Surface-assisted Laser Desorption/ionization Research Articles

The Cooperativity of Fe3 O4 and Metal-Organic Framework as Multifunctional Nanocomposites for Laser Desorption Ionization Process.

A novel and facile strategy in developing a water stable magnetic metal-organic framework nanocomposite (Fe3 O4 @MOF) is herein reported, in which a Keggin polyoxometalate, phosphotungstic acid (HPW), was encapsulated within the MOF framework via one-pot synthesis method. The combination of HPW-embedded MOF and Fe3 O4 endowed the composite with high surface area, strong UV absorption, good hydrophilicity, and enhanced water stability. With these unique properties, the Fe3 O4 @MOF embedded HPW served as adsorbent as well as matrix for SALDI-MS (surface-assisted laser desorption ionization mass spectrometry) analysis of polar and non-polar compounds. The synergistic effect of Fe3 O4 and MOF showed an interference-free background at low mass region than the pristine MOF or Fe3 O4 counterparts. This simple approach can be used as new platform in developing magnetic MOF composites without the time consuming and labor-intensive preparation.

Metal oxide nanoparticles for latent fingerprint visualization and analysis of small drug molecules using surface-assisted laser desorption/ionization mass spectrometry.

We explored the applicability of different metal oxide nanoparticles (NPs; ZnO, TiO2, Fe2O3, and CeO2) for the optical imaging and mass spectrometric determination of small drug molecules in latent fingerprints (LFPs). Optical imaging was achieved using a dry method-simply dusting the LFPs with a minute amount of NP powder-and still images were captured using a digital microscope and a smartphone camera. Mass spectrometric determination was performed using the NPs as substrates for surface-assisted laser desorption ionization/mass spectrometry (SALDI-MS), which enabled the detection of small drug molecules with high signal intensities. The reproducibility of the results was studied by calculating the % error, SD, and RSD in the results obtained with the various metal oxide NPs. Collectively, the findings showed that using NPs can boost the intensity of the detected signal while minimizing background noise which is an issue predominantly associated with conventional organic matrices of MALDI-MS. Among the four metal oxide NPs, utilization of the Fe2O3 NPs led to the best SALDI performance and the highest detection sensitivity for the analytes of interest. The study was then extended by investigating the influence of time elapsed since the generation of the LFP on the detection of drug molecules in the LFP. The results demonstrated that this method allows the analysis of drug molecules after as long as one week at low and intermediate temperatures (0 and 25°C). Therefore, the SALDI analysis of small molecules using inorganic NPs, which can be implemented in forensic laboratories for screening and detection purposes, as a powerful alternative to the use of organic matrices. Graphical abstract ᅟ.

A Versatile Integrated Ambient Ionization Source Platform.

The pursuit of high-throughput sample analysis from complex matrix demands development of multiple ionization techniques with complementary specialties. A versatile integrated ambient ionization source (iAmIS) platform is proposed in this work, based on the idea of integrating multiple functions, enhancing the efficiency of current ionization techniques, extending the applications, and decreasing the cost of the instrument. The design of the iAmIS platform combines flowing atmospheric pressure afterglow (FAPA) source/direct analysis in real time (DART), dielectric barrier discharge ionization (DBDI)/low-temperature plasma (LTP), desorption electrospray ionization (DESI), and laser desorption (LD) technique. All individual and combined ionization modes can be easily attained by modulating parameters. In particular, the FAPA/DART&DESI mode can realize the detection of polar and nonpolar compounds at the same time with two different ionization mechanisms: proton transfer and charge transfer. The introduction of LD contributes to the mass spectrometry imaging and the surface-assisted laser desorption (SALDI) under ambient condition. Compared with other individual or multi-mode ion source, the iAmIS platform provides the flexibility of choosing different ionization modes, broadens the scope of the analyte detection, and facilitates the analysis of complex samples. Graphical abstract ᅟ.

Transition metal oxide nanoparticles as surfaces for surface-assisted laser desorption/ionization mass spectrometry of asphaltenes

ABSTRACTWe report the first use of NiO, Fe3O4, TiO2, and Co3O4 nanoparticles as surfaces for surface-assisted laser desorption/ionization (SALDI) mass spectrometry of asphaltenes. Higher signal-to-noise ratios (S/Ns) for asphaltene species were observed using NiO and Fe3O4 nanoparticles for SALDI as compared to LDI, where both surfaces consistently provided 2- to 3-fold improved S/Ns. The new SALDI detection method showed reliable adsorption data measuring supernatant solutions after 24 hour asphaltene adsorption on NiO, Fe3O4, and Co3O4. These results indicated that NiO has a higher adsorption affinity than Fe3O4 and Co3O4 for asphaltene molecules, corroborating reported asphaltene adsorption on metal oxide nanoparticles.

