• Mass Spectrometry Letters
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• 제5권2호
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• pp.49-51
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• 2014

The effectiveness of tertiary matrices composed of the combination of three common matrices (dihydrobenzoic acid (DHB), ${\alpha}$-cyano-4-hydroxycinnamic acid (CHCA), and sinapinic acid (SA)) was compared with that of single or binary matrices in the analysis of polyethylene glycol (PEG) polymers ranging from 1400 to 10000 Da using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). A tertiary matrix of 2,5-DHB+CHCA+SA was the most effective in terms of S/N ratios. CHCA and CHCA+SA produced the highest S/N ratios among the single matrices and the binary matrices, respectively. The improvement observed when using a tertiary matrix in analyses of PEG polymers by MALDI-TOF MS is believed to be due to the uniform morphology of the MALDI sample spots and synergistic effects arising from the mixture of the three matrix materials.

• Bulletin of the Korean Chemical Society
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• 제31권1호
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• pp.116-119
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• 2010

Adsorption structures of the self-assembled thin films of $\alpha$-cyano-4-hydroxycinnamic acid (CHCA) anchoring on $TiO_2$ surfaces have been studied by using temperature-dependent diffuse reflectance infrared Fourier-transform (DRIFT) spectroscopy. From the presence of the strong $\nu(COO^-)$ band at ~1390 $cm^{-1}$ along with the disappearance of the OH bands in the carboxylic acid group in the DRIFT spectra at room temperature, CHCA appeared to adsorb onto $TiO_2$ surfaces as a carboxylate form. The absence of the out-of-plane benzene ring modes of CHCA in the DRIFT spectra suggests a rather vertical orientation of CHCA on $TiO_2$. Above ~220$ ^{\circ}C$, CHCA seemed to start to thermally degrade on $TiO_2$ surfaces referring from the disappearance of most vibrational modes in the DRIFT spectra, whereas the $\nu$(C ≡ N) bands were found to remain relatively conspicuous as the temperature increased even up to ~460$^{\circ}C$.

• Bulletin of the Korean Chemical Society
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• 제33권9호
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• pp.2955-2960
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• 2012

Product ion yields in the in- and post-source decays of three peptide ions, $[Y_5X+H]^+$ (X = Y (tyrosine), K (lysine), and R (arginine)), generated by matrix-assisted laser desorption ionization (MALDI) were measured at six wavelengths, 307, 317, 327, 337, 347, and 357 nm, using ${\alpha}$-cyano-4-hydroxycinnamic acid (CHCA) and 2,5-dihydroxybenzoic acid (DHB) as the matrices. The temperatures of the early and late plumes generated by MALDI were estimated via kinetic analysis of the product ion yield data. For both matrices, the temperature drop (${\Delta}T$), i.e. the difference in the temperature between the early and late plumes, displayed negative correlation with the absorption coefficient. This was in agreement with the previous reasoning that deeper laser penetration and larger amount of material ablation arising from smaller absorption coefficient would result in larger extent of expansion cooling. The results support the postulation of the expansion cooling occurring in the plume presented previously.

• Mass Spectrometry Letters
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• 제2권3호
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• pp.69-72
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• 2011

Defective synthesis of the steroid hormones by the adrenal cortex has profound effects on human development and homeostasis. Due to the time-consuming chromatography procedure combined with mass spectrometry, the matrix-assisted laser desorption ionization method coupled to the linear ion-trap tandem mass spectrometry (MALDI-LTQ-MS/MS) was developed for quantitative analysis of 10 adrenal steroids in human serum. Although MALDI-MS can be introduced for its applicability as a high-throughput screening method, it has a limitation on reproducibility within and between samples, which renders poor reproducibility for quantification. For quantitative MALDI-MS/MS analysis, the stable-isotope labeled internal standards were used and the conditions of crystallization were tested. The precision and accuracy were 3.1~35.5% and 83.8~138.5%, respectively, when a mixture of 10 mg/mL ${\alpha}$-cyano-4-hydroxycinnamic acid in 0.2% TFA of 70% acetonitrile was used as the MALDI matrix. The limit of quantification ranged from 5 to 340 ng/mL, and the linearity as a correlation coefficient was higher than 0.988 for all analytes in the calibration range. Clinical applications include quantitative analyses of patients with congenital adrenal hyperplasia. The devised MALDI-MS/MS technique could be successfully applied to diagnosis of clinical samples.

• Bulletin of the Korean Chemical Society
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• 제31권8호
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• pp.2293-2298
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• 2010

Focused electrospray (FES) deposition method is presented for matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. FES ion optics consists of two cylindrical focusing electrodes capped with a truncated conical electrode through which an electrospray emitter passes along the cylindrical axis. A spray of charged droplets is focused onto a sample well on a MALDI target plate under atmospheric pressure. The shape and size distributions of matrix crystals are visualized by scanning electron microscope and the mass spectra are obtained by time-of-flight mass spectrometry. Angiotensin II, bradykinin, and substance P are used as test samples, while $\alpha$-cyano-4-hydroxycinnamic acid and dihydroxybenzoic acid are employed as matrices. FES of a sample/matrix mixture produces fine crystal grains on a 1-3 mm spot and reproducibly yields the mass spectra with little shot-to-shot and spot-to-spot variations. Although FES greatly stabilizes the signals, the space charge due to matrix ions limits the detection sensitivity of peptides. To avoid the space charge problem, we adopted a dual FES/FES mode, which separately deposits matrix and sample by FES in sequence. The dual FES/FES mode reaches the detection sensitivity of 0.88 amol, enabling ultrasensitive of peptides by homogeneously depositing matrix and sample under atmospheric pressure.