Ion desorption efficiency and internal energy transfer were probed and correlated in carbon-based surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) using benzylpyridinium (BP) salt as the thermometer chemical. In a SALDI-MS experiment with a N(2) laser (at 337 nm) used as the excitation light source and with multiwalled carbon nanotubes (CNT), buckminsterfullerene (C(60)), nanoporous graphitic carbon (PGC), non-porous graphite particles (G), highly oriented pyrolytic graphite (HOPG), or nanodiamonds (ND) as the SALDI substrate, both the desorption efficiency in terms of ion intensity of BP and the extent of internal energy transfer to the ions are dependent on the type and size of the carbon substrates. The desorption efficiency (CNT approximately C(60) > PGC > G > HOPG > ND) in general exhibits an opposite trend to the extent of internal energy transfer (CNT < C(60) approximately PGC < G approximately HOPG < ND), suggesting that increasing the extent of internal energy transfer in the SALDI process may not enhance the ion desorption efficiency. This phenomenon cannot be explained by a thermal desorption mechanism, and a non-thermal desorption mechanism is proposed to be involved in the SALDI process. The morphological change of the substrates after the laser irradiation and the high initial velocities of BP ions (1100-1400 ms(-1)) desorbed from the various carbon substrates suggest that phase transition/destruction of substrates is involved in the desorption process. Weaker bonding/interaction and/or a lower melting point of the carbon substrates favor the phase transition/destruction of the SALDI substrates upon laser irradiation, consequently affecting the ion desorption efficiency.

Latent fingerprint (LFP) detection is a top-priority task in forensic science. It is a simple and effective means for the identification of individuals. Development of nanomaterials which maximize the surface interaction with endogenous substances on the ridges to enhance the contrast of the fingerprints is an important application of nanotechnology in LFP detection. However, most developments in this area have mainly focused on the visualization of the physical pattern of the fingerprints and failed to explore the molecular information embedded in LFPs. Here, we have integrated certain distinctive properties of gold nanoparticles (AuNPs) with imaging mass spectrometry for both the visualization and molecular imaging of LFPs. Two contrasting colors (blue and pink), arising from different surface plasmon resonance (SPR) bands of the AuNPs, reveal the optical images of LFPs. The laser desorption/ionization property of the AuNPs allows the direct analysis of endogenous and exogenous compounds embedded in LFPs and imaging their distributions without disturbing the fingerprint patterns. The simultaneous visualization of LFP and the recording of its molecular images not only provide evidence on individual identity but also resolve overlapping fingerprints and detect hazardous substances.

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 determining the ion-desorption efficiency. Moreover, metal NPs with lower melting points could also facilitate the ion-desorption process via the phase-transition process, which could lower the activation barrier (ΔG # ) of the iondesorption process by increasing the entropic change (ΔS # ). The study reveals that high photoabsorption efficiency, weak binding interaction with analyte molecule, and low melting point could be critical for the design of SALDI substrates with efficient ion desorption. ■ INTRODUCTIONSurface-assisted laser desorption/ionization (SALDI), a major branch of laser desorption/ionization (LDI) techniques, has been widely applied to mass spectrometry (MS) analysis of small molecules, and has become increasingly popular for analysis of environmental samples, forensic samples, drugs, metabolomics, and proteomics, and for imaging mass spectrometric analysis. 1−7 A key to its success is the adoption of effective substrates for the efficient absorption and controllable transfer of laser energy, which enables the efficient desorption/ionization of analyte molecules, without inducing extensive fragmentation and without introducing serious interfering background ions. Although SALDI-MS using carbon particles as the substrate was first developed in 1995, 8 the technique became popular after the introduction of nanostructured porous silicon surface as the substrate to attain a high LDI efficiency at low laser fluence. 9−11 Since then, different types and forms of inorganic-based nanomaterials, including silicon-based, 12−15 carbon-based, 1,8,16−21 and metalbased nanomaterials, 22−31 have been developed as SALDI substrates, though their analytical performances are varied and are highly dependent on their sizes, shapes, and surface properties.Fundamental study of the LDI process remains a challenging issue. While matrix-assisted laser desorption/ionization (MALDI), using organic acids as a matrix, has been developed since the 1980s, it took about two decades for its mechanism to become better studied and unde...

