Watching Paint Dry: Organic Vapor Emissions from Architectural Coatings and their Impact on Secondary Organic Aerosol Formation.

Emissions from volatile chemical products (VCPs) are emerging as a major source of anthropogenic secondary organic aerosol (SOA) precursors. Paints and coatings are an important class of VCPs that emit both volatile and intermediate volatility organic compounds (VOCs and IVOCs). In this study, we directly measured I/VOC emissions from representative water- (latex) and oil-based paints used in the U.S. Paint I/VOC emissions vary by several orders of magnitude by both the solvent and gloss level. Oil-based paints had the highest emissions (>105 µg/g-paint), whereas low-gloss interior paints (Flat, Satin, and Semigloss) all emitted ∼102 µg/g-paint. Emissions from interior paints are dominated by VOCs, whereas exterior-use paints emitted a larger fraction of IVOCs. Extended emission tests showed that most I/VOC emissions occur within 12-24 h after paint application, though some paints continue to emit IVOCs for 48 h or more. We used our data to estimate paint I/VOC emissions and the subsequent SOA production in the U.S. Total annual paint I/VOC emissions are 48-155 Gg (0.15-0.48 kg/person). These emissions contribute to the formation of 2.2-7.5 Gg of SOA annually. Oil-based paints contribute 70-98% of I/VOC emissions and 61-99% of SOA formation, even though they only account for a minority of paint usage.

Mechanospray Ionization MS of Proteins Including in the Folded State and Polymers.

Mechanospray ionization (MoSI) is a technique that produces ions directly from solution-like electrospray ionization (ESI) but without the need of a high voltage. In MoSI, mechanical vibrations aerosolize solution phase analytes, whereby the resulting microdroplets can be directed into the inlet orifice of a mass spectrometer. In this work, MoSI is applied to biomolecules up to 80 kDa in mass in both denatured and native conditions as well as polymers up to 12 kDa in mass. The various MoSI devices used in these analyses were all comprised of a piezoelectric annulus attached to a central metallic disk containing an array of 4 to 7 µm diameter holes. The devices vibrated in the 100-170 kHz range to generate a beam of microdroplets that ultimately resulted in ion formation. A linear quadrupole ion trap (LIT) and orbitrap mass spectrometer were used in the analysis to investigate higher mass proteins at both native (folded) and denatured (unfolded) conditions. MoSI native mass spectra of proteins acquired on the orbitrap and LIT instrument demonstrated that proteins could remain intact and in a folded state. In the case of native MS of holomyoglobin, the intact folded protein remained mostly bound noncovalently to the heme group, and typically, the spectra showed reduced loss of the heme group by MoSI as compared to ESI. In both non-native and native protein analyses examples, broader often multimodal distributions to lower charge states were observed. When using the LIT instrument, a significant increase in the relative abundance of dimers was observed by MoSI as compared to ESI. The softness of the MoSI technique was evidenced by the lack of fragmentation, the formation of dimers as also noted by others ( J. Mass Spectrom. 2016, 424-429) and under native conditions, the retention of proteins in one or more presumed folded structures and for holomyoglobin the high retention of the heme group. When analyzing polyethylene glycol (PEG) and polypropylene glycol (PPG), MoSI also generated a broader distribution to lower charge states than ESI. By using the improved separation of peaks at lower charge states and all the charge states available, MoSI data should provide an improved ionization method to obtain more accurate mass and dispersity values for some polymers.

Anatomy of Protein Electrospray Ionization Mass Spectra by Superconducting Tunnel Junction Mass and Energy Spectrometry.

Cryogenic superconducting tunnel junction (STJ) detectors have the advantage of single-particle sensitivity, high quantum efficiency, low noise, and the ability to detect the time and relative impact energy of deposited ions. This makes them attractive for use in mass spectrometry (MS) and as a form of energy spectrometry. STJ cryodetectors have been coupled to time-of-flight (TOF) mass spectrometers equipped with a matrix-assisted laser desorption ionization (MALDI) source and to an electrospray ionization (ESI) TOF mass spectrometer. Here, a lab-made linear quadrupole ion trap (LIT) mass spectrometer system was coupled to an ESI source and a 16-channel Nb-STJ array with improved readout electronics. The goal was to investigate fundamentals of ESI-generated protein ions by further exploiting the advantage of resolving these ions in a third dimension of the relative energy deposited into the STJs. The proteins equine cytochrome c, bovine carbonic anhydrase, bovine serum albumin, and murine immunoglobulin G were studied using this ESI-LIT-STJ-MS instrument. Multiply charged monomers, multimers, and fragments from metastable ions were resolved from monomer peaks by differences in ion deposition energy even when these ions have the same mass-to-charge ratio as the corresponding monomer. The determination of a fragment mass from metastable decomposition is accomplished without knowing the charge state of the fragment. The average charge state of the multimers is reduced with each addition of a protein which is presumed to be a direct reflection of the surface area available for charging. Multiply charged in-source fragments have also been observed and distinguished in the mass spectrum of carbonic anhydrase by using the differences in the energy deposited in the STJs.

