Electrospray tandem mass spectrometric analysis of zeaxanthin and its oxidation products

Carotenoids have been implicated in protection of the eye from light-mediated photo-toxicity caused by free radicals. Under conditions of normal oxidative stress the carotenoids serve as protective antioxidants; however, when the oxidative stress exceeds the antioxidant capacity, carotenoids can be oxidized into numerous cleavage products. The determination and identification of oxidized carotenoids in biological samples remains a major challenge due to the small sample size and low stability of these compounds. We investigated the reaction of various zeaxanthin cleavage products with O-ethyl hydroxylamine to evaluate their levels in a biological sample. For this, a sensitive and specific electrospray tandem mass spectrometry (ESI-MS/MS) was developed, avoiding the classical lower sensitive and specific HPLC-UV and fluorescence absorption methods. Protonated molecules [M + H](+) of carotenoids upon collision-induced dissociation produced a number of structurally characteristic product ions. A series of complicated clusters of product ions differing in 14 (CH(2))and 26 (C(2)H(2))Da was characteristic of the polyene chain of intact carotenoids. All carotenoid ethyl oximes of zeaxanthin cleavage products were characterized by the losses of 60 and 61 Da in their MS/MS spectra. Through the application of the LC/MS/MS method, we identified two oxime derivatives of 3-hydroxy-beta-ionone and 3-hydroxy-14'-apocarotenal with protonated molecules at m/z 252 and m/z 370 respectively, in a human eye sample.     

Mechanisms of water oxidation catalyzed by the cis,cis-[(bpy)2Ru(OH2)]2O4+ ion

The cis,cis-[(bpy)(2)Ru(III)(OH(2))](2)O(4+) micro-oxo dimeric coordination complex is an efficient catalyst for water oxidation by strong oxidants that proceeds via intermediary formation of cis,cis-[(bpy)(2)Ru(V)(O)](2)O(4+) (hereafter, [5,5]). Repetitive mass spectrometric measurement of the isotopic distribution of O(2) formed in reactions catalyzed by (18)O-labeled catalyst established the existence of two reaction pathways characterized by products containing either one atom each from a ruthenyl O and solvent H(2)O or both O atoms from solvent molecules. The apparent activation parameters for micro-oxo ion-catalyzed water oxidation by Ce(4+) and for [5,5] decay were nearly identical, with DeltaH(++) = 7.6 (+/-1.2) kcal/mol, DeltaS() = -43 (+/-4) cal/deg mol (23 degrees C) and DeltaH(++) = 7.9 (+/-1.1) kcal/mol, DeltaS(++) = -44 (+/-4) cal/deg mol, respectively, in 0.5 M CF(3)SO(3)H. An apparent solvent deuterium kinetic isotope effect (KIE) of 1.7 was measured for O(2) evolution at 23 degrees C; the corresponding KIE for [5,5] decay was 1.6. The (32)O(2)/(34)O(2) isotope distribution was also insensitive to solvent deuteration. On the basis of these results and previously established chemical properties of this class of compounds, mechanisms are proposed that feature as critical reaction steps H(2)O addition to the complex to form covalent hydrates. For the first pathway, the elements of H(2)O are added as OH and H to the adjacent terminal ruthenyl O atoms, and for the second pathway, OH is added to a bipyridine ring and H is added to one of the ruthenyl O atoms.     

布氏田鼠的嗅觉通讯II：2种不同方法下气味辨别实验的…

利用重复测量方差分析，研究２种不同的实验设计方法对布氏田鼠气味辨识别实验的影响，结果表明：给予单个气味刺激同时给予多个气味刺激的２种不同实验方法，所得到的数据结果没有显性差异，都能够反映出动物对气味的辨别能力。     

布氏四鼠的嗅觉通讯Ⅱ──2种不同方法下气味辨别实验的重复测量方差分析

利用重复测量方差分析，研究2种不同的实验设计方法对布氏四鼠气味辨别实验的影响．结果表明：给予单个气味刺激和同时给予多个气味刺激的2种不同实验方法，所得到的数据结果没有显著性差异，都能够反映出动物对气味的辨别能力．     

观察箱内成年雄性布氏田鼠间的行为和行为序

研究了不同大小观察箱内布氏田鼠（Ｍｉｃｒｏｔｕｓ ｂｒａｎｄｔｉ）陌生成年雄性个体间的行为和行为序。在大，小观察箱内，除了追逐行为，优势鼠，从属鼠的行为没有明显的差别。在观察期内，虽然一对鼠中优势鼠的非社会，社会探究，攻击行为都明显地高于从属鼠，但它们在遭遇后的第１个回合的交往中，２只鼠的社会行为没有显示的区别，社会探究，争斗行为之间相互独立，为负相关关系，而其各自内部均为正相关关系，其中社会探究     

北京小龙门林场夏季小型鼠类群落结构及其年变化

北京小龙门林场夏季小型鼠类群落结构及其年变化房继明，赵欣如，宋杰，张正旺，郭冬生，倪喜军，张懿（北京师范大学生物学系，１００８７５，北京；第一作者３０岁，男，副教授）关键词群落结构；年变化；小型啮齿类分类号Ｑ９５８．８３７；Ｑ９５８．１５５ＹＥＡＲＬ...     

Metabolic network analysis of the causes and evolution of enzyme dispensability in yeast

Under laboratory conditions 80% of yeast genes seem not to be essential for viability. This raises the question of what the mechanistic basis for dispensability is, and whether it is the result of selection for buffering or an incidental side product. Here we analyse these issues using an in silico flux model of the yeast metabolic network. The model correctly predicts the knockout fitness effects in 88% of the genes studied and in vivo fluxes. Dispensable genes might be important, but under conditions not yet examined in the laboratory. Our model indicates that this is the dominant explanation for apparent dispensability, accounting for 37-68% of dispensable genes, whereas 15-28% of them are compensated by a duplicate, and only 4-17% are buffered by metabolic network flux reorganization. For over one-half of those not important under nutrient-rich conditions, we can predict conditions when they will be important. As expected, such condition-specific genes have a more restricted phylogenetic distribution. Gene duplicates catalysing the same reaction are not more common for indispensable reactions, suggesting that the reason for their retention is not to provide compensation. Instead their presence is better explained by selection for high enzymatic flux.