Site specific gas-phase protonation of 2-t-butylmaleates and 2-t-butylsuccinates upon chemical ionization: stereochemical effects and kinetic control

1989 ◽  
pp. 331 ◽  
Author(s):  
Adrian Weisz ◽  
Miriam Cojocaru ◽  
Asher Mandelbaum
Keyword(s):  
Gas Phase ◽  
Chemical Ionization ◽  
Kinetic Control ◽  
Site Specific

Ion chemistry of second-row transition metals in hydrocarbon flames: cations and anions of Y, Zr, Nb, and Mo

1995 ◽  
Vol 73 (12) ◽  
pp. 2263-2271 ◽  
Author(s):  
Christine C.Y. Chow ◽  
John M. Goodings
Keyword(s):  
Transition Metals ◽  
Gas Phase ◽  
Atmospheric Pressure ◽  
Chemical Ionization ◽  
Negative Ions ◽  
Ion Concentration ◽  
Oxidation States ◽  
Metallic Ions ◽  
Ion Chemistry ◽  
Hydrocarbon Flames

A pair of laminar, premixed, CH4–O2 flames above 2000 K at atmospheric pressure, one fuel-rich (FR) and the other fuel-lean (FL), were doped with ~10−6 mol fraction of the second-row transition metals Y, Zr, Nb, and Mo. Since these hydrocarbon flames contain natural ionization, metallic ions were produced in the flames by the chemical ionization (CI) of metallic neutral species, primarily by H3O+ and OH− as CI sources. Both positive and negative ions of the metals were observed as profiles of ion concentration versus distance along the flame axis by sampling the flames through a nozzle into a mass spectrometer. For yttrium, the observed ions include the YO+•nH2O (n = 0–3) series, and Y(OH)4−. With zirconium, they include the ZrO(OH)+•nH2O (n = 0–2) series, and ZrO(OH)3−. Those observed with niobium were the cations Nb(OH)3+ and Nb(OH)4+, and the single anion NbO2(OH)2−. For molybdenum, they include the cations MoO(OH)2+ and MoO(OH)3+, and the anions MoO3− and MoO3(OH)−. Not every ion was observed in each flame; the FL flame tended to favour the ions in higher oxidation states. Also, flame ions in higher oxidation states were emphasized for these second-row transition metals compared with their first-row counterparts. Some ions written as members of hydrate series may have structures different from those of simple hydrates; e.g., YO+•H2O = Y(OH)2+ and ZrO(OH)+•H2O = Zr(OH)3+, etc. The ion chemistry for the production of these ions by CI in flames is discussed in detail. Keywords: transition metals, ions, flame, gas phase, negative ions.

scholarly journals State-of-the-Art Native Mass Spectrometry and Ion Mobility Methods to Monitor Homogeneous Site-Specific Antibody-Drug Conjugates Synthesis

2021 ◽  
Vol 14 (6) ◽  
pp. 498
Author(s):  
Evolène Deslignière ◽  
Anthony Ehkirch ◽  
Bastiaan L. Duivelshof ◽  
Hanna Toftevall ◽  
Jonathan Sjögren ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Ion Mobility ◽  
State Of The Art ◽  
Native Mass Spectrometry ◽  
Site Specific ◽  
Drug Conjugates ◽  
Conjugation Process ◽  
Antibody Drug

