Ion mobility (IM) is now a well-established and fast analytical technique. The IM hardware constantly being improved, especially in terms of the resolving power. Drift Tube (DTIMS), Traveling Wave (TWIMS), Trapped Mobility Spectrometry (TIMS) coupled to mass spectrometry are used determine Collision Cross-Sections (CCS) ions. In chemistry, CCS approached as descriptor for ion identification it also physical chemistry 3D structure elucidation with computational support. extracted from reduced...

We have probed for reaction intermediates involved in the dual-gold-catalyzed activation of a conjugated 1,5-diyne substrate and its further coupling to benzene liquid phase. This was done by sampling mixture electrospray ionization followed high-resolution ion mobility mass spectrometry—under conditions allowing resolution structural isomers differing their collision cross sections less than 0.5%. For cationic corresponding catalyst + diyne (activation stage) we resolve four isomers. At...

Over the years, polymer analyses using ion mobility-mass spectrometry (IM-MS) measurements have been performed on different mobility (IMS) setups. In order to be able compare literature data taken IM(-MS) instruments, heating and temperature evaluations already explored. Nevertheless, extrapolations other analytes are difficult thus straightforward same-sample instrument comparisons seem only reliable way make sure that setups do not greatly change gas-phase behavior. We used a large range...

Ion mobility-mass spectrometry (IM-MS) has emerged as a powerful separation and identification tool to characterize synthetic polymer mixtures topologies (linear, cyclic, star-shaped,…). Electrospray coupled IM-MS already revealed the coexistence of several charge state-dependent conformations for single state biomolecules with strong intramolecular interactions, even when limited resolving power instruments were used. For polymers, sample's polydispersity allows observation chain lengths. A...

Disulfide bonds are post-translationnal modifications that can be crucial for the stability and biological activities of natural peptides. Considering importance these disulfide bond-containing peptides, development new techniques in order to characterize is great interest. For this purpose, collision cross cections (CCS) a large data set 118 peptides (displaying various sequences) bearing zero, one, two, or three bond(s) have been measured study at different charge states using ion...

We report the use of ion mobility mass spectrometry (IMMS) and energy-resolved collisional activation to investigate gas-phase reactions protonated aniline phenol. Protonated prototropic tautomerization nucleophilic substitution (SN1) produce phenol with traces water in IMMS cell are reported. Tautomerization its ability form presence ammonia gas phase also observed. These results supported by energy landscapes obtained from computational chemistry. structure modifications affected measured...

Disulfide bonds between cysteine residues are commonly involved in the stability of numerous peptides and proteins crucial for providing biological activities. In such peptides, appropriate connectivity ensures proper conformation allowing an efficient binding to their molecular targets. bond characterization is still challenging a critical issue analysis structured peptides/proteins targeting pharmaceutical or pharmacological utilizations. This study describes development new fast gas-phase...

Abstract Ion mobility spectrometry (IMS) is a gas‐phase separation technique based on ion differences in an electric field. It largely used for the detection of specific ions such as small molecule explosives. IMS system includes use e. g. Faraday cupor mass (MS). The presence interfering signals standalone may lead to false positives or negatives due lacking resolving power. In this case, selective shifts obtained using shift reagents (SR), i. ligands complexing target, can bring help....

Experimental ion mobility-mass spectrometry (IM-MS) results are often correlated to three-dimensional structures based on theoretical chemistry calculations. The bottleneck of this approach is the need for accurate values, both experimentally and theoretically predicted. Here, we continue development trend-based analyses extract structural information from experimental IM-MS data sets. collision cross-sections (CCSs) synthetic systems such as homopolymers small ionic clusters investigated in...

Plasma-induced free-radical polymerizations rely on the formation of radical species to initiate polymerization, leading some extent monomer fragmentation. In this work, plasma-induced polymerization an allyl ether-substituted six-membered cyclic carbonate (A6CC) is demonstrated and emphasizes retention moieties. Taking advantage low tendency monomers, characterization oligomeric studied obtain insights into effect plasma exposure inducing polymerization. less than 5 min exposure, a...

Disulfide connectivity in peptides bearing at least two intramolecular disulfide bonds is highly important for the structure and biological activity of peptides. In that context, analytical strategies allowing a characterization cysteine pairing are prime interest chemists, biochemists, biologists. For purpose, this study evaluates potential MALDI in-source decay (ISD) characterizing pairs through systematic analysis identical bonds, but not same connectivity. Three different matrices have...

Polymer characterizations are often performed using mass spectrometry (MS). Aside from MS and different tandem (MS/MS) techniques, ion mobility-mass (IM-MS) has been recently added to the inventory of characterization technique. However, only few studies have focused on reproducibility robustness polymer IM-MS analyses. Here, we perform collisional electron-mediated activation ions before measuring IM drift times, collision cross-sections (CCS), or reduced mobilities (K0). The resulting...

When polymer mixtures become increasingly complex, the conventional analysis techniques insufficient for complete characterization. Mass spectrometric can satisfy this increasing demand detailed sample Even though isobaric polymers are indistinguishable using simple mass spectrometry (MS) analyses, more advanced such as tandem MS (MS/MS) or ion mobility (IM) be used. Here, we report proof of concept characterizing isomeric polymers, namely poly(2-n-propyl-2-oxazoline) (Pn-PrOx) and...

Lipid screening of biological substrates is an important step during biomarker detection and identification.

The two-dimensional shape information yielded by ion mobility-mass spectrometry (IM-MS), usually reported as collision cross section (CCS), is often correlated to the underlying three-dimensional structures of ions through computational chemistry. Here, we used theoretical approaches based on molecular mechanics (MM), dynamics (MD), and density functional theory (DFT) elucidate sodiated poly(ethoxy phosphate) polymer at different degrees polymerization (DP) for three charge states (1+, 2+,...

In the past, we developed a method inferring physicochemical properties from ion mobility mass spectrometry (IM-MS) data polydisperse synthetic homopolymers. We extend here to biomolecules that are generally monodisperse. Similarities in IM-MS behavior were illustrated on proteins and peptides. This allows one identify ionic species for which intramolecular interactions lead specific structures.

Ion mobility–mass spectrometry (IM-MS) experiments are mostly used hand in with computational chemistry to correlate mobility measurements the shape of ions. Recently, we developed an automatable method fit IM data obtained synthetic homopolymers (i.e., collision cross sections; CCS) without resorting chemistry. Here, further develop experimental interpretation explore physicochemical properties a series nine polymers and their monomer units by monitoring relationship between CCS degree...

Experimental ion mobility-mass spectrometry (IM-MS) results are often correlated to three-dimensional structures owing theoretical chemistry calculations. The bottleneck of this approach is the need for accurate values, both experimentally and theoretically predicted. Here, we analyze experimental collision cross-section (CCS) evolutions instead interpreting absolute CCS values. Experimentally, trends synthetic homopolymers analyzed as a function increasing degrees polymerization (DP)...