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51.
Tomohiro Kuwabara Takahiro Takayama Kenichiro Todoroki Koichi Inoue Jun Zhe Min Toshimasa Toyo’oka 《Analytical and bioanalytical chemistry》2014,406(11):2641-2649
Mass spectrometry has become a popular analytical tool because of its high sensitivity and specificity. The use of a chiral derivatization reagent for the mass spectrometry (MS) detection seems to be efficient for the enantiomeric separation of racemates. However, the number of chiral reagents for the liquid chromatography (LC)–MS/MS analysis is very limited. According to these observations, we are currently in the process of developing novel labeling reagents for chiral molecules in MS/MS analysis. The derivatization reagent that is effective for enhancing not only the electrospray ionization–MS/MS sensitivity but also the reversed-phase LC resolution of carboxylic acid enantiomers should have a highly proton-affinitive moiety and an asymmetric structure near the reactive functional group. Furthermore, the resulting derivative has to provide a characteristic product ion suitable for the selected reaction monitoring. Based upon these considerations, a series of prolylamidepyridines ((S)-N-pyrrolidine-2-carboxylic acid N-(pyridine-2-yl)amide (PCP2), (S)-N-pyrrolidine-2-carboxylic acid N-(pyridine-3-yl)amide, and (S)-N-pyrrolidine-2-carboxylic acid N-(pyridine-4-yl)amide) was synthesized as ideal labeling reagents for the enantioseparation of chiral carboxylic acids and evaluated in terms of separation efficiency and detection sensitivity by ultra-performance LC (UPLC)–MS/MS. Among the synthesized reagents, PCP2 was the most efficient chiral derivatization reagent for the enantioseparation of carboxylic acid. The Rs values and the detection limits of the derivatives of non-steroidal anti-inflammatory drugs, which were selected as the representative carboxylic acids, were in the range of 2.52–6.07 and 49–260 amol, respectively. The sensitive detection of biological carboxylic acids (detection limits, 32–520 amol) was also carried out by the proposed method using PCP2 and UPLC–MS/MS. The PCP2 was applied to the determination of carboxylic acids in human saliva. Several biological carboxylic acids, such as lactic acid (LA), 3-hydroxybutylic acid, maric acid, succinic acid, α-ketoglutalic acid, and citric acid, were clearly identified in the saliva of healthy persons and diabetic patients. Furthermore, the ratio of d-LA in diabetic patients was higher than that in normal subjects. Judging from these results, PCP2 seems to be a useful chiral derivatization reagent for the determination not only of chiral, but also achiral, carboxylic acids in real samples. Figure
Labeling reagent for carboxylic acids in chiral metabolomics study 相似文献
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53.
Dr. Neil J. Stewart Hitomi Nakano Shuto Sugai Mitsushi Tomohiro Yuki Kase Yoshiki Uchio Dr. Toru Yamaguchi Yujirou Matsuo Dr. Tatsuya Naganuma Dr. Norihiko Takeda Dr. Ikuya Nishimura Dr. Hiroshi Hirata Dr. Takuya Hashimoto Dr. Shingo Matsumoto 《Chemphyschem》2021,22(10):915-923
Hyperpolarized [1-13C]fumarate is a promising magnetic resonance imaging (MRI) biomarker for cellular necrosis, which plays an important role in various disease and cancerous pathological processes. To demonstrate the feasibility of MRI of [1-13C]fumarate metabolism using parahydrogen-induced polarization (PHIP), a low-cost alternative to dissolution dynamic nuclear polarization (dDNP), a cost-effective and high-yield synthetic pathway of hydrogenation precursor [1-13C]acetylenedicarboxylate (ADC) was developed. The trans-selectivity of the hydrogenation reaction of ADC using a ruthenium-based catalyst was elucidated employing density functional theory (DFT) simulations. A simple PHIP set-up was used to generate hyperpolarized [1-13C]fumarate at sufficient 13C polarization for ex vivo detection of hyperpolarized 13C malate metabolized from fumarate in murine liver tissue homogenates, and in vivo 13C MR spectroscopy and imaging in a murine model of acetaminophen-induced hepatitis. 相似文献
54.
Kawada Y Hirata H Fujii H 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,184(1):29-38
This article reports experimental investigations on the use of RF resonators for continuous-wave electron paramagnetic resonance (cw-EPR) and proton nuclear magnetic resonance (NMR) imaging. We developed a composite resonator system with multi-coil parallel-gap resonators for co-registration EPR/NMR imaging. The resonance frequencies of each resonator were 21.8MHz for NMR and 670MHz for EPR. A smaller resonator (22mm in diameter) for use in EPR was placed coaxially in a larger resonator (40mm in diameter) for use in NMR. RF magnetic fields in the composite resonator system were visualized by measuring a homogeneous 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy (4-hydroxy-TEMPO) solution in a test tube. A phantom of five tubes containing distilled water and 4-hydroxy-TEMPO solution was also measured to demonstrate the potential usefulness of this composite resonator system in biomedical science. An image of unpaired electrons was obtained for 4-hydroxy-TEMPO in three tubes, and was successfully mapped on the proton image for five tubes. Technical problems in the implementation of a composite resonator system are discussed with regard to co-registration EPR/NMR imaging for animal experiments. 相似文献
55.
