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PubMed2000

IR and UV spectra of the matrix-isolated peroxy radicals CF3OO, trans-FC(O)OO, and cis-FC(O)OO

The peroxy radicals CF3OO and FC(O)OO are prepared in high yields by vacuum flash pyrolysis of ROONO2 or ROOOR (R=CF3, FC(O)), highly diluted in inert gases, and subsequent isolation in inert-gas matrices by quenching the product mixtures at low temperatures. The IR spectrum of FC(O)OO was observed for the first time and eight fundamentals as well as several combinations were measured and assigned for both cis and trans rotamers of FC(O)OO. Discrepancies in an earlier assignment of the fundamentals of CF3OO have been eliminated and its IR spectrum is reported fully. The matrix UV spectra of both peroxy radicals (X2A"--> 2(2)A" transition) are in agreement with the gas-phase spectra; however, there are differences in the absorption cross-sections, for which possible reasons are discussed. The X2A"--> 1(2)A' transitions in the near IR region are too weak to be detected with our instrumentation.

Journal Article↗

PubMed2000

Nickel-catalyzed

Oxabenzonorbornadienes 1 and 2 and azabenzonorbornadiene 3 undergo [2+2] cycloaddition with alkynes (PhC triple bond Ph, PhC triple bond CMe, PhC triple bond CCO2Et, PhC triple bond CCH(OEt)2, and HC triple bond C(CH2)4Me) in the presence of [Ni(PPh3)2Cl2], PPh3, and Zn powder in toluene to afford the corresponding exo-cyclobutene derivatives 4a-e, 5a-e, and 6 in fair to excellent yields. Under similar conditions. EtCO2C triple bond CCO2Et does not react with 1 in toluene to give the [2+2] cycloaddition product, but in acetonitrile, the catalytic [2+2] cycloaddition proceeds and cycloadduct 4 f is isolated in 83% yield. At high temperature, these cyclobutene derivatives readily undergo ring expansion to yield the corresponding 8-membered carbocyclic dienes. Thus, flash vacuum pyrolysis of 4a, 4d, 4f, 6, and 14 at 500 degrees C affords dienes 13a-d and 15 in 70-96% yields. This interesting ring expansion may be viewed as the insertion of an alkyne moiety into the carbon-carbon double bond of a cyclic olefin resulting in the enlargement of the ring by two carbons. Compound 13a is readily deoxygenated by TiCl4 and Zn in THF to give a cyclooctatetraene derivative 16 in 89% yield.

Journal Article↗

PubMed2001

Syntheses of halogenated ethenyl isocyanide chromium complexes as organometallic precursor molecules for ethenyl and ethynyl isocyanides.

The radical alkylation of tetraethylammonium pentacarbonyl(cyano)chromate 1 yielded the halogenated ethyl isocyanide complexes [(CO)5Cr(CN-CClX-CClYF)] 3 (a, X= Cl, Y= F; b, X = F, Y= F and c, X=Y= Cl). Dehalogenation of 3 using zinc in diethyl ether gave [(CO)5Cr(CN-CX=CFY)] 4. The compounds 4a, b reacted with various nucleophiles exclusively at the difluoromethylene group. The unstable phosphorane 5, which is formed on reaction of 4b with trimethylphosphane, decomposed thermally and on hydrolysis yielding pentacarbonyl(1,2-difluoroethenyl isocyanide)chromium (6). The cyano substituent can be introduced in the beta position of the isocyanide function by reaction of 4a, b with potassium cyanide, leading to the formation of [(CO)5Cr(CN-CX=CF-CN)] (7). Reactions of 4a, b with organolithium or organomagnesium compounds yielded [(CO)5Cr(CN-CX=CF-R)] (8) and [(CO)5Cr(CN-CF=CF-C...C-CF=CF-NC)Cr(CO)5] (10). The trimethylsilyl group in 8a, b, d could be removed by a solution of potassium carbonate in methanol leading to [(CO)5Cr(CN-CX=CF-Cn-H)] (11) (n=2,4). Octacarbonyldicobalt reacted with 8e under coordination of the C-C triple bond to the hexacarbonyldicobalt fragment, resulting in the cluster compound 12. The crystal and molecular structure of 8i, 11 a, b, and 12 were elucidated by X-ray crystallography. The alkenyl and alkynyl isocyanides CN-CCl=CF2 (13a), CN-CF=CF2 (13b), CN-CCl=CClF (13c), CN-CF=CFH (14), CN-CC-H (15), CN-CC-CN (16), and CN-CCl=CF-CN (17) were obtained by flash vacuum pyrolysis of 4a, 4b, 4c, 6, and 7a, respectively.

Journal Article↗

PubMed2001

First experimental observation on different ionic states of the tert-butoxy [(CH3)3CO*] radical.

