirect detection methods, but mass spectroscopy has reduced much of the ambiguity associated with that process. Quantitation of end groups and of co-polymer composition can now be accomplished directly through mass spectroscopy. Mass spectroscopy is particularly well suited as an on-line GPC technique, since common GPC solvents interfere with other on-line detectors, including UV-VIS absorbance, nuclear magnetic resonance and infrared spectroscopic detectors. By contrast, common GPC solvents are readily adaptable to mass spectroscopic interfaces. No detection technique offers a combination of universality of analyte detection, specificity of information, and ease of use comparable to that of mass spectroscopy. 

Figure 5.3. TDS of solution-processed a-Si films. Three samples were prepared by the thermal decomposition of polysilane under the following conditions sample a, 300 °C for 10 min sample b, 300 °C for 120 min and sample c, 540 °C for 120 min. Desorbed gases from the samples were analyzed using mass spectroscopy while the samples were heated in a vacuum. [Reproduced with permission from Ref. 10. Copyright 2006 Nature Publishing Group.]...

Synthesis of Compound I. As shown in Scheme II, 3-(thiophene-3-yl)propyl bromide can be prepared by a two-carbon homologation(2 ) of 3-thenyl bromide via reaction with diethyl malonate to form diethyl 3-thenylmalonate. This is followed by saponification, decarboxylation, reduction of acid to alcohol, (2 ) and replacement of the hydroxyl group with bromide by reacting with PBr3.(22) Compound 2 is synthesized by mono-quaternization of an excess of 4,4 -bipyridine with 3-(thiophene-3-yl)propyl bromide followed by N-methylation with CH3I. All the intermediates in Scheme II have been identified by NMR spectroscopy. 2 has been characterized by NMR and high resolution mass spectroscopy and by electrochemistry. 

Typical mass spectroscopy, AFM and gel electrophoresis (PAGE) results are shown in Table 27.2 for structures in the core-shell series [X] (Y)(Z) , where [X] = core, (Y) = shell, (Z) = capping groups and n = number of shell-type dendrimers bonded to the core (Table 27.2). 

Iwasita et used the similar techniques and confirmed that the adsorbate contains a proton atom but concluded that the adsorbate is C-OHad ie same group executed electrochemical thermal desorption mass spectroscopy, in which the methanol absorbing electrode was washed by the supporting electrolyte, transferred to the UHV environment, heated to desorb the adsorbates to analyze them by mass spectroscopy. They found hydrogen molecules in the desorbed gas as well as CO and the ratio of hydrogen to CO decreased as the concentration of methanol increased. 

H or R = H R = Me or R = R = Me) exist in the solid state as cyclic isomers, but exhibit a slowly reached (6-18 hours) equilibrium 83A 83B in chloroform solution. By means of IR spectroscopy, it was shown that the introduction of a methyl group at position 5 (R = Me) destabilizes the cyclic tautomer 83B, while two methyl groups at position 4 (R = Me) act strongly in the opposite direction. Mass spectroscopy has revealed that in the gas phase these compounds exist almost entirely as open-chain tautomers (92KGS985). 

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