Matrix For Matrix-assisted Laser Research Articles

Boron nitride quantum dots-enhanced laser desorption/ionization mass spectrometry analysis and imaging of bisphenol A

Bisphenol A (BPA) displays harmful effects on the human health, including potent endocrine activity and potential impact on the development of cancer. Analysis BPA residues in water and plastic products attracted considerable attention in the past decades. However, dominantly used conventional analysis techniques are unable to directly and non-destructively identify the correct species of BPA in plastic products. Hence, this study demonstrates the effective utilisation of boron nitride quantum dots (BNQDs) as an inorganic matrix in matrix-assisted laser desorption/ionization mass spectrometry analysis and imaging (MALDI-MS & MSI) for BPA. The presence of abundant hydroxyl and amino groups on the BNQDs’ surface is favourable for the formation of hydrogen bonds with BPA, and increases their ionization and chemoselectivity. Intriguingly, the BNQDs matrix offers a distinct signal for phenolic hazardous molecules featuring different hydroxyl groups. The method was applied to detect BPA at nanomolar level in environmental water, and also allowed non-destructive and in situ mapping of BPA in plastics and pacifiers. This research provides a novel strategy for adapting nanomaterials as inorganic matrices for analysis of small molecular pollutants in environmentally relevant samples using MALDI-MS & MSI.

Sublimation application of 5-chloro-2-mercaptobenzothiazole matrix for matrix-assisted laser desorption/ionization mass spectrometry imaging of mouse kidney.

Sublimation is a solvent-free technique used to apply a uniform matrix coating over a large sample plate, improving the matrix's purity and enhancing the analyte signal. Although the 5-chloro-2-mercaptobenzothiazole (CMBT) matrix was introduced years ago, there are no reports of its application via sublimation. We investigated the experimental parameters that are optimal for CMBT matrix sublimation on mouse kidney samples. We also evaluated the stability of the sublimed CMBT matrix under a vacuum environment. Using kidney samples prepared with a sublimated CMBT matrix, we conducted matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) analysis of specific phospholipids (phosphatidylcholine and phosphatidylglycerol in the positive ion mode and phosphatidylinositol in the negative ion mode). We also explored various spatial resolutions (50, 20, and 10μm) and performed sequential MALDI-hematoxylin and eosin (H&E) staining. The CMBT matrix was applied to kidney samples using a sublimation apparatus connected to a vacuum pump to achieve a pressure of 0.05 Torr. The matrix was then subjected to different temperatures and sublimation times to determine the optimal conditions for matrix application. Subsequently, a Q-Exactive mass spectrometer equipped with a Spectroglyph MALDI ion source was employed for MALDI-MSI experiments. Standard protocols were followed for H&E staining after MALDI analysis. A matrix thickness of 0.15 mg/cm2 yielded high-quality images. The sublimated matrix exhibited minimal loss after approximately 20 h of exposure to a vacuum of 7Torr, indicating its stability under these conditions. Ion images were successfully obtained at spatial resolutions of 50, 20, and 10μm. Furthermore, orthogonal histological information was obtained through sequential MALDI-H&E staining. We demonstrate that samples prepared for MALDI-MSI using sublimation to apply the CMBT matrix yield high-quality mass spectrometric images of mouse kidney sections. We also provide data for the impact of various experimental parameters on image quality (e.g., temperature, time, matrix thickness, and spatial resolution).

Mass Spectrometry Imaging of Low-Molecular-Weight Phenols Liberated from Plastics.

The abundant and heterogeneous distribution of toxic phenol from plastics has drawn worldwide attention. However, the common analysis methods failed to identify the accurate species of these phenolic hazards from plastics in a direct and nondestructive approach. Herein, we demonstrate the layered double hydroxides (LDHs) as a novel matrix in matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI) for low-molecular-weight phenols leaked from plastics. LDHs own abundant hydroxyl groups to facilitate chemoselectivity and ionization of phenols through the formation of hydrogen bonds with these phenols. More importantly, the LDH matrix could provide a distinguishable signal for the homolog and isomeride of these phenolic hazards. The developed method could realize nondestructive and in situ mapping of phenolic hazards in plastics. Our success could help to track the low-molecular-weight compounds liberated from plastics and supply spatial information for polluted plastics. We anticipated that the proposed approach could provide sufficient information to evaluate and alarm the safety of food packaging plastics.

