Stereochemistry of the thermal isomerizations of (2S,3R-methoxymethyl-2,3-dideuterio-1-(dideuteriomethylene)cyclopropane

The (2S,3R) isomer of 2-methoxymethyl-2,3-dideuterio-1-(dideuteriomethylene)cyclopropane has been synthesized and heated at 198.8°: from the experimentally observed mol fractions of the eight isomers of 2,3,α,α,- and 2,3,3,α - tetradeuterio - 2 - methoxymethyl - 1 - methylenecyclopropane in the pyrolysis product mixture have been derived rate constants for seven distinct modes of isomerization. One-center thermal epimerizations at C(2) and C(3) and the C(2)C(3) two-center epimerization are of kinetic importance. Only two of four observable stereochemical modes for carbon [1,3] shifts are seen: there is inversion of stereochemistry at the migrating C atom, while the C(3)H trans to C(2)-CH₂OCH₃ in starting material becomes syn 4 : 1 C(α)-H in the [1,3] shift product. Stereomutation at C(2) does not occur along the reaction coordinate for [1,3] carbon shifts.     

Synthesis and Mesogenic Properties of Liquid Crystals Containing Terminal Cyclohexylmethanol,Cyclopentylmethanol, Cyclobutylmethanol and Cyclopropylmethanol Moiety

Four series of compounds 11?50 containing terminal alicyclic rings such as cyclohexylmethyl, cyclopentylmethyl, cyclobutylmethyl, and cyclopropylmethyl rings were synthesized and their liquid crystal behavior studied. The ring size and the length of flexible alkoxy chain influence the phase formation in different ways. While the smaller ring and the shorter alkoxy chain tend to favor the formation of the N phase, the larger ring and the longer alkoxy chain tend to favor the formation of the SmC phase. All the compounds except 11 and 21 exhibit SmA phases. The widest temperature range of the N, SmA, and SmC phases are found in the compounds 41 , 46 , and 20 , respectively, which are 75 °C for 41 , 115 °C for 46 , and 100 °C for 20 .     

Comparative studies of various run buffers for chiral capillary electrophoresis using chiral crown ether as a chiral selector

In the capillary electrophoretic separation of primary amine enantiomers using (+)-(18-crown-6)-tetracarboxylic acid (18C6H4) as a chiral selector, the presence of run buffer constituents such as tris(hydroxymethyl)aminomethane (Tris) or Na+ competing with analytes for 18C6H4, diminishes the effectiveness of 18C6H4. In order to determine appropriate buffer systems for 18C6H4, various run buffer cationic components including Tris, 1,3-bis[tris(hydroxymethyl)methylamino]propane, bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane, triethanolamine, tetramethylammonium, and Na+ were compared. Quantitative studies of the effects of the competitive constituents were carried out by measuring the electrophoretic mobilities of histidine as a function of the 18C6H4 concentration. We also derived a simple equation to estimate the optimal chiral selector concentration for a maximum mobility difference in the presence of a competitive inhibitor.     

Enhancement of phosphoprotein analysis using a fluorescent affinity tag and mass spectrometry

A fluorescent affinity tag (FAT) was synthesized and was utilized to selectively modify phosphorylated serine and threonine residues via beta-elimination and Michael addition chemistries in a 'one-step' reaction. This labeling technique was used for covalent modification of both phosphoproteins and phosphopeptides, allowing identification of these molecular species by fluorescence imaging after solution- or gel-based separation methods. In addition to the strong fluorescence of the rhodamine tag, a commercially available antibody can be used to enrich low-abundance post-labeled phosphopeptides present in complex mixtures. Application of this methodology to phosphorylation-site mapping has been evaluated for a phosphoprotein standard, bovine beta-casein. Initial results demonstrated low femtomole detection limits after fluorescence image analysis of FAT-labeled proteins or peptides.     

