Optics Concept for a Pair of Undulator Beamlines for MX

We describe a concept for x-ray optics to feed a pair of macromolecular crystallography (MX) beamlines which view canted undulator radiation sources in the same storage ring straight section. It can be deployed at NSLS-II and at other low-emittance third-generation synchrotron radiation sources where canted undulators are permitted, and makes the most of these sources and beamline floor space, even when the horizontal angle between the two canted undulator emissions is as little as 1-2 mrad. The concept adopts the beam-separation principles employed at the 23-ID (GM/CA-CAT) beamlines at the Advanced Photon Source (APS), wherein tandem horizontally-deflecting mirrors separate one undulator beam from the other, following monochromatization by a double-crystal monochromator. The scheme described here would, in contrast, deliver the two tunable monochromatic undulator beams to separate endstations that address rather different and somewhat complementary purposes, with further beam conditioning imposed as required. A downstream microfocusing beamline would employ dual-stage focusing for work at the micron scale and, unique to this design, switch to single stage focusing for larger beams. On the other hand, the upstream, more highly automated beamline would only employ single stage focusing.     

Formation of defect-free latex films on porous fiber supports

We present here the creation of a defect-free polyvinylidene chloride barrier layer on the lumen-side of a hollow fiber sorbent. Hollow fiber sorbents have previously been shown to be promising materials for enabling low-cost CO(2) capture, provided a defect-free lumen-side barrier layer can be created. Film experiments examined the effect of drying rate, latex age, substrate porosity (porous vs nonporous), and substrate hydrophobicity/hydrophilicity. Film studies show that in ideal conditions (i.e., slow drying, fresh latex, and smooth nonporous substrate), a defect-free film can be formed, whereas the other permutations of the variables investigated led to defective films. These results were extended to hollow fiber sorbents, and despite using fresh latex and relatively slow drying conditions, a defective lumen-side layer resulted. XRD and DSC indicate that polyvinylidene chloride latex develops crystallinity over time, thereby inhibiting proper film formation as confirmed by SEM and gas permeation. This and other key additional challenges associated with the porous hollow fiber substrate vs the nonporous flat substrate were overcome. By employing a toluene-vapor saturated drying gas (a swelling solvent for polyvinylidene chloride) a defect-free lumen-side barrier layer was created, as investigated by gas and water vapor permeation.     

Multi-wavelength raman imaging using a small-diameter image guide with a dimension-reduction imaging array

A commercially available fiber-optic Raman probe was modified for high-resolution spectral Raman imaging using a 350 microm diameter optical fiber image guide coupled to a dimension-reduction imaging array (DRIA). The DRIA comprised 672 optical fibers, arranged as a square array (21 x 32 fibers) on one end and a linear array (672 x 1 fibers) on the other. An imaging spectrograph was used with the DRIA to acquire multi-wavelength Raman images from -250 to 1800 cm(-1) at a spectral resolution of approximately 5 cm(-1). The utility of this technique for in situ and remote Raman imaging is demonstrated by monitoring the polymerization of a model polymer, dibromostyrene (DBS), while simultaneously measuring the Raman Stokes/ anti-Stokes ratio as a function of sample heating time, over a sample area of approximately 4 x 1.6 mm.     

Interpreting satellite column observations of formaldehyde over tropical South America

Space-borne column measurements of formaldehyde (HCHO), a high-yield oxidation product of volatile organic compounds (VOCs), represent important constraints for quantifying net regional fluxes of VOCs. Here, we interpret observed distributions of HCHO columns from the Global Ozone Monitoring Experiment (GOME) over tropical South America during 1997-2001. We present the first comparison of year-long in situ isoprene concentrations and fire-free GOME HCHO columns over a tropical ecosystem. GOME HCHO columns and in situ isoprene concentrations are elevated in the wet and dry seasons, with the highest values in the dry season. Previous analysis of the in situ data highlighted the possible role of drought in determining the elevated concentrations during the dry season, inferring the potential of HCHO columns to provide regional-scale constraints for estimating the role of drought on isoprene emissions. The agreement between the observed annual cycles of GOME HCHO columns and Along-Track Scanning Radiometer firecount data over the Amazon basin (correlations typically greater than 0.75 for a particular year) illustrates the potential of HCHO column to provide quantitative information about biomass burning emissions.     

