5- And 6-exocyclic products, cis-2,3,5-trisubstituted tetrahydrofurans, and cis-2,3,6-trisubstituted tetrahydropyrans via Prins-type cyclization

Exocyclic products having cis-2,5 and cis-2,6 substitution were synthesized from terminally substituted alkynyl alcohols with various aldehydes via Prins-type cyclization in good yields. It is of interest that synthesized 5- and 6-exocyclic vinyl cations generated as a result of Prins-type cyclization could be trapped as a vinyl triflate in CH2Cl2 to give 3-furanylidenes and 3-pyranylidenes. Those 3-furanylidenes and 3-pyranylidenes underwent hydrolysis to give the corresponding 3-acyl-substituted products having all-cis-configured isomers, such as 2,3,5-trisubstituted tetrahydrofurans and 2,3,6-trisubstituted tetrahydropyrans.     

Ultraviolet cavity ringdown spectra and the S1(n,pi) ring-inversion potential energy function for 2-cyclohexen-1-one-d0 and Its 2,6,6-d3 isotopomer

The cavity ringdown spectra of 2-cyclohexen-1-one (2CHO) and its 2,6,6-d3 isotopomer (2CHO-d3) have been recorded in the spectral region near their S1(n,pi)<--S0 band origins which are at 26,081.3 and 26,075.3 cm-1, respectively. The data allow several of the quantum states of nu39, the ring inversion, to be determined for both the ground and excited electronic states. These were utilized to calculate the one-dimensional potential energy functions which best fit the data. The barriers to inversion for the S0 and S1(n,pi) states were found to be 1,900 +/- 300 and 3,550 +/- 500 cm-1, respectively. Density functional theory calculations predict values of 2,090 and 2,265 cm-1, respectively.     

Two-dimensional fluorescence difference gel electrophoresis for comparison of affinity and non-affinity based downstream processing of recombinant monoclonal antibody

Although Staphylococcus Protein A (SpA) affinity chromatography is the state of the art capture step for antibody purification, non-affinity methods are more economical. We used two-dimensional fluorescence difference gel electrophoresis (2-D DIGE) to evaluate the purification of a recombinant IgG₁ antibody from cultured cells, with two different processes: (1) SpA capture followed by cation-exchange chromatography (CEX); and (2) CEX capture, followed by anion exchanger, then hydrophobic interaction chromatography. Efficiencies were similar in sodium dodecylsulphate polyacrylamide gel electrophoresis and size-exclusion chromatography; however, 2-D DIGE revealed higher efficiency with SpA than with CEX capture. Thus, 2-D DIGE is a valuable tool for downstream process development.     

Quantitative analysis of human serum leptin using a nanoarray protein chip based on single-molecule sandwich immunoassay

We report a method for the quantitative analysis of human serum leptin, which is a protein hormone associated with obesity, using a nanoarray protein chip based on a single-molecule sandwich immunoassay. The nanoarray patterning of a biotin-probe with a spot diameter of 150 nm on a self-assembled monolayer functionalized by MPTMS on a glass substrate was successfully accomplished using atomic force microscopy (AFM)-based dip-pen nanolithography (DPN). Unlabeled leptin protein molecules in human serum were detected based on the sandwich fluorescence immunoassay by total internal reflection fluorescence microscopy (TIRFM). The linear regression equation for leptin in the range of 100 zM-400 aM was determined to be y = 456.35x + 80,382 (R = 0.9901). The accuracy and sensitivity of the chip assay were clinically validated by comparing the leptin level in adult serum obtained by this method with those measured using the enzyme-linked immunosorbent assay (ELISA) performed with the same leptin standards and serum samples. In contrast to conventional ELISA techniques, the proposed chip methodology exhibited the advantages of ultra-sensitivity, a smaller sample volume and faster analysis time.     

Biomodification of coal to remove mercury

A biological process for removal of mercury from coal is under investigation. Iron and sulfur oxidizing bacteria have previously been used for desulfurization of coal and for mineral mining. We have shown that removal of mercury from coal is also possible via the same principles. Two pure cultures, Leptospirillum ferrooxidans and Acidithiobacillus ferrooxidans and four environmental consortium samples obtained from an acid mine drainage site were studied for mercury removal from coal. Four different coal samples were included in the study and the preliminary results have shown that up to 20% of the mercury can be removed in batch cultures compared to control. Additional parameters such as media composition and inoculum size were also studied. This is the first report demonstrating successful leaching of mercury from coal using biological treatment.     

