Effects of nitrate and water on the oxygen isotopic analysis of barium sulfate precipitated from water samples

BaSO₄ precipitated from mixed salt solutions by common techniques for SO isotopic analysis may contain quantities of H₂O and NO that introduce errors in O isotope measurements. Experiments with synthetic solutions indicate that δ¹⁸O values of CO produced by decomposition of precipitated BaSO₄ in a carbon reactor may be either too low or too high, depending on the relative concentrations of SO and NO and the δ¹⁸O values of the H₂O, NO, and SO. Typical δ¹⁸O errors are of the order of 0.5 to 1‰ in many sample types, and can be larger in samples containing atmospheric NO, which can cause similar errors in δ¹⁷O and Δ¹⁷O. These errors can be reduced by (1) ion chromatographic separation of SO from NO, (2) increasing the salinity of the solutions before precipitating BaSO₄ to minimize incorporation of H₂O, (3) heating BaSO₄ under vacuum to remove H₂O, (4) preparing isotopic reference materials as aqueous samples to mimic the conditions of the samples, and (5) adjusting measured δ¹⁸O values based on amounts and isotopic compositions of coexisting H₂O and NO. These procedures are demonstrated for SO isotopic reference materials, synthetic solutions with isotopically known reagents, atmospheric deposition from Shenandoah National Park, Virginia, USA, and sulfate salt deposits from the Atacama Desert, Chile, and Mojave Desert, California, USA. These results have implications for the calibration and use of O isotope data in studies of SO sources and reaction mechanisms. Published in 2008 by John Wiley & Sons, Ltd.     

Comparison of the silver nitrate and bacterial denitrification methods for the determination of nitrogen and oxygen isotope ratios of nitrate in surface water

Nitrogen (N) and oxygen (O) isotope ratios of NO are often used to trace dominant NO pollution sources in water. Both the silver nitrate (AgNO₃) method and the bacterial denitrification method are frequently used analytical techniques to determine δ¹⁵N‐ and δ¹⁸O‐NO in aqueous samples. The AgNO₃ method is applicable for freshwater and requires a concentration of 100–200 µmol of NO for isotope determination. The bacterial denitrification method is applicable for seawater and freshwater and for KCl extracts of soils with a NO concentration as low as 1 µmol. We have carried out a thorough method comparison using 42 real surface water samples having a wide range of δ¹⁵N‐ and δ¹⁸O‐NO values and NO concentrations. Various correction pairs using three international references and blanks were used to correct raw δ¹⁵N‐ and δ¹⁸O‐NO values. No significant difference between the corrected data was observed when using various correction pairs for each analytical method. Both methods also showed excellent repeatability with high intraclass correlation coefficients (ICC). The ICC of the AgNO₃ method was 0.992 for δ¹⁵N and 0.970 for δ¹⁸O. The ICC of the bacterial denitrification method was 0.995 for δ¹⁵N and 0.954 for δ¹⁸O. Moreover, a positive linear relationship with a high correlation coefficient (r ≥ 0.88) between the two methods was found for δ¹⁵N‐ and δ¹⁸O‐NO. The comparability of the methods was assessed by the Bland‐Altman technique using 95% limits of agreement. The average difference between results obtained by the bacterial denitrification and the AgNO₃ method for δ¹⁵N was ?1.5‰ with 95% limits of agreement ?3.6 and +0.5‰. For δ¹⁸O this was +2.0‰, with 95% limits of agreement ?3.3 and +7.3‰. We found that for δ¹⁵N and for δ¹⁸O, 97% of the differences fell within these 95% limits of agreement. In conclusion, the AgNO₃ and the bacterial denitrification methods are highly correlated and statistically interchangeable. Copyright © 2010 John Wiley & Sons, Ltd.     