Fullerenol as a water-soluble MALDI-MS matrix for rapid analysis of small molecules and efficient quantification of saccharin sodium in foods

Due to the strong background interferences in the low-mass region and poor reproducibility of conventional organic matrices, it is of great importance to develop a novel matrix for matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) to qualitatively and quantitatively analyze small molecules. In this work, water-soluble fullerenol C60(OH)24–26 was selected as a MALDI matrix for the analysis of low-molecular-weight compounds in consideration of optical absorption property, water solubility and stability. Compared with the traditional matrices, fullerenol demonstrated lower background interference and stronger peak intensity. In addition, the hydrophilic fullerenol could avoid the heterogeneous crystallization in sample preparation, increase the reproducibility and sensitivity of MALDI-MS, and ameliorate quantitative analysis of small molecules. With saccharin as model analyte, quantitative analysis was carried out using fullerenol as matrix. The results demonstrated satisfying reproducibility and good tolerance to salt. The limit-of-detection of the quantitative analysis was as low as 4 pmol, and the linear range is 1–100 μg mL−1 with R2 greater than 0.99. The analytical results also showed excellent precision and accuracy, low matrix effect and good recovery rate. Fullerenol as a potential matrix was further validated in the quantification of saccharin sodium in different real food samples, such as nuts and drinks. This work not only confirms the potential of fullerenol for the quantitative analysis in food field, but also provides a new technique for rapid analysis of small molecules.

Using solid-state nuclear magnetic resonance to rationalize best efficiency of 2,6-dihydroxybenzoic acid over other 2,X-dihydroxybenzoic acid isomers in solvent-free matrix-assisted laser desorption/ionization of poly(ethylene glycol).

Among isomers of dihydroxybenzoic acid (DHB), 2,5-DHB is often the most efficient matrix in matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) for a great variety of compounds. Yet, when performing solvent-free MALDI, 2,6-DHB yields better results for poly(ethylene glycol [PEG]). This intriguing feature is explored here using solid-state nuclear magnetic resonance (NMR). Ternary mixtures were prepared by grinding 2,X-DHB (X = 3-6), poly(ethylene glycol) (Mn = 2000 g mol-1 ) and lithium fluoride (LiF) in a matrix/analyte/salt molar ratio of 50/1/10 for 16 min under a controlled atmosphere. After mixing, a few grains were applied to the MALDI target for MS analysis, whereas the major part of the ground sample was transferred into rotors to perform 13 C, 7 Li, and 19 F NMR experiments. Lithiated PEG chains are mainly formed with 2,6-DHB in solvent-free MALDI, but their abundance increases with 2,3-DHB and 2,4-DHB when water uptake is favored by a humid atmosphere. Solid-state NMR shows that grinding 2,6-DHB-based samples in atmospheric conditions leads to a solid phase in which the matrix, PEG, and salt molecules exhibit a high mobility compared with systems involving other 2,X-DHB isomers. This mobile environment would favor (as a solvent) LiF dissociation and best promote PEG cationization. Complementary data in 13 C, 7 Li, and 19 F NMR spectra are consistent with the formation of a solid phase of high mobility composed of 2,6-DHB, PEG, and the two salt components that ultimately favor the production of lithiated PEG chains.

