Site-specific detection of S-nitrosylated PKB alpha/Akt1 from rat soleus muscle using CapLC-Q-TOF(micro) mass spectrometry

Protein Kinase Balpha(PKBalpha, or Akt1) is believed to play a crucial role in programmed cell death, cancer progression and the insulin-signaling cascade. The protein is activated by phosphorylation at multiple sites and subsequently phosphorylates and activates eNOS. Free cysteine residues of the protein may capture reactive, endogenously produced nitric oxide (NO) as S-nitrosothiols. Site-specific detection of S-nitrosylated cysteine residues, usually at low stoichiometry, has been a major challenge in proteomic research largely due to the lack of mass marker for S-nitrosothiols that are very labile under physiologic conditions. In this report we describe a sensitive and specific MS method for detection of S-nitrosothiols in PKB alpha/Akt1 in rat soleus muscle. PKB alpha/Akt1 was isolated by immunoprecipitation and 2D-gel electrophoresis, subjected to in-gel tryptic digestion, and cysteinyl nitrosothiols were reacted with iodoacetic acids [2-C(12)/C(13) = 50/50] under ascorbate reduction conditions. This resulted in the production of relatively stable carboxymethylcysteine (CMC) immonium ions (m/z 134.019 and m/z 135.019) within a narrow argon collision energy (CE = 30 +/- 5 V) in the high MS noise region. In addition, free and disulfide-linked cysteine residues were converted to carboxyamidomethylcysteines (CAM). Tryptic S-nitrosylated parent ion was detected with a mass accuracy of 50 mDa for the two CMC immonium ions at the triggered elution time during capillary liquid chromatography (LC) separation. A peptide containing Cys(296) was discriminated from four co-eluting tryptic peptides under lock mass conditions (m/z 785.8426). S-nitrosothiol in the tryptic peptide, ITDFGLBKEGIK (B: CAM, [M + 2H](2+) = 690.86, Found: 690.83), is believed to be present at a very low level, since the threshold for the CMC immonium trigger ions was set at 3 counts/s in the MS survey. The high levels of NO that are produced under stress conditions may result in increased S-nitrosylation of Cys(296) which blocks disulfide bond formation between Cys(296) and Cys(310) and suppresses the biological effects of PKB alpha/Akt1. With the procedures developed here, this process can be studied under physiological and pathological conditions.     

Doping-dependent evolution of low-energy excitations and quantum phase transitions within an effective model for high-T<Subscript>c</Subscript> copper oxides

In this paper a mean-field theory for the spin-liquid paramagnetic non-superconducting phase of the p- and n-type high-T_c cuprates is developed. This theory applied to the effective t-t'-t′′-J^* model with the ab initio calculated parameters and with the three-site correlated hoppings. The static spin-spin and kinematic correlation functions beyond Hubbard-I approximation are calculated self-consistently. The evolution of the Fermi surface and band dispersion is obtained for the wide range of doping concentrations x. For p-type systems the three different types of behavior are found and the transitions between these types are accompanied by the changes in the Fermi surface topology. Thus a quantum phase transitions take place at x = 0.15 and at x = 0.23.Due to the different Fermi surface topology we found for n-type cuprates only one quantum critical concentration, x = 0.2. The calculated doping dependence of the nodal Fermi velocity and the effective mass are in good agreement with the experimental data.     

五轴加工中心范成铣磨离轴非球面研究

离轴非球面作为非球面的一部分,是空间光学系统、天文学和高精度测量系统不可或缺的光学器件.针对空间光学对离轴非球面光学元件制造技术的重大需求,开展了离轴非球面反射镜的精密铣磨加工技术研究.分析了五轴联动范成法铣磨离轴非球面的原理,将离轴非球面所在的同轴母镜离散为一系列不同半径的球面环带,将工件坐标系建立在待加工离轴非球面...     

d = 3 anisotropic and d = 2 tJ models: phase diagrams, thermodynamic properties, and chemical potential shift

The anisotropic d=3 tJ model is studied by renormalization-group theory, yielding the evolution of the system as interplane coupling is varied from the isotropic three-dimensional to quasi-two-dimensional regimes. Finite-temperature phase diagrams, chemical potential shifts, and in-plane and interplane kinetic energies and antiferromagnetic correlations are calculated for the entire range of electron densities. We find that the novel τ phase, seen in earlier studies of the isotropic d=3 tJ model, persists even for strong anisotropy. While the τ phase appears at low temperatures at 30–35% hole doping away from 〈 n_i〉=1, at smaller hole dopings we see a complex lamellar structure of antiferromagnetic and disordered regions, with a suppressed chemical potential shift, a possible marker of incommensurate ordering in the form of microscopic stripes. An investigation of the renormalization-group flows for the isotropic two-dimensional tJ model also shows a clear pre-signature of the τ phase, which in fact appears with finite transition temperatures upon addition of the smallest interplane coupling.     