Mass Spectrometry of Au10(4-tert-butylbenzenethiolate)10 Nanoclusters Using Superconducting Tunnel Junction Cryodetection Reveals Distinct Metastable Fragmentation.

Cryodetection mass spectrometry (MS) was used to study the Au10(TBBT)10 (TBBT = 4-tert-butylbenzenethiolate) catenane nanocluster. The matrix-assisted laser desorption ionization (MALDI) process generates distinct fragments that can be arranged into two distinct regimes: (i) in-source fragmentation, which occurs rapidly in a relatively short (<170 ns) time frame, and (ii) metastable fragmentation, which occurs postacceleration during a time-of-flight (TOF) mass analysis over a longer time frame (>170 ns-250 µs). Using MALDI-TOF MS with superconducting tunnel junction (STJ) cryodetection, distinct metastable nanocluster fragments were resolved at lower energies deposited into the detector. The results also demonstrated that STJ cryodetection MS can be used to acquire multiple (>10), simultaneous tandem mass spectra in a single experiment. Simulated fragmentation of the Au10 nanocluster using ab initio molecular dynamics (AIMD) revealed the different fragmentation processes and confirmed the MS results. Using both the empirical MS data and AIMD calculations, fragmentation pathways are proposed for Au10(TBBT)10, which terminate with two small, stable ringed species.

Characterization of Mega-Dalton-Sized Nanoparticles by Superconducting Tunnel Junction Cryodetection Mass Spectrometry.

The characterization of nanomaterials is critical to understand the size/structure-dependent properties of these particles. In this report, a form of heavy ion mass spectrometry, namely, superconducting tunnel junction (STJ) cryodetection mass spectrometry (MS) is used to characterize quantum dot semiconductor nanocrystals and gold nanoparticles. The nanoparticles studied ranged in mass from 200 kDa to >1.5 MDa and included lead sulfide quantum dots, various cadmium selenide and/or telluride-based core-shell quantum dots coated with different ligands, and gold nanoparticles. Nanoparticles were ionized by both matrix-assisted laser desorption ionization (MALDI) and laser desorption ionization (LDI), shot with an aimed ion gun into a flight tube, mass separated by time-of-flight (TOF), and detected by an energy-sensitive STJ cryodetector. STJ cryodetection MS can be used to analyze intact heterogeneous nanoparticles, allowing determination of average particle mass, dispersity, and ligand loading. Some nanoparticles, however, do undergo fragmentation during the MALDI or LDI-TOF mass analyses. The measurement of the energy deposited into the detector was found to be different for different types of particles. Metastable fragments from these nanoparticles were observed at lower energies. The lower energies deposited for metastable fragments can provide insight into the stability and surface compositions of these materials. Cadmium selenide core-shell quantum dots (655 nm emission) conjugated to biomacromolecules, such as cholera toxin B and human serum transferrin, were also analyzed. When compared to unconjugated particles by mass, it was determined that ∼96 cholera toxin B and ∼14 transferrin proteins were attached to the surface of these nanoparticles.

Characterization of ZnO Nanoparticles using Superconducting Tunnel Junction Cryodetection Mass Spectrometry.