Contribution of atmospheric nitrate to stream‐water nitrate in Japanese coniferous forests revealed by the oxygen isotope ratio of nitrate

Evaluation of the openness of the nitrogen (N) cycle in forest ecosystems is important in efforts to improve forest management because the N supply often limits primary production. The use of the oxygen isotope ratio (δ¹⁸O) of nitrate is a promising approach to determine how effectively atmospheric nitrate can be retained in a forest ecosystem. We investigated the δ¹⁸O of nitrate in stream water in order to estimate the contribution of atmospheric NO in stream‐water NO (f_atm) from 26 watersheds with different stand ages (1–87 years) in Japan. The stream‐water nitrate concentrations were high in young forests whereas, in contrast, old forests discharged low‐nitrate stream water. These results implied a low f_atm and a closed N cycle in older forests. However, the δ¹⁸O values of nitrate in stream water revealed that f_atm values were higher in older forests than in younger forests. These results indicated that even in old forests, where the discharged N loss was small, atmospheric nitrate was not retained effectively. The steep slopes of the studied watersheds (>40°) which hinder the capturing of atmospheric nitrate by plants and microbes might be responsible for the inefficient utilization of atmospheric nitrate. Moreover, the unprocessed fraction of atmospheric nitrate in the stream‐water nitrate in the forest (f_unprocessed) was high in the young forest (78%), although f_unprocessed was stable and low for other forests (5–13%). This high f_unprocessed of the young forest indicated that the young forest retained neither atmospheric NO nor soil NO effectively, engendering high stream‐water NO concentrations. Copyright © 2010 John Wiley & Sons, Ltd.     

Laser ablation of AgSbS2 and cluster analysis by time‐of‐flight mass spectrometry

Thin films of AgSbS₂ are important for phase‐change memory applications. This solid is deposited by various techniques, such as metal organic chemical vapour deposition or laser ablation deposition, and the structure of AgSbS₂(s), as either amorphous or crystalline, is already well characterized. The pulsed laser ablation deposition (PLD) of solid AgSbS₂ is also used as a manufacturing process. However, the processes in plasma have not been well studied. We have studied the laser ablation of synthesized AgSbS₂(s) using a nitrogen laser of 337 nm and the clusters formed in the laser plume were identified. The ablation leads to the formation of various single charged ternary Ag_pSb_qS_r clusters. Negatively charged AgSbS, AgSb₂S, AgSb₂S, AgSb₂S and positively charged ternary AgSbS⁺, AgSb₂S⁺, AgSb₂S, AgSb₂S clusters were identified. The formation of several singly charged Ag⁺, Ag, Ag, Sb, Sb, S ions and binary Ag_pS_r clusters such as AgSb, Ag₃S^?, SbS (r = 1–5), Sb₂S^?, Sb₂S, Sb₃S (r = 1–4) and AgS, SbS⁺, SbS, Sb₂S⁺, Sb₂S, Sb₃S (r = 1–4), AgSb was also observed. The stoichiometry of the clusters was determined via isotopic envelope analysis and computer modeling. The relation of the composition of the clusters to the crystal structure of AgSbS₂ is discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Laser ablation of ternary As‐S‐Se glasses and time‐of‐flight mass spectrometric study

Ternary chalcogenide As‐S‐Se glasses, important for optics, computers, material science and technological applications, are often made by pulsed laser deposition (PLD) technology but the plasma composition formed during the process is mostly unknown. Therefore, the formation of clusters in a plasma plume from different glasses was followed by laser desorption ionization (LDI) or laser ablation (LA) time‐of‐flight mass spectrometry (TOF MS) in positive and negative ion modes. The LA of glasses of different composition leads to the formation of a number of binary As_pS_q, As_pSe_r and ternary As_pS_qSe_r singly charged clusters. Series of clusters with the ratio As:chalcogen = 3:3 (As₃S, As₃S₂Se⁺, As₃SSe), 3:4 (As₃S, As₃S₃Se⁺, As₃S₂Se, As₃SSe, As₃Se), 3:1 (As₃S⁺, As₃Se⁺), and 3:2 (As₃S, As₃SSe⁺, As₃Se), formed from both bulk and PLD‐deposited nano‐layer glass, were detected. The stoichiometry of the As_pS_qSe_r clusters was determined via isotopic envelope analysis and computer modeling. The structure of the clusters is discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

