New dammarane triterpenes from Maytenus macrocarpa

Two new dammarane triterpenes have been isolated from the stem bark exudates of Maytenus macrocarpa. Their structures were determined by extensive 1D and 2D NMR spectroscopic studies as 24(Z)-3-oxodammara-20(21),24-dien-27-oic acid (1) and octa-nor-13-hydroxydammara-1-en-3,17-dione (2). These compounds were tested for antitumoral activity.     

A Series of Collaborations between Various Pharmaceutical Companies and Regulatory Authorities Concerning the Analysis of Biomolecules Using Capillary Electrophoresis: Additional Instruments/Buffer

An international project team (including members from US, Canada and UK) was formed from a number of interested biopharmaceutical companies and regulatory authorities to conduct a cross-organisation collaboration exercise. The results of the first comparison with eight different organisations that used instruments of the same equipment model, the same reagents, and the same methodology has been reported previously [1]. This report represents the addition of other instruments using a different run buffer. The relative migration times were different, as expected, prohibiting a direct comparison between companies. The within-organisation variability was low for both relative migration time (<0.34% RSD% for all companies save one) and the peak area (<5% RSD% for all companies save one) when measuring the purity of a representative IgG sample. The apparent molecular weight of bovine serum albumin was measured with good precision (less than 10% RSD% across all companies) to the theoretical value when all data is utilized (67.5 kDa compared to 66.4 kDa). For a representative IgG sample, the three main components, IgG Light Chain, IgG Non-glycosylated Heavy Chain, and IgG Heavy Chain, could not be separated, specifically the IgG Non-glycosylated Heavy Chain and IgG Heavy Chain. When the IgG Non-glycosylated Heavy Chain and IgG Heavy Chain were combined for all organisations, the fractional peak area for the IgG Light Chain and IgG Non-glycosylated Heavy Chain + IgG Heavy Chain peak also showed excellent agreement, with less than 7.5 and 3.5% RSD%, respectively. The value of this exercise is in demonstrating the reliability of CE for the determination of apparent size of biopharmaceutical proteins. This underpins the appropriate use of such CE data in support of regulatory submissions.

     

Totally selective reaction of CO2 with enantiopure amino epoxides under mild reaction conditions. synthesis and synthetic applications of enantiopure (4R,1'S)- or (4S,1'S)-4-(1-Aminoalkyl)-2-oxo-1,3-dioxolanes

The reaction of chiral (2R,1'S)- or (2S,1'S)-2-(1-aminoalkyl)epoxides 1 or 2 with CO2, generated from acidic treatment of an aqueous solution of NaHCO3 at room temperature, efficiently afforded enantiopure cyclic carbonates 3 or 4, respectively, with total selectivity. Compounds 3 and 4 were readily transformed into the corresponding diols 7 and 8 by reaction with LiAlH4 or by basic hydrolysis. When compounds 3 or 4 were allowed to react with methyllithium at -78 degrees C, O1-acetylalkane-1,2-diols 9 and 10 were obtained with total or high selectivity.     

Variability of UVR effects on photosynthesis of summer phytoplankton assemblages from a tropical coastal area of the South China Sea

From June to September 2005, we carried out experiments to determine the ultraviolet radiation (UVR) -induced photoinhibition of summer phytoplankton assemblages from a coastal site of the South China Sea. Variability in taxonomic composition was determined throughout the summer, with a peak chlorophyll a (chl a approximately 20 microg chl a L(-1)) dominated by the diatom Skeletonema costatum that was detected early in the study period; the rest of the time samples were characterized by monads and flagellates, with low chl a values (1-5 chl a microg L(-1)). Surface water samples were placed in quartz tubes, inoculated with radiocarbon and exposed to solar radiation for 2-3 h to determine photosynthetic rates under three quality radiation treatments (i.e. PAB, 280-700 nm; PA, 320-700 nm and P, 400-700 nm) using different filters and under seven levels of ambient irradiance using neutral density screens (P vs E curves). UVR inhibition of samples exposed to maximum irradiance (i.e. at the surface) varied from -12.2% to 50%, while the daytime-integrated UVR-related photoinhibition in surface seawater varied from -62% to 7%. The effects of UVR on the photosynthetic parameters P(B)(max) and E(k) were also variable, but UV-B accounted for most of the observed variability. During sunny days, photosynthesis of microplankton (>20 microm) and piconanoplankton (<20 microm) were significantly inhibited by UVR (mostly by UV-B). However, during cloudy days, while piconanoplankton cells were still inhibited by UVR, microplankton cells used UVR (mostly UV-A) as the source of energy for photosynthesis, resulting in higher carbon fixation in samples exposed to UVR than the ones exposed only to photosynthetically active radiation (PAR). Our results indicate that size structure and cloudiness clearly condition the overall impact of UVR on phytoplankton photosynthesis in this tropical site of South China. In addition, model predictions for this area considering only PAR for primary production might have underestimated carbon fixation due to UVR contribution.     

