Degree of ionization (DI) in matrix-assisted laser desorption ionization (MALDI) was measured for five peptides using α-cyano-4-hydroxycinnanmic acid (CHCA) as the matrix. DIs were low 10(-4) for peptides and 10(-7) for CHCA. Total number of ions (i.e., peptide plus matrix) was the same regardless of peptides and their concentration, setting the number of gas-phase ions generated from a pure matrix as the upper limit to that of peptide ions. Positively charged cluster ions were too weak to support the ion formation via such ions. The total number of gas-phase ions generated by MALDI, and that from pure CHCA, was unaffected by the laser pulse energy, invalidating laser-induced ionization of matrix molecules as the mechanism for the primary ion formation. Instead, the excitation of matrix by laser is simply a way of supplying thermal energy to the sample. Accepting strong Coulomb attraction felt by cations in a solid sample, we propose three hypotheses for gas-phase peptide ion formation. In Hypothesis 1, they originate from the dielectrically screened peptide ions in the sample. In Hypothesis 2, the preformed peptide ions are released as part of neutral ion pairs, which generate gas-phase peptide ions via reaction with matrix-derived cations. In Hypothesis 3, neutral peptides released by ablation get protonated via reaction with matrix-derived cations.

Preformed ion emission is the main assumption in one of the prevailing theories for peptide and protein ion formation in matrix-assisted laser desorption ionization (MALDI). Since salts are in preformed ion forms in the matrix-analyte mixture, they are ideal systems to study the characteristics of preformed ion emission. In this work, a reliable method to measure the ion yield (IY) in MALDI was developed and used for a solid salt benzyltriphenylphosphonium chloride and two room-temperature ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate and trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate. IY for the matrix (α-cyano-4-hydroxycinnamic acid, CHCA) was also measured. Taking 1 pmol salts in 25 nmol CHCA as examples, IYs for three salts were similar, (4-8)×10−4 , and those for CHCA were (0.8-1.2)×10 −7. Even though IYs for the salts and CHCA remained virtually constant at low analyte concentration, they decreased as the salt concentrations increased. Two models, Model 1 and Model 2, were proposed to explain low IYs for the salts and the concentration dependences. Both models are based on the fact that the ion-pair formation equilibrium is highly shifted toward the neutral ion pair. In Model 1, the gas-phase analyte cations were proposed to originate from the same cations in the solid that were dielectrically screened from counter anions by matrix neutrals. In Model 2, preformed ions were assumed to be released from the solid sample in the form of neutral ion pairs and the anions in the ion pairs were assumed to be eliminated via reactions with matrix-derived cations.

OBJECTIVES We aimed to validate a multi–sensor‐based kiosk (automatically measured Short Physical Performance Battery [eSPPB] kiosk) that can perform automated measurement of the SPPB. DESIGN Prospective, cross‐sectional study. SETTING Rehabilitation clinic of a tertiary‐care hospital. PARTICIPANTS Ambulatory outpatients, aged 65 years or older (N = 40). MEASUREMENTS The eSPPB kiosk was developed to measure the three components of the SPPB: standing balance, gait speed, and chair stand test with embedded sensors and algorithms. Correlations between the total and component‐specific scores of the eSPPB and manually measured SPPB (mSPPB), assessed by a physical therapist, were assessed. Further, correlations between SPPB parameters and geriatric functional measures were also evaluated. RESULTS This study included 40 participants with a mean age of 74.4 ± 6.5 years, a mean total eSPPB score of 10.1 ± 2.1, and a mean total mSPPB score of 10.2 ± 2.1. The intraclass correlation coefficient between the eSPPB and mSPPB total score was 0.97 (P < .001), and the κ agreement was 0.79 (P < .001). The intraclass coefficients between the components of eSPPB and mSPPB were 0.77 (P < .001), 0.88 (P < .001), and 0.99 (P < .001) for standing balance, gait speed, and chair stand test, respectively. CONCLUSION The newly developed kiosk might be a viable and efficient method for performing the SPPB in older adults. J Am Geriatr Soc 67:2605–2609, 2019

Machinery operating in a nonstationary mode generates a signature that at each instant of time has a distinct frequency. A Time-frequency domain representation is needed to characterize such a signature. Pseudo Wigner–Ville distribution is ideally suited for portraying a nonstationary signal in the time-frequency domain and is carried out by adapting the fast Fourier transform algorithm. The important parameters affecting the pseudo Wigner–Ville distribution are discussed and sensitivity analyses are also performed. Practical examples of an actual transient signal are used to illustrate its dynamic features jointly in time and frequency.

A tandem time-of-flight mass spectrometer was built for photodissociation (PD) of singly protonated peptides and small proteins generated by matrix-assisted laser desorption/ionization. PD was performed in a second source after deceleration of precursor ions. The delayed extraction/post-acceleration scheme was used for the product ions. For the PD at 193 nm of small singly protonated peptides, the present instrument showed much better sensitivity and resolution for product ions than the previous one (Moon JH, Yoon SH, Kim MS, Bull. Korean Chem. Soc. 2005; 26: 763) even though the overall spectral patterns obtained with the two instruments were similar. The present instrument was inferior in precursor ion selection and background noise level. PD was achieved for precursor ions as large as the singly protonated ubiquitin (m/z 8560.63), indicating that the photoexcitation is capable of supplying a sufficient amount of internal energy to dissociate large singly protonated proteins. As the precursor ion m/z increased, however, product ion signals deteriorated rather rapidly. As in the PD of small peptide ions with m/z around 1000, the types of the product ions generated from singly protonated peptides with m/z in the range 2000-4000 were mostly determined by the positions of arginine residues. Namely, a(n) and d(n) ions dominated when an arginine residue(s) was near the N-terminus while v(n), w(n), x(n) and y(n) dominated when the same residue(s) was near the C-terminus. In addition, d(n), v(n) and w(n) ions were generated according to the correlation rules previously observed in the collisionally activated dissociation. Isoleucine and leucine isomers could be easily distinguished based on the w(n) and d(n) ions.

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Public reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing instruction, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing the collection of information. 12b. DISTRIBUTION CODE ABSTRACT (maximum 200 words)Many weapon effectiveness tools are implemented using a Monte Carlo simulation approach since closed form solutions are too mathematically intractable to compute. A question that usually arises in connection with such simulations is to ask how many iterations of a particular Monte Carlo simulation are needed. This report proposed the probability-based approach to computing effectiveness measures for better feedback to the user regarding the relationship between the number of iterations executed and confidence measures associated with the result. Reproduction of all or part of this report is authorized. NUMBER OF PAGES 30 SUBJECT TERMS

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