The natural abundance of 15N in plant and soil‐available N indicates a shift of main plant N resources to NO from NH along the N leaching gradient

To investigate which of ammonium (NH) or nitrate (NO) is used by plants at gradient sites with different nitrogen (N) availability, we measured the natural abundance of ¹⁵N in foliage and soil extractable N. Hinoki cypress (Chamaecyparis obtusa Endlicher) planted broadly in Japan was selected for use in this study. We estimated the source proportion of foliar N (NH vs. NO) quantitatively using mass balance equations. The results showed that C. obtusa used mainly NH in N‐limited forests, although the dependence of C. obtusa on NO was greater in other NO‐rich forests. We regarded dissolved organic N (DON) as a potential N source because a previous study demonstrated that C. obtusa can take up glycine. Thus we added DON to our mass balance equations and calculated the source proportion using an isotope‐mixing model (IsoSource model). The results still showed a positive correlation between the calculated plant N proportion of NO and the NO pool size in the soil, indicating that high NO availability increases the reliance of C. obtusa on NO. Our data suggest the shift of the N source for C. obtusa from NH to NO according to the relative availability of NO. They also show the potential of the foliar δ¹⁵N of C. obtusa as an indicator of the N status in forest ecosystems with the help of the δ¹⁵N values of soil inorganic and organic N. Copyright © 2010 John Wiley & Sons, Ltd.     

Error assessment of nitrogen and oxygen isotope ratios of nitrate as determined via the bacterial denitrification method

Currently, bacterial denitrification is becoming the accepted method for δ¹⁵N‐ and δ¹⁸O‐NO determination. However, proper correction methods with international references (USGS32, USGS34 and USGS35) are needed. As a consequence, it is important to realize that the corrected isotope values are derived from a combination of several other measurements with associated uncertainties. Therefore, it is necessary to consider the propagated uncertainty on the final isotope value. This study demonstrates how to correctly estimate the uncertainty on corrected δ¹⁵N‐ and δ¹⁸O‐NO values using a first‐order Taylor series approximation. The bacterial denitrification method errors from 33 batches of 561 surface water samples varied from 0.2 to 2.1‰ for δ¹⁵N‐NO and from 0.7 to 2.3‰ for δ¹⁸O‐NO, which is slightly wider than the machine error, which varied from 0.2 to 0.6‰ for δ¹⁵N‐N₂O and from 0.4 to 1.0‰ for δ¹⁸O‐N₂O. The overall uncertainties, which are composed of the machine error and the method error, for the 33 batches ranged from 0.3 to 2.2‰ for δ¹⁵N‐NO and from 0.8 to 2.5‰ for δ¹⁸O‐NO. In addition, the mean corrected δ¹⁵N and δ¹⁸O values of 132 KNO₃‐IWS (internal working standard) measurements were computed as 8.4 ± 1.0‰ and 25.1 ± 2.0‰, which is a slight underestimation for δ¹⁵N and overestimation for δ¹⁸O compared with the accepted values (δ¹⁵N = 9.9 ± 0.3‰ and δ¹⁸O = 24.0 ± 0.3‰). The overall uncertainty of the bacterial denitrification method allows the use of this method for source identification of NO. Copyright © 2010 John Wiley & Sons, Ltd.     

Laser desorption ionization time‐of‐flight mass spectrometric study of binary As‐Se glasses

Binary chalcogenide As‐Se glasses and their thin films are important for optics, computers, materials science and technological applications. To increase understanding of the properties of thin films fabricated by plasma deposition techniques, more information concerning the physics of plasma plume is needed. In this study the formation of clusters in plasma plume from different As‐Se glasses by laser desorption ionization (LDI) or laser ablation (LA) was studied by time‐of‐flight mass spectrometry (TOF MS) in positive and negative ion modes. Formation of a number of As_pSe_q singly charged clusters As₃Se (q = 1–5), AsSe (q = 1–3), As₂Se (q = 2–4), and As₃Se (q = 2–5) was found from As‐Se glasses with the molar ratio As:Se in the range from 1:2 to 7:3. The stoichiometry of the As_pSe_q clusters was determined via isotopic envelope analysis and computer modeling. The structure of the clusters is proposed and the relationship to the structure of the parent glasses, as also suggested by Raman scattering spectra, is discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Energy‐resolved depth profiling of metal‐polymer interfaces using dynamic quadrupole secondary ion mass spectrometry

