Reducing the molecule-substrate coupling in C60-based nanostructures by molecular interactions

Codeposition of C60 and the three-dimensional molecular hydrocarbon 1,3,5,7-tetraphenyladamantane (TPA) on Au(111) leads to the spontaneous formation of molecular nanostructures in which each fullerene is locked into a specific orientation by three surrounding TPA. Scanning tunneling spectroscopy shows that the electronic coupling of C60 with the surface is significantly reduced in these nanostructures, enhancing the free-molecule properties. As evidenced by density functional theory simulations, the nanostructures are stabilized by 18 local electrostatic forces between C60 and TPA, resulting in a lifting of the C60 cage from the surface.     

AMP-activated protein kinase: structure and regulation

Mammalian AMP-activated protein kinase (AMPK) is a serine/threonine protein kinase that acts as a sensor of cellular energy status. It is activated by a large variety of cellular stresses that increase cellular AMP and decrease ATP levels and also by physiological stimuli, such as muscle contraction, or by hormones such as leptin and adiponectin. AMPK modulates multiple metabolic pathways. As a result, it has become a target for the development of new drugs for the treatment of type II diabetes, obesity or even cancer. In fact, it has been recently reported that drugs used in the treatment of diabetes, such as metformin and thiazolidinediones (TZDs), exert their beneficial effects through the activation of AMPK. AMPK is a heterotrimeric complex composed of a catalytic subunit (AMPK-alpha) and two regulatory subunits (AMPK-beta and AMPK-gamma). Functional orthologues of this kinase complex are found throughout eukaryotic kingdom, from yeast to humans, indicating that the function of this complex is evolutionarily conserved. This review summarizes the recent studies on the structure and regulation of the AMPK heterotrimeric complex.     

Profit maximization and reduction of the cannibalization effect in chain expansion

We consider the facility location problem for an expanding chain which competes with other chains offering the same goods or service in a geographical area. Customers are supposed to select the facility with maximum utility to be served and facilities in the expanding chain may have different owners. We first use the weighted method to develop an integer linear programming model to obtain Pareto optimal locations related to the inner competition between the owners of the old facilities and the owners of the new facilities. This model is applied to maximizing the profit of the expanding chain taking into account the loss in market share of its old facilities caused by the entering of new facilities (cannibalization effect). A study with data of Spanish municipalities shows that the cannibalization effect can be significantly reduced by sacrificing a small portion of profit.     

Anti-EPO and anti-NESP antibodies raised against synthetic peptides that reproduce the minimal amino acid sequence differences between EPO and NESP

Erythropoietin (EPO) is a hormone that regulates red blood cell production. Recombinant human EPO (rHuEPO) and NESP (novel erythropoiesis stimulating protein) have been produced for therapeutic purposes and also to improve sports performance. The primary sequences of rHuEPO and NESP differ by just five amino acids. Due to the high homology, no antibodies that are able to discriminate between both molecules have been obtained until now. The aim of the present work was to design synthetic peptides corresponding to the sequence that differs between EPO and NESP (87–90aa), that can then be used as immunogens to develop specific rabbit polyclonal antibodies for selectively detecting EPO and NESP. Three peptides were synthesized: EPO (81–95), NESP (81–95), and NESP (86–104), and these were coupled to KLH and OVA for immunization and screening purposes, respectively. The sera obtained were tested by ELISA on synthetic peptide–OVA conjugates and purified by immunoaffinity chromatography against the corresponding synthetic peptide. The specific purified antibodies were characterized by ELISA, SDS-PAGE, and isoelectric focusing, followed by western blot. Antisera raised against EPO (81–95) recognized rHuEPO but not NESP. In contrast, anti-NESP (84–106) sera gave a specific anti-NESP response only after immunoaffinity purification on a NESP (86–91) column. An efficient strategy for generating specific antibodies against EPO and NESP can be achieved by selecting suitable synthetic peptides. The antibodies obtained are able to differentiate between rHuEPO and NESP, and may be particularly useful for screening purposes in both therapeutic and antidoping contexts.     