Nanoaggregates of Diverse Asphaltenes by Mass Spectrometry and Molecular Dynamics

Asphaltene nanoaggregates for three diverse source materials—coal-derived asphaltenes dominated by aromatic carbon, petroleum asphaltenes with comparable abundances of aromatic and aliphatic carbon, and immature source-rock asphaltenes dominated by aliphatic carbon—are examined by means of surface-assisted laser desorption ionization mass spectrometer (SALDI-MS) coupled with laser desorption laser ionization mass spectrometry (L2MS). All three types of asphaltenes form nanoaggregates with aggregation numbers close to 7. Molecular dynamics calculations for proposed island molecular structures show the important roles that π-stacking and alkane steric hindrance play in nanoaggregate formation. These results are discussed in terms of entropy and enthalpy changes. All results are consistent with the Yen-Mullins model, which bodes well for its expanded use in oilfield reservoir evaluations.

Salt Segregation and Sample Cleanup on Perfluoro-Coated Nanostructured Surfaces for Laser Desorption Ionization Mass Spectrometry of Biofluid Samples.

We present a surface assisted laser desorption ionization (SALDI) technique, coupled with fluorocarbon coating, to achieve selective segregation of ionic and/or hydrophilic analytes from background biofluid electrolytes for quantiatve mass spectrometric analysis. By controlling the contact angle of (1H,1H,2H,2H-perfluorooctyl) trichlorosilane or (1H,1H,2H,2H-perfluorooctyl) dimethylchlorosilane to a specific range (105-120°), background electrolytes can be made to segregate from hydrophilic analytes during a drying step on the surface of a highly nanoporous thin film. Nanoporous silicon films were prepared using glancing angle deposition (GLAD) thin film technology, then coated with fluorcarbon. This desalting method directly separates highly polar, ionic metabolites, such as amino acids, from salty biofluids such as aritificial cerebrospinal fluid (aCSF) and serum. Derivatization, extraction and rinsing steps are not required to separate the analytes from the bioelectrolytes. With on-chip desalting, the limit of quantitation for histidine spiked in aCSF is ∼1 μM, and calibration curves with internal standards can achieve a precision of 1-9% within a 1 to 50 μM range. Five highly polar organic acids in serum were successfully quantified, and the SALDI-MS results obtained on the desalted serum sample spots show both good reproducibility and compare well to results from NMR and liquid chromatography-mass spectrometry. Putative identification of a total of 32 metabolites was accomplished in blood using time-of-flight MS with perfluoro coated Si-GLAD SALDI, by comparison to tabulated data.

Silver-gold alloy nanoparticles as tunable substrates for systematic control of ion-desorption efficiency and heat transfer in surface-assisted laser desorption/ionization.

Systematically controlling heat transfer in the surface-assisted laser desorption/ionization (SALDI) process and thus enhancing the analytical performance of SALDI-MS remains a challenging task. In the current study, by tuning the metal contents of Ag-Au alloy nanoparticle substrates (AgNPs, Ag55Au45NPs, Ag15Au85NPs and AuNPs, ∅: ∼2.0 nm), it was found that both SALDI ion-desorption efficiency and heat transfer can be controlled in a wide range of laser fluence (21.3 mJ cm-2 to 125.9 mJ cm-2). It was discovered that ion detection sensitivity can be enhanced at any laser fluence by tuning up the Ag content of the alloy nanoparticle, whereas the extent of ion fragmentation can be reduced by tuning up the Au content. The enhancement effect of Ag content on ion desorption was found to be attributable to the increase in laser absorption efficiency (at 355 nm) with Ag content. Tuning the laser absorption efficiency by changing the metal composition was also effective in controlling the heat transfer from the NPs to the analytes. The laser-induced heating of Ag-rich alloy NPs could be balanced or even overridden by increasing the Au content of NPs, resulting in the reduction of the fragmentation of analytes. In the correlation of experimental measurement with molecular dynamics simulation, the effect of metal composition on the dynamics of the ion desorption process was also elucidated. Upon increasing the Ag content, it was also found that phase transition temperatures, such as melting, vaporization and phase explosion temperature, of NPs could be reduced. This further enhanced the desorption of analyte ions via phase-transition-driven desorption processes. The significant cooling effect on the analyte ions observed at high laser fluence was also determined to be originated from the phase explosion of the NPs. This study revealed that the development of alloy nanoparticles as SALDI substrates can constitute an effective means for the systematic control of ion-desorption efficiency and the extent of heat transfer, which could potentially enhance the analytical performance of SALDI-MS.