Large area impingement spray cooling from multiple normal and inclined spray nozzles

An inclined spray chamber with four multiple nozzles to cool a 1 kW 6U electronic test card has been designed and tested in this study. The multiple inclined sprays can cover the same heated surface area as that with the multiple normal sprays but halve the volume of the spray chamber. The spray cooling system used R134a as a working fluid in a modified refrigeration cycle. It is observed that increasing mass flow rate and pressure drop across the nozzles improved the heat transfer coefficient with a maximum enhancement of 117 %, and reduced the maximum temperature difference at the heated surface from 13.8 to 8.4 °C in the inclined spray chamber with a heat flux of 5.25 W/cm², while the heat transfer coefficient of the normal spray increased with a maximum enhancement of 215 % and the maximum temperature difference decreased from 10.8 to 5.4 °C under similar operating conditions. We conclude that the multiple inclined sprays could produce a higher heat transfer coefficient but with an increase in non-uniformity of the surface temperature compared with the multiple normal sprays.     

Research on the Longitudinal Section of River Restoration Using Probabilistic Theory

Since the 1960s, many rivers have been destroyed as a consequence of the process of rapid urbanization. As accurate figures are important to repair rivers, there have been many research reports on methods to obtain the exact river slope and elevation. Until now, many research efforts have analyzed the river using measured river topographic factors, but when the flow velocity changes rapidly, such as during a flood, surveying is not easy; and due to cost, frequent measurements are difficult. Previous research has focused on the cross section of the river, so the information on the river longitudinal profile is insufficient. In this research, using informational entropy theory, equations are presented that can calculate the average river slope, river slope, and river longitudinal elevation for a river basin in real time. The applicability was analyzed through a comparison with the measured data of river characteristic factors obtained from the river plan. The parameters were calculated using informational entropy theory and nonlinear regression analysis using actual data, and then the longitudinal elevation entropy equation for each river and the average river slope were calculated. As a result of analyzing the applicability of the equations presented in this study by R² and Root Mean Square Error, all R² values were over 0.80, while RMSE values were analyzed to be between 0.54 and 2.79. Valid results can be obtained by calculating river characteristic factors.     

Determination and pharmacokinetics of [6]-gingerol in mouse plasma by liquid chromatography-tandem mass spectrometry

This study describes the development of a rapid and sensitive high‐performance liquid chromatography–electrospray ionization tandem mass spectrometry (LC‐MS/MS) assay for the quantification of [6]‐gingerol in mouse plasma and application to a pharmacokinetic study after dose ranging in mice. The assay involved a protein precipitation step with acetonitrile and an isocratic elution using a mobile phase consisting of acetonitrile and water containing 0.1% formic acid (80:20 v/v). The multiple reaction monitoring was based on the transition of m/z = 277.2 → 177.1 for [6]‐gingerol and 294.2 → 137.1 for nonivamide (internal standard). The assay was validated to demonstrate the specificity, linearity, recovery, accuracy, precision and stability. The calibration curves were linear over the wide concentration range of 10–10,000 ng/mL (r ≥ 0.9988). The lower limit of quantification was 10 ng/mL using a small volume of mouse plasma (20 μL). The method was successfully applied to a pharmacokinetic study in mice after intravenous injection of [6]‐gingerol at 1.5, 3 and 6 mg/kg doses. The pharmacokinetics of [6]‐gingerol were linear over the dose range studied as demonstrated by the linear increase in area under the concentration‐time curve (AUC_inf) with no significant change in the systemic clearance (Cl_s), volume of distribution (V_ss) and elimination half‐life (t_1/2) as a function of dose. Copyright © 2011 John Wiley & Sons, Ltd.     

Chromatographic analyses of tocopherols and tocotrienols in palm oil

Analyses of tocols (tocopherols and tocotrienols) in palm oil have been extensively reported in the past. However, due to the scarcity of individual tocotrienol standards, calibrations have mostly been carried out using only α-tocopherol as standard. Moreover, even if the individual tocotrienols are being used, their reliability is often questioned, because tocotrienols are highly susceptible to oxidation and deterioration. This paper reports on the study of the deterioration rate of individual tocotrienol standards upon storage as well as different calibration methods for the tocols in palm oil.