A continuous tert-butoxy (CH3)+CO* radical beam is produced in situ by respective pyrolysis of both (CH3)3CONO at 115(+/-0.5) degrees C and (CH3)3COOC(CH3)3 at 87(+/- 0.5) degrees C. By combining the HeI photoelectron (PE) spectrum with the improved density function theory (DFT) calculations, we have concluded that the (CH3)3CO* radical has C3V symmetry and X2E ground state. The study does not only provide the ionization energies of different ionic states of the (CH3)3CO* radical for the first time, but also the first example in which there have been similar vibrational structures in different ionic states caused by removal of the electron on an orbital. It is also pointed out that (CH3)3CONO is a good source for obtaining the (CH3)3CO* radical beam, and that NO is a stable regent for the active radical. The results will promote the studies in electron spin resonance (ESR) research on the mechanisms of both the initiation of the formation of a new radical and the radical-chain polymerization in which the (CH3)3CO* radical participates.

Journal Article↗

PubMed2002

The trifluoromethoxycarbonyl radical CF(3)OCO.

The trifluoromethoxycarbonyl radical CF(3)OCO is formed by low-pressure flash pyrolysis of CF(3)OC(O)OOC(O)OCF(3) or CF(3)OC(O)OOCF(3) in the presence of a high excess of CO and subsequent quenching of the reaction mixture as a CO matrix. The IR and UV spectra are recorded, and a DFT study of CF(3)OCO is presented. According to the quantum chemical calculations, two rotamers should exist with an energy difference between the isomers equal or larger than 12 kJmol(-1). By comparing calculated and observed IR spectra, the presence of the trans form of the CF(3)OCO radical is identified in the matrix. The reaction of CF(3)O radicals with CO leading to CF(3)OCO is calculated to be exothermic by 33.6 kJmol(-1). CF(3)OCO dissociates when irradiated by UV light with lambda<370 nm into CF(3) radicals and CO(2). Experiments show that CF(3) radicals do not react with solid CO to give CF(3)CO.

Journal Article↗

PubMed2001

The CH3 N Diradical: Experimental and Theoretical Determinations of the Ionization Energies.

Pyrolysis of CH3 N3 under the protection of NO generates a continuous methylnitrene CH3 N diradical beam that enables the ionization energies of different ionic states of the CH3 N diradical to be determined by HeI photoelectron spectroscopy (PES; see spectrum) and both ab initio and density functional theory (DFT) calculations. The ab initio and DFT results are in excellent agreement with the PES experiment and show that the CH3 N diradical has C3v symmetry and the ground state of the CH3 N radical cation is the (2) E state.

ab initio calculations↗

PubMed2005

Slurry sampling techniques for the determination of lead in Bangladeshi fish samples by electrothermal atomic absorption spectrometry with a metal tube atomizer.

Ultrasonic slurry sampling electrothermal atomic absorption spectrometry with a metal tube atomizer has been applied to the determination of lead in Bangladeshi fish samples. The slurry sampling conditions, such as slurry stabilizing agent, slurry concentration, pyrolysis temperature for the slurried fish samples, particle size and ultrasonic agitation time, were optimized for electrothermal atomic absorption spectrometry with the Mo tube atomizer. Thiourea was used as the chemical modifier for the interference of matrix elements. The detection limit was 53 fg (3S/N). The determined amount of lead in Bangladeshi fish samples was consistent with those measured in the dissolved acid-digested samples. The advantages of the proposed methods are easy calibration, simplicity, low cost and rapid analysis.

Animals↗

PubMedDate not supplied

Distribution and occurence of polycyclic aromatic hydrocarbons (PAHs) in sediments from the Mar Grande and Gulf of Taranto (Ionian Sea, southern Italy).

Marine sediments from the Mar Grande and Gulf of Taranto were analysed for 17 parent PAHs, with molecular weight from 128 to 278 Daltons. The analyses were performed by gas chromatography coupled to mass spectrometry (GC-MS). Total PAHs content in sediments ranged from 464 to 12522 microg kg(-1) dry wt for Mar Grande and from 593 to 72275 microg kg(-1) dry wt for Gulf of Taranto. The analytical results were compared with the published results for other coastal areas in the Mediterranean Sea. PAHs levels in the Gulf of Taranto sediments were the highest in the Mediterranean sea, while PAHs concentrations in Mar Grande were higher than the ones reported in the Adriatic and Cretan Sea and with the same order of magnitude of the ones known for coastal areas of the Western and the Eastern Mediterranean Sea. PAHs concentration ratios were consistent with the main source of these compounds, in most areas, being pyrolysis. Based on the comparison of both the individual and the total PAHs concentrations with proposed sediment quality guidelines, the acute biological effects on the marine organisms were probable, especially for the Gulf of Taranto, in which almost all PAHs concentrations in sediments were higher than the guidelines limit values. The statistical analysis effected by HCA and PCA methods was used in order to classify sediment samples and to identify accumulation areas.

