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71.
Ion/molecule reactions were explored in a newly developed miniature mass spectrometer fitted with a rectilinear ion trap (RIT) mass analyzer. The tandem mass spectrometry performance of this instrument is demonstrated using collision induced dissociation (CID) and ion/molecule reactions. The latter includes Eberlin transacetalization reactions and electrophilic additions. Selective detection of the chemical warfare simulant dimethyl methyl phosphonate (DMMP) was achieved through selective Eberlin reactions of its characteristic phosphonium fragment ion CH3OP(+)(O)CH3 (m/z 93), with 1,4-dioxane or 1,3-dioxolane. Efficient adduct formation as a result of electrophilic attack by the phosphonium ion on various nucleophilic reagents, including 1,1,3,3-tetramethyl urea, methanesulfonic acid methyl ester, dimethyl sulfoxide and methyl salicylate, was also observed using the RIT device. The product ions of these reactions were analyzed using CID and the characteristic fragmentation patterns of the ionic addition products were recorded using multiple-stage experiments in the miniature RIT instrument. This study clearly demonstrates that a small, home-built, miniature RIT mass spectrometer can be used to perform analytically useful ion/molecule reactions and also that instruments like this have the potential to provide a portable platform for in situ detection of organophosphorus esters and related compounds with high specificity using tandem mass spectrometry. 相似文献
72.
Virginie Gueu Hongpeng You Tomokatsu Hayakawa Masayuki Nogami 《Journal of Sol-Gel Science and Technology》2007,41(3):231-236
Fluorescence and spectral hole burning properties of Eu3+ ions were studied in nanocrystals-precipitated SnO2-SiO2 glasses. The glasses were prepared to contain various amount of Eu2O3 using the sol-gel method, in which SnO2 nanocrystals were precipitated by heating in air. In the glasses containing Eu2O3 less than 1%, the Eu3+ ions were preferentially doped in the SnO2 nanocrystals and their fluorescence intensities were enhanced by the energy transfer due to the recombination of electrons
and holes excited in SnO2 crystals. The SnO2 nanocrystals-precipitated glasses exhibited the persistent spectral holes with the depth of ∼25% of the total fluorescence
intensities of the Eu3+ ions. With the increasing Eu2O3 concentration, the amount of SnO2 nanocrystals decreased and the Sn4+ ions formed the random glass structure together with the silica network. This structure change induced the fluorescence intensities
and the hole depth to decrease. 相似文献
73.
W.Franklin Smyth Clare Joyce Venkataraman N. Ramachandran Edmund O’Kane Danny Coulter 《Analytica chimica acta》2004,506(2):203-214
The electrospray ionisation-ion trap mass spectrometry (ESI-MSn) of selected hypnotic drugs, i.e. zopiclone, zolpidem, flunitrazepam and their metabolites have been investigated. Sequential product ion fragmentation experiments (MSn) have been performed in order to elucidate the degradation pathways for the [M+H]+ ions and their predominant fragment ions. These MSn experiments show certain characteristic fragmentations in that functional groups are generally cleaved from the ring systems as neutral molecules such as H2O, CO, CO2, NO2, amines and HF. When an aromatic entity is present in a drug molecule together with a nitrogen-containing saturated ring structure as with zopiclone and its N-desmethyl metabolite fragmentation initially occurs at the latter ring with the former being resistant to fragmentation. The structures of fragment ions proposed for ESI-MSn can be supported by electrospray ionisation-quadrupole time-of-flight mass spectrometry (ESI-QTOF-MS).These molecules can be identified and determined in mixtures at low ng/ml concentrations by the application of liquid chromatography (LC)-ESI-MSn which can be used for their analysis in saliva samples.This paper includes a tabulation of mass losses/signals at low m/z values for these hypnotic drugs and many others in recent publications which will be of value in the characterisation of drug metabolites of unknown structure and also natural product pharmaceuticals isolated from plants, etc. 相似文献
74.
Determination of trichothecenes in cereals by gas chromatography with ion trap detection 总被引:1,自引:0,他引:1
Summary A method for determination of the trichothecene toxins, deoxynivalenol, 3α-acetyl-deoxynivalenol, nivalenol, T-2 toxin, HT-2
toxin and diacetoxyscirpenol in cereals (wheat, barley, oats, corn) is described. Extraction was performed according to Tanaka
et al. (J. Chromatogr.328, 271 (1985)) [33], derivatization by trifluoroacylation with trifluoroacetic acid anhydride. For quantitation and confirmation
a capillary gas chromatograph combined with a selective mass detector (ion trap) working in CI-mode with methanol as reagent
gas was used. The quantitation limit for the complete method is 1–5 μg/kg, depending on the chemical characteristics of each
toxin and cleanness of the extracts. Recoverics from spiked cereals were 78–89%. 相似文献
75.