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) was applied to the direct analysis of melamine cyanurate (MC). The three commonly used MALDI matrixes, namely, alpha-cyano-4-hydroxycinnamic acid (CHCA), sinapinic acid (SA), and 2,5-dihydroxybenzoic acid (DHB), were able to desorb/ionize melamine from MC upon N(2) laser irradiation, with CHCA showing the highest detection sensitivity in the positive mode. Only DHB and SA were able to desorb/ionize cyanuric acid from MC in the negative mode but with remarkably lower sensitivity. The method is able to detect melamine unambiguously from a small amount of MC (down to 12.5 microg) spiked into urine and was successfully applied for the rapid and sensitive detection of melamine in urine stones/residues of the samples collected from patients clinically confirmed of having kidney stones associated with the consumption of melamine-tainted food products. The urine matrix resulted in interfering ion peaks and suppressed the ion intensity of melamine, while a cleanup process consisting of simply washing with water eliminated such interference and enhanced the ion intensity. The merit of the method is simplicity in sample preparation. The analytical time of the method for high-throughput analysis from the time of sample treatment to analysis is less than 7 minutes per sample, with sensitive detection of the presence of melamine in the urine stones/residues of the patient samples.

Tissue-spray ionization mass spectrometry is developed for the in situ chemical analysis of raw herbs under ambient conditions. We demonstrated that analyte molecules could be directly sprayed and ionized from solvent-wetted ginseng tissues upon the application of high electrical voltage to the tissue sample. Abundant phytochemicals/ metabolites, including ginsenosides, amino acids and oligosaccharides, could be detected from ginseng tissues when the tissue-spray experiments were conducted in positive ion mode. Thermally labile and easily hydrolyzed malonyl-ginsenosides were also detected in negative ion mode. The tissue-spray ionization method enables the direct detection of analytes from raw herb samples and preserves the sample integrity for subsequent morphological and/ or microscopic examination. In addition, this method is simple and fast for chemical profiling of wild-type and cultivated-type American ginsengs with differentiation.

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 solidstate laser, pulse width: 6 ns, laser fluence range: 21.3 to 125.9 mJ/cm 2 ). 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 abrupt increase in both the ion desorption efficiency and the survival yield, when the laser fluence exceeded the AuNPs' phase explosion threshold temperature (5800 K). Compared with phase explosion, vaporization only exhibited a limited effect on the ion desorption efficiency, while the effect of melting was not noticeable and even overridden by the thermal-driven desorption. The significant effect of phase explosion on enhancing the ion desorption efficiency could be attributed to the weaker binding interaction between the BP ions and the Au atoms which were rapidly ablated during the phase explosion stage, and the cooling effect on the BP ions could be due to the adiabatic expansion of the ablation plume during the phase explosion. The study revealed that the SALDI substrate with a lower phase explosion threshold would have a higher potential in enhancing the analytical performance of SALDI-MS.

Gold nanoparticles (AuNPs) were applied and optimized as matrix for matrix-assisted laser desorption/ionization mass spectrometry analysis of animal tissues, and enabled histological analysis of animal tissues at molecular level by imaging mass spectrometry (IMS). AuNPs were coated on animal tissue in a solvent-free manner via argon ion sputtering. Metabolites, including neurotransmitters, fatty acids and nucleobases, were directly detected from mouse brain tissue. Based on region-specific chemical profiles, fine histological features of mouse brain tissue and heterogeneous regions of tumor tissue were both revealed.

Both the polarity and the porosity of the spraying tip materials could significantly affect detection sensitivity for a wide variety of analytes. With proper choice of spraying tip material, ESI on a porous spraying tip could be a sensitive method for the direct analysis of daily life samples.