Carbon nanocoatings: A new approach to recording mass spectra of low-molecular compounds using surface-assisted laser desorption/ionization mass spectrometry

A simple and rapid approach to obtaining target plates for the investigation of low-molecularweight compounds by surface-assisted laser desorption/ionization (SALDI) mass spectrometry is proposed. It consists in the vacuum sputtering of a carbon layer with a thickness of about 50 nm onto a metal surface. The resulting coatings are characterized by homogeneity, hydrophobicity, and high mechanical strength, which eliminates a possibility of mass spectrometer contamination. A comparison of the SALDI mass spectra of test compounds recorded using conventional carbon materials and carbon nanocoatings demonstrates advantages of the last named materials, such as high spectral resolution and the absence of spectral interferences at low m/z values.

Revisiting the quantitative features of surface-assisted laser desorption/ionization mass spectrometric analysis.

Surface-assisted laser desorption/ionization (SALDI) coupled with mass spectrometry (MS) is frequently used to analyse small organics owing to its clean background. Inorganic materials can be used as energy absorbers and the transfer medium to facilitate the desorption/ionization of analytes; thus, they are used as SALDI-assisting materials. Many studies have demonstrated the usefulness of SALDI-MS in quantitative analysis of small organics. However, some characteristics occurring in SALDI-MS require certain attention to ensure the reliability of the quantitative analysis results. The appearance of a coffee-ring effect in SALDI sample preparation is the primary factor that can affect quantitative SALDI-MS analysis results. However, to the best of our knowledge, there are no reports relating to quantitative SALDI-MS analysis that discuss or consider this effect. In this study, the coffee-ring effect is discussed using nanoparticles and nanostructured substrates as SALDI-assisting materials to show how this effect influences SALDI-MS analysis results. Potential solutions for overcoming the existing problems are also suggested.This article is part of the themed issue 'Quantitative mass spectrometry'.

“RaMassays”: Synergistic Enhancement of Plasmon-Free Raman Scattering and Mass Spectrometry for Multimodal Analysis of Small Molecules

SiO2/TiO2 core/shell (T-rex) beads were exploited as “all-in-one” building-block materials to create analytical assays that combine plasmon-free surface enhanced Raman scattering (SERS) and surface assisted laser desorption/ionization (SALDI) mass spectrometry (RaMassays). Such a multi-modal approach relies on the unique optical properties of T-rex beads, which are able to harvest and manage light in both UV and Vis range, making ionization and Raman scattering more efficient. RaMassays were successfully applied to the detection of small (molecular weight, M.W. <400 Da) molecules with a key relevance in biochemistry and pharmaceutical analysis. Caffeine and cocaine were utilized as molecular probes to test the combined SERS/SALDI response of RaMassays, showing excellent sensitivity and reproducibility. The differentiation between amphetamine/ephedrine and theophylline/theobromine couples demonstrated the synergistic reciprocal reinforcement of SERS and SALDI. Finally, the conversion of L-tyrosine in L-DOPA was utilized to probe RaMassays as analytical tools for characterizing reaction intermediates without introducing any spurious effects. RaMassays exhibit important advantages over plasmonic nanoparticles in terms of reproducibility, absence of interference and potential integration in multiplexed devices.

Nanosecond UV Laser Ablation of Gold Nanoparticles: Enhancement of Ion Desorption by Thermal-Driven Desorption, Vaporization, or Phase Explosion

The phase transition of surface-assisted laser desorption/ionization (SALDI) substrates has been identified as a driving process for ion desorption in many previous SALDI fundamental studies. Here, the effects of various phase transition stages, including substrate melting, vaporization, and phase explosion, on SALDI ion desorption efficiency and extent of heat transfer were investigated. We employed molecular dynamics to simulate the phase transition (from melting, vaporization, to phase explosion) of gold nanoparticles (AuNPs, ⌀: 2.5 nm) upon laser-induced heating and experimentally probed the corresponding SALDI ion desorption efficiency and extent of heat transfer to a chemical thermometer, benzylpyridinium (BP) salt (using 355 nm solid-state laser, pulse width: 6 ns, laser fluence range: 21.3 to 125.9 mJ/cm2). The results showed that substrate phase explosion has the most significant effect on enhancing the ion desorption efficiency and lowering the extent of heat transfer, which were reflected by an...