Synthesis and application of nitrogen-doped carbon dots as a matrix in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Nitrogen-doped carbon dots (N-CDs) were synthesized by microwave-assisted pyrolysis of citric acid and urea for use as an alternative matrix for the detection of small molecules using matrix-assisted laser desorption/ionization spectrometry (MALDI-MS). The synthesis of N-CDs is much simpler than that of other nitrogen-doped carbon matrices used in MALDI-MS, which has been a major limitation to its application. The synthesized N-CDs were characterized using various analytical methods. The high optical absorbance and good dispersibility of the obtained N-CDs showed them to be an ideal matrix for detecting analytes such as glucose, sucrose, amino acids, nilotinib, and polyethylene glycols. The application of N-CDs as a MALDI matrix improved the signal response of small molecules due to the specific aromatic structure and the doping of nitrogen atoms. The minimum detectable amounts using an N-CDs matrix in MALDI-MS were found to be in the range of 1 nmol–1 pmol, with a lower minimum detectable amount of arginine (1 pmol) than previously reported.

Analysis of Nitropolycyclic Aromatic Hydrocarbons in Fine Particulate Matter by Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Using Fe3O4/ZIF-8 Magnetic Nanocomposites as Matrix

Core-shell magnetic metal organic nanocrystals were synthesized and used as matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). Four nitropolycyclic aromatic hydrocarbons (nitro-PAHs) were successfully detected by using negative-ion MALDI-TOF MS without background interference. Furthermore, the magnetic nanocomposites (MNCs) coated with zeolitic imidazolate framework-8 (ZIF-8) showed excellent adsorption and enrichment capacity, and can be isolated with a magnet and directly spotted on the stainless steel plate for MALDI measurement. It was also analyzed nitro-PAHs in PM2.5 samples using the ZIF-8-coated magnetic nanocomposite as adsorbent and matrix.

Wafer-level detection of organic contamination by ZnO-rGO hybrid-assisted laser desorption/ionization time-of-flight mass spectrometry

A technique for wafer-level detection of organic contaminations via surface-assisted laser desorption/ionization time-of-flight mass spectrometry was developed. To replace the organic matrix in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, zinc oxide-reduced graphene oxide (ZnO-rGO) hybrid was prepared by a hydrothermal reaction and used as the matrix in the detection of benzo[a]pyrene (B[a]P). By varying the rGO content and the amount of hybrid, the optimal rGO content in the hybrid for the detection of B[a]P was determined to be 4 wt% and the optimal amount of hybrid was 20 ng. The limit of detection of this method was found to be 1.6 × 1014 C atoms cm−2, which is lower than the concentration of residual organic contamination at which serious failure occurs during semiconductor fabrication. This method was also successfully used to detect other aromatic and aliphatic species on a semiconductor wafer. This approach is fast, accurate, simple, and inexpensive compared to other conventional methods, and can be used to identify localized micro-contamination in the semiconductor industry.

Investigation of colloidal graphite as a matrix for matrix-assisted laser desorption/ionisation mass spectrometry of low molecular weight analytes.

The analysis of low molecular weight compounds by matrix-assisted laser desorption/ionisation mass spectrometry is problematic due to the interference and suppression of analyte ionisation by the matrices typically employed - which are themselves low molecular weight compounds. The application of colloidal graphite is demonstrated here as an easy to use matrix that can promote the ionisation of a wide range of analytes including low molecular weight organic compounds, complex natural products and inorganic complexes. Analyte ionisation with colloidal graphite is compared with traditional organic matrices along with various other sources of graphite (e.g. graphite rods and charcoal pencils). Factors such as ease of application, spectra reproducibility, spot longevity, spot-to-spot reproducibility and spot homogeneity (through single spot imaging) are explored. For some analytes, considerable matrix suppression effects are observed resulting in spectra completely devoid of matrix ions. We also report the observation of radical molecular ions [M(-●) ] in the negative ion mode, particularly with some aromatic analytes. Copyright © 2016 John Wiley & Sons, Ltd.