Takayuki Suzuki Tomohiko Kitsukawa Yasushi Hirata Satomi Tanaka Naoya Iwasaki 《先进技术聚合物》2014,25(1):123-129
The copolymer of hydroxypropyl methacrylate (HPMA) and photochromic spiropyran methacrylate (SPMA) has been synthesized. The films of the copolymer (P(HPMA‐SPMA)) in a hydrated state showed reversible swelling–shrinking behavior in response to photoreversible isomerization and metal complexation of SPMA units in spite of covalently noncross‐linked copolymers. In addition, the protonated open form of the SPMA units of the copolymer was possibly stabilized thermodynamically by the HPMA units from ultraviolet–visible absorption measurement of the hydrated P(HPMA‐SPMA) film. On the other hand, the difference in color of the hydrated films between P(HPMA‐AABMA) and P(NIPMA‐AABMA), which was a copolymer of N‐isopropyl methacryl amide (NIPMA) and azobenzene methacrylate (AABMA) as a pH indicator, was suggestive of the interference of the proximal hydroxyl groups of the immobilized HPMA units with protonation of the AABMA units. The HPMA units of the copolymers also contributed to improvement of thermodynamic stability of the metal complexes with the SPMA units. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
56.
S. Nagadome H. Oda Y. Hirata H. Igimi A. Yamauchi Y. Sasaki G. Sugihara 《Colloid and polymer science》1995,273(7):701-707
In order to study how the bile salts and lipids behave in the vicinity of microvillus, the transport properties of a sodium salt of deoxycholic acid (NaDC) and its mixture with monooleoylglycerol (MO) through artificial membranes were investigated in 0.15 M NaCl saline solution at 37°C.The hydrodynamic radius of MO-solubilized micelles was estimated to be approximately 17–20 Å from the transport study. The thermodynamically stable MO-NaDC mixed micelles formed above critical micelle concentration in the higher region of mole fraction of NaDC in the mixture (X
NaDC>ca. 0.6), can behave as a single species in transport process and freely pass through the porous membranes of both pore sizes, 0.01 m and 0.1 m.The permeabilities of MO-NaDC mixed micelles are large compared with those of pure NaDC micelles. MO molecules solubilized may probably enhance the interaction between MO and NaDC molecules by better contacting with the respective hydrophobic groups in a mixed micelle (the flexible structure of MO molecule enables it), and in this situation, the smaller micelles compared with those of pure NaDC must be more favorable. 相似文献
57.
58.
59.
Masayuki Tomiya Takeshi Fukushima Tadahiro Ogaya Yukiko Sone Shogo Mitsuhashi Toshimasa Toyo'oka 《Biomedical chromatography : BMC》2010,24(6):569-573
The levels of kynurenic acid, an endogenous antagonist of α7 nicotinic acetylcholine and N‐methyl‐D ‐aspartate receptors, were measured in microdialysis samples obtained from the prefrontal cortices of rats using column‐switching high‐performance liquid chromatography with fluorescence detection. When the perfusate was constantly infused at a rate of 1.0 μ/min, the in vitro recovery of kynurenic acid through the dialysis membrane was approximately 20.4%, and the precision was within 1.31%. Endogenous kynurenic acid in the microdialysis sample was clearly detected using column‐switching high‐performance liquid chromatography. As an application study, N‐acetyl‐L ‐aspartic acid, an endogenous metabolite and precursor of N‐acetyl‐L ‐aspartyl‐L ‐glutamic acid, which is an agonist of metabotropic glutamate receptors, was infused for 120 min through the microdialysis probe. The kynurenic acid level significantly increased during the infusion of N‐acetyl‐L ‐aspartic acid, suggesting that kynurenic acid might have some association with N‐acetyl‐L ‐aspartic acid in vivo. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
60.
Uto Y Hirata A Fujita T Takubo S Nagasawa H Hori H 《The Journal of organic chemistry》2002,67(7):2355-2357
We have demonstrated that prenylation of p-halophenols was dependent on the solvent effect and succeeded in o,o'-diprenylation of p-halophenols in water. Following the Mizoroki-Heck coupling of the diprenyl-p-iodophenol 3c with methyl acrylate and then hydrolysis, we first synthesized artepillin C [3-(4-hydroxy-3,5-di(3-methyl-2-butenyl)phenyl)-2(E)-propenoic acid] (1), which is a biologically active constituent of propolis. These reactions may be applicable to the synthesis of various useful natural products such as 2,4,6-trisubstituted phenol derivatives. 相似文献