Zinc oxide (ZnO) nanoparticles coated with either n-octylamine (OA) or α-amino poly(styrene-co-acrylonitrile) (PSAN) ligands (L) have been analyzed using laser desorption/ionization and matrix assisted laser desorption/ionization (MALDI) time-of-flight (TOF) superconducting tunnel junction (STJ) cryodetection mass spectrometry. STJ cryodetection has the advantage of high m/z detection and allows for the determination of average molecular weights and dispersities for 500-600 kDa ZnO-L nanoparticles. The ability to detect the relative energies deposited into the STJs has allowed for investigation of ZnO-L metastable fragmentation. ZnO-L precursor ions gain enough internal energy during the MALDI process to undergo metastable fragmentation in the flight tube. These fragments produced a lower energy peak, which was assigned as ligand-stripped ZnO cores whereas the individual ligands were at too low of an energy to be observed. From these STJ energy resolved peaks, the average weight percentage of inorganic material making up the nanoparticle was determined, where ZnO-OA and ZnO-PSAN nanoparticles are comprised of ~62% and ~68% wt ZnO, respectively. In one example, grafting densities were calculated based on the metastable fragmentation of ligands from the core to be 16 and 1.1 nm-2 for ZnO-OA and ZnO-PSAN, respectively, and compared with values determined by thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). Graphical Abstract ᅟ.

Determination of iron content and dispersity of intact ferritin by superconducting tunnel junction cryodetection mass spectrometry.

Ferritin is a common iron storage protein complex found in both eukaryotic and prokaryotic organisms. Although horse spleen holoferritin (HS-HoloFt) has been widely studied, this is the first report of mass spectrometry (MS) analysis of the intact form, likely because of its high molecular weight ∼850 kDa and broad iron-core mass distribution. The 24-subunit ferritin heteropolymer protein shell consists of light (L) and heavy (H) subunits and a ferrihydrite-like iron core. The H/L heterogeneity ratio of the horse spleen apoferritin (HS-ApoFt) shell was found to be ∼1:10 by liquid chromatography-electrospray ionization mass spectrometry. Superconducting tunneling junction (STJ) cryodetection matrix-assisted laser desorption ionization time-of-flight MS was utilized to determine the masses of intact HS-ApoFt, HS-HoloFt, and the HS-HoloFt dimer to be ∼505 kDa, ∼835 kDa, and ∼1.63 MDa, respectively. The structural integrity of HS-HoloFt and the proposed mineral adducts found for both purified L and H subunits suggest a robust biomacromolecular complex that is internally stabilized by the iron-based core. However, cross-linking experiments of HS-HoloFt with glutaraldehyde, unexpectedly, showed the complete release of the iron-based core in a one-step process revealing a cross-linked HS-ApoFt with a narrow fwhm peak width of 31.4 kTh compared to 295 kTh for HS-HoloFt. The MS analysis of HS-HoloFt revealed a semiquantitative description of the iron content and core dispersity of 3400 ± 1600 (2σ) iron atoms. Commercially prepared HS-ApoFt was estimated to still contain an average of 240 iron atoms. These iron abundance and dispersity results suggest the use of STJ cryodetection MS for the clinical analysis of iron deficient/overload diseases.

Interactive effects of competition and predator cues on immune responses of leopard frogs at metamorphosis.

Recent hypotheses suggest that immunosuppression, resulting from altered environmental conditions, may contribute to the increased incidence of amphibian disease around the world. Antimicrobial peptides (AMPs) in amphibian skin are an important innate immune defense against fungal, viral and bacterial pathogens. Their release is tightly coupled with release of the stress hormone noradrenaline (norepinephrine). During metamorphosis, AMPs may constitute the primary immune response in the skin of some species because acquired immune functions are temporarily suppressed in order to prevent autoimmunity against new adult antigens. Suppression of AMPs during this transitional stage may impact disease rates. We exposed leopard frog tadpoles (Lithobates pipiens) to a factorial combination of competitor and caged-predator environments and measured their development, growth and production of hydrophobic skin peptides after metamorphosis. In the absence of predator cues, or if the exposure to predator cues was late in ontogeny, competition caused more than a 250% increase in mass-standardized hydrophobic skin peptides. Predator cues caused a decrease in mass-standardized hydrophobic skin peptides when the exposure was late in ontogeny under low competition, but otherwise had no effect. Liquid chromatography tandem mass spectrometry of the skin peptides showed that they include six AMPs in the brevinin and temporin families and at least three of these peptides are previously uncharacterized. Both of these peptide families have previously been shown to inhibit harmful microbes including Batrachochytrium dendrobatidis, the fungal pathogen associated with global amphibian declines. Our study shows that amphibians may be able to adjust their skin peptide defenses in response to stressors that are experienced early in ontogeny and that these effects extend through an important life-history transition.

Larval exposure to predator cues alters immune function and response to a fungal pathogen in post-metamorphic wood frogs.