Molecular recognition of adeninium cations on anionic metal-oxalato frameworks: an experimental and theoretical analysis

Reactions of adenine with water-soluble oxalato complexes at acidic pH give the compounds (1H,9H-ade)2[Cu(ox)2(H2O)] (1) [H2ade=adeninium cation (1+), ox=oxalato ligand (2-)] and (3H,7H-ade)2[M(ox)2(H2O)2].2H2O [M(II)=Co (2), Zn (3)]. The X-ray single crystal analyses show that the supramolecular architecture of all compounds is built up of anionic sheets of metal-oxalato-water complexes and ribbons of cationic nucleobases among them to afford lamellar inorganic-organic hybrid materials. The molecular recognition process between the organic and the inorganic frameworks determines the isolated tautomeric form of the adeninium cation found in the crystal structures: the canonical 1H,9H for compound 1, and the first solid-state characterized 3H,7H-adeninium tautomer for compounds 2 and 3. Density functional theory calculations have been performed to study the stability of the protonated nucleobase forms and their hydrogen-bonded associations by comparing experimental and theoretical results.     

壁面热特性对超声速燃烧室热环境的影响

在分析燃烧室壁面的对流-辐射耦合换热特性基础上,考虑燃烧室热环境与冷却系统间的相互关系,提出了一种以燃烧室材料许用温度为约束的非均匀冷却壁面热特性设计方法.以某型超声速燃烧室为例,采用混合分数平衡化学反应和液滴离散相模型,计算分析了壁面热特性对燃烧室壁面热流构成、热环境及冷却系统热负荷的影响.结果表明,壁面热特性对超声速燃烧室热环境的影响值得重视,非均匀冷却壁面热特性设计能有效减少燃烧室热损失.     

多孔氧化铝模板制备ZnS纳米线阵列及其光致发光谱

利用阳极氧化铝（AAO）模板,采用电化学沉积方法制备出了ZnS纳米线阵列。扫描电子显微镜（SEM）结果显示,AAO模板孔洞分布均匀,孔径基本一致（约50nm）,孔口呈六边形。TEM结果显示硫化锌纳米线的直径约50nm（与AAM模板孔径一致）,长度约为20μm（与AAM模板厚度一致）。电子衍射结果表明ZnS纳米线为多晶结构。比较了AAO模板组装ZnS纳米线阵列前后的光致发光谱,所得光谱显示,组装了ZnS纳米线阵列的模板的光致发光谱比没有组装的空模板相比多出两个发射峰,分别位于409,430nm,且其发光强度随激发波长的增长而增强。解谱分析表明,这即为ZnS纳米线阵列的发光光谱的两个发射峰,是由导带与受主能级间的跃迁发光和施主与受主能级间的复合跃迁发光共同作用所致。发现由于纳米线尺寸的单一性,发射峰窄化明显,半峰全宽较小,这种现象在其他文献中未曾报道过。     

Assessing the instability of the isoelectric focusing patterns of erythropoietin in urine

IEF can be used to differentiate human urinary erythropoietin (uEPO), recombinant human erythropoietin or epoetin (rEPO) and darbepoetin (novel erythropoiesis stimulating protein (NESP)). This is the basis of the method currently used to detect misuse of rEPO and NESP by elite athletes. Recently, an unknown activity has been attributed to some urine samples (denominated 'unstable' urine by the World Anti-Doping Agency; WADA). This activity has shown to give rise to artefactual profiles for both rEPO and NESP when incubated with such urine and, thus, raised concerns with respect to doping control. We have evaluated which charges produce the characteristic IEF profiles of uEPO, rEPO and NESP and how these profiles respond to distinct enzymatic reactions. From sialidase digestions it became evident that only uEPO contains charges different from sialic acid, and a comparison of all substances after complete de-N-glycosylation localized these charges in the carbohydrate moiety. Partial desialylation, or digestion with arylsulfatase from Helix pomatia yielded profiles for recombinants species similar to those observed for unstable urine samples. The contributions from our studies to the anti-doping problem include: (i) protocols that may corroborate the potential misuse of rEPO or NESP based on the particular enzymatic activity of an arylsulfatase preparation, or a broad-specificity sialidase; (ii) assurance that the instability observed in some urine samples may only result from false-negatives, but not from false-positive testing; and (iii) a simple remedy to prevent an unstable urine from altering the IEF profile by adding selective competitive substrates.