A Novel Dimeric Eremophilane from Ligularia virgaurea spp. oligocephala

A novel dimeric eremophilane, ligulolide B, was isolated from the alcoholic extract of the whole plant of Ligularia virgaurea spp. oligocephala. The structure was elucidated by various spectroscopic methods including intensive 2D NMR techniques （^1H-^1H COSY, gHMQC, gHMBC and ^1H-^1H NOESY） and HR-ESI-MS.     

Shotgun proteomics‐based clinical testing for diagnosis and classification of amyloidosis

Shotgun proteomics technology has matured in the research laboratories and is poised to enter clinical laboratories. However, the road to this transition is sprinkled with major technical unknowns such as long‐term stability of the platform, reproducibility of the technology and clinical utility over traditional antibody‐based platforms. Further, regulatory bodies that oversee the clinical laboratory operations are unfamiliar with this new technology. As a result, diagnostic laboratories have avoided using shotgun proteomics for routine diagnostics. In this perspectives article, we describe the clinical implementation of a shotgun proteomics assay for amyloid subtyping, with a special emphasis on standardizing the platform for better quality control and earning clinical acceptance. This assay is the first shotgun proteomics assay to receive regulatory approval for patient diagnosis. The blueprint of this assay can be utilized to develop novel proteomics assays for detecting numerous other disease pathologies. Copyright © 2013 John Wiley & Sons, Ltd.     

The nature of the lowest triplet configuration of flavins

Abstract— The phosphorescence spectrum of riboflavin has been reexamined at 77°K in an ethylene glycol: water matrix. The phosphorescence occurs at approximately the 605 nm (ca. 2-·05 eV) region, in reasonable agreement with the theoretical calculations of 1·6–1·8 eV [21]. The emission was found to be negatively polarized, and to have a relatively long lifetime (0·56 sec). On the basis of this data and additional theoretical results, it is concluded that the lowest triplet of riboflavin is of ³(τ,τ*) type. Upon addition of potassium iodide, the phosphorescence emission is enhanced through spin-orbit perturbation. The presence of oxygen (atmospheric pressure) in the frozen glass apparently has no effect on the emission. The phosphorescence spectra of alloxazine are also presented. Results of the present work have been applied to the photodephosphorylation of menadiol diphosphate in elucidating its mechan ism involving the riboflavin triplet and singlet oxygen.     

一类齐次对称多项式上的切比雪夫不等式

本文借助于控制不等式及数学归纳法，将著名的切比雪夫不等式推广到m次一般齐次对称多项式上(如文中定理及引理7)，并将此结果用于对称平均等．旨在展示证明解析不等式的一些有效的方法和技巧，同时为数学研究特别是高维几何研究提供一些新的有趣而有用的解析不等式．     

Photochemistry of the model phototropic system involving flavins and indoles. I. Fluorescence polarization and MO calculations of the direction of the electronic transition moments in flavins

Abstract— The fluorescence polarization spectra of riboflavin, lumiflavin, and alloxazine under different conditions have been obtained. It has been shown that the polarization spectrum of riboflavin is not affected significantly by media such as D₂O-glycerol (50: 50) and castor oil. Our data do not indicate the anomalous spectral shift of riboflavin in castor oil, in contrast to the previous finding described by Thomas. The electronic structures of lumiflavin and alloxazine are similar to that of riboflavin, as revealed by the fluorescence polarization measurements and the molecular orbital calculations. The Pariser-Parr-Pople semiempirical SCF ASMO CI computations have been performed to compare the calculated transition moments with the polarization data. The theory predicts an angle of 42° between the 450 and 365 nm transition oscillators, in reasonable agreement with the experimental angle of about 49°. It has been shown, from the comparison of the calculated and observed spectral quantities, that the pseudo-heteroatom model for treating methyl groups in the flavin molecule is not adequate. The group orbital and inductive approximations appear to be satisfactory. Finally, the implication of the present findings has been briefly discussed in connection with phototropism.     

A study of photochemistry of flavins in pyridine and with a donor

Abstract— Both anaerobic and aerobic photolysis of riboflavin in pyridine yielded several photoproducts, analogous to the photochemical reaction in aqueous solution. Lumiflavin was also photoreduced in pyridine (an electron donor) without decomposition of the isoall-oxazine ring Differences in the reactivity of excited singlet and triplet states with respect to formation of photoproducts have been confirmed in pyridine. In the photoreduction of riboflavin by N, N'-dimethyl-N-benzylethylene diamine, an initial rate with a higher relative quantum yield than that of the reaction at a later stage was observed both in water and pyridine. Photolysis in D₂O with the donor showed no significant solvent isotope effect. These results strongly suggest that the photolysis of riboflavin in water does not involve the water molecule in the primary photochemical act. A detailed mechanism of flavin photoreaction in water to account for solvent oxygen incorporation into a photoproduct (benzaldehyde) from N, N'-dimethyl-N-benzylethylene diamine has been proposed without involving photochemical splitting of water based on our results and molecular orbital computations. Preliminary results on the kinetics of free radical decay were obtained using an ESR spectrometer and the significance of the results are discussed.     

SPECTROSCOPY AND PHOTOCHEMISTRY OF BILIRUBIN PHOTOPRODUCTS. I. METHYLVINYLMALEIMIDE*

Abstract— Methylvinylmaleimide, a product of the photooxidation of bilirubin, exhibits a broad luminescence band at approximately 450 nm on filter paper at room temperature. In methanol solvent, at 77 K, a broad phosphorescence band centered at 465 nm is observed. The experimental and theoretical spectroscopic properties of this compound are compared to those of the related molecules maleimide and phthalimide. Methylvinylmaleimide is photodegraded at pH 7.6 in a self-sensitized reaction that in part involves singlet oxygen.     

Investigation of the quantitative properties of the quadrupole orthogonal acceleration time-of-flight mass spectrometer with electrospray ionisation using 3,4-methylenedioxymethamphetamine

This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time-of-flight mass spectrometer (Q-TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4-methylenedioxymethamphetamine standards and 3,4-methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4-methylenedioxymethamphetamine and its metabolite 3,4-methylenedioxyamphetamine was prepared in each of these matrices again using 3,4-methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q-TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2-10 000 pg on-column, r(2) = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC-fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q-TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright 1999 John Wiley & Sons, Ltd.     

Noncommutative Differential Calculus Approach to Discrete Symplectic Schemes on Regular Lattice

By means of a noncommutative differential calculus on function space of discrete Abelian groups and that of the regular lattice with equal spacing as well as the discrete symplectic geometry and a kind of classical mechanical systems with separable Hamiltonian of the type H(p, q) = T(p) + V(q) on regular lattice, we introduce the discrete symplectic algorithm, i.e., the phase-space discrete counterpart of the symplectic algorithm including original symplectic schemes and the jet-symplectic schemes in terms of the discrete time jet bundle formalism, on the regular lattice. We show some numerical calculation examples and compare the results of different schemes.