For the past several decades, amphibian populations have been decreasing around the globe at an unprecedented rate. Batrachochytrium dendrobatidis (Bd), the fungal pathogen that causes chytridiomycosis in amphibians, is contributing to amphibian declines. Natural and anthropogenic environmental factors are hypothesized to contribute to these declines by reducing the immunocompetence of amphibian hosts, making them more susceptible to infection. Antimicrobial peptides (AMPs) produced in the granular glands of a frog's skin are thought to be a key defense against Bd infection. These peptides may be a critical immune defense during metamorphosis because many acquired immune functions are suppressed during this time. To test if stressors alter AMP production and survival of frogs exposed to Bd, we exposed wood frog (Lithobates sylvaticus) tadpoles to the presence or absence of dragonfly predator cues crossed with a single exposure to three nominal concentrations of the insecticide malathion (0, 10, or 100 parts per billion [ppb]). We then exposed a subset of post-metamorphic frogs to the presence or absence of Bd zoospores and measured frog survival. Although predator cues and malathion had no effect on survival or size at metamorphosis, predator cues increased the time to metamorphosis by 1.5 days and caused a trend of a 20% decrease in hydrophobic skin peptides. Despite this decrease in peptides determined shortly after metamorphosis, previous exposure to predator cues increased survival in both Bd-exposed and unexposed frogs several weeks after metamorphosis. These results suggest that exposing tadpoles to predator cues confers fitness benefits later in life.

Activity regulates functional connectivity from the vomeronasal organ to the accessory olfactory bulb.

The mammalian accessory olfactory system is specialized for the detection of chemicals that identify kin and conspecifics. Vomeronasal sensory neurons (VSNs) residing in the vomeronasal organ project axons to the accessory olfactory bulb (AOB), where they form synapses with principal neurons known as mitral cells. The organization of this projection is quite precise and is believed to be essential for appropriate function of this system. However, how this precise connectivity is established is unknown. We show here that in mice the vomeronasal duct is open at birth, allowing external chemical stimuli access to sensory neurons, and that these sensory neurons are capable of releasing neurotransmitter to downstream neurons as early as the first postnatal day (P). Using major histocompatibility complex class I peptides to activate a selective subset of VSNs during the first few postnatal days of development, we show that increased activity results in exuberant VSN axonal projections and a delay in axonal coalescence into well defined glomeruli in the AOB. Finally, we show that mitral cell dendritic refinement occurs just after the coalescence of presynaptic axons. Such a mechanism may allow the formation of precise connectivity with specific glomeruli that receive input from sensory neurons expressing the same receptor type.

Crystal structures of Au2 complex and Au25 nanocluster and mechanistic insight into the conversion of polydisperse nanoparticles into monodisperse Au25 nanoclusters.

We previously reported a size-focusing conversion of polydisperse gold nanoparticles capped by phosphine into monodisperse [Au(25)(PPh(3))(10)(SC(2)H(4)Ph)(5)Cl(2)](2+) nanoclusters in the presence of phenylethylthiol. Herein, we have determined the crystal structure of [Au(25)(PPh(3))(10)(SC(2)H(4)Ph)(5)Cl(2)](2+) nanoclusters and also identified an important side-product-a Au(I) complex formed in the size focusing process. The [Au(25)(PPh(3))(10)(SC(2)H(4)Ph)(5)Cl(2)](2+) cluster features a vertex-sharing bi-icosahedral core, resembling a rod. The formula of the Au(I) complex is determined to be [Au(2)(PPh(3))(2)(SC(2)H(4)Ph)](+) by electrospray ionization (ESI) mass spectrometry, and its crystal structure (with SbF(6)(-) counterion) reveals Au-Au bridged by -SC(2)H(4)Ph and with terminal bonds to two PPh(3) ligands. Unlike previously reported [Au(2)(PR(3))(2)(SC(2)H(4)Ph)](+) complexes in the solid state, which exist as tetranuclear complexes (i.e., dimers of [Au(2)(PR(3))(2)(SC(2)H(4)Ph)](+) units) through a Au···Au aurophilic interaction, in our case we found that the [Au(2)(PPh(3))(2)(SC(2)H(4)Ph)](+) complex exists as a single entity, rather than being dimerized to form a tetranuclear complex. The observation of this Au(I) complex allows us to gain insight into the intriguing conversion process from polydisperse Au nanoparticles to monodisperse Au(25) nanoclusters.

