Analysis of biodiesel/petroleum diesel blends with comprehensive two-dimensional gas chromatography

Comprehensive two-dimensional gas chromatography (GCxGC) is used to analyze petroleum diesel, biodiesel, and biodiesel/petroleum diesel blends. The GCxGC instrument is assembled from a conventional gas chromatograph fitted with a simple, in-line fluidic modulator. A 5% phenyl polydimethylsiloxane primary column is coupled to a polyethylene glycol secondary column. This column combination generates chromatograms where the fatty acid methyl esters (FAMEs) found in biodiesel occupy a region that is also populated by numerous cyclic alkanes and monoaromatics found in petroleum. Fortunately, the intensities of the petroleum hydrocarbon peaks are far lower than the intensities of the FAME peaks, even for blends with low biodiesel content. This allows the FAMEs to be accurately quantitated by direct integration. The method is calibrated by analyzing standard mixtures of soybean biodiesel in petroleum diesel with concentrations ranging from 1 to 20% v/v. The resulting calibration curve displays excellent linearity. This curve is used to determine the concentration of a B20 biodiesel/petroleum diesel blend obtained from a local retailer. Excellent precision and accuracy are obtained.     

Simultaneous spectrophotometric flow-through measurements of pH, carbon dioxide fugacity, and total inorganic carbon in seawater

An autonomous multi-parameter flow-through CO₂ system has been developed to simultaneously measure surface seawater pH, carbon dioxide fugacity (fCO₂), and total dissolved inorganic carbon (DIC). All three measurements are based on spectrophotometric determinations of solution pH at multiple wavelengths using sulfonephthalein indicators. The pH optical cell is machined from a PEEK polymer rod bearing a bore-hole with an optical pathlength of ∼15 cm. The fCO₂ optical cell consists of Teflon AF 2400 (DuPont) capillary tubing sealed within the bore-hole of a PEEK rod. This Teflon AF tubing is filled with a standard indicator solution with a fixed total alkalinity, and forms a liquid core waveguide (LCW). The LCW functions as both a long pathlength (∼15 cm) optical cell and a membrane that equilibrates the internal standard solution with external seawater. fCO₂ is then determined by measuring the pH of the internal solution. DIC is measured by determining the pH of standard internal solutions in equilibrium with seawater that has been acidified to convert all forms of DIC to CO₂. The system runs repetitive measurement cycles with a sampling frequency of ∼7 samples (21 measurements) per hour. The system was used for underway measurements of sea surface pH, fCO₂, and DIC during the CLIVAR/CO₂ A16S cruise in the South Atlantic Ocean in 2005. The field precisions were evaluated to be 0.0008 units for pH, 0.9 μatm for fCO₂, and 2.4 μmol kg⁻¹ for DIC. These field precisions are close to those obtained in the laboratory. Direct comparison of our measurements and measurements obtained using established standard methods revealed that the system achieved field agreements of 0.0012 ± 0.0042 units for pH, 1.0 ± 2.5 μatm for fCO₂, and 2.2 ± 6.0 μmol kg⁻¹ for DIC. This system integrates spectrophotometric measurements of multiple CO₂ parameters into a single package suitable for observations of both seawater and freshwater.     

Microwave digestion-ICP-MS for elemental analysis in ambient airborne fine particulate matter: rare earth elements and validation using a filter borne fine particle certified reference material

NIST standard reference material SRM 2783 was employed to validate a high temperature, high pressure, two-stage microwave assisted acid digestion procedure using HNO₃, HF and H₃BO₃ developed for the analysis of trace elements (including rare earths) in atmospheric fine particulate matter (PM_2.5) prior to inductively coupled plasma mass spectrometry (ICP-MS). This method quantitatively solubilized Na, Mg, Al, K, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sb, Cd, Cs, Ba, Pb, Th, U and several rare earth elements (REEs) (La, Ce, Pr, Nd, Gd, Dy, Er, Sm and Eu) from SRM 1648 and SRM 2783. A small amount of HF in the first stage was required to dissolve silicates necessitating the corresponding addition of H₃BO₃ in second stage to dissolve fluoride precipitates of Mg, La, Ce and Th. The optimized microwave dissolution—ICP-MS method detected Na, Mg, Al, K, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Cd, Mo, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Gd, Pb, Th and U at trace to ultra-trace levels in ambient airborne fine particles from three sites in North Carolina. La to light lanthanide signature ratios suggested that soil and motor vehicles are the dominant REE sources in SRM 2783 and PM_2.5 samples collected during this study.     

Ultraviolet photoelectron spectroscopy study of the thermochromic phase transition in urethane-substituted polydiacetylenes

Threshold solid-state ionization energies determined from ultraviolet photoelectron spectra are reported for the thermochromic polydiacetylenes (PDAs) from the bis-ethyl- and bis-n-propyl urethanes of 5,7-dodecadiyn-1,12-diol (ETCD and PUDO, respectively) and the nonthermochromic 1,6-bis-p-toluenesulfonate of 2,4-hexadiyne-1,6-diol (PTS) at temperatures above and below the thermochromic phase transition. PDA-PTS has an ionization energy of 5.66 eV which does not change significantly as the temperature is raised above 140 degrees C. At 25 degrees C, PDA-ETCD and PDA-PUDO have threshold ionization energies of 5.65 and 5.51 eV, respectively. The ionization energies of these PDAs increase by approximately 0.34 eV as temperature is raised above 140 degrees C and returns to the lower values as temperature is reduced to 25 degrees C. The magnitude of the increase in ionization energy on heating to temperatures above the thermochromic transition is very close to the shift in energy of the electronic spectrum over the same temperature range. These observations suggest that the structural changes that take place in the course of the thermochromic transition are primarily associated with the valence band and are consistent with partial relief of mechanical strains.     