Quadrupole secondary ion mass spectrometry (qSIMS) characterization of a metallized polypropylene film used in the manufacturing of capacitors has been performed. Ar⁺ primary ions were used to preserve the oxidation state of the surface. The sample exhibits an incomplete metallization that made it difficult to determine the exact location of the metal‐polymer interface due to the simultaneous contribution of ions with identical m/z values from the metallic and the polymer layers. Energy filtering by means of a 45° electrostatic analyzer allowed resolution of the metal‐polymer interface by selecting a suitable kinetic energy corresponding to the ions generated in the metallized layer but not from the polymer. Under these conditions, selective analyses of isobaric interferences such as ²⁷Al⁺ and ²⁷C₂H or ⁴³AlO⁺ and ⁴³C₃H have been successfully performed. Copyright © 2009 John Wiley & Sons, Ltd.     

δ15N of soil N and plants in a N‐saturated,subtropical forest of southern China

We investigated the δ¹⁵N profile of N (extractable NH, NO, and organic N (EON)) in the soil of a N‐saturated subtropical forest. The order of δ¹⁵N in the soil was EON > NH > NO. Although the δ¹⁵N of EON had been expected to be similar to that of bulk soil N, it was higher than that of bulk soil N by 5‰. The difference in δ¹⁵N between bulk soil N and EON (Δ¹⁵N_bulk‐EON) was correlated significantly with the soil C/N ratio. This correlation implies that carbon availability, which determines the balance between N assimilation and dissimilation of soil microbes, is responsible for the high δ¹⁵N of EON, as in the case of soil microbial biomass δ¹⁵N. A thorough δ¹⁵N survey of available N (NH, NO, and EON) in the soil profiles from the organic layer to 100 cm depth revealed that the δ¹⁵N of the available N forms did not fully overlap with the δ¹⁵N of plants. This mismatch in δ¹⁵N between that of available N and that of plants reflects apparent isotopic fractionation during N uptake by plants, emphasizing the high N availability in this N‐saturated forest. Copyright © 2010 John Wiley & Sons, Ltd.     

Negative ion fragmentations of deprotonated peptides containing post‐translational modifications. An unusual cyclisation/rearrangement involving phosphotyrosine; a joint experimental and theoretical study

The characteristic fragmentations of a pTyr group in the negative ion electrospray mass spectrum of the [M–H]^? anion of a peptide or protein involve the formation of PO (m/z 79) and the corresponding [(M‐H)^?–HPO₃]^? species. In some tetrapeptides where pTyr is the third residue, these characteristic anion fragmentations are accompanied by ions corresponding to H₂PO and [(M‐H)^?–H₃PO₄]^? (these are fragmentations normally indicating the presence of pSer or pThr). These product ions are formed by rearrangement processes which involve initial nucleophilic attack of a C‐terminal ‐CO [or ‐C(?NH)O^?] group at the phosphorus of the Tyr side chain [an S_N2(P) reaction]. The rearrangement reactions have been studied by ab initio calculations at the HF/6‐31+G(d)//AM1 level of theory. The study suggests the possibility of two processes following the initial S_N2(P) reaction. In the rearrangement (involving a C‐terminal carboxylate anion) with the lower energy reaction profile, the formation of the H₂PO and [(M‐H)^?–H₃PO₄]^? anions is endothermic by 180 and 318 kJ mol^?1, respectively, with a maximum barrier (to a transition state) of 229 kJ mol^?1. The energy required to form H₂PO by this rearrangement process is (i) more than that necessary to effect the characteristic formation of PO from pTyr, but (ii) comparable with that required to effect the characteristic α, β and γ backbone cleavages of peptide negative ions. Copyright © 2009 John Wiley & Sons, Ltd.     