Humic acids as both matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and adsorbent for magnetic solid phase extraction

In the present study, humic acids (HAs) were applied as both a matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and an adsorbent of magnetic solid phase extraction (MSPE) for the first time. As natural macromolecule compounds, HAs are inherently highly functionalized and contain laser energy absorbing–transferring aromatic structures. This special molecular structure made HAs a good candidate for use as a MALDI matrix in small molecule analysis. At the same time, due to its good adsorption ability, HAs was prepared as MSPE adsorbent via a simple co-mixing method, in which the commercially available HAs were directly mixed with Fe3O4 magnetic nanoparticles (MNPs) in a mortar and grinded evenly and completely. In this process, MNPs were physically wrapped and adhered to tiny HAs leading to the formation of magnetic HAs (MHAs). To verify the bi-function of the MHAs, Rhodamine B (RdB) was chosen as model compound. Our results show that the combination of MHAs-based MSPE and MALDI-TOF-MS can provide a rapid and sensitive method for the determination of RdB in chili oil. The whole analytical procedure could be completed within 30 min for simultaneous determination of more than 20 samples, and the limit of quantitation for RdB was found to be 0.02 μg/g. The recoveries in chili oil were in the range 73.8–81.5% with the RSDs less than 21.3% (intraday) and 20.3% (interday). The proposed strategy has potential applications for high-throughput analysis of small molecules in complex samples.

5-Methoxysalicylic acid matrix for ganglioside analysis with matrix-assisted laser desorption/ionization mass spectrometry.

In this note, we report that high quality ganglioside profiles with minimal loss of sialic acid residues can be obtained in the positive ion mode by using a 5-methoxysalicylic acid (MSA) matrix for matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS). Our results showed that MSA produced much less sialic acid losses from gangliosides than DHB, although MSA and DHB are differ only by their functional groups at their 5-positions (-OH for DHB and -OCH(3) for MSA). Furthermore, our data also demonstrated that addition of an alkali metal additive was effective for simplifying ganglioside profiles, but not necessary for stabilizing glycosidic bonds of gangliosides if MSA was used as a matrix. This suggests that MALDI MS with MSA has a potential to gain additional benefits from the positive-ion mode analyses without losing performance in ganglioside profiling.

Application of Modified Mesoporous Silica Materials for Analysis of Small Molecules by MALDI-TOF-MS

Abstract Mesoporous silica SBA-15 with a small organic molecular (1,8-naphthalimide) was synthesized as the matrix for matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS) analysis. A modified SBA-15 matrix, SBA-15-NA (1,8-naphthalimide) was synthesized by covalently attaching SBA-15 to an 1,8-naphthalimide formed by 1,8-naphthalic anhydride and 3-(trimethoxysilyl) propylamine. The mass spectra obtained with SBA-15-NA exhibited less background interference ions, higher desorption/ionization efficiency, higher peak intensity. The matrix were initially prepared in methanol and mixed with analyte at a 1:1 volume ratio in vial. The solution of mixture was at a 10:1 concentration ratio of matrix/analyte on a stainless steel target and allowed to air dry. The method was used to analyze various types of low molecular weight (less than 500) chemical compounds such as monosaccharides, amino acids, phytohormones, drugs. Under the optimum conditions, a low detection limit of 1 × 10 −9 g L −1 (Leucine, S / N = 5) and a good reproducibility of ≤ 30% were obtained. The modified mesoporous silica materials were employed in the urinary study for the direct detection of metabolites.

Electrospun polystyrene/oxidized carbon nanotubes film as both sorbent for thin film microextraction and matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