Carcinogenic Chromium(VI) Compounds Formed by Intracellular Oxidation of Chromium(III) Dietary Supplements by Adipocytes

Chromium(III) nutritional supplements are widely consumed for their purported antidiabetic activities. X‐ray fluorescence microscopy (XFM) and X‐ray absorption near‐edge structure (XANES) studies have now shown that non‐toxic doses of [Cr₃O(OCOEt)₆(OH₂)₃]⁺ ( A ), a prospective antidiabetic drug that undergoes similar H₂O₂ induced oxidation reactions in the blood as other Cr supplements, was also oxidized to carcinogenic Cr^VI and Cr^V in living cells. Single adipocytes treated with A had approximately 1 μm large Cr hotspots containing Cr^III, Cr^V, and Cr^VI (primarily Cr^VI thiolates) species. These results strongly support the hypothesis that the antidiabetic activity of Cr^III and the carcinogenicity of Cr^VI compounds arise from similar mechanisms involving highly reactive Cr^VI and Cr^V intermediates, and highlight concerns over the safety of Cr^III nutritional supplements.     

A Unique Tryptophan C‐Prenyltransferase from the Kawaguchipeptin Biosynthetic Pathway

Cyanobactins are a rapidly growing family of linear and cyclic peptides produced by cyanobacteria. Kawaguchipeptins A and B, two macrocyclic undecapeptides reported earlier from Microcystis aeruginosa NIES‐88, are shown to be products of the cyanobactin biosynthetic pathway. The 9 kb kawaguchipeptin (kgp) gene cluster was identified in a 5.26 Mb draft genome of Microcystis aeruginosa NIES‐88. We verified that this gene cluster is responsible for the production of the kawaguchipeptins through heterologous expression of the kgp gene cluster in Escherichia coli. The KgpF prenyltransferase was overexpressed and was shown to prenylate C‐3 of Trp residues in both linear and cyclic peptides in vitro. Our findings serve to further enhance the structural diversity of cyanobactins to include tryptophan‐prenylated cyclic peptides.     

Oxidative Conversion of a Europium(II)‐Based T1 Agent into a Europium(III)‐Based paraCEST Agent that can be Detected In Vivo by Magnetic Resonance Imaging

The Eu^II complex of 1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid (DOTA) tetra(glycinate) has a higher reduction potential than most Eu^II chelates reported to date. The reduced Eu^II form acts as an efficient water proton T₁ relaxation reagent, while the Eu^III form acts as a water‐based chemical exchange saturation transfer (CEST) agent. The complex has extremely fast water exchange rate. Oxidation to the corresponding Eu^III complex yields a well‐defined signal from the paraCEST agent. The time course of oxidation was studied in vitro and in vivo by T₁‐weighted and CEST imaging.     

Facile Recoding of Selenocysteine in Nature

Selenocysteine (Sec or U) is encoded by UGA, a stop codon reassigned by a Sec‐specific elongation factor and a distinctive RNA structure. To discover possible code variations in extant organisms we analyzed 6.4 trillion base pairs of metagenomic sequences and 24 903 microbial genomes for tRNA^Sec species. As expected, UGA is the predominant Sec codon in use. We also found tRNA^Sec species that recognize the stop codons UAG and UAA, and ten sense codons. Selenoprotein synthesis programmed by UAG in Geodermatophilus and Blastococcus, and by the Cys codon UGU in Aeromonas salmonicida was confirmed by metabolic labeling with ⁷⁵Se or mass spectrometry. Other tRNA^Sec species with different anticodons enabled E. coli to synthesize active formate dehydrogenase H, a selenoenzyme. This illustrates the ease by which the genetic code may evolve new coding schemes, possibly aiding organisms to adapt to changing environments, and show the genetic code is much more flexible than previously thought.     

Structure–Activity Studies of Cysteine‐Rich α‐Conotoxins that Inhibit High‐Voltage‐Activated Calcium Channels via GABAB Receptor Activation Reveal a Minimal Functional Motif

α‐Conotoxins are disulfide‐rich peptides that target nicotinic acetylcholine receptors. Recently we identified several α‐conotoxins that also modulate voltage‐gated calcium channels by acting as G protein‐coupled GABA_B receptor (GABA_BR) agonists. These α‐conotoxins are promising drug leads for the treatment of chronic pain. To elucidate the diversity of α‐conotoxins that act through this mechanism, we synthesized and characterized a set of peptides with homology to α‐conotoxins known to inhibit high voltage‐activated calcium channels via GABA_BR activation. Remarkably, all disulfide isomers of the active α‐conotoxins Pu1.2 and Pn1.2, and the previously studied Vc1.1 showed similar levels of biological activity. Structure determination by NMR spectroscopy helped us identify a simplified biologically active eight residue peptide motif containing a single disulfide bond that is an excellent lead molecule for developing a new generation of analgesic peptide drugs.     

Factors Affecting the Production of Aromatic Immonium Ions in MALDI 157 nm Photodissociation Studies

Immonium ions are commonly observed in the high energy fragmentation of peptide ions. In a MALDI-TOF/TOF mass spectrometer, singly charged peptides photofragmented with 157 nm VUV light yield a copious abundance of immonium ions, especially those from aromatic residues. However, their intensities may vary from one peptide to another. In this work, the effect of varying amino acid position, peptide length, and peptide composition on immonium ion yield is investigated. Internal immonium ions are found to have the strongest intensity, whereas immonium ions arising from C-terminal residues are the weakest. Peptide length and competition among residues also strongly influence the immonium ion production. Quantum calculations provide insights about immonium ion structures and the fragment ion conformations that promote or inhibit immonium ion formation.

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