Multiply charged anions (MCAs) represent exotic, highly energetic species in the gas-phase due to their propensity to undergo unimolecular decay via electron loss or ionic fragmentation. There is considerable fundamental interest in these systems since they display novel potential energy surfaces that are characterized by Coulomb barriers. Over recent years, considerable progress has been made in understanding the factors that affect the stability, decay pathways and reactivity of gas-phase MCAs, mainly as a result of the application of electrospray ionization as a generic technique for transferring solution-phase MCAs into the gas-phase for detailed characterization. We review contemporary work in this field, focusing on the factors that control the intrinsic stability of MCAs, both as isolated gas-phase ions, and on their complexation with solvent molecules and counter-ions. While studies of MCAs are primarily of fundamental interest, several classes of important biological ions are commonly observed as MCAs in the gas-phase (e.g. oligonucleotides, sugars). Recent results for biologically relevant ions are emphasised, since a fundamental understanding of the properties of gas-phase MCAs will be highly valuable for developing further analytical methods to study these important systems.

Multiply charged anions (MCAs) represent highly energetic species in the gas phase but can be stabilized through formation of molecular clusters with solvent molecules or counterions. We explore the intramolecular stabilization of excess negative charge in gas-phase MCAs by probing the intrinsic stability of the [adenosine 5'-triphosphate-2H](2-) ([ATP-2H](2-)), [adenosine 5'-diphosphate-2H](2-) ([ADP-2H](2-)), and H(3)P(3)O(10)(2-) dianions and their protonated monoanionic analogues. The relative activation barriers for decay of the dianions via electron detachment or ionic fragmentation are investigated using resonance excitation of ions isolated within a quadrupole trap. All of the dianions decayed via ionic fragmentation demonstrating that the repulsive Coulomb barriers (RCB) for ionic fragmentation lie below the RCBs for electron detachment. Both the electrospray ionization mass spectra (ESI-MS) and total fragmentation energies for [ATP-2H](2-), [ADP-2H](2-), and H(3)P(3)O(10)(2-) indicate that the multiply charged H(3)P(3)O(10)(2-) phosphate moiety is stabilized by the presence of the adenosine group and the stability of the dianions increases in the order H(3)P(3)O(10)(2-) < [ADP-2H](2-) < [ATP-2H](2-). Fully optimized, B3LYP/6-31+G* minimum energy structures illustrate that the excess charges in all of the phosphate anions are stabilized by intramolecular hydrogen bonding either within the phosphate chain or between the phosphate and the adenosine. We develop a model to illustrate that the relative magnitudes of the RCBs and hence the stability of these ions is dominated by the extent of intramolecular hydrogen bonding.

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The intrinsic gas-phase stability of the IrCl(6)(3-) trianion and its microsolvated clusters, IrCl(6)(3-).(H(2)O)(n) n = 1-10, have been investigated using density functional theory (DFT) calculations. Although IrCl(6)(3-) is known to exist as a stable complex ion in bulk solutions, our calculations indicate that the bare trianion is metastable with respect to decay via both electron detachment and ionic fragmentation. To estimate the lifetime of IrCl(6)(3-), we have computed the electron tunneling probability using an adaption of the Wentzel-Kramer-Brillouin theory and predict that the trianion will decay spontaneously via electron tunneling on a time scale of 2.4 x 10(-13) s. The global minimum structure for IrCl(6)(3-).H(2)O was found to contain a bifurcated hydrogen bond, whereas for IrCl(6)(3-).(H(2)O)(2), two low energy minima were identified; one involving two bifurcated water-ion hydrogen bonds and a second combining a bifurcated hydrogen bond with a water-water hydrogen bond. Clusters based on each of these structural motifs were obtained for all of the n = 3-10 systems, and the effect of solvation on the possible decay pathways was explored. The calculations reveal that solvation stabilizes IrCl(6)(3-) with respect to both electron detachment decay and ionic fragmentation, with the magnitude of the repulsive Coulomb barrier for ionic fragmentation increasing smoothly with sequential solvation. This study is the first to compare the propensity for electron detachment versus ionic fragmentation decay for a sequentially solvated triply charged anion.

An electrospray ionisation mass spectrometer (ESI-MS) whose main components are all fabricated using silicon microelectromechanical systems (MEMS) techniques is demonstrated for the first time. The ion source consists of a microengineered alignment bench containing a V-groove mounting for a nanospray capillary, an ion extraction electrode, and a pneumatic nebuliser. The vacuum interface consists of two plates, each carrying a 50 µm diameter capillary, that are selectively etched and bonded together to provide a differentially pumped internal cavity. The quadrupole filter consists of a microfabricated frame that provides mountings for stainless steel rods measuring 650 µm in diameter and 30 mm in length. Two different quadrupoles are compared: a firstgeneration bonded silicon device, and a second-generation silicon-on-glass device with a Brubaker prefilter. Differential pumping of a MEMS component is demonstrated for the first time, atmospheric pressure ionisation and ion transfer into vacuum are characterised, ESI-MS operation is demonstrated and spectra are presented for a variety of compounds. KEYWORDS:Mass spectrometry, Electrospray, Quadrupole filter, MEMS IntroductionOver 25 years have passed since an electrospray ionisation (ESI) source was first coupled to a quadrupole mass spectrometer (MS) by Yamashita and Fenn [1]. Since then, ESI-MS has become a workhorse of analytical chemistry, allowing analytes to be ionised at atmospheric pressure with little fragmentation and passed into a vacuum system for analysis.Conventional ESI sources employ spray tips with an internal diameter (ID) of ≈100 µm[2]. In order to establish a Taylor cone and maintain stable emission of charged droplets, minimum flow rates of 0.5 -5 µL min -1 and voltages of 2.5 -4 kV are used. However, it has been convincingly demonstrated that high sensitivity and stable emission can be achieved at much lower flow rates and voltages using spray tips with IDs of ≈ 5 µm, and silica nanospray capillaries with a range of coatings have become widely available [3][4][5][6][7][8].Unfortunately, while these are inexpensive, operator expertise and costly positioning apparatus are often required for stable and reproducible performance.Electrosprayed ions are passed into a low-pressure chamber via a vacuum interface. The simplest interface is a single orifice or capillary that allows gas and entrained ions to pass directly into the vacuum chamber. Clearly, the orifice must be small enough or the pumps large enough to ensure that the pressure is consistent with mass analysis. However, the susceptibility of very small orifices to clogging and the inconvenience of large pumps led to this approach being abandoned. Modern instruments employ one or more stages of 4 differential pumping. Larger orifices can be tolerated since only a fraction of the flow is transmitted to the vacuum chamber, while the majority of the gas load can be pumped away at higher pressure using more modest pumps.The effective transfer of ions and molecules from atmospheric pressu...