Explicit constructions of separating hash families from algebraic curves over finite fields

Let X be a set of order n and Y be a set of order m. An (n,m,{w ₁, w ₂})-separating hash family is a set of N functions from X to Y such that for any with , |X ₁| = w ₁ and |X ₂| = w ₂, there exists an element such that . In this paper, we provide explicit constructions of separating hash families using algebraic curves over finite fields. In particular, applying the Garcia–Stichtenoth curves, we obtain an infinite class of explicitly constructed (n,m,{w ₁,w ₂})–separating hash families with for fixed m, w ₁, and w ₂. Similar results for strong separating hash families are also obtained. As consequences of our main results, we present explicit constructions of infinite classes of frameproof codes, secure frameproof codes and identifiable parent property codes with length where n is the size of the codes. In fact, all the above explicit constructions of hash families and codes provide the best asymptotic behavior achieving the bound , which substantially improve the results in [ 8, 15, 17] give an answer to the fifth open problem presented in [11].     

Resonant two‐magnon Raman scattering in high‐Tc cuprates

Resonance enhancement of one‐phonon, two‐phonon, and two‐magnon Raman scattering in a general, exactly solvable, multiband model is explained in a way that is in accordance with the general analytical properties of the total optical conductivity tensor. Using this approach, the charge‐transfer limit of the Emery three‐band model is examined to explain resonance enhancement of the two‐magnon Raman spectra of high‐T_c cuprates, which is found in experiments to be of 3 orders of magnitude. While previous Raman and optical conductivity analyzes of the cuprates, based on the single‐band Hubbard model, are found to be consistent with the picture where one hole per one CuO₂ unit is localized on the Cu ion, the present three‐band approach allows the study of the opposite, strong copper‐oxygen hybridization limit, which is found to be in agreement with the results of nuclear magnetic resonance (NMR) and one‐phonon Raman scattering experiments. Copyright © 2010 John Wiley & Sons, Ltd.     

2017年版有机化合物命名原则在链状烃类母体氢化物教学中的应用

以链状烃类母体氢化物为例,从主链的选取、编号,取代基的表达与排序,化合物名称的书写等几个方面,对比分析了新旧命名原则的异同。以帮助大学有机化学授课教师和学生温故知新,尽快理清思路,有的放矢地开展有机物2017年版命名原则的教和学。     

Reconstruction of Protein‐Like Globular Structure for Random and Designed Copolymers

We present the results of computer simulation of Langevin dynamics of AB‐copolymer coil‐globule transition. The method for estimation of the quality of reconstruction of protein‐like globular structure after cooling procedure is proposed. We study specially designed “protein‐like” and random primary sequences and carry out a comparative analysis of the corresponding globular conformations for different intramolecular interactions. It is found that the energy of intramolecular interactions, as well as the type of primary sequence, are important in the process of parent globular structure reconstruction. As a rule, protein‐like sequences exhibit better reconstruction of initial globular structure after cooling procedure. There is a region of energy parameters enabling optimum reconstruction of initial globular structure.     

前体离子扫描法在快速筛查中药及保健食品中非法添加的5型磷酸二酯酶抑制剂及其未知衍生物中的应用

改造有明确疗效的药物,合成新的衍生物以避开法定检验方法是目前化学药物非法添加的趋势之一。本文提出将液相色谱-三重四极杆质谱联用仪的质谱前体离子扫描模式应用于中药及保健食品等复杂体系中非法添加药物衍生物的快速筛查策略,以5型磷酸二酯酶抑制剂为实验对象,通过分析该类化合物的结构和质谱特点将其分类,筛选各类共有的子离子碎片,优化质谱参数,建立了前体离子扫描模式的LC-MS筛查方法,讨论了质谱参数和碎片离子的选择对筛选结果的影响,并应用于实际样品的测定。结果表明,该方法既可以满足已知化合物的测定需要,又可以对复杂体系中未知的同类衍生物进行快速筛查,防止未知衍生物的漏检。该方法灵敏、专属、高效,值得进一步研究。     

On k‐ary spanning trees of tournaments

It is well known that every tournament contains a Hamiltonian path, which can be restated as that every tournament contains a unary spanning tree. The purpose of this article is to study the general problem of whether a tournament contains a k‐ary spanning tree. In particular, we prove that, for any fixed positive integer k, there exists a minimum number h(k) such that every tournament of order at least h(k) contains a k‐ary spanning tree. The existence of a Hamiltonian path for any tournament is the same as h(1) = 1. We then show that h(2) = 4 and h(3) = 8. The values of h(k) remain unknown for k ≥ 4. © 1999 John & Sons, Inc. J Graph Theory 30: 167–176, 1999