Impact of Laboratory-Induced Thermal Maturity on Asphaltene Molecular Structure

The structure of asphaltenes of various maturities prepared by semiopen pyrolysis of Green River Shale is measured by elemental analysis, laser desorption laser ionization mass spectrometry (L2MS), surface assisted laser desorption ionization (SALDI) mass spectrometry, sulfur X-ray absorption near edge structure (XANES) spectroscopy, and infrared (IR) spectroscopy. These measurements demonstrate systematic changes in the composition of asphaltenes during thermal maturation. At low maturities, the evolution of asphaltene composition is dominated by changes in the heteroatoms: total sulfur as well as carbon–oxygen, sulfur–oxygen (sulfoxide), and aliphatic carbon–sulfur (sulfide) bonds are lost, while the molecular weight increases. At high maturities, the sulfur content and speciation as well as molecular weight are relatively constant while the evolution in composition is dominated by changes in the carbon backbone: the abundance of aromatic relative to aliphatic carbon increases, the length of aliphatic chains shortens, and the abundance of aromatic C–H bonds increases greatly. The distribution of different carbon–oxygen functional groups is relatively unchanged over the entire maturity range. These changes sometimes mirror and sometimes oppose compositional changes in the bitumen, suggesting that the composition of the asphaltene and maltene fractions of bitumen evolve differently. The observed changes in asphaltene structure are not fully independent of one another, as the composition of asphaltenes is constrained to maintain a balance of the strength of intermolecular forces to ensure solubility in aromatic solvent and insolubility in aliphatic solvent (the definition of asphaltenes). That constraint leads to a decrease in sulfoxide content (weakening intermolecular forces by reducing dipole interactions) concurrent with an increase in molecular weight (strengthening intermolecular forces). These trends in asphaltene composition with maturity are expected to occur in naturally occurring source rocks, such as some tight-oil formations, but not necessarily in conventional reservoir rocks where the asphaltenes escape from the source rock and enter the reservoir during maturation.

Surface-Transfer Mass Spectrometry Imaging of Renal Tissue on Gold Nanoparticle Enhanced Target.

Renal cell carcinoma (RCC) accounts for several percent of all adult malignant tumor cases and is directly associated with over 120 thousand death cases worldwide annually. Therefore, there is a need for cancer biomarker tests and methods capable of discriminating between normal and malignant tissue. It is demonstrated that gold nanoparticle enhanced target (AuNPET), a nanoparticle-based, surface-assisted laser desorption/ionization (SALDI)-type mass spectrometric method for analysis and imaging, can differentiate between normal and cancerous renal tissue. Diglyceride DG(18:1/20:0)-sodium adduct and protonated octadecanamide ions were found to have greatly elevated intensities in cancerous part of analyzed tissue specimen. Compounds responsible for mentioned ions formation were pointed out as a potential clear cell RCC biomarkers. Their biological properties and localization on the tissue surface are also discussed. Potential application of presented results may also facilitate clinical decision making during surgery for large renal masses.

Hybrid organic–inorganic silica based particles for latent fingermarks development: A review

Recent progress in nanotechnology has led to the emergence of many new methods of latent fingermarks development. However, there is still need for a material that is easy to detect and has a high affinity to the latent fingermarks ridges. One way to combine these two features are hybrid organic–inorganic silica based composite materials. The chemical nature of silica lets for its simple modification with various organic moieties by organosilanes chemistry. Moreover, nanoparticles, quantum dots, molecules etc. can be easily embedded in the silicate matrix. In this work, the use of silica based materials for fingermarks development have been summarized. Three main groups of the materials have been isolated: SiO2 based composites, porous phosphate heterostructures and desorption/ionization facilitating agents for surface-assisted laser desorption ionization time-of-flight mass spectrometry.

Assemblies of gold nanorods for efficient SALDI mass spectrometry

Surface-assisted laser desorption/ionization (SALDI) mass spectrometry was performed using gold nanorods deposited on ITO plates. The degree of aggregation of the nanorods was controlled on the plates, and the relationship between the SALDI signals and the longitudinal surface plasmon (SP) bands of the gold nanorods were examined. Highly efficient SALDI processes were obtained when the bandwidth of the SP bands was about 300 nm. Optical dark field and SEM observations showed that fusion and ablation of nanorod-assemblies consisting of 4–10 gold nanorods contributed to the efficient SALDI processes.

Laser Desorption Ionization Mass Spectrometry Imaging of Drosophila Brain Using Matrix Sublimation versus Modification with Nanoparticles.

