Many molecules exhibit multiple rotational isomers (conformers) that interconvert thermally and are difficult to isolate. Consequently, a precise characterization of their role in chemical reactions has proven challenging. We have probed the reactivity of specific conformers by using an experimental technique based on their spatial separation in a molecular beam by electrostatic deflection. The separated conformers react with a target of Coulomb-crystallized ions in a trap. In the reaction of Ca(+) with 3-aminophenol, we find a twofold larger rate constant for the cis compared with the trans conformer (differentiated by the O-H bond orientation). This result is explained by conformer-specific differences in the long-range ion-molecule interaction potentials. Our approach demonstrates the possibility of controlling reactivity through selection of conformational states.

The phenolic composition of juice derived from fruits of sea buckthorn (Hippophae rhamnoides) was investigated by high-performance liquid chromatography (HPLC) with diode array and electrochemical detection. Flavonols were found to be the predominating polyphenols while phenolic acids and catechins represent minor components. Of the seven flavonols identified, isorhamnetin 3-O-glycosides were the most important representatives quantitatively. However, because of their structural properties, they were poor radical scavengers as shown by electron spin resonance spectroscopy. Phenolic compounds such as quercetin 3-O-glycosides, catechins, and hydroxybenzoic acids with a catechol structure exhibited good antioxidant capacities, but their concentration in sea buckthorn juice was small. These phenolic compounds, determined by HPLC, accounted for less than 5% of the total antioxidant activity of the filtered juice. Ascorbic acid was shown to be the major antioxidant in sea buckthorn juice. Because of its high concentration of 1.22 g/L, it contributes approximately 75% to total antioxidant activity. The remaining difference can be attributed to higher molecular weight flavan-3-ols (proanthocyanidins), which were determined photometrically after acid depolymerization to colored anthocyanidins.

Water is one of the most fundamental molecules in chemistry, biology and astrophysics. It exists as two distinct nuclear-spin isomers, para- and ortho-water, which do not interconvert in isolated molecules. The experimental challenges in preparing pure samples of the two isomers have thus far precluded a characterization of their individual chemical behavior. Capitalizing on recent advances in the electrostatic deflection of polar molecules, we separate the ground states of para- and ortho-water in a molecular beam to show that the two isomers exhibit different reactivities in a prototypical reaction with trapped diazenylium ions. Based on ab initio calculations and a modelling of the reaction kinetics using rotationally adiabatic capture theory, we rationalize this finding in terms of different rotational averaging of ion-dipole interactions during the reaction.

Four flavonol glycosides were isolated from an extract of sea buckthorn pomace (Hippophaë rhamnoides) by Sephadex LH-20 gel chromatography and semipreparative HPLC. Their structures were elucidated by hydrolysis studies, ESI-MS(n), UV, and (1)H and (13)C NMR spectroscopy. The occurrence of the major flavonol glycoside kaempferol 3-O-beta-sophoroside-7-O-alpha-rhamnoside in sea buckthorn is described here for the first time. A further 21 flavonol glycosides of Sephadex LH-20 fractions of sea buckthorn pomace were characterized by HPLC-DAD-ESI-MS. The characteristic MS-MS and MS(3) fragmentation pattern of flavonol glycosides previously identified in sea buckthorn juice and of flavonol glycosides identified by NMR spectroscopy gave valuable indications for their identification. The results demonstrate that loss of the sugar moiety from C-7 of the aglycon is more favored than fission of the glycosidic linkage at the C-3 position. Thus, most of the compounds identified were 7-rhamnosides of isorhamnetin, kaempferol, and quercetin, which exhibit different substitution patterns at the C-3 position, mainly glucosides, rutinosides, and sophorosides. In addition, numerous flavonol glycosides were detected lacking a sugar moiety at C-7. Finally, eight flavonol derivatives were identified that are acylated by hydroxybenzoic or hydoxycinnamic acids.

Methanol is a benchmark for understanding tropospheric oxidation, but is underpredicted by up to 100% in atmospheric models. Recent work has suggested this discrepancy can be reconciled by the rapid reaction of hydroxyl and methylperoxy radicals with a methanol branching fraction of 30%. However, for fractions below 15%, methanol underprediction is exacerbated. Theoretical investigations of this reaction are challenging because of intersystem crossing between singlet and triplet surfaces – ∼45% of reaction products are obtained via intersystem crossing of a pre-product complex – which demands experimental determinations of product branching. Here we report direct measurements of methanol from this reaction. A branching fraction below 15% is established, consequently highlighting a large gap in the understanding of global methanol sources. These results support the recent high-level theoretical work and substantially reduce its uncertainties.

Many molecules exhibit multiple conformers that often easily interconvert under thermal conditions. Therefore, single conformations are difficult to isolate which renders the study of their distinct chemical reactivities challenging. We have recently reported a new experimental method for the characterization of conformerspecific effects in chemical reactions [Y. P. Chang et al., Science 342, 98 (2013)]. Different conformers are spatially separated using inhomogeneous electric fields and reacted with a Coulomb crystal of cold, spatially localized ions in a trap. As a first application, we studied reactions between the two conformers of 3-aminophenol and Ca + . We observed a twofold larger rate constant for the cis compared to the trans conformer which was rationalized in terms of the differences in the long-range ion-molecule interactions. The present article provides a detailed description of the new method and a full account of the experimental results as well as the accompanying theoretical calculations.

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We present and discuss in detail the design and characterization of a new linear quadrupole ion trap with additional ion ejection and acceleration electrodes that is coupled to a time-of-flight mass spectrometer. Mass spectra of Coulomb crystals consisting of Ca + ,CaO + and CaOH + ions were recorded with a post-ejectionacceleration scheme yielding a mass resolution of m/ m ≈ 700. The second order rate constant for the reaction Ca + + N 2 O → CaO + + N 2 was measured to test the usability of this apparatus for ion-molecule reaction studies. The rate constant was found to be 5.49(32) · 10 −11 cm 3 s −1 which is compared with previous literature values. Owing to the high mass resolution achieved, the present instrument is an ideal tool for the study of the products of complex chemical reactions involving Coulomb crystals.