Rapid, biomimetic degradation in water of the persistent drug sertraline by TAML catalysts and hydrogen peroxide.

Iron TAML activators (oxidation catalysts based upon tetraamido macrocyclic ligands) at nanomolar concentrations in water activate hydrogen peroxide to rapidly degrade sertraline, the persistent, active pharmaceutical ingredient (API) in the widely used drug Zoloft. Although all the API is readily consumed, degradation slows significantly at one intermediate, sertraline ketone. The process occurs from neutral to basic pH. The pathway has been characterized through four early intermediates which reflect the metabolism of sertraline, providing further evidence that TAML activator/peroxide reactive intermediates mimic those of cytochrome P450 enzymes. TAML catalysts have been designed to exhibit considerable variability in reactivity and this provides an excellent tool for observing degradation intermediates of widely differing stabilities. Two elusive, hydrolytically sensitive intermediates and likely human metabolites, sertraline imine and N-desmethylsertraline imine, could be identified only by using a fast-acting catalyst. The more stable intermediates and known human metabolites, desmethylsertraline and sertraline ketone, were most easily detected and studied using a slow-acting catalyst. The resistance of sertraline ketone to aggressive TAML activator/peroxide treatment marks it as likely to be environmentally persistent and signals that its environmental effects are important components of the full implications of sertraline use.

Minimally invasive monitoring of cellulose degradation by desorption electrospray ionization and laser ablation electrospray ionization mass spectrometry.

Minimally invasive desorption electrospray ionization-mass spectrometry (DESI-MS) and laser ablation electrospray ionization-MS (LAESI-MS) were used to look for soluble cellulose degradation products produced by accelerated aging in unsized cotton paper. Soluble extracts from papers aged 144 to 26,856 hours were first analyzed in solution using traditional electrospray ionization-MS (ESI-MS). Results were compared to those from direct analysis of condensed phase degradation products extracted from the absorbent paper substrate using DESI-MS and LAESI-MS. ESI-MS results showed evidence of oligosaccharide degradation products ranging from cellobiose to cellononaose; using DESI-MS and LAESI-MS, products from cellobiose to cellodecaose and glucose to cellooctaose, respectively, were observed. As degradation proceeded, increased quantities of both low and high molecular weight oligosaccharides were observed. The analytical approaches developed in the control study were applied for the detection of degradation products in two naturally-aged books dating from the 19th century, both made from cotton and linen. Oligosaccharides ranging from glucose to cellopentaose were observed.

High yield, large scale synthesis of thiolate-protected Ag7 clusters.

We report a high yielding synthesis of truly monodisperse, thiolate-protected silver clusters via a rationally designed approach. The cluster composition was determined by electrospray ionization (ESI) mass spectrometry to be Ag(7)(DMSA)(4), where DMSA represents meso-2,3-dimercaptosuccinic acid. The Ag(7) thiolate clusters exhibit distinct optical properties. The approach developed in this work provides some insight into the cluster growth kinetics and may be extendable to the synthesis of other sized silver nanoclusters.

Hydrolysis of the amorphous cellulose in cotton-based paper.

Hydrolysis of cellulose in Whatman no. 42 cotton-based paper was studied using gel permeation chromatography (GPC), electrospray ionization-mass spectrometry (ESI-MS), and uniaxial tensile testing to understand the course and kinetics of the reaction. GPC results suggested that scission reactions passed through three stages. Additionally, the evolution of soluble oligomers in the ESI-MS data and the steady course of strength loss showed that the hydrolysis reaction occurred at a constant rate. These findings are explained with a more detailed description of the cellulose hydrolysis, which includes multiple chain scissions on amorphous segments. The breaks occur with increasing frequency near the ends of amorphous segments, where chains protrude from crystalline domains. Oligomers unattached to crystalline domains are eventually created. Late-stage reactions near the ends of amorphous segments produce a kinetic behavior that falsely suggests that hydrolysis had ceased. Monte Carlo simulations of cellulose degradation corroborated the experimental findings.

The analysis of polystyrene and polystyrene aggregates into the mega dalton mass range by cryodetection MALDI TOF MS.