In the current study, polystyrene/oxidized carbon nanotubes (PS/OCNTs) film was prepared and applied as both an adsorbent of thin film microextraction (TFME) and matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI–TOF–MS) for the first time. The uniform size of PS/OCNTs film with OCNTs evenly and firmly immobilized in PS was obtained by electrospinning. And a novel TFME device was developed using the prepared PS/OCNTs film to enrich benzo[a]pyrene (BaP) from water, and also BaP and 1-hydroxypyrene (1-OHP) from urine sample. Then the extracted analytes on the PS/OCNTs film were directly applied to MALDI–MS analysis with PS/OCNTs film as the MALDI matrix. Our results show that PS/OCNTs film is a good TFME adsorbent toward the analytes and an excellent matrix for the sensitive determination of BaP and 1-OHP using MALDI–TOF–MS. The employment of PS/OCNTs as the matrix for MALDI can effectively avoid the large variation of signal intensity normally resulting from heterogeneous distribution of the adsorbed analyte on matrix layer, which therefore significantly improve spot-to-spot reproducibility. The introduction of PS in the film can prevent OCNTs from flying out of MALDI plate to damage the equipment. In addition, PS/OCNTs film also largely extended the duration of ion signal of target analyte compared to OCNTs matrix. The developed method was further successfully used to quantitatively determine BaP in environmental water and 1-OHP in urine samples. The results show that BaP and 1-OHP could be easily detected at concentrations of 50pgmL−1 and 500pgmL−1, respectively, indicating the high detection sensitivity of this method. For BaP analysis, the linear range was 0.1–20ngmL−1 with a correlation coefficient of 0.9970 and the recoveries were in the range of 81.3 to 123.4% with the RSD≤8.5% (n=3); for urinary 1-OHP analysis, the linear range was 0.5–20ngmL−1 with a correlation coefficient of 0.9937 and the recoveries were in the range of 79.2 to 103.4% with the RSD≤7.6% (n=3). Taken together, the developed method provides a simple, rapid, cost-effective and high-throughput approach for the analysis of BaP in environmental water and endogenous 1-OHP in urine samples.

A Thiophene-Containing Compound as a Matrix for Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry and the Electrical Conductivity of Matrix Crystals

The electrical conductivity of the matrix crystal might be a new factor to enhance matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) sensitivity. In MALDI-MS, several compounds are used as a standard matrix. Utilization of such compounds is based on an a posteriori approach, but there is no theoretical guidance for selecting a matrix. In an attempt to further understand performance in MALDI-MS, we utilized peptide detection for random screening of a chemical library (12,383 compounds) for compounds with matrix functions in MALDI-MS. A lot of thiophene compounds were found to be a matrix, in which 2-[5-(2,4-dichlorobenzoyl)-2-thienyl] acetic acid (DCBTA) provided an important clue to measure the electrical conductivity of the matrix crystal, because the structure of DCBTA is analogous to conductive polymers and organic solar cells. Most of the crystals of standard matrices, such as alpha-cyano-4-hydroxycinnamic acid (CHCA), 3,5-dimethoxy-4-hydroxycinnamic acid [sinapinic acid, (SA)], and DCBTA showed electrical conductivity, whereas the conductivity of crystal was not observed in 2,5-dihydroxybenzoic acid (2,5-DHB). On the other hand, super-DHB using 2-hydroxy-5-methoxybenzoic acid [5-methoxysalicylic acid, (MSA)] as an additive to 2,5-DHB, improved the electrical conductivity of the crystal, that followed the enhancement of peak intensity in MS spectrum. These observations might indicate that the electrical conductivity of matrix crystals is a key consideration in obtaining efficient MALDI performance.

Molecular histology analysis by matrix‐assisted laser desorption/ionization imaging mass spectrometry using gold nanoparticles as matrix

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.

In-Source Decay and Fragmentation Characteristics of Peptides Using 5-Aminosalicylic Acid as a Matrix in Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

