Spectroscopic study of the benchmark Mn+-H2 complex

We have recorded the rotationally resolved infrared spectrum of the weakly bound Mn+-H2 complex in the H-H stretch region (4022-4078 cm(-1)) by monitoring Mn+ photodissociation products. The band center of Mn+-H2, the H-H stretch transition, is shifted by -111.8 cm(-1) from the transition of the free H2 molecule. The spectroscopic data suggest that the Mn+-H2 complex consists of a slightly perturbed H2 molecule attached to the Mn+ ion in a T-shaped configuration with a vibrationally averaged intermolecular separation of 2.73 A. Together with the measured Mn+...H2 binding energy of 7.9 kJ/mol (Weis, P.; et al. J. Phys. Chem. A 1997, 101, 2809.), the spectroscopic parameters establish Mn+-H2 as the most thoroughly characterized transition-metal cation-dihydrogen complex and a benchmark for calibrating quantum chemical calculations on noncovalent systems involving open d-shell configurations. Such systems are of possible importance for hydrogen storage applications

Wavelength-gated photoreversible polymerization and topology control

We exploit the wavelength dependence of [2 + 2] photocycloadditions and-reversions of styrylpyrene to exert unprecedented control over the photoreversible polymerization and topology of telechelic building blocks. Blue light (λmax = 460 nm) initiates a catalyst-free polymerization yielding high molar mass polymers (Mn = 60 000 g mol-1), which are stable at wavelengths exceeding 430 nm, yet highly responsive to shorter wavelengths. UVB irradiation (λmax = 330 nm) induces a rapid depolymerization affording linear oligomers, whereas violet light (λmax = 410 nm) generates cyclic entities. Thus, different colors of light allow switching between a depolymerization that either proceeds through cyclic or linear topologies. The light-controlled topology formation was evidenced by correlation of mass spectrometry (MS) with size exclusion chromatography (SEC) and ion mobility data. Critically, the color-guided topology control was also possible with ambient laboratory light affording cyclic oligomers, while sunlight activated the linear depolymerization pathway. These findings suggest that light not only induces polymerization and depolymerization but that its color can control the topological outcomes.</p

Structural elucidation of hydroxy fatty acids by photodissociation mass spectrometry with photolabile derivatives

© 2020 John Wiley & Sons, Ltd. Rationale: Eicosanoids are short-lived bio-responsive lipids produced locally from oxidation of polyunsaturated fatty acids (FAs) via a cascade of enzymatic or free radical reactions. Alterations in the composition and concentration of eicosanoids are indicative of inflammation responses and there is strong interest in developing analytical methods for the sensitive and selective detection of these lipids in biological mixtures. Most eicosanoids are hydroxy FAs (HFAs), which present a particular analytical challenge due to the presence of regioisomers arising from differing locations of hydroxylation and unsaturation within their structures. Methods: In this study, the recently developed derivatization reagent 1-(3-(aminomethyl)-4-iodophenyl)pyridin-1-ium (4-I-AMPP+) was applied to a representative set of HFAs including bioactive eicosanoids. Photodissociation (PD) mass spectra obtained at 266 nm of 4-I-AMPP+-modified HFAs exhibit abundant product ions arising from photolysis of the aryl–iodide bond within the derivative with subsequent migration of the radical to the hydroxyl group promoting fragmentation of the FA chain and facilitating structural assignment. Results: Representative polyunsaturated HFAs (from the hydroxyeicosatetraenoic acid and hydroxyeicosapentaenoic acid families) were derivatized with 4-I-AMPP+ and subjected to a reversed-phase liquid chromatography workflow that afforded chromatographic resolution of isomers in conjunction with structurally diagnostic PD mass spectra. Conclusions: PD of these complex HFAs was found to be sensitive to the locations of hydroxyl groups and carbon–carbon double bonds, which are structural properties strongly associated with the biosynthetic origins of these lipid mediators

Preparation of an ion with the highest calculated proton affinity: ortho-diethynylbenzene dianion

Owing to the increased proton affinity that results from additional negative charges, multiply-charged anions have been proposed as one route to prepare and access a range of new and powerful superbases . Paradoxically, while the additional electrons in polyanions increase basicity they serve to diminish the electron binding energy and thus, it had been thought, hinder experimental synthesis. We report the synthesis and isolation of the ortho-diethynylbenzene dianion (ortho-DEB2−) and present observations of this novel species undergoing gas-phase proton-abstraction reactions. Using a theoretical model based on Marcus-Hush theory, we attribute the stability of ortho-DEB2− to the presence of a barrier that prevents spontaneous electron detachment. The proton affinity of 1843 kJ mol−1 calculated for this dianion superbase using high-level quantum chemistry calculations significantly exceeds that of the lithium monoxide anion, the most basic system previously prepared. The ortho-diethynylbenzene dianion is therefore the strongest base that has been experimentally observed to date

Resolving sphingolipid isomers using cryogenic infrared spectroscopy

1‐Deoxysphingolipids are a recently described class of sphingolipids that have been shown to be associated with several disease states including diabetic and hereditary neuropathy. The identification and characterization of 1‐deoxysphingolipids and their metabolites is therefore highly important. However, exact structure determination requires a combination of sophisticated analytical techniques due to the presence of various isomers, such as ketone/alkenol isomers, carbon–carbon double‐bond (C=C) isomers and hydroxylation regioisomers. Here we demonstrate that cryogenic gas‐phase infrared (IR) spectroscopy of ionized 1‐deoxysphingolipids enables the identification and differentiation of isomers by their unique spectroscopic fingerprints. In particular, C=C bond positions and stereochemical configurations can be distinguished by specific interactions between the charged amine and the double bond. The results demonstrate the power of gas‐phase IR spectroscopy to overcome the challenge of isomer resolution in conventional mass spectrometry and pave the way for deeper analysis of the lipidome

Ozone-enabled fatty acid discovery reveals unexpected diversity in the human lipidome.

