Is energy pooling necessary in ultraviolet matrix-assisted laser desorption/ionization?

RATIONALE: Energy pooling has been suggested as the key process for generating the primary ions during ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI). In previous studies, decreases in fluorescence quantum yields as laser fluence increased for 2-aminobenzoic acid, 2,5-dihydroxybenzoic acid (2,5-DHB), and 3-hydroxypicolinic acid were used as evidence of energy pooling. This work extends the research to other matrices and addresses whether energy pooling is a universal property in UV-MALDI. METHODS: Energy pooling was investigated in a time-resolved fluorescence experiment by using a short laser pulse (355 nm, 20 ps pulse width) for excitation and a streak camera (1 ps time resolution) for fluorescence detection. RESULTS: The excited-state lifetime of 2,5-DHB decreased with increases in laser fluence. This suggests that a reaction occurs between two excited molecules, and that energy pooling may be one of the possible reactions. However, the excited-state lifetime of 2,4,6-trihydroxyacetophenone (THAP) did not change with increases in laser fluence. The upper limit of the energy pooling rate constant for THAP is estimated to be approximately 100-500 times smaller than that of 2,5-DHB. CONCLUSIONS: The small energy pooling rate constant for THAP indicates that the potential contribution of the energy pooling mechanism to the generation of THAP matrix primary ions should be reconsidered.

Fluorescence spectroscopy of UV-MALDI matrices and implications of ionization mechanisms.

Matrix-assisted laser desorption ionization (MALDI) has been widely used in the mass analysis of biomolecules; however, there are a lot of debates about the ionization mechanisms. Previous studies have indicated that S1-S1 annihilation might be a key process in the generation of primary ions. This study investigates S1-S1 annihilation by examining the time-resolved fluorescence spectra of 12 matrices. No S1-S1 annihilation was observed in six of these matrices (3-hydroxy-picolinic acid, 6-aza-2-thiothymine, 2,4-dihydroxy-acetophenone, 2,6-dihydroxy-acetophenone, 2,4,6-trihydroxy-acetophenone, and ferulic acid). We observed two matrix molecules reacting in an electronically excited state (S1) in five of these matrices (2,5-dihydroxybenzoic acid, α-cyano-4-hydroxycinnamic acid, 2,5-dihydroxy-acetophenone, 2,3-dihydroxybenzoic acid, and 2,6-dihydroxybenzoic acid), and S1-S1 annihilation was a possible reaction. Among these five matrices, no S1-S1 annihilation was observed for 2,3-dihydroxybenzoic acid in typical peak power region of nanosecond laser pulses in MALDI, but a very small value of reaction rate constant was observed only in the high peak power region. The excited-state lifetime of sinapinic acid was too short to determine whether the molecules reacted in an electronically excited state. No correlation was observed between the ion generation efficiency of MALDI and S1-S1 annihilation. The results indicate that the proposal of S1-S1 annihilation is unnecessary in MALDI and energy pooling model for MALDI ionization mechanism has to be modified.

Production of silver ions from colloidal silver by nanoparticle iontophoresis system.

Metal ions, especially the silver ion, were used to treat infection before the initiation of antibiotic therapy. Unfortunately, there is a lack of research on the metallic nanoparticle suspension as a reservoir for metal ion release application. For medical purposes, conversion of colloidal silver into an ionic form is necessary, but not using silver salts (e.g., AgNO3, Ag2SO4), due to the fact that the counter-ion of silver salts may cause problems to the body as the silver ion (Ag+) is consumed. The goal of this research is to develop a silver nanoparticle iontophoresis system (NIS) which can provide a relatively safe bactericidal silver ion solution with a controllable electric field. In this study, ion-selective electrodes were used to identify and observe details of the system's activity. Both qualitative and quantitative data analyses were performed. The experimental results show that the ion releasing peak time (R(PT)) has an inversely proportional relationship with the applied current and voltage. The ion releasing maximum level (R(ML)) and dosage (R(D)) are proportional to the current density and inversely proportional to the voltage, respectively. These results reveal that the nanoparticle iontophoresis system (NIS) is an alternative method for the controlled release of a metal ion and the ion's concentration profile, by controlling the magnitude of current density (1 microA/cm2 equal to 1 ppm/hour) and applied voltage.

Control release of bactericidal ion by an electronically driven system.

There is a dramatic proliferation of research related to electronically generated metallic bactericidal ions. Unfortunately, there are no literature reviews or discussions concerning metallic-nanoparticle suspension as a drug reservoir for iontophoretic applications. Heavy metals, especially silver, are frequently used to treat infection before the development of systemic antimicrobial agents. For medical applications, the conversion of colloidal silver into its ionic form is required; however, it does not directly use silver salts to provide the silver ions, due to the counter-ion (e.g., NO3-, SO4-) content of silver salts, which may cause severe problems to the body as the silver ion is consumed. The goal of this research is to develop an electronic dissociation system (EDS), which can provide a relatively safe bactericidal ion (Ag+) solution from the silver nanoparticles that has a controllable electric field. In this study, an ionic selective electrode (ISE) was used to observe and identify the details of the system activity throughout the course of the experiment. Both qualitative and quantitative data analyses were performed. The experimental data indicated that EDS can control the parameters of ion-releasing profiles, including the area under curve (AUC, dosage), rate of profile rise and fall, total dissociation time, peak time, and peak level concentration by a constant voltage (CV) mode or constant current (CC) mode. However, the CC mode was proved to be more controllable (an increase of 200 microA, equal to an increase of 1 ppm/hour), as the premeditated driving force is more precise, and relies on the current not voltage. This technology will be used to develop a chemical residue-free administration of control-released medical devices for iontophoretic applications.

Colloidal silver fabrication using the spark discharge system and its antimicrobial effect on Staphylococcus aureus.

Nanoscale techniques for silver production may assist the resurgence of the medical use of silver, especially given that pathogens are showing increasing resistance to antibiotics. Traditional chemical synthesis methods for colloidal silver (CS) may lead to the presence of toxic chemical species or chemical residues, which may inhibit the effectiveness of CS as an antibacterial agent. To counter these problems a spark discharge system (SDS) was used to fabricate a suspension of colloidal silver in deionized water with no added chemical surfactants. SDS-CS contains both metallic silver nanoparticles (Ag(0)) and ionic silver forms (Ag(+)). The antimicrobial affect of SDS-CS on Staphylococcus aureus was studied. The results show that CS solutions with an ionic silver concentration of 30 ppm or higher are strong enough to destroy S. aureus. In addition, it was found that a solution's antimicrobial potency is directly related to its level of silver ion concentration.

Ion intensity and thermal proton transfer in ultraviolet matrix-assisted laser desorption/ionization.

The ionization mechanism of ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI) was investigated by measuring the total cation intensity (not including sodiated and potasiated ions) as a function of analyte concentration (arginine, histidine, and glycine) in a matrix of 2,4,6-trihydroxyacetophenone (THAP). The total ion intensity increased up to 55 times near the laser fluence threshold as the arginine concentration increased from 0% to 1%. The increases were small for histidine, and a minimal increase occurred for glycine. Time-resolved fluorescence intensity was employed to investigate how analytes affected the energy pooling of the matrix. No detectable energy pooling was observed for pure THAP and THAP/analyte mixtures. The results can be described by using a thermal proton transfer model, which suggested that thermally induced proton transfer is crucial in the primary ion generation in UV-MALDI.