The use of 5-aminosalicylic acid (5-ASA) as a new matrix for in-source decay (ISD) of peptides including mono- and di-phosphorylated peptides in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) is described. The use of 5-ASA in MALDI-ISD has been evaluated from several standpoints: hydrogen-donating ability, the outstanding sharpness of molecular and fragment ion peaks, and the presence of interference peaks such as metastable peaks and multiply charged ions. The hydrogen-donating ability of several matrices such as alpha-cyano-4-hydroxycinnamic acid (CHCA), 2,5-dihydroxybenzoic acid (2,5-DHB), 1,5-diaminonaphthalene (1,5-DAN), sinapinic acid (SA), and 5-ASA was evaluated by using the peak abundance of a reduction product [M + 2H + H](+) to that of non-reduced protonated molecule [M + H](+) of the cyclic peptide vasopressin which contains a disulfide bond (S-S). The order of hydrogen-donating ability was 1,5-DAN > 5-ASA > 2,5-DHB > SA = CHCA. The chemicals 1,5-DAN and 5-ASA in particular can be classified as reductive matrices. 5-ASA gave peaks with higher sharpness for protonated molecules and fragment ions than other matrices and did not give any interference peaks such as multiply-protonated ions and metastable ions in the ISD mass spectra of the peptides used. Particularly, 1,5-DAN and 5-ASA gave very little metastable peaks. This indicates that 1,5-DAN and 5-ASA are more "cool" than other matrices. The 1,5-DAN and 5-ASA can therefore be termed "reductive cool" matrix. Further, it was confirmed that ISD phenomena such as N-Calpha bond cleavage and reduction of S-S bond is a single event in the ion source. The characteristic fragmentations, which form a- and (a + 2)-series ions, [M + H - 15](+), [M + H - 28](+), and [M + H - 44](+) ions in the MALDI-ISD are described.

Effect of the Addition of Diammonium Citrate to α-Cyano-4-Hydroxycinnamic Acid (CHCA) Matrix for the Detection of Phosphorylated Peptide in Phosphorylation Reactions Using Cell and Tissue Lysates

The ionization of phosphorylated peptides is usually suppressed by non-phosphorylated peptides when alpha-cyano-4-hydroxycinnamic acid (CHCA) is used as a matrix for matrix-assisted laser desorption/ionization-time-of-Flight (MALDI-TOF) mass spectrometry analysis. In the present study, we examined the effect of diammonium citrate addition to the CHCA matrix on the detection of phosphorylated peptides. Substrates for protein kinase C (PKC) and c-Src were synthesized and phosphorylated by reaction with cell and tissue lysate samples. The addition of diammonium citrate to the CHCA matrix increased the sensitivity for distinguishing phosphorylated peptides from background noise. However, the effect depended on substrate concentration.

2,5-Dihydroxybenzoic acid instead of α-cyano-4-hydroxycinnamic acid as matrix in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for analyses of in-gel digests of silver-stained proteins

2,5-Dihydroxybenzoic acid instead of α-cyano-4-hydroxycinnamic acid as matrix in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for analyses of in-gel digests of silver-stained proteins

Silver nanoparticles as matrix for laser desorption/ionization mass spectrometry of peptides

Silver nanoparticle synthesized from chemical reduction has been successfully utilized as a matrix in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) of peptides. Acting as a substrate to adsorb analytes, as well as a transmission medium for UV laser, silver nanoparticle was found to assist in the desorption/ionization of peptides with little or no induced fragmentation. The size of the nanoparticle was typically in the range of 160 ± 20 nm. One of the key advantages of silver nanoparticle for peptides analysis is its simple step for on-probe sample preparation. In addition, it also minimizes the interferences of sodium dodecyl sulfate (SDS) surfactant background signal, resulting in cleaner mass spectra and more sensitive signal, when compared to α–cyano-4-hydroxycinnamic acid (CCA) matrix.

Mesoporous tungsten titanate as matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis of biomolecules

In this paper, mesoporous tungsten titanate (WTiO) with different nano-pore structures was utilized as matrix for the analysis of short peptides by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). Effect of characteristic features of mesoporous matrices on laser desorption/ionization process was investigated. Experiments showed that the ordered two-dimensional and three-dimensional mesoporous matrices were superior in performance to the non-ordered WTiO matrix. The dramatic enhancement of signal sensitivity by the ordered mesoporous matrices can be reasonably attributed to the ordered structure, which facilitated the understanding on structure–function relationship in mesoporous cavity for laser desorption process of adsorbed biomolecules. With the ordered mesoporous matrix, the short peptides are successfully detected. The presence of trace alkali metal salt effectively increased the analyte ion yields and the MALDI-TOFMS using the inorganic mesoporous matrices displayed a high salt tolerance. The developed technique also showed a satisfactory performance in peptide-mapping and amino-acid sequencing analysis.