Antibody-drug conjugates (ADCs) are biotherapeutics consisting of a tumor-targeting monoclonal antibody (mAb) linked covalently to a cytotoxic drug. Early generation ADCs were predominantly obtained through non-selective conjugation methods based on lysine and cysteine residues, resulting in heterogeneous populations with varying drug-to-antibody ratios (DAR). Site-specific conjugation is one of the current challenges in ADC development, allowing for controlled conjugation and production of homogeneous ADCs. We report here the characterization of a site-specific DAR2 ADC generated with the GlyCLICK three-step process, which involves glycan-based enzymatic remodeling and click chemistry, using state-of-the-art native mass spectrometry (nMS) methods. The conjugation process was monitored with size exclusion chromatography coupled to nMS (SEC-nMS), which offered a straightforward identification and quantification of all reaction products, providing a direct snapshot of the ADC homogeneity. Benefits of SEC-nMS were further demonstrated for forced degradation studies, for which fragments generated upon thermal stress were clearly identified, with no deconjugation of the drug linker observed for the T-GlyGLICK-DM1 ADC. Lastly, innovative ion mobility-based collision-induced unfolding (CIU) approaches were used to assess the gas-phase behavior of compounds along the conjugation process, highlighting an increased resistance of the mAb against gas-phase unfolding upon drug conjugation. Altogether, these state-of-the-art nMS methods represent innovative approaches to investigate drug loading and distribution of last generation ADCs, their evolution during the bioconjugation process and their impact on gas-phase stabilities. We envision nMS and CIU methods to improve the conformational characterization of next generation-empowered mAb-derived products such as engineered nanobodies, bispecific ADCs or immunocytokines.

Newly developed instrumentation for measuring highly oxidized molecules at atmospheric pressure

2021 ◽  
Author(s):  
Paap Koemets ◽  
Sander Mirme ◽  
Kuno Kooser ◽  
Heikki Junninen
Keyword(s):  
Gas Phase ◽  
Atmospheric Chemistry ◽  
Atmospheric Pressure ◽  
Chemical Ionization ◽  
Measurement Technology ◽  
Differential Mobility Analyzer ◽  
Neutral Cluster ◽  
Differential Mobility ◽  
Alpha Pinene ◽  
Ambient Measurements

<p>The Highly Oxidized Molecule Ion Spectrometer (HOMIS) is a novel instrument for measuring the total concentration of highly oxidized molecules (HOM-s) (Bianchi et al., 2019) at atmospheric pressure. The device combines a chemical ionization charger with a multi-channel differential mobility analyzer. The chemical ionization charger is based on the principles outlined by Eisele and Tanner (1993). The charger is attached to a parallel differential mobility analyzer identical to the ones used in the Neutral cluster and Air Ion Spectrometer (NAIS, Mirme 2011), but with modified sample and sheath air flow rates to improve the mobility resolution of the device. The complete mobility distribution in the range from 3.2 to 0.056 cm<sup>2</sup>/V/s is measured simultaneously by 25 electrometers. The range captures the charger ions, monomers, dimers, trimers but also extends far towards larger particles to possibly detect larger HOM-s that have not been measured with existing instrumentation. The maximum time resolution of the device is 1 second allowing it to detect rapid changes in the sample. The device has been designed to be easy to use, require little maintenance and work reliably in various environments during long term measurements.</p><p>First results of the prototype were acquired from laboratory experiments and ambient measurements. Experiments were conducted at the Laboratory of Environmental Physics, University of Tartu. The sample was drawn from a reaction chamber where alpha-pinene and ozone were introduced. Initial results show a good response when concentrations of alpha-pinene and ozone were changed. </p><p>Ambient measurements were conducted at the SMEAR Estonia measurement station in a hemiboreal forest for 10 days in the spring and two months in the winter of 2020. The HOMIS measurements were performed together with a CI-APi-TOF (Jokinen et al., 2012).</p><p> </p><p>References:</p><p>Bianchi, F., Kurtén, T., Riva, M., Mohr, C., Rissanen, M. P., Roldin, P., Berndt, T., Crounse, J. D., Wennberg, P. O., Mentel, T. F., Wildt, J., Junninen, H., Jokinen, T., Kulmala, M., Worsnop, D. R., Thornton, J. A., Donahue, N., Kjaergaard, H. G. and Ehn, M. (2019), “Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol”, Chemical Reviews, 119, 6, 3472–3509</p><p>Eisele, F. L., Tanner D. J. (1993), “Measurement of the gas phase concentration of H2SO4 and methane sulfonic acid and estimates of H2SO4 production and loss in the atmosphere”, JGR: Atmospheres, 98, 9001-9010</p><p>Jokinen T., Sipilä M., Junninen H., Ehn M., Lönn G., Hakala J., Petäjä T., Mauldin III R. L., Kulmala M., and Worsnop D. R. (2012), “Atmospheric sulphuric acid and neutral cluster measurements using CI-APi-TOF”, Atmospheric Chemistry and Physics, 12, 4117–4125</p><p>Mirme, S. (2011), “Development of nanometer aerosol measurement technology”, Doctoral thesis, University of Tartu</p>