This study examines the reagent gas pressure and ion source temperature dependence for dimethyl ether chemical ionization (DME CI) mass spectra recorded with an external source ion trap mass spectrometer (ITMS). Information for better controls of the reagent gas pressure in order to obtain fair CI spectra is provided. The origin of M+? ions observed in DME CIMS is discussed in detail. Furthermore, the ion source temperature effect on the DME CI is also investigated. 相似文献
76.
Studies on photo-catalytic reduction of CO2 using TiO2 photo-catalyst (0.1%, w/v) as a suspension in water was carried out at 350 nm light. CO2 from both commercially available source, as well as generated in situ through 2-propanol oxidation, was used for this study. The photolytic products such as hydrogen (H2), carbon monoxide (CO) andmethane (CH4) generated were monitored in TiO2 suspended aqueous solution with and without a hole scavenger, viz., 2-propanol. Similar photolytic experiments were also carried out with varying ambient such as air, O2, N2 and N2O. The yields of CO and CH4 in all these systems under the present experimental conditions were found to be increasing with light exposure time. H2 yield in N2-purged systems containing 2-propanol was found to be more as compared to the without 2-propanol system. The rate of H2 production in N2-purged aqueous solutions containing 0.1% TiO2 suspension were evaluated to be 0.226 and 5.8 μl/h, without and with 0.5 M 2-propanol, respectively. This confirmed that
2-propanol was an efficient hole scavenger and it scavenged photo-generated holes (h+), allowing its counter ion, viz., e−, to react with water molecule/H+ to yield more H2. The formation of both CO and CH4 in the photolysis of CO2-purged aqueous solutions containing suspended TiO2 in absence of 2-propanol reveal that the generation of CH4 is taking place mainly through CO intermediate. In presence of air/O2, the yield of H2 in the system without 2-propanol was observed to be negligible as compared to the system containing 2-propanol in which low
yield of H2 was obtained with a formation rate of approx. 0.5 μl/h. 相似文献
77.
X射线辐照前后,在BaF(Cl,Br):Sm^2+中以560nm的Nd:YAG脉冲光在液氮温度下进行了双光子烧孔实验和光激励发光实验,结果表明,Sm^2+掺杂的碱土金属氟卤化物光谱烧孔过程中伴随着光激励发光过程,这一过程直接影响光谱烧孔过程的进行。 相似文献
78.
Kolárová L Holcapek M Jambor R Dostál L Nádvorník M Růzicka A 《Journal of mass spectrometry : JMS》2004,39(6):621-629
Electrospray ionization (ESI) mass spectrometry was applied to the structural analysis of 23 2,6-[bis(alkyloxy)methyl]phenyltin(IV) derivatives. The mass spectra were measured in both polarity modes and multistage tandem mass spectrometric (MS(n)) measurements were performed on the ion trap analyser for positively charged tin-containing ions. The sum of complementary ions observed in the positive-ion mode (i.e. [M-R(3)](+) ion) and in the negative-ion mode (i.e. [R(3)](-) ion) permits molecular mass determination in spite of the fact that the molecular adducts were often missing even in the first-order mass spectra. The subsequent fragmentation of [M-R(3)](+) ions studied by MS(n) and the correlation of observed fragment ions with the expected structures of synthesized organotin(IV) compounds allowed us to understand the fragmentation behaviour and the mechanism of the ion formation for studied compounds. The typical neutral losses are alkenes, alcohols and aldehydes. The fragmentation pattern of one selected compound was supported by MS(n) measurements of an isotopically labelled analogue to confirm unusual ion-molecule reactions of some fragment ions with water in the ion trap. 相似文献
79.
The recently proposed electron-hole potential (EHP) method for excited states is extended to the multi-configurational case. The variation equation is solved using the quadratic convergence method. The EHP methods are shown to be approximations to the complete singly excited configuration interaction (CSECI) in the variational sense. Extended Brillouin theorems are proved for the EHP methods. The excitation energies and wave functions obtained by one and two configurational EHP methods agree well with those of the CSECI method. The EHP methods have clear advantage in the computer time requirement over the CI method and are especially suited for a calculation of approximate excited states of large molecules. The EHP methods are applicable to excited states which belong to the same irreducible representation as the ground state. 相似文献
80.
Ion-molecule reactions between the O=P(OCH(3))(2) (+) phosphonium ions and five aliphatic esters (methyl acetate, methyl propionate, methyl 2-methylpropionate, methyl butyrate and ethyl acetate) were performed in a quadrupole ion trap mass spectrometer. The O=P(OCH(3))(2) (+) phosphonium ions, formed by electron ionization from neutral trimethyl phosphite, were found to react with aliphatic esters to give an adduct ion [RR'CHCOOR", O=P(OCH(3))(2)](+), which loses spontaneously a molecule of ketene CH(2)=CO or substituted ketenes RR'C=CO. Isotope-labeled methyl acetate was used to elucidate fragmentation mechanisms. The potential energy surface obtained from B3LYP/6-31G(d,p) calculations for the reaction between O=P(OCH(3))(2) (+) and methyl acetate is described. 相似文献