Solid-phase synthesis of enantio-controlled lactic acid oligomers

A synthetic method for lactic acid oligomers via solid-phase synthesis under mild reaction conditions with up to 99% yield is presented. The fine control of the chirality on each lactic acid unit of the oligomers was easily achieved by the substitution of (R)-THP-protected lactic acid (R)-2 by (S)-2 without alternating the procedure. The overall synthesis of the trimer and tetramer was completed in one and two days, respectively. Intramolecular cyclizations of enantio-controlled lactic acids were also attempted through the Yamaguchi macrolactonization or the Mitsunobu reaction. However, we were unable to isolate single cyclic oligomers but always obtained a mixture of cyclic oligomers.     

Development and validation of a rapid RP‐HPLC method for analysis of (−)‐copalic acid in copaíba oleoresin

The Copaifera species (Leguminoseae) are popularly known as ‘copaíba’ or ‘copaíva’ and are grown in the states of Amazonas, Pará and Ceará in northern Brazil. The oleoresins obtained from these species have been extensively used owing to their pharmacological potential and their application in cosmetic and pharmaceutical preparations. In the present study, the development and validation of a novel, rapid and efficient RP‐HPLC methodology for the analysis of the diterpene (?)‐copalic acid (CA), pointed out as the only chemical marker of the Copaifera genus, are described. The regression equation (Y = 26,707x ? 29,498) was obtained with good linearity (r² = 0.9993) and the limits of quantification and detection were 9.182 and 3.032 µg/mL, respectively. The precision and the accuracy of the method were adequate (lower than 4%). Finally, the validation parameters evaluated were satisfactorily met, so the developed method represents a suitable tool for application in the quality control of such natural products. Further studies aiming to develop analytical methodologies for each Copaifera species using a more representative number of chemical markers should be performed. Copyright © 2012 John Wiley & Sons, Ltd.     

Chromium(VI) oxide oxidation of non‐ethoxylated and ethoxylated alcohols for determination by electrospray ionization mass spectrometry

A new derivatization procedure to increase the sensitivity of electrospray ionization mass spectrometry (ESI‐MS) to non‐ethoxylated and ethoxylated alcohols was investigated. The analytes were oxidized with chromium(VI) oxide and the resulting carboxylic and ethoxy‐carboxylic acids were isolated by extraction with ethyl acetate; the extracts were alkalinized and infused into the ESI‐MS system working in the negative‐ion mode. The yields of the combined oxidation‐extraction were ca. 100% for non‐ethoxylated fatty alcohols dissolved in acetone and they decreased moderately in samples containing increasing amounts of water (e.g., a 75% yield was obtained with 50% water). Ethoxylated alcohols with more than two ethylene oxide units resulted in yields of ca. 60%. Low limits of detection (LODs) were obtained when the procedure was applied to the analysis of body‐care products and cosmetics containing fatty alcohols, e.g., in a varicose‐vein cream, the LODs were 25 µg cetyl alcohol and 7.5 µg stearyl alcohol (detected as palmitic acid and stearic acid, respectively) per gram of sample. High molecular mass alcohols were also detected in seawater after pre‐concentration by solid‐phase extraction. Thus, the proposed method is particularly valuable for use in industrial samples having complex matrices and in environmental samples and it is competitive with other methods for the analysis of trace amounts of fatty alcohols. Copyright © 2010 John Wiley & Sons, Ltd.     

Oxidation of glycated phosphatidylethanolamines: evidence of oxidation in glycated polar head identified by LC-MS/MS

Phosphatidylethanolamine glycation occurs in diabetic patients and was found to be related with oxidative stress and with diabetic complications. Glycated phosphatidylethanolamines seem to increase oxidation of other molecules; however, the reason why is not understood. In this work, we have studied the oxidation of glycated phosphatidylethanolamines (1-palmitoyl-2-linoleoyl-sn-glycero-3-phosphatidylethanolamine (PLPE) and 1,2-dipalmitoyl-sn-glycero-3-phosphatidylethanolamine (dPPE)) using a Fenton system. Liquid chromatography–electrospray ionization (ESI)–mass spectrometry and ESI–tandem mass spectrometry in both positive and negative modes were used for detecting and identifying the oxidation products. We were able to identify several oxidation products with oxidation in unsaturated sn-2 acyl chain of PLPE, as long- and short-chain products with main oxidation sites on C-7, C-8, C-9, and C-12 carbons. Other products were identified in both glycated PLPE and glycated dPPE, revealing that oxidation also occurs in the glycated polar head. This fact has not been reported before. These products may be generated from oxidation of glycated phosphatidylethanolamines (PE) as Schiff base, leading to short-chain product without the amine moiety, due to cleavage of glycated polar head and long-chain product with two keto groups linked to the glycated polar head or from glycated PE as Amadori product, short-chain products with –NHCHO and –NHCHOHCHO terminal in polar head. Oxidation of glycated phosphatidylethanolamines occurred more quickly than the oxidation of non-glycated phosphatidylethanolamines probably because of the existence of more oxidation sites derived from glycation of polar head group. Monitoring glycated polar head oxidation could be important to evaluate oxidative stress modifications that occur in diabetic patients.     

Adaptive thermo-fluid moving boundary computations for interfacial dynamics

In this study,we present adaptive moving boundary computation technique with parallel implementation on a distributed memory multi-processor system for large scale thermo-fluid and interfacial flow computations.The solver utilizes Eulerian-Lagrangian method to track moving(Lagrangian) interfaces explicitly on the stationary(Eulerian) Cartesian grid where the flow fields are computed.We address the domain decomposition strategies of Eulerian-Lagrangian method by illustrating its intricate complexity of the computation involved on two different spaces interactively and consequently,and then propose a trade-off approach aiming for parallel scalability.Spatial domain decomposition is adopted for both Eulerian and Lagrangian domain due to easy load balancing and data locality for minimum communication between processors.In addition,parallel cell-based unstructured adaptive mesh refinement(AMR) technique is implemented for the flexible local refinement and even-distributed computational workload among processors.Selected cases are presented to highlight the computational capabilities,including Faraday type interfacial waves with capillary and gravitational forcing,flows around varied geometric configurations and induced by boundary conditions and/or body forces,and thermo-fluid dynamics with phase change.With the aid of the present techniques,large scale challenging moving boundary problems can be effectively addressed.     

Electromagnetic interference shielding characteristics of fabric complexes coated with conductive polypyrrole and thermally evaporated Ag

Through the chemical coating of polypyrrole (PPy) doped with naphthalene sulfonic acid (NSA) on electrically insulating poly (ethylene terephthalate) (PET) woven fabric, PPy–NSA/PET complexes were synthesized. By using the electrochemical coating of PPy doped anthraquinone-2-sulfonic acid (AQSA) on PPy–NSA/PET complexes, PPy–AQSA/PPy–NSA/PET complexes were synthesized. The silver (Ag) was thermally vacuum evaporated on the surface of PPy–AQSA/PPy–NSA/PET complexes (Ag|PPy–AQSA/PPy–NSA/PET). Electromagnetic interference (EMI) shielding efficiency (SE) and dc conductivity (σ_dc) of fabric complexes were measured for EMI shielding characteristics and theoretical simulation. The measurement of EMI SE in the frequency range from 50 MHz to 1.5 GHz was performed by using ASTM D4935-99 method. The EMI shielding characteristics such as transmittance, reflectance and absorbance were obtained from the S (scattering)-parameter analysis. We control the contribution of the absorbance or the reflectance to total EMI SE through the coating of conductive PPy and the evaporation Ag.