scholarly journals Chemical ionization mass spectrometry (CIMS) may not measure all gas-phase sulfuric acid if base molecules are present

2010 ◽  
Vol 10 (12) ◽  
pp. 30539-30568
Author(s):  
T. Kurtén ◽  
T. Petäjä ◽  
J. Smith ◽  
I. K. Ortega ◽  
M. Sipilä ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Sulfuric Acid ◽  
Gas Phase ◽  
Chemical Ionization ◽  
Measurement Data ◽  
Ionization Mass Spectrometry ◽  
Chemical Ionization Mass Spectrometry ◽  
Ionization Mass ◽  
Proton Affinities ◽  
Reaction Thermodynamics

Abstract. The state-of-the art method for measuring atmospheric gas-phase sulfuric acid is chemical ionization mass spectrometry (CIMS) based on nitrate reagent ions. Using computed proton affinities and reaction thermodynamics for the relevant charging reactions, we show that in the presence of strong bases such as amines, which tend to cluster with the sulfuric acid molecules, a significant fraction of the total gas-phase sulfuric acid may not be measured by a CIMS instrument. If this is the case, this effect has to be taken into account in the interpretation of atmospheric sulfuric acid measurement data, as well as in intercomparison of different CIMS instruments, which likely have different susceptibilities to amine-sulfuric acid clustering.

scholarly journals Formation of Highly Oxygenated Low-Volatility Products from Cresol Oxidation

2016 ◽  
Author(s):  
Rebecca H. Schwantes ◽  
Katherine A. Schilling ◽  
Renee C. McVay ◽  
Hanna Lignell ◽  
Matthew M. Coggon ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Ring Opening ◽  
Chemical Ionization ◽  
First Generation ◽  
Direct Analysis ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Ionization Mass ◽  
Particle Phase

Abstract. Hydroxyl radical (OH) oxidation of toluene produces the ring-retaining products cresol and benzaldehyde, and the ring-opening products bicyclic intermediate compounds and epoxides. Here, first- and later-generation OH oxidation products from cresol and benzaldehyde are identified in laboratory chamber experiments. For benzaldehyde, first-generation ring-retaining products are identified, but later-generation products are not detected. For cresol, low-volatility (saturation mass concentration, C* ~ 3.5 × 104–7.7 × 10−3 μg m−3) first- and later-generation ring-retaining products are identified. Subsequent OH addition to the aromatic ring of o-cresol leads to compounds such as hydroxy, dihydroxy, and trihydroxy methyl benzoquinones and dihydroxy, trihydroxy, tetrahydroxy, and pentahydroxy toluenes. These products are detected in the gas phase by chemical ionization mass spectrometry (CIMS) and in the particle phase using offline direct analysis in real time mass spectrometry (DART-MS). Our data suggest that the yield of trihydroxy toluene from dihydroxy toluene is substantial. While an exact yield cannot be reported as authentic standards are unavailable, we find that a yield for trihydroxy toluene from dihydroxy toluene of ~ 0.7 (equal to the yield of dihydroxy toluene from o-cresol) is consistent with experimental results for o-cresol oxidation under low-NO conditions. These results suggest that even though the cresol pathway accounts for only ~ 20 % of the oxidation products of toluene, it is the source of a significant fraction (~ 20–40 %) of toluene secondary organic aerosol (SOA) due to the formation of low-volatility products.

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