Laser desorption ionization mass spectrometry (LDI-MS) is used to image brain lipids in the fruit fly, Drosophila, a common invertebrate model organism in biological and neurological studies. Three different sample preparation methods, including sublimation with two common organic matrixes for matrix-assisted laser desorption ionization (MALDI) and surface-assisted laser desorption ionization (SALDI) using gold nanoparticles, are examined for sample profiling and imaging the fly brain. Recrystallization with trifluoroacetic acid following matrix deposition in MALDI is shown to increase the incorporation of biomolecules with one matrix, resulting in more efficient ionization, but not for the other matrix. The key finding here is that the mass fragments observed for the fly brain slices with different surface modifications are significantly different. Thus, these approaches can be combined to provide complementary analysis of chemical composition, particularly for the small metabolites, diacylglycerides, phosphatidylcholines, and triacylglycerides, in the fly brain. Furthermore, imaging appears to be beneficial using modification with gold nanoparticles in place of matrix in this application showing its potential for cellular and subcellular imaging. The imaging protocol developed here with both MALDI and SALDI provides the best and most diverse lipid chemical images of the fly brain to date with LDI.

Silver nanoparticle functionalized glass fibers for combined surface-enhanced Raman scattering spectroscopy (SERS)/surface-assisted laser desorption/ionization (SALDI) mass spectrometry via plasmonic/thermal hot spots.

We presented the fabrication of a silver nanoparticle (Ag NP) functionalized glass fiber (Ag-GF) substrate for combined surface-enhanced Raman scattering spectroscopy (SERS)/surface-assisted laser desorption/ionization (SALDI) mass spectrometry. Ag NPs were immobilized onto the surface of glass fibers through a simple sputter deposition process. The SERS and SALDI activities strongly depended on the nanostructures of the deposited Ag NPs on the GFs. The closely-packed Ag NPs with a size of 20-50 nm and an inter-particle nanoscale gap of less than 10 nm were effective for the simultaneously enhanced SERS/SALDI substrate via plasmonic/thermal "hot spots", while the interconnected continuous Ag film reduced both the SERS/SALDI activities. The SERS enhanced factor (EFSERS) and SALDI enhanced factor (EFSALDI) were newly proposed. Finally, the concentration-dependent signal intensities of SERS and SALD-MS of sulfur compounds using an identical Ag NP-GF substrate were examined, and the linear dependence relationship in the log-log plot was demonstrated for the combined quantitative SERS/SALDI-MS analysis.

Ion-Desorption Efficiency and Internal-Energy Transfer in Surface-Assisted Laser Desorption/Ionization: More Implication(s) for the Thermal-Driven and Phase-Transition-Driven Desorption Process

Fundamental factors governing the ion-desorption efficiency and extent of internal-energy transfer to a chemical thermometer, benzylpyridinium ion ([BP]+), generated in the surface-assisted laser desorption/ionization (SALDI) process, were systematically investigated using noble metal nanoparticles (NPs), including AuNPs, AgNPs, PdNPs, and PtNPs, as substrates, with an average particle size of 1.7–3.1 nm in diameter. In the correlation of ion-desorption efficiency and internal-energy transfer with physicochemical properties of the NPs, laser-induced heating of the NPs, which are dependent on their photoabsorption efficiencies, was found to be a key factor in governing the ion-desorption efficiency and the extent of internal-energy transfer. This suggested that the thermal-driven desorption played a significant role in the ion-desorption process. In addition, a stronger binding affinity of [BP]+ to the surface of the NPs could hinder its desorption from the NPs, and this could be another factor in determin...

Analytical capabilities of surface-assisted laser desorption/ionization in the determination of low-molecular-weight volatile compounds

Main approaches to the determination of low-molecular-weight chemical compounds by surfaceassisted laser desorption/ionization (SALDI) are considered. Analytes are adsorbed from a gas phase on the surface of a specially prepared solid-state substrate. Then, the surface is exposed to pulse laser radiation, which leads to ionization and desorption of ions to be detected with a mass analyzer. The factors responsible for the efficiency of ionization are examined, the instrumental versions of SALDI are presented, and the metrological characteristics of this method are given. The high ionization efficiency of basic compounds, which is higher than the efficiency of traditional ionization methods by orders of magnitude, the mild conditions of ionization, the simplicity of performance, and the possibility of combinations with analyte separation systems characterize SALDI as an exceptionally promising method for the determination of low-molecular-weight volatile compounds.

A novel type of matrix for surface-assisted laser desorption–ionization mass spectrometric detection of biomolecules using metal-organic frameworks

A 3D metal-organic framework (MOF) nanomaterial as matrix for surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) and tandem mass spectrometry (MS/MS) was developed for the analysis of complex biomolecules. Unlike other nanoparticle matrices, this MOF nanomaterial does not need chemical modification prior to use. An exceptional signal reproducibility as well as very low background interferences in analyzing mono-/di-saccharides, peptides and complex starch digests demonstrate its high potential for biomolecule assays, especially for small molecules.