Search

Quantitative analysis of binary mixtures of tris(2-phenylpyridinato)iridium(III) (Ir(ppy)3) and tris(8-hydroxyquinolinato)aluminum (Alq3) by using an artificial neural network (ANN) system to mass spectra was attempted based on the results of a VAMAS (Versailles Project on Advanced Materials and Standards) interlaboratory study (TW2 A31) to evaluate matrix-effect correction and to investigate interface determination. Monolayers of binary mixtures having different Ir(ppy)3ratios (0, 0.25, 0.50, 0.75, and 1.00), and the multilayers containing these mixtures and pure samples were measured using time-of-flight secondary ion mass spectrometry (ToF-SIMS) with different primary ion beams, OrbiSIMS (SIMS with both Orbitrap and ToF mass spectrometers), laser desorption ionization (LDI), desorption/ionization induced by neutral clusters (DINeC), and X-ray photoelectron spectroscopy (XPS). The mass spectra were analyzed using a simple ANN with one hidden layer. The Ir(ppy)3ratios of the unknown samples and the interfaces of the multilayers were predicted using the simple ANN system, even though the mass spectra of binary mixtures exhibited matrix effects. The Ir(ppy)3ratios at the interfaces indicated by the simple ANN were consistent with the XPS results and the ToF-SIMS depth profiles. The simple ANN system not only provided quantitative information on unknown samples, but also indicated important mass peaks related to each molecule in the samples without a prioriinformation. The important mass peaks indicated by the simple ANN depended on the ionization process. The simple ANN results of the spectra sets obtained by a softer ionization method, such as LDI and DINeC, suggested large ions such as trimers. From the first step of the investigation to build an ANN model for evaluating mixture samples influenced by matrix effects, it was indicated that the simple ANN method is useful for obtaining candidate mass peaks for identification and for assuming mixture conditions that are helpful for further analysis.

In this study, we investigate the formation and composition of Gas Cluster Ion Beams (GCIBs) and their application in Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) analysis. We focus on altering the carrier gas composition, leading to the formation of (Ar/CO2)nor (H2O)nGCIBs. Our results demonstrate that the addition of a reactive species (CO2) to water GCIBs significantly enhances the secondary ion yield of small pharmaceutical compounds in the positive ion mode. In negative ion mode, the addition of CO2resulted in either a positive enhancement or no effect, depending on the sample. However, an excess of CO2in the carrier gas leads to the formation of carbon dioxide clusters, resulting in reduced yields compared to that of water cluster beams. Cluster size also plays a crucial role in overall yields. In a simple two-drug system, CO2-doped water clusters prove effective in mitigating matrix effects in positive ion mode compared to pure water cluster, while in negative ion mode, this effect is limited. These clusters are also applied to the analysis of drugs in a biological matrix, leading to more quantitative measurements as shown by a better fitting calibration curve. Overall, the doping of water clusters with small amounts of a reactive gas demonstrates promising benefits for higher sensitivity, higher resolution molecular analysis, and imaging using ToF-SIMS. The effectiveness of these reactive cluster beams varies depending on the experimental parameters and sample type.

This paper sets out in vitro protocols for studying the relative effectiveness of chelators used in the dissolution-based treatment of hard calcinosis. Pulverized hard calcinosis samples from human donors or synthetic hydroxyapatite nanoparticles were deposited by electrophoretic deposition on the surface of a quartz crystal microbalance sensor. Over 150 deposits of <20 μg were dissolved over the course of 1 h by aliquots of buffered, aqueous solutions of two calcium chelators, EDTA and citrate, with the surface-limited dissolution kinetics monitored with <1 s time resolution. There was no statistically significant difference in dissolution rate between the four synthetic hydroxyapatite materials in EDTA, but the dissolution rates in citrate were lower for hydroxyapatite produced by acetate or nitrate metathesis. Hard calcinosis and synthetic hydroxyapatites showed statistically identical dissolution behavior, meaning that readily available synthetic mimics can replace the rarer samples of biological origin in the development of calcinosis treatments. EDTA dissolved the hydroxyapatite deposits more than twice as fast as citrate at pH 7.4 and 37 °C, based on a first-order kinetic analysis of the initial frequency response. EDTA chelated 6.5 times more calcium than an equivalent number of moles of citrate. Negative controls using nonchelating N,N,N′,N′-tetraethylethylenediamine (TEEDA) showed no dissolution effect. Pharmaceutical dissolution testing of synthetic hydroxyapatite tablets over 6 h showed that EDTA dissolved the tablets four to nine times more quickly than citrate.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging has been used for the direct analysis of single intact Xenopus laevisembryo surfaces, locating multiple lipids during fertilization and the early embryo development stages with subcellular lateral resolution (∼4 μm). The method avoids the complicated sample preparation for lipid analysis of the embryos, which requires selective chemical extraction of a pool of samples and chromatographic separation, while preserving the spatial distribution of biological species. The results show ToF-SIMS is capable of profiling multiple components (e.g., glycerophosphocholine, SM, cholesterol, vitamin E, diacylglycerol, and triacylglycerol) in a single X. laevisembryo. We observe lipid remodeling during fertilization and early embryo development via time course sampling. The study also reveals the lipid distribution on the gamete fusion site. The methodology used in the study opens the possibility of studying developmental biology using high resolution imaging MS and of understanding the functional role of the biological molecules.