Fatty acid isomers are responsible for an under-reported lipidome diversity across all kingdoms of life. Isomers of unsaturated fatty acids are often masked in contemporary analysis by incomplete separation and the absence of sufficiently diagnostic methods for structure elucidation. Here, we introduce a comprehensive workflow, to discover unsaturated fatty acids through coupling liquid chromatography and mass spectrometry with gas-phase ozonolysis of double bonds. The workflow encompasses semi-automated data analysis and enables de novo identification in complex media including human plasma, cancer cell lines and vernix caseosa. The targeted analysis including ozonolysis enables structural assignment over a dynamic range of five orders of magnitude, even in instances of incomplete chromatographic separation. Thereby we expand the number of identified plasma fatty acids two-fold, including non-methylene-interrupted fatty acids. Detection, without prior knowledge, allows discovery of non-canonical double bond positions. Changes in relative isomer abundances reflect underlying perturbations in lipid metabolism

Mass spectrometry-directed structure elucidation and total synthesis of ultra-long chain (O-acyl)-ω-hydroxy fatty acids

The (O-acyl)-ω-hydroxy FAs (OAHFAs) comprise an unusual lipid subclass present in the skin, vernix caseosa, and meibomian gland secretions. Although they are structurally related to the general class of FA esters of hydroxy FAs (FAHFAs), the ultra-long chain (30-34 carbons) and the putative -substitution of the backbone hydroxy FA suggest that OAHFAs have unique biochemistry. Complete structural elucidation of OAHFAs has been challenging because of their low abundance within complex lipid matrices. Furthermore, because these compounds occur as a mixture of closely related isomers, insufficient spectroscopic data have been obtained to guide structure confirmation by total synthesis. Here, we describe the full molecular structure of ultra-long chain OAHFAs extracted from human meibum by exploiting the gas-phase purification of lipids through multistage MS and novel multidimensional ion activation methods. The analysis elucidated sites of unsaturation, the stereochemical configuration of carbon-carbon double bonds, and ester linkage regiochemistry. Such isomer-resolved MS guided the first total synthesis of an ultra-long chain OAHFA, which, in turn, confirmed the structure of the most abundant OAHFA found in human meibum, OAHFA 50:2. The availability of a synthetic OAHFA opens new territory for future investigations into the unique biophysical and biochemical properties of these lipids

Infrared spectra of mass-selected Mg+-H2 and Mg +-D2 complexes

Rotationally resolved infrared spectra of Mg(+)-H(2) and Mg(+)-D(2) are recorded in the H-H (4025-4080 cm(-1)) and D-D (2895-2945 cm(-1)) stretch regions by monitoring Mg(+) photofragments. The nu(HH) and nu(DD) transitions of Mg(+)-H(2) and Mg(+)-D(2) are red-shifted by 106.2 +/- 1.5 and 76.0 +/- 0.1 cm(-1) respectively from the fundamental vibrational transitions of the free H(2) and D(2) molecules. The spectra are consistent with a T-shaped equilibrium structure in which the Mg(+) ion interacts with a slightly perturbed H(2) or D(2) molecule. From the spectroscopic constants, a vibrationally averaged intermolecular separation of 2.716 A (2.687 A) is deduced for the ground state of Mg(+)-H(2) (Mg(+)-D(2)), decreasing by 0.037 A (0.026 A) when the H(2) (D(2)) subunit is vibrationally excited

The Ontario psychologist

In this perspective article we describe recent infrared spectroscopic investigations of mass-selected M+-H-2 and M+-D-2 complexes in the gas-phase, with targets that include Li+-H-2, B+-H-2, Na+-H-2, Mg+-H-2, Al+-H-2, Cr+-D-2, Mn+-H-2, Zn+-D-2 and Ag+-H-2. Interactions between molecular hydrogen and metal cations play a key role in several contexts, including in the storage of molecular hydrogen in zeolites, metal-organic frameworks, and doped carbon nanostructures. Arguably, the clearest view of the interaction between dihydrogen and a metal cation can be obtained by probing M+-H-2 complexes in the gas phase, free from the complicating influences of solvents or substrates. Infrared spectra of the complexes in the H-H and D-D stretch regions are obtained by monitoring M+ photofragments as the excitation wavelength is scanned. The spectra, which feature full rotational resolution, confirm that the M+-H-2 complexes share a common T-shaped equilibrium structure, consisting essentially of a perturbed H-2 molecule attached to the metal cation, but that the structural and vibrational parameters vary over a considerable range, depending on the size and electronic structure of the metal cation. Correlations are established between intermolecular bond lengths, dissociation energies, and frequency shifts of the H-H stretch vibrational mode. Ultimately, the M+-H-2 and M+-D-2 infrared spectra provide a comprehensive set of benchmarks for modelling and understanding the M+center dot center dot center dot H-2 interaction