Analysis of urban dust (PM<Subscript>2</Subscript>/PM<Subscript>10-2</Subscript>) in Daejeon city by instrumental neutron activation analysis

Summary As part of an air pollution monitoring study, airborne particulate matter (PM₂/PM_10-2) samples were collected from 2000 to 2003 at two sampling sites in an urban region, Daejeon, the middle of Korea. Mass concentrations of both fine and coarse fractions and that of the black carbon in the fine particles were measured using the Gent stacked filter unit sampler and the smoke stain reflectometer, respectively. In the collected samples the concentrations of 24 elements were analyzed using instrumental neutron activation analysis. Monitored data were investigated for their temporal trends under different environmental conditions and their seasonal correlation patterns. Crustal enrichment factors were also estimated to establish the contribution between anthropogenic and crustal origin. Patterns for airborne particle matter (APM) and elemental concentrations, seasonal variation of some marker elements were investigated. The results can be applied for the investigation of further air pollution sources and for the evaluation of air quality.     

Airborne particulates (PM2.5/PM10) monitoring in Korea by instrumental neutron activation analysis

Instrumental neutron activation analysis was used for the analysis of 25 trace elements in airborne particulate matter (PM) for air pollution monitoring. For the collection of air samples, the Gent stacked filter unit low volume sampler and two types of Nuclepore polycarbonate filters were employed. Samples were collected at selected sampling dates in suburban and industrial regions of Daejon city in the Republic of Korea. Mass concentrations and black carbon of PM were measured, and enrichment factors were calculated. The results were used to describe the emission sources and their correlation patterns.     

Simultaneous measurement of glucose and glutamine in aqueous solutions by near infrared spectroscopy

A method is described for measuring the concentrations of both glucose and glutamine in binary mixtures from near infrared (NIR) absorption spectra. Spectra are collected over the range from 5000–4000/cm (2.0–2.5μm) with a 1-mm optical path length. Glucose absorbance features at 4710, 4400, and 4300/cm and glutamine features at 4700, 4580, and 4390/cm provide the analytical information required for the measurement. Multivariate calibration models are generated by using partial least squares (PLS) regression alone and PLS regression combined with a preprocessing digital Fourier filtering step. The ideal number of PLS factors and spectral range are identified separately for each analyte. In addition, the optimum Fourier filter parameters are established for both compounds. The best overall analytical performance is obtained by combining Fourier filtering and PLS regression. Glucose measurements are established over the concentration range from 1.66–59.91 mM, with a standard error of prediction (SEP) of 0.32 mM and a mean percent error of 1.84%. Glutamine can be measured over the concentration range from 1.10–30.65 mM with a SEP of 0.75 mM and a mean percent error of 6.67%. These results demonstrate the analytical utility of NIR spectroscopy for monitoring glucose and glutamine levels in mammalian and insect cell cultures.     

A novel photoinduced ring opening and isomerization of adamantane-2-spiro isoxazolines using Mo(CO)6

The Mo(CO)₆-mediated photoinduced ring-opening reactions of adamantane isoxazolines involve novel rearrangement that provide enaminoketones as major products and β-hydroxy ketones as minor ones; in contrast, only β-hydroxy ketones and α,β-unsaturated ketones were obtained under thermal condition.     

Direct determination of estriol 3- and 16-glucuronides in pregnancy urine by column-switching liquid chromatography with electrospray tandem mass spectrometry

Using column-switching liquid chromatography/tandem mass spectrometry (LC-MS/MS), we developed an improved analytical method of urinary estriol glucuronides. This new method is derived predominantly from maternal and fetal precursors in pregnancy. We used in the following procedure: first, we filtered urine samples with a membrane filter. Next, we directly injected the 50 microL aliquot of urine samples onto a pre-column. Then, after activating the column-switching valve, we backflushed the loaded samples onto the C(18) analytical column. Urine samples can be assayed within 20 min without any sample preparation steps. We monitored separated estriol glucuronides by negative electrospray ionization (ESI) and selected-reaction monitoring (SRM). The calibration range of estriol-3-glucuronide (E3-3G) and estriol-16-glucuronide (E3-16G) was 0.1-20 microg/mL and the linearity of the method was 0.9984 for E3-3G and 0.9987 for E3-16G. The limits of detection at a signal-to-noise (S/N) ratio of 3 were 10 ng/mL (E3-3G) and 5 ng/mL (E3-16G). The analytical recovery was over 85% and, in general, inter-day and intra-day variability for precision and accuracy were less than 10%. When applied to a pregnancy urine sample to biomedical monitoring of the function of the maternal/fetal unit, the proposed method allowed rapid and sensitive screening for the detection of E3-3G and E3-16G.