Mass spectrometric evidence for collisionally induced removal of H2 from monoanions of 10B nido‐carborane derivatives investigated by electrospray ionization quadrupole linear ion trap and Fourier transform ion cyclotron resonance mass spectrometry

Some newly synthesized ¹⁰B nido‐carborane derivatives, i.e., 7,8‐dicarba‐nido‐undecaborane monoanions ([7‐Me‐8‐R‐C₂B₉H₁₀]^‐K⁺, R = H, butyl, hexyl, octyl and decyl), have been fully characterised and examined by electrospray ionization and Fourier transform ion cyclotron resonance mass spectrometry with liquid chromatographic separation (LC/ESI‐FTICR‐MS). These boron‐containing compounds exhibit abundant molecular ions ([M]^?) at m/z 140.22631 [CB₉H₁₄]^?, m/z 196.28883 [CB₉H₂₂]^?, m/z 224.32032 [CB₉H₂₆]^?, m/z 252.35133 [CB₉H₃₀]^? and m/z 280.38354 [CB₉H₃₄]^? at the normal tube lens voltage setting of ?90 V, which was an instrumental parameter value selected in the tuning operation. Additional [M–nH₂]^? (n = 1?4) ions were observed in the mass spectra when higher tube lens voltages were applied, i.e., ?140 V. High‐resolution FTICR‐MS data revealed the accurate masses of fragment ions, bearing either an even or an odd number of electrons. Collision‐induced dissociation of the [M–nH₂]^? ions (n = 0–4) in the quadrupole linear ion trap (LTQ) analyzer confirmed the loss of hydrogen molecules from the molecular ions. It is suggested that the loss of H₂ molecules from the alkyl chain is a consequence of the stabilization effect of the nido‐carborane charged polyhedral skeleton. Copyright © 2009 John Wiley & Sons, Ltd.     

A fragmentation study of dihydroquercetin using triple quadrupole mass spectrometry and its application for identification of dihydroflavonols in Citrus juices

A mass spectrometric method using electrospray ionization with triple quadrupole and quadrupole time‐of‐flight hybrid (Q‐Tof) mass spectrometry has been applied to the structural characterization of dihydroflavonols. This family of compounds has been studied by liquid chromatography/tandem mass spectrometry (LC/MS/MS) for the first time in this work. A comprehensive study of the product ion MS spectra of the [M+H]⁺ ion of a commercially available standard has been performed. The most useful fragmentations in terms of structural identification are those that involve cleavage of the C‐ring, resulting in diagnostic ions of dihydroflavonol family: ^1,3A, ^1,2B, ^1,2B‐CO, ^0,2A, ^0,2A‐H₂O, ^0,2A‐CO, and ^0,2A‐H₂O‐CO, that allow the characterization of the substituents in the A‐ and B‐rings. In addition to those ions, other product ions due to losses of H₂O and CO molecules from the Y ion were observed. Their fragmentation mechanisms and ion structures have been proposed. The established fragmentation patterns have been used to successfully identity three dihydroflavonols found in tangerine juices for the first time. Copyright © 2009 John Wiley & Sons, Ltd.     

Evidence for the production of NO and N2O in two contrasting subsoils following the addition of synthetic cattle urine

