N-tert-Butoxy-1-aminopyrenyl Radicals. Isolation,Electronic Structure,and Magnetic Characterization

N-tert-Butoxy-2,7-di-tert-butyl-1-pyrenylaminyl (4), N-tert-butoxy-2-tert-butyl-1-pyrenylaminyl (5), and N-tert-butoxy-7-tert-butyl-1-pyrenylaminyl (6) free radicals were generated by the reaction of the lithium amides of the corresponding 1-aminopyrenes with tert-butyl peroxybenzoate in THF at -78 degrees C. Although 6 could not be isolated due to the gradual decomposition in solution, 4 and 5 were quite persistent and could be isolated as monomeric radical crystals. The X-ray crystallographic analyses for the isolated free radicals were successfully carried out, indicating that the N and O atoms are almost coplanar with the pyrene ring. The ESR spectra of 4 and 5 were very complex due to the presence of many magnetically unequivalent protons. Therefore, the proton hyperfine coupling (hfc) constants were determined by (1)H ENDOR/TRIPLE resonance spectroscopy. To assign the hfc constants for the pyrene ring protons, a partially deuterated radical, 4-d(4), was prepared and the ENDOR and ESR spectra were measured. To discuss the spin density distribution for 4 and 5 ab initio molecular orbital calculations were performed by the DFT UBecke 3LYP method, using the STO 6-31G basis set. Magnetic susceptibility measurements were carried out for 4 and 5 with a SQUID magnetometer. For 4 a weak antiferromagnetic interaction was observed, and for 5 a very strong antiferromagnetic interaction was observed. The antiferromagnetic interactions were explained by their crystal structures.     

Lipid peroxidation of the erythrocyte membrane caused by stimulated polymorphonuclear leukocytes in the presence of ferritin

Lipid peroxidation of erythrocyte membrane was caused by phorbol myristate acetate (PMA)-stimulated polymorphonuclear leukocytes (PMN) in the presence of ferritin. PMN themselves were not peroxidized. A lag period was observed before the start of the peroxidation reaction. In contrast, ferritin iron was continuously released by PMA-stimulated PMN, suggesting that accumulation of free iron in the reaction system was important for proceeding of the peroxidation reaction. Superoxide dismutase, catalase, hydroxyl radical scavengers and an iron chelator, diethylenetriaminepenta-acetic acid, inhibited the lipid peroxidation, indicating that the lipid peroxidation is initiated by a hydroxyl radical generated from the interaction of H2O2 with ferrous iron released from ferritin.     

Analysis of plasma catecholamines by high-performance liquid chromatography with fluorescence detection: simple sample preparation for pre-column fluorescence derivatization

Analysis of plasma catecholamines (norepinephrine, epinephrine and dopamine) by high-performance liquid chromatography using 1,2-diphenylethylenediamine as a fluorescent reagent is described. We have developed an automatic catecholamine analyser, based on pre-column fluorescence derivatization and column switching. The analysis time for one assay was 15 min. The correlation coefficients of the linear regression equations were greater than 0.9996 in the range 10-10,000 pg/ml. The detection limit, at a signal-to-noise ratio of 3, was 2 pg/ml for dopamine. A new method of sample preparation for the pre-column fluorescence derivatization of plasma catecholamines was used. In order to protect the catecholamines from decomposition, an ion-pair complex between boric acid and the diol group in the catecholamine was formed at a weakly alkaline pH. The stabilities of plasma catecholamines were evaluated at several temperatures. After complex formation, the catecholamines were very stable at 17 degrees C for 8 h, and the coefficients of variation for norepinephrine, epinephrine and dopamine were 1.2, 4.2 and 9.3%, respectively.     

Preparation of Secondary Carbinamines via Alkylation of N-Boryl Imines Generated from Partial Reduction of Nitriles with NABH4-Carboxylic Acid

Secondary carbinamines have been prepared from alkylation of N-boryl imines which were generated in situ from partial reduction of nitriles with sodium brohydride modified by carboxylic acid.     

Power of isotopic fine structure for unambiguous determination of metabolite elemental compositions: In silico evaluation and metabolomic application

In mass spectrometry (MS)-based metabolomics studies, reference-free identification of metabolites is still a challenging issue. Previously, we demonstrated that the elemental composition (EC) of metabolites could be unambiguously determined using isotopic fine structure, observed by ultrahigh resolution MS, which provided the relative isotopic abundance (RIA) of ¹³C, ¹⁵N, ¹⁸O, and ³⁴S. Herein, we evaluated the efficacy of the RIA for determining ECs based on the MS peaks of 20,258 known metabolites. The metabolites were simulated with a ≤25% error in the isotopic peak area to investigate how the error size effect affected the rate of unambiguous determination of the ECs. The simulation indicated that, in combination with reported constraint rules, the RIA led to unambiguous determination of the ECs for more than 90% of the tested metabolites. It was noteworthy that, in positive ion mode, the process could distinguish alkali metal-adduct ions ([M + Na]⁺ and [M + K]⁺). However, a significant degradation of the EC determination performance was observed when the method was applied to real metabolomic data (mouse liver extracts analyzed by infusion ESI), because of the influence of noise and bias on the RIA. To achieve ideal performance, as indicated in the simulation, we developed an additional method to compensate for bias on the measured ion intensities. The method improved the performance of the calculation, permitting determination of ECs for 72% of the observed peaks. The proposed method is considered a useful starting point for high-throughput identification of metabolites in metabolomic research.     

Synthesis of Seven-Membered Benzolactones by Nickel-Catalyzed C−H Coupling of Benzamides with Oxetanes

A NiCl₂(PEt₃)₂-catalyzed regioselective C−H coupling of 8-aminoquinoline-derived benzamides with oxetanes has been developed. The reaction proceeds with concomitant removal of the 8-aminoquinoline auxiliary to directly form the corresponding seven-membered benzolactones, which frequently occur in natural products and bioactive molecules. Additionally, no stereochemical erosion is observed during the course of the reaction, and the use of enantioenriched and substituted oxetane thus provides a new avenue to the optically active benzolactone.     

<Emphasis Type="Italic">C</Emphasis><Superscript>1</Superscript>-Classification of Gapped Parent Hamiltonians of Quantum Spin Chains

We consider the C ¹-classification of gapped Hamiltonians introduced in Fannes et al. (Commun Math Phys 144:443–490, 1992) and Nachtergaele (Commun Math Phys 175:565–606, 1996) as parent Hamiltonians of translation invariant finitely correlated states. Within this family, we show that the number of edge modes, which is equal at the left and right edge, is the complete invariant. The construction proves that translation invariance of the ‘bulk’ ground state does not need to be broken to establish C ¹-equivalence, namely that the spin chain does not need to be blocked.