Biomass↗

PubMed1985

Benzene: standards, occurrence, and exposure.

The national occupational standard values for benzene are 10 ppm for Australia, 10 ppm for Denmark, 10 ppm for Finland, 10 ppm for Japan, 10 ppm for The Netherlands, 10 ppm for the United States, and 5 ppm for Sweden; in the Federal Republic of Germany the technical guideline value is 8 ppm. Crude mineral oil contains benzene as a natural constituent of approximately 0.1%. Gasoline in Sweden may contain 4-5% benzene by volume. The 8-hour time-weighted average (TWA) exposure levels of Swedish petroleum refinery workers vary between 0.1 to 1 mg benzene/m3 in air. The exposures of benzene in various other occupations were measured and described. Other environmental exposures to benzene may have their origin in pyrolysis, such as tobacco smoking and burning of substances such as polyvinylchloride.

Air Pollutants, Occupational↗

PubMed1992

Excited carbonyl formation in the combination and disproportionation of free radicals.

The pyrolyisis of di-tert-butyl peroxyoxalate in the presence of para-substituted benzaldehydes produces almost quantitatively the corresponding p,p'-disubstituted benzils. The formation of these products is accompanied by chemiluminescence arising from excited triplets. From the quantum yield of excited triplet generation and the rate constants for the triplet photocleavage it is possible to obtain the change in Gibbs free energy associated with triplet formation. The values obtained are -5.6, -5.7 and -8.1 kcal/mol for benzil, p,p'-dimethylbenzil and p,p'-dimethoxybenzil, respectively. The pyrolysis of di-tert-butyl peroxyoxalate in the presence of isopropanol or benzoin leads to the formation of acetone and benzil. These products are generated in disproportionation processes involving the alpha-hydroxy radical produced by hydrogen abstraction. The luminescence observed in these reactions constitutes the first experimental indication of excited species generation in the disproportionation of uncorrelated free radicals.

1-Propanol↗

PubMed2002

Monitoring of complex industrial bioprocesses for metabolite concentrations using modern spectroscopies and machine learning: application to gibberellic acid production.

Two rapid vibrational spectroscopic approaches (diffuse reflectance-absorbance Fourier transform infrared [FT-IR] and dispersive Raman spectroscopy), and one mass spectrometric method based on in vacuo Curie-point pyrolysis (PyMS), were investigated in this study. A diverse range of unprocessed, industrial fed-batch fermentation broths containing the fungus Gibberella fujikuroi producing the natural product gibberellic acid, were analyzed directly without a priori chromatographic separation. Partial least squares regression (PLSR) and artificial neural networks (ANNs) were applied to all of the information-rich spectra obtained by each of the methods to obtain quantitative information on the gibberellic acid titer. These estimates were of good precision, and the typical root-mean-square error for predictions of concentrations in an independent test set was <10% over a very wide titer range from 0 to 4925 ppm. However, although PLSR and ANNs are very powerful techniques they are often described as "black box" methods because the information they use to construct the calibration model is largely inaccessible. Therefore, a variety of novel evolutionary computation-based methods, including genetic algorithms and genetic programming, were used to produce models that allowed the determination of those input variables that contributed most to the models formed, and to observe that these models were predominantly based on the concentration of gibberellic acid itself. This is the first time that these three modern analytical spectroscopies, in combination with advanced chemometric data analysis, have been compared for their ability to analyze a real commercial bioprocess. The results demonstrate unequivocally that all methods provide very rapid and accurate estimates of the progress of industrial fermentations, and indicate that, of the three methods studied, Raman spectroscopy is the ideal bioprocess monitoring method because it can be adapted for on-line analysis.

Algorithms↗

PubMed1978

The interpretation of the mass spectrum of an ornithine-containing lipid from Thiobacillus thiooxidans.

The electron impact mass spectrum of a previously identified ornithine-containing lipid from Thiobacillus thiooxidans has been interpreted using exact mass measurements, low and high energy ionization, and defocused metastable studies. The spectrum, which did not contain a molecular ion for the intact lipid, was consistent with cyclization of the ornithine zwitterionic moiety with elimination of water to give 3[3'-(11,12-methylene-2-hydroxyoctadecanoxy)hexadecanylamine]-2-piperidone. Production of this sufficiently volatile species for mass spectral analysis was accomplished by gentle pyrolysis in the mass spectrometer source. The spectrum can be understood to arise by three primary decompositions which serve to separate the two fatty acid constituents. The remainder of the spectrum is consistent with the expected fragmentations of these constituents.

Acidithiobacillus thiooxidans↗

PubMed1982

Determination of peptidoaminobenzophenone (2-o-chlorobenzoyl-4-chloro-N-methyl-N'-glycylglycinanilide) and its metabolites in human plasma by glass capillary gas chromatography negative ion chemical ionization mass spectrometry--1.