Nitrogenous materials can be transferred out of the topsoil, either vertically to a greater depth, or in lateral pathways to surface waters, and they may also become transformed, with the potential of generating environmentally active agents. We measured the production of NO and N₂O in two contrasting subsoils (70 to 90 cm): one poorly drained and the other freely drained and compared this with the topsoil (0 to 20 cm) of the corresponding soils. The soils were incubated aerobically in jars with subtreatments of either synthetic cattle urine or deionised water and sampled at intervals up to 34 days. ¹⁵N‐NO was used to determine the processes responsible for NO and N₂O production. The headspace was analysed for the concentrations of N₂O, NO and CO₂ and ¹⁵N enrichment of N₂O. The soil samples were extracted and analysed for NO, NO and NH, and the ¹⁵N enrichment of the extracts was measured after conversion into N₂O and N₂. The study demonstrated the potential for NO, N₂O and NO to be generated from subsoils in laboratory incubations. Differences in these N dynamics occurred due to subsoil drainage class. In the freely drained subsoil the rates of NO and NO production were higher than those observed for the corresponding topsoil, with mean maximum production rates of 3.5 µg NO‐N g⁻¹ dry soil on day 16 and 0.12 µg NO‐N g⁻¹ dry soil on day 31. The calculated total losses of N₂O‐N as percentages of the applied synthetic urine N were 0.37% (freely drained subsoil), 0.24% (poorly drained subsoil), 0.43% (freely drained topsoil) and 2.09% (poorly drained topsoil). The calculated total losses of NO‐N as percentages of the applied synthetic urine N were 1.53% (freely drained subsoil), 0.02% (poorly drained subsoil), 0.25% (freely drained topsoil) and 0.08% (poorly drained topsoil). Copyright © 2010 John Wiley & Sons, Ltd.     

Charge stripping C

Measurements of the translational energy loss accompanying the charge-stripping reactions M⁺+N→M²⁺+N+e⁻ and M²⁺+N→M³⁺+N+e⁻ have been performed for C, C and C, C respectively. The energy nesessary to remove the second electron from Buckminsterfullerene was determined, Q=IE(C→C=12.25±0.5 eV.     

Adaptation of a proton transfer reaction mass spectrometer instrument to employ NO+ as reagent ion for the detection of 1,3‐butadiene in the ambient atmosphere

A proton transfer reaction mass spectrometer (PTR‐MS) instrument was adapted to employ NO⁺ as a chemical reagent ion without any hardware changes by switching the reagent ion source gas from water vapor to dry air. Ionization of dry air within the hollow cathode ion source generates a very intense source of NO⁺ with only a minor impurity of NO. The intensities of the primary NO⁺ reagent ion and the unwanted impurity NO are controllable and dependent on the operational conditions of the hollow cathode ion source. Ion source tuning parameters are described, which maintain an intense source of NO⁺ while keeping the impurity NO signal to less than 2% of the total reagent ion intensity. This method is applied to the detection of 1,3‐butadiene. NO⁺ reacts efficiently with 1,3‐butadiene via a charge exchange reaction to produce only the molecular ion, which is detected at m/z 54. Detection sensitivities of the order of 45 pptv for a 1‐s measurement of 1,3‐butadiene are demonstrated. We present the first real‐time on‐line sub parts per billion measurement of 1,3‐butadiene in the ambient atmosphere. The only likely interference is from 1,2‐butadiene. Concurrent measurements of benzene are provided and suggest that the vehicular emissions are the predominant source of 1,3‐butadiene in a suburban Boston area monitoring location. Copyright © 2009 John Wiley & Sons, Ltd.     

Gas‐phase synthesis and detection of the benzenediazonium ion,C6H5N. A joint atmospheric pressure chemical ionization and guided ion beam experiment

An ion of formula C₆H₅N (m/z 105) has been produced by atmospheric pressure chemical ionization (APCI) of benzene and clearly detected in the corresponding positive ion mass spectrum. Its elemental composition has been established by the mass shift at m/z 110 observed when measurements were carried out with hexadeuterated benzene. MS² experiments performed in the ion‐trap analyzer, and guided ion beam (GIB) experiments on the reaction of the phenyl cation with nitrogen molecules, allow us to establish that the detected C₆H₅N ion is the benzenediazonium ion. To the best of our knowledge, this is the first report on the gas‐phase total synthesis of the benzenediazonium ion within the APCI source. Copyright © 2005 John Wiley & Sons, Ltd.     

