A new strategy to induce gamma-turns: peptides composed of alternating alpha-aminoxy acids and alpha-amino acids

It is known that the seven-membered-ring intramolecular hydrogen bond (gamma-turn) is seldom formed in naturally occurring peptides composed of alpha-amino acids. Here we report a new strategy to induce gamma-turns in short linear peptides. We designed and synthesized several peptides (1-5) containing alternating alpha-l-aminoxy acids and alpha-d-amino acids. 1H NMR studies revealed that the gamma-turn could be initiated by the following N-O turn, an eight-membered-ring intramolecular hydrogen bond induced by an alpha-aminoxy acid. Moreover, NOESY and CD studies suggested peptides 4 and 5 form a novel secondary structure, a mixed 7-8 helix. Theoretical calculations on several di-, tri-, and tetrapeptide models provided strong support to the above conclusions.     

Simultaneous analysis of caffeic acid derivatives and alkamides in roots and extracts of Echinacea purpurea by high-performance liquid chromatography-photodiode array detection-electrospray mass spectrometry

High-performance liquid chromatography (HPLC) coupled with UV photodiode-array detection and electrospray ionization mass spectrometry was developed for the simultaneous analysis of caffeic acid derivatives and alkamides in the roots and extracts of Echinacea purpurea. Caffeic acid derivatives and alkamides produced very abundant peaks in the total ion current chromatogram during negative and positive cone voltage switching. Cichoric acid and the isomer pair, dodeca-2E,4E,8Z,10E/Z-tetraenoic acid isobutylamide, were used as a standard for quantification of caffeic acid derivatives and alkamides in E. purpurea. This novel method surpasses previously published ones in product quality control and providing the HPLC chromatographic fingerprints of biological active components in E. purpurea.     

A new strategy for solid phase synthesis of a secondary amide library using sulfonamide linker via radical traceless cleavage

A new strategy for solid phase synthesis of a secondary amide library using sulfonamide linker via radical traceless cleavage is reported. Polystyrylsulfonyl chloride (1) reacted with primary amines to afford polystyryl-supported N-alkyl sulfonamides (2), which were acylated with acid chlorides and followed by radical cleavage with TiCl₄/Zn to afford secondary amides. It was interestingly found that the products released from acyl alkanesulfonamide resins are closely dependent on the substituents of benzene rings of alkyl or acyl groups on the resins. When the substituent on benzene ring of N-benzyl group of sulfonamides is an electron rich MeO-group, the products released from sulfonamide resins are dependent on the substitution position on benzene ring: para-MeO- to yield 1,2-bis (p-methoxylphenyl)ethane and N-p-methoxylbenzyl benzamide (30:1); ortho-MeO- to give 1,2-bis (o-methoxylphenyl)ethane and N-o-methoxylbenzyl benzamide (1:15); and meta-MeO- only to release N-m-methoxylbenzyl benzamide. Neither N-benzoyl sulfonamide resins on benzene ring with electron-drawing para-O₂N-, nor the one with electron-donating para-H₂N- could release any amide product, while the N-benzoyl sulfonamide resins on benzene ring with para-acetamido group released para-acetamidobenzamides. The conjugation effect to stabilize the radical groups in the radical cleaving process was observed.     

Hadronic loop corrections to the muon anomalous magnetic moment

The dominant theoretical uncertainties in both the anomalous magnetic moment of the muon and the value of the electromagnetic coupling at the Z scale, M(Z), arise from their hadronic contributions. Since these will ultimately dominate the experimental errors, we study the correlation between them, as well as with other fundamental parameters. To this end we present analytical formulas for the QCD contribution from higher energies and from heavy quarks. Including these correlations affects the Higgs boson mass extracted from precision data.     

Asymptotic approach to the truncated cosh-Gaussian beams

The propagation behavior and M ²-factor of truncated cosh-Gaussian (ChG) beams are studied by using the asymptotic approach. Detailed numerical results are given to illustrate the dependence of M ²-factor on the beam decentered parameter , truncation fraction p and power fraction f. Our results are self-consistent and reduce to those of Pare and Belanger [Opt. Commun. 123, p. 679 (1996a); Proc. SPIE 2870, p. 104 (1996b)]. The advantage of the approach is shown, and the problems introduced by the hard-aperture diffraction and the approach used are discussed.     

Characterization of spiroiminodihydantoin as a product of one-electron oxidation of 8-Oxo-7,8-dihydroguanosine

[reaction: see text] Further oxidation of the common DNA lesion 8-oxo-7,8-dihydroguanosine by one-electron oxidants such as IrCl6(2-), Fe(CN)6(3-), or SO4-* leads to two major products, depending upon reaction conditions. In nucleosides at pH 7, 22 degrees C, the principal product is shown herein to be a spiroiminodihydantoin nucleoside, as a diastereomeric mixture, that can be characterized by NMR, ESI-MS/MS, and independent synthesis.     

高纯硅低能粒子辐照E′色心形成动力学研究

考虑固有点缺陷形成E′色心的情况，建立了E′色心形成的动力学模型，得到了高纯硅低能粒子辐照E′色心浓度与辐照剂量的关系式.结果表明，在低辐照剂量下，E′色心浓度随剂量的变化呈线性增长；随着辐照剂量的增加，E′色心浓度随剂量的变化呈饱和趋势.如果进一步考虑E′色心和其他物质反应形成新的稳定结构，E′色心浓度随剂量的变化呈双指数关系，E′色心浓度随剂量的变化不再趋于饱和状态，而是偏离饱和状态.理论结果和实验结果很好地符合，说明建立的模型是有效的.     

Some basic principles in dynamic theory of viscoelastic materials with voids

According to the basic idea of classical yin-yang complementarity and modern dual-complementarity, in a simple and unified way proposed by Luo, some basic principles in the dynamic theory of viscoelastic materials with voids can be estab- lished systematically. In this paper, an important integral relation in terms of con- volutions is given, which can be considered as the generalized principle of virtual work in mechanics. Based on this relation, it is possible not only to obtain the principle of virtual work and the reciprocal theorem, but also to derive systemati- cally the complementary functionals for the eight-field, six-field, four-field simpli- fied Gurtin-type variational principles and the potential energy-functional for the two-field one in the dynamic theory of viscoelastic materials with voids by the generalized Legendre transformations given in this paper. Furthermore, with this approach, the intrinsic relationship among various principles can be explained clearly.