A highly sensitive and selective glass capillary gas chromatographic negative ion chemical ionization mass spectrometric assay was developed to measure peptidoaminobenzophenone(2-o-chlorobenzoyl-4-chloro-N-methyl-N'-glycylglycinanilide) and its metabolites; chlorodiazepam, chlorodesmethyldiazepam and lorazepam in human plasma. As peptidoaminobenzophenone underwent pyrolysis during gas chromatography, it was converted to a thermally stable aminoquinolone. Internal standards for these compounds were the respective deuterium labelled compounds. Calibration curves were prepared for the range of 1-100 ng ml-1. Interference by endogenous substances was negligible in the isobutane negative ion chemical ionization mode in contrast to the electron impact or positive ion chemical ionization mode. This method was used to determine the plasma levels in humans following oral administration of two 5 mg doses.

Anti-Anxiety Agents↗

PubMed1983

Systematic analysis of desorption chemical ionization (DCI) mass spectra of nucleic acids--7.

The positive ion and negative ion pyrolysis mass spectra of the herring sperm DNA have been studied using desorption chemical ionization. The positive ion desorption chemical ionization spectra have been produced with CH4, i-C4H10, NH3, HCl and Cl2; the negative ones with N2O/CH4, N2O/i-C4H10, Cl2, CCl4, HCl and via electron capture. These spectra have been compared with the electron impact ionization spectra. We have observed an important increase of sensitivity when negative ionization has replaced the positive ionization mode. The series of diagnostic ions resulting from direct chemical ionization belong to the family of base + reagent ion X [BH + X] and base + X - HX ion [B]. Their abundance has increased considerably compared to the electron impact spectra. The application of these new diagnostic ions in nucleic acid studies is interesting especially for the much higher abundance of the usually weak dG fragment ion obtained in the negative ionization mode. The dG-base segment of the DNA is the most nucleophilic centre of the whole nucleic acid and is implicated in numerous important biochemical reactions involving, for example, proteins.

Animals↗

PubMed1985

Investigations on antipyrine metabolism V. Differentiation of two isomeric hydroxyantipyrine glucuronides by field desorption and fast atom bombardment mass spectrometry.

The glucuronide conjugates of the two isomeric antipyrine phase I metabolites of antipyrine in man, 4-hydroxyantipyrine and 3-hydroxymethylantipyrine have been analysed by field desorption and fast atom bombardment mass spectrometry. These isomers could be clearly distinguished on the basis of their fragmentation behaviour which was found to correlate with that observed under pyrolysis electron impact conditions.

Antipyrine↗

PubMed1988

Direct chemical ionization-pattern recognition: characterization of bacteria and body fluid profiling.

Direct chemical ionization is ideally suited for profiling purposes because it is a relatively soft ionization method, easy to operate, reproducible and with a high sample throughput. Moreover, for non-volatile matrices the method combines pyrolysis with an optimal pyrolysate transfer to the ionization region enabling the detection of high molecular weight compounds. Application of the technique to urine analysis of women with a premenstrual syndrome and characterization of Salmonella bacteria illustrates its usefulness. Optimal information extraction from the profiles is, because of their complex nature, only possible using pattern recognition techniques. A new approach based on the data analysis of trend spectra is discussed.

Bacteria↗

PubMed1991

Application of FRIT fast atom bombardment liquid chromatography/mass spectrometry for the determination of acetylcholine levels in rat brain regions.

This report describes the use of FRIT fast atom bombardment (FAB) liquid chromatography/mass spectrometry for the analysis of acetylcholine in rat brain regions. Direct assessment of acetylcholine levels is possible without the need for either derivatization or extensive sample preparation. Quantification is accomplished by monitoring intact molecular cations of acetylcholine and a deuterated internal standard. The results are compared with those obtained by conventional pyrolysis gas chromatography/mass spectrometry and by liquid chromatography with electrochemical detection.

Acetylcholine↗

PubMed2005

Templated ceramic microstructures by using the breath-figure method.

We describe the synthesis of two cyclobutadiene(cyclopentadienyl)cobalt-containing poly(p-phenylene ethynylene)s (PPEs) and their use as precursors for stable ceramic surface coatings. Organometallic PPEs were shaped into hexagonally ordered assemblies by using the breath-figure method. Such breath figures can be washed away with an appropriate solvent. Upon pyrolysis at 500 degrees C under either nitrogen or air, the bubble arrays persist as ceramics and are insoluble in organic solvents or water. The formed pyrolyzed bubble arrays were analyzed by optical and scanning electron microscopy, as well as energy dispersive X-ray microanalysis (EDX). The composition of the ceramic materials is discussed based on EDX and IR data.

Journal Article↗