Amino acid catalyzed neogenesis of carbohydrates: a plausible ancient transformation

Hexose sugars play a fundamental role in vital biochemical processes and their biosynthesis is achieved through enzyme-catalyzed pathways. Herein we disclose the ability of amino acids to catalyze the asymmetric neogenesis of carbohydrates by sequential cross-aldol reactions. The amino acids mediate the asymmetric de novo synthesis of natural L- and D-hexoses and their analogues with excellent stereoselectivity in organic solvents. In some cases, the four new stereocenters are assembled with almost absolute stereocontrol. The unique feature of these results is that, when an amino acid is employed as the catalyst, a single reaction sequence can convert a protected glycol aldehyde into a hexose in one step. For example, proline and its derivatives catalyze the asymmetric neogenesis of allose with >99 % ee in one chemical manipulation. Furthermore, all amino acids tested catalyzed the asymmetric formation of natural sugars under prebiotic conditions, with alanine being the smallest catalyst. The inherent simplicity of this catalytic process suggests that a catalytic prebiotic "gluconeogenesis" may occur, in which amino acids transfer their stereochemical information to sugars. In addition, the amino acid catalyzed stereoselective sequential cross-aldol reactions were performed as a two-step procedure with different aldehydes as acceptors and nucleophiles. The employment of two different amino acids as catalysts for the iterative direct aldol reactions enabled the asymmetric synthesis of deoxysugars with >99 % ee. In addition, the direct amino acid catalyzed C(2)+C(2)+C(2) methodology is a new entry for the short, highly enantioselective de novo synthesis of carbohydrate derivatives, isotope-labeled sugars, and polyketide natural products. The one-pot asymmetric de novo syntheses of deoxy and polyketide carbohydrates involved a novel dynamic kinetic asymmetric transformation (DYKAT) mediated by an amino acid.     

毛细管电泳在线化学发光分离及检测铬（Ⅲ）与钒（Ⅴ）

基于在碱性介质中 Cr( )和 V( )对鲁米诺和过氧化氢的催化化学发光反应 ,研究了毛细管电泳在线化学发光分离和检测 Cr( )和 V( )。方法简便、快速、灵敏、进样量少。 Cr( )和 V( )的检出限分别为 7.8× 1 0 - 8mol/L和 5.0× 1 0 - 6mol/L ,线性范围分别是 32～ 80 ng/m L和 0 .55～ 3.0μg/m L     

Quantification of the effect of nonphotochemical quenching on the determination of in vivo chl a from phytoplankton along the water column of a freshwater reservoir

Nonphotochemical quenching (NPQ) is a well-known collection of different photoprotective mechanisms of plants and algae to avoid photodamage under an excess of light energy. In order to evaluate the overall effect of NPQ processes on the fluorometric determination of in vivo Chl a from a phytoplankton community dominated by diatoms, we compared the results obtained by two different fluorometric field devices with the total concentration of extracted Chl a measured by HPLC ( in vitro Chl a ). A different set of measurements were made to assess the performance of these fluorometers at high, moderate and low irradiance conditions. The Fbbe fluorometer, which is capable of distinguishing different algal groups according to their pigment content, allowed a better determination of in vivo Chl a under high irradiance conditions, with only a 10% mean difference from the in vitro Chl a concentration. In turn, the FMII fluorometer underestimated by as much as 50% the in vitro Chl a concentration under the same light conditions. As data from both fluorometers were in accordance with the in vitro Chl a values at moderate irradiance levels, the differences observed at high irradiances were attributed to the decrease in the yield of Chl a fluorescence caused by photoprotective NPQ processes. Accordingly, we estimated the effect of NPQ processes on the in vivo Chl a determination and the results allow us to provide an equation to correct this effect when in situ fluorometric measurements are carried out under high irradiance regimes. Our results demonstrate that under certain circumstances NPQ seriously compromises the results obtained by in situ fluorometric probes and highlight the need for a cautious interpretation of field data under such environmental conditions.     

Dose distribution in electron-irradiated PMMA: effect of dose and geometry

Depth-dose distributions for an electron beam are generally determined with either a stack irradiation geometry or a wedge (generally with an angle of about 50°–60°) made from an electrically-conducting material (such as, aluminium) or a non-conducting material (such as, PMMA). If the non-conducting wedge is thicker than the electron range, the stored charge in the material could influence the measured depth-dose distribution. This effect was investigated for 7-MeV electrons for PMMA with the wedge angle varying from 0° to 60°. The maximum-to-surface dose ratio was used as a characteristic parameter of the shape of the distribution. The depth-dose distribution measured by a dosimetry film placed inside the wedge-pair was similar to the standard shape when the wedge angle was larger than about 55° (dose ratio 1.5). However, as the angle was decreased, this ratio sharply increased almost linearly up to about 15°, and then leveled off at about 3. We also studied the effect of the surface dose on this dose ratio for the wedge angle of 0°, where we found that the ratio increased with the dose. Both of these effects can be explained by the presence of the electrostatic field around the dosimetry film due to stored charge in the non-conducting PMMA.     

On the Differential Polynomial of a Graph

We introduce the differential polynomial of a graph. The differential polynomial of a graph G of order n is the polynomial B(G; x) :=∑?(G)k=-nB_k(G) x~(n+k), where B_k(G) denotes the number of vertex subsets of G with differential equal to k. We state some properties of B(G;x) and its coefficients.In particular, we compute the differential polynomial for complete, empty, path, cycle, wheel and double star graphs. We also establish some relationships between B(G; x) and the differential polynomials of graphs which result by removing, adding, and subdividing an edge from G.     

Plasmonic wave plate based on subwavelength nanoslits

We propose a quarter-wave plate based on nanoslits and analyze it using a semianalytical theory and simulations. The device comprises two nanoslits arranged perpendicular to one another where the phases of the fields transmitted by the nanoslits differ by λ/4. In this way, the polarization state of the incident light can be changed from linear to circular or vice versa. The plasmonic nanoslit wave plate is thin and has a subwavelength lateral extent. We show that the predictions for the phase shift obtained from a semianalytical model are in very good agreement with simulations by the finite difference time domain method.     

Wildland fire growth prediction method based on Multiple Overlapping Solution

Several Data-Driven Methods have been developed to try to solve the input parameters uncertainty when considering problems like Wildfires Prediction. In general, these methods operate over a large number of input parameters, and consider the most recent known behavior of wildfires. The purpose of the methods is to find the parameter set that best describes the real situation under consideration. Therefore, it is presumed that the same set of values could be used to predict the immediate future.However, because this kind of prediction is based on a single set of parameters, for those parameters that present a dynamic behavior (e.g. wind direction and speed), the new optimized values are not adequate to make a prediction.In this paper we propose an alternative method developed in a new branch of Data-Driven Prediction, which we called Multiple Overlapping Solution. This method combines statistical concepts and HPC (High Performance Computing) to obtain a higher quality prediction.