Ring opening of chiral 2-(1-aminoalkyl)epoxides by aliphatic thiols with total selectivity: synthesis of enantiopure 3-amino-1-(alkylthio)alkan-2-ols

We have studied the thiolysis of (2R,1′S)- or (2S,1′S)-2-(1-aminoalkyl)epoxides 1 or 2 in the presence of BF₃·OEt₂. The ring opening took place at C-3 with complete regioselectivity, affording the corresponding enantiopure (2R,3S)- or (2S,3S)-3-amino-1-(alkylthio)alkan-2-ols 3 or 4 in good or high yield. The structures of compounds 3 and 4 have been proposed based on HMBC NMR experiments.     

Detection of microbial food contaminants and their products by capillary electromigration techniques

This work reviews the different analytical strategies based on capillary electromigration techniques developed for detecting microbial contaminants and their products in food matrices. Namely, this work presents an exhaustive and critical review, including works published till March 2007, on CE methods developed to detect and identify contaminants of microbial origin that represent a hazard to humans in foods. First, an overview on the strategies adopted for the analysis of intact microorganisms is presented. Next, CE methodologies based on the analysis of microbial constituents, including those based on genomics and proteomics approaches, are described. Finally, CE methods developed for detecting microbial toxins are discussed.     

Rapid characterization of alkylpolyphosphonates by CZE with indirect photometric and mass spectrometric detection

Methods for the rapid characterization of industrial alkylpolyphosphonates (APPs) by infusion MS and CZE with indirect photometric (IPD) and MS detection are described. Technical-grade APPs, including alkylaminepolyphosphonates with 3-5 phosphonate groups and different hydrocarbon skeletons, hydroxyethyl-amino-bis(methylenephosphonic acid), hydroxyethylidene-diphosphonic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid, were examined. A 10 mM solution of adenosine triphosphate disodium salt at pH 2.2 was used as BGE. The nominal compounds of the industrial APPs and their impurities were well resolved in less than 15 min. The peaks were identified by using extracted ion electropherograms, which were obtained at the m/z values indicated by the peaks of the infusion spectra. Low concentrations of esters, anhydrides, and APPs having different hydrocarbon skeletons compared to nominal compounds, and lacking phosphonate and methylene-phosphonate groups with respect to them, were found. Also, hydroxyethyl-aminobis(methylenephosphonic acid) contained an intramolecular ester at a concentration close to that of the nominal compound. Application of CZE-IPD and CZE-MS to the quality control of industrial APPs, and of CZE-MS to the identification and characterization of APPs in cleaning products, was demonstrated.     

On Metric Regularity and the Boundary of the Feasible Set in Linear Optimization

This paper deals with semi-infinite linear inequality systems in ? ⁿ and studies the stability of the boundary of their feasible sets. We analyze the equivalence between the metric regularity of the inverse of the boundary set mapping, $\mathcal{N}$ , and the stability of the feasible set mapping in the sense of the maintenance of the consistency. In doing this we provide operational formulae for distances from points to some useful sets. We also include relationships between the regularity moduli corresponding to the mappings $\mathcal{N}$ and the inverse, $\mathcal{M}$ , of the feasible set mapping, and prove their equality for finite systems and some special cases in the semi-infinite framework. Moreover, we provide conditions to assure that the metric regularity of $\mathcal{N}$ is equivalent to the lower semi-continuity of the boundary set mapping, which is important because the latter property has many characterizations. Since the boundary of a feasible set may not be convex, we cannot make use of the general theory for mappings with convex graph, as for example, the Robinson–Ursescu theorem.     

Tunable properties of graphene oxide reduced by laser irradiation

The authors present a nano-plasmonic disk resonator with a gap structure using the multi-mode interference effect coupling. The coupling intensity of the multi-mode interference effect coupling is 1.5 times greater than that of the conventional side coupling. The multi-mode interference effect is adopted as the coupling between the input bus waveguide and the nano-plasmonic disk resonator. The thickness of the dielectric layer, the width of the bus waveguide, and the length of the coupling portion are designed by theoretical calculations.