Secondary ion emission from water ice has been studied using Au+, Au3+, and C60+primary ions. In contrast to the gas phase in which the spectra are dominated by the (H2O)nH+series of ions, the spectra from ice using all three primary ions are principally composed of two series of cluster ions (H2O)nH+and (H2O)n+. Dependent on the conditions, the unprotonated series can dominate the spectra. Since in the gas phase (H2O)n+is unstable with respect to the formation of the protonated ion series, the presence of the solid must provide a means to stabilize their formation. The cluster ion yields under Au+bombardment are very low and can be understood in terms of sputtering on the borderline between linear cascade and thermal spike behavior. There is a 104increase in yield across the whole spectrum compared to Au+when Au3+and C60+species are used as primary ions. The character of the spectra differed between these two primary ions, but insights into the mechanism of secondary ion emission for both is discussed within an energy deposition framework provided by the fluid flow-based mesoscale energy deposition footprint (MEDF) model that predicts a cone-shaped zone of activation and emission. C60+differs from Au3+in that it delivers its energy closer to the surface, and it is argued this has consequences for the cluster ion distribution and yield. Increasing the ion dose by sputtering suppresses the yield of (H2O)n+and increases the yield of the protonated ions in the small cluster region, whereas the yield in the large cluster regime is suppressed significantly. The three primary ions show rather different behavior, and this is discussed in the light of the sputtering models. Finally, negative ion spectra including cluster ions have been observed for the first time. C60+delivers the highest yields, but these are less than 10 times the positive ion yields, probably because the O and OH fragment ions on which the clusters are based are easily neutralized by protons.

Various epidemiological studies show a positive correlation between high intake of dietary FAs and metastatic prostate cancer (CaP). Moreover, CaP metastasizes to the bone marrow, which harbors a rich source of lipids stored within adipocytes. Here, we use Fourier transform infrared (FTIR) microspectroscopy to study adipocyte biochemistry and to demonstrate that PC-3 cells uptake isotopically labeled FA [deuterated palmitic acid (D31-PA)] from an adipocyte. Using this vibrational spectroscopic technique, we detected subcellular locations in a single adipocyte enriched with D31-PA using the as+s(C-D)2+3(D31-PA): as+s(C-H)2+3(lipid hydrocarbon) signal. In addition, larger adipocytes were found to consist of a higher percentage of D31-PA of the total lipid found within the adipocyte. Following background subtraction, the as(C-D)2+3signal illuminated starved PC-3 cells cocultured with D31-PA-loaded adipocytes, indicating translocation of the labeled FA. This study demonstrates lipid-specific translocation between adipocytes and tumor cells and the use of FTIR microspectroscopy to characterize various biomolecular features of a single adipocyte without the requirement for cell isolation and lipid extraction.

Various epidemiological studies show a positive correlation between high intake of dietary FAs and metastatic prostate cancer (CaP). Moreover, CaP metastasizes to the bone marrow, which harbors a rich source of lipids stored within adipocytes. Here, we use Fourier transform infrared (FTIR) microspectroscopy to study adipocyte biochemistry and to demonstrate that PC-3 cells uptake isotopically labeled FA [deuterated palmitic acid (D31-PA)] from an adipocyte. Using this vibrational spectroscopic technique, we detected subcellular locations in a single adipocyte enriched with D31-PA using the υas+s(C-D)2+3(D31-PA): υas+s(C-H)2+3(lipid hydrocarbon) signal. In addition, larger adipocytes were found to consist of a higher percentage of D31-PA of the total lipid found within the adipocyte. Following background subtraction, the υas(C-D)2+3signal illuminated starved PC-3 cells cocultured with D31-PA-loaded adipocytes, indicating translocation of the labeled FA. This study demonstrates lipid-specific translocation between adipocytes and tumor cells and the use of FTIR microspectroscopy to characterize various biomolecular features of a single adipocyte without the requirement for cell isolation and lipid extraction.

Three hydroxyapatite bioceramics incorporating either titaniumiv and fluoride, or titaniumiv, fluoride and salicylate have been prepared. Each bioceramic was analysed using XPS, ToF-SIMS, X-ray powder diffraction, 31P19F MAS solid state NMR and Diffuse Reflectance FTIR spectroscopic techniques. The results acquired suggest that titaniumiv substitutes for calcium, and fluoride substitutes for hydroxide ion within the HA matrix, the two processes being essentially independent. Data obtained also reveal a greater incorporation of titaniumiv in the bioceramic containing titanium, fluoride and salicylate.