Mass spectra of atactic polystyrene were collected into the mega-dalton mass range with a matrix-assisted laser desorption ionization time of flight (MALDI TOF) mass spectrometer, which incorporates a cryodetector comprised of an array of 16 superconducting tunnel junctions (STJ). The STJ cryodetector, theoretically, has no loss in signal response at any mass compared with the reduced signal found at high mass when using a conventional secondary-ionization detector. Since ion detection at high m/z is one of the fundamental limitations of mass spectrometry (MS), the cryodetector was used to explore the high m/z limit of the MALDI TOF technique for the analysis of two polymer types. Mass spectra were collected for polystyrene at Mn 170, 400, 900, and 2000 kDa and polymethyl methacrylate (PMMA) at Mn 62.6 kDa and 153.7 kDa. For polystyrene, the data showed a trend toward increased aggregation and charge state with mass. The Mn 2 MDa polystyrene data revealed a peak at m/z 2.2 MegaTh and a charge state analysis revealed that these ions were primarily polystyrene aggregates with a mass of approximately 4 MDa. This aggregate assignment was possible because the cryodetector response allows for the determination of a charge state up to about four. The contribution of each charge state for a selected peak can be determined in this fashion. This analysis revealed the preferential formation of doubly charged even-numbered aggregates over odd-numbered aggregates for high molecular mass polystyrene. A potential mechanism for the aggregation process for doubly charged species is discussed.

An electrospray membrane probe for the analysis of volatile and semi-volatile organic compounds in water.

A new membrane probe incorporating electrospray ionization (ESI) was designed, built and coupled to an ion trap mass spectrometer to detect low levels of semi-volatile organic compounds (SVOCs) in water. Similar to other membrane introduction mass spectrometry (MIMS) systems, the probe contains a capillary polydimethylsiloxane (PDMS) membrane to allow for the preferential permeation of small molecules but, in contrast, the interface uses a liquid/membrane/liquid interface rather than liquid/membrane/gas. The ESI source allows the probe to be operated at atmospheric pressure in positive or negative ionization mode and the lack of fragmentation in ESI allows for the simultaneous screening of many analytes with high sensitivity. The interface allows for the addition of additives to both the external and the internal liquid mobile phases to selectively improve permeation and/or the ionization efficiency of various classes of compounds. Characterization of the probe with methanol as the internal mobile phase showed that the signal for aniline optimized at 60 degrees C and an internal flow rate between 2-5 microL/min. The transfer of analyte through the membrane from water to methanol ensures a strong signal and robust electrospray for both positive and negative ion mode which is not typical when spraying pure water. Detection limits for aniline, pyridine and pentachlorophenol, and for the herbicides alachlor, atrazine, butachlor, metolachlor and simazine, were in the ppb to pptr range.

Quadruplex formation by a guanine-rich PNA oligomer.

A guanine-rich PNA dodecamer having the sequence H-G4T4G4-Lys-NH2 (G-PNA) hybridizes with a DNA dodecamer of homologous sequence to form a four-stranded quadruplex (Datta, B.; Schmitt, C.; Armitage, B. A. J. Am. Chem. Soc. 2003, 125, 4111-4118). This report describes quadruplex formation by the PNA alone. UV melting curves and fluorescence resonance energy transfer experiments reveal formation of a multistranded structure stabilized by guanine tetrads. The ion dependency of these structures is analogous to that reported for DNA quadruplexes. Electrospray ionization mass spectrometry indicates that both dimeric and tetrameric quadruplexes are formed by G4-PNA, with the dimeric form being preferred. These results have implications for the use of G-rich PNA for homologous hybridization to G-rich targets in chromosomal DNA and suggest additional applications in assembling quadruplex structures within lipid bilayer environments.

Investigation of the rapid scan on an electrospray ion trap mass spectrometer.

A rapid scan on a quadrupole ion trap mass spectrometer can improve the signal intensity by over 200 times when scanning at 12 times the normal scan rate. This intensity increase is due to a 5.5-fold increase in mass peak height due to a reduction in the mass peak width over time and a 40-fold increase in signal from the increased number of ions that can be trapped without the deleterious effects of space charge. Detection limits can be further improved by signal averaging more scans in the same period that is required for the normal scan, and the greatest advantage occurs when scanning over the full mass range. The rapid scan impacts the mass accuracy and the resolution is reduced by 6 times. The molecular weight determination of 40 fmol/microL apomyoglobin was determined in 3 s using a rapid scan, but this was not possible when using the normal scan rate. Quantitation results showed that the relative standard deviations for the total ion current peak areas of 500 fmol of angiotensin I were improved by a factor of 2.6 when the rapid scan was used.