Gas‐phase formation of protonated benzene during collision‐induced dissociation of certain protonated mono‐substituted aromatic molecules produced in electrospray ionization

Protonated benzene, C₆H, has been studied extensively to understand the structure and energy of a protonated organic molecule in the gas phase. The formation of C₆H is either through direct protonation of benzene, i.e., chemical ionization, or through fragmentation of certain radical cations produced from electron ionization or photon ionization. We report a novel observation of C₆H as a product ion formed in the collision‐induced dissociation (CID) of protonated benzamide and related molecules produced via electrospray ionization (ESI). The formation of C₆H from these even‐electron precursor ions during the CID process, which has not been previously reported, is proposed to occur from the protonated molecules via a proton migration in a five‐membered ring intermediate followed by the cleavage of the mono‐substituent C? C bond and concurrent formation of an ion‐molecule complex. This unique mechanism has been scrutinized by examining some deuterated molecules and a series of structurally related model compounds. This finding provides a convenient mean to generate C₆H, a reactive intermediate of considerable interest, for further physical or chemical investigation. Further studies indicate that the occurrence of C₆H in liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI‐MS/MS) appears to be a rather common phenomenon for many compounds that contain ‘benzoyl‐type’ moieties. Hence, the observation of the C₆H ion in LC/ESI‐MS/MS can be used as an informative fragmentation pathway which should facilitate the identification of a great number of compounds containing the ‘benzoyl‐type’ and similar structural features. These compounds are frequently present in food and pharmaceutical products as leachable impurities that require strict control and rapid elucidation of their identities. Copyright © 2010 John Wiley & Sons, Ltd.     

Experimental and theoretical investigation on binary semiconductor clusters of B/Si and Al/Si

ASi (A = B and Al; n = 1–6) binary cluster anions were generated by laser ablation of samples composed of mixtures of Si and A (A = B and Al), and studied in the gas phase by tandem time‐of‐flight mass spectrometry. Some abundant ions are present in the mass spectrum, indicating that the clusters with these ions have stable structures. The structures of ASi clusters were investigated theoretically by the density functional theory (DFT) method and the energetically lowest‐lying structures were obtained. The binary clusters BSi and AlSi, with the same number of n, share different geometric structures except for ASi with n = 1 and 6, which have the same geometric structures in the ground state. For all the anionic clusters ASi, the lower spin state is lower in energy than the higher spin state in their optimized structures except for the linear ASi^? anions, for which the triplet state is lower in energy than the singlet. Calculations of the bonding energy (BE), energy gain (Δ) and HOMO‐LUMO energy gaps confirm that the cluster ASi has a very stable structure, which agrees well with the experimental results. Copyright © 2007 John Wiley & Sons, Ltd.     

Mass spectrometric investigations of α‐ and β‐cyclodextrin complexes with ortho‐, meta‐ and para‐coumaric acids by negative mode electrospray ionization

The mass spectrometric characterization of aqueous solutions of α‐ and β‐cyclodextrins (CDs) and o‐, m‐ and p‐coumaric acids (CAs) by negative ion electrospray ionization (ESI) indicates that the [CD+CA]^? ions were sourced from the inclusion complex present in solution and from the anion attached to CD molecules formed in the spray processes. The anion adducts formed in the spray process contribute significantly to the signal intensity of an ionized inclusion complex thus overestimating the calculated stability constant (K) of solution‐phase complexes by one to two orders of magnitude. The relative intensities of anion adducts in mass spectra depend on the concentration ratio of the anion and the CD in spray droplets, while the relative intensity of the ionized inclusion complex depends on CD and CA concentrations in solutions and the value of K. Ion Mobility Spectrometry Mass Spectrometry [IMS‐MS] measurements show that the collision cross‐section (Ω) values of the [CD+CA]^? or [(CD)₂₊CA]^2? and [CD+CA] complex ions are 5–6% larger than or equal to CD^? or [CD], respectively. Therefore, in the gas phase the anion adducts [CD+CA^?] on cyclodextrin molecules possess the same conformations as the ionized inclusion complexes [CD+CA]^?. Copyright © 2008 John Wiley & Sons, Ltd.