Radiolytic modification of sulfur-containing amino acid residues in model peptides: fundamental studies for protein footprinting

Protein footprinting based on hydroxyl radical-mediated modification and quantitative mass spectroscopic analysis is a proven technique for examining protein structure, protein-ligand interactions, and structural allostery upon protein complex formation. The reactive and solvent-accessible amino acid side chains function as structural probes; however, correct structural analysis depends on the identification and quantification of all the relevant oxidative modifications within the protein sequence. Sulfur-containing amino acids are oxidized readily and the mechanisms of oxidation are particularly complex, although they have been extensively investigated by EPR and other spectroscopic methods. Here we have undertaken a detailed mass spectrometry study (using electrospray ionization mass spectrometry and tandem mass spectrometry) of model peptides containing cysteine (Cys-SH), cystine (disulfide bonded Cys), and methionine after oxidation using gamma-rays or synchrotron X-rays and have compared these results to those expected from oxidation mechanisms proposed in the literature. Radiolysis of cysteine leads to cysteine sulfonic acid (+48 Da mass shift) and cystine as the major products; other minor products including cysteine sulfinic acid (+32 Da mass shift) and serine (-16 Da mass shift) are observed. Radiolysis of cystine results in the oxidative opening of the disulfide bond and generation of cysteine sulfonic acid and sulfinic acid; however, the rate of oxidation is significantly less than that for cysteine. Radiolysis of methionine gives rise primarily to methionine sulfoxide (+16 Da mass shift); this can be further oxidized to methionine sulfone (+32 Da mass shift) or another product with a -32 Da mass shift likely due to aldehyde formation at the gamma-carbon. Due to the high reactivity of sulfur-containing amino acids, the extent of oxidation is easily influenced by secondary oxidation events or the presence of redox reagents used in standard proteolytic digestions; when these are accounted for, a reactivity order of cysteine > methionine approximately tryptophan > cystine is observed.     

Mapping tropospheric ozone profiles from an airborne ultraviolet-visible spectrometer

We present a novel technique for retrieving ozone (O3) profiles and especially tropospheric O3 from airborne UV/visible spectrometer measurements. This technique utilizes radiance spectra from one down-looking and two up-looking (85 degrees and 75 degrees) directions, taking advantage of the O3 absorption structure in the Huggins (300-340-nm) and Chappuis (530-650-nm) bands. This technique is especially sensitive to tropospheric O3 below and < or =8 km above the aircraft with a vertical resolution of 2-6 km and is sensitive to lower and middle stratospheric O3 with a vertical resolution of 8-15 km. It can measure tropospheric O3 at spatial resolutions of 2 km x 2 km or higher and is therefore well suited for regional air-quality studies and validation of satellite measurements.     

Cerebral oxygenation during warming after cardiopulmonary bypass

OBJECTIVES: To evaluate jugular venous oxygen saturation (SjVO2), measured with a fiberoptic oximetry catheter, and brain tissue oxygen saturation, measured by near-infrared spectroscopy (NIRSO2), as monitors of cerebral oxygenation during cardiopulmonary bypass surgery. DESIGN: Prospective, clinical study. SETTING: Operating room of a Veterans Administration Hospital. PATIENTS: Nineteen patients undergoing moderate hypothermic cardiopulmonary bypass surgery. INTERVENTIONS: SjvO2 and NIRSO2 were monitored in the patients during the surgical procedure. MEASUREMENTS AND MAIN RESULTS: Moderate hypothermic cardiopulmonary bypass surgery had two distinct cerebral hemodynamic phases. While the patients were hypothermic, SjvO2 averaged 80 +/- 7% and none of the patients had an increase in cerebral lactate production. During the rewarming period, however, reductions in SjvO2 to < 50% occurred in 16 (84%) patients and increased cerebral anaerobic metabolism developed in 11 (58%) patients. SjvO2 during rewarming was dependent on mean arterial pressure, with 60 mm Hg appearing to be a critical value. Two other factors appeared to also contribute to the jugular desaturation, a low hematocrit and a rapid warming time. The SjvO2 catheter had excellent performance during the surgery. The average difference between paired measurements of SjvO2 by the catheter and in blood samples was -0.4 +/- 4.25%, and the correlation between the two measurements was highly significant (r2 = .93; p < .001). The NIRSO2 trended with the SjvO2 in most patients (r2 = .63; p < .001). CONCLUSIONS: The study confirms other studies showing that jugular venous desaturation can occur during rewarming after cardiopulmonary bypass surgery. Presently, SjvO2 appears to be a better monitor of cerebral oxygenation than NIRSO2. However, NIRSO2 has promise as a noninvasive monitor of cerebral oxygenation if future developments allow more quantitative measurements of oxygen saturation.     

Connexin mutations in X-linked Charcot-Marie-Tooth disease

X-linked Charcot-Marie-Tooth disease (CMTX) is a form of hereditary neuropathy with demyelination. Recently, this disorder was mapped to chromosome Xq13.1. The gene for the gap junction protein connexin32 is located in the same chromosomal segment, which led to its consideration as a candidate gene for CMTX. With the use of Northern (RNA) blot and immunohistochemistry technique, it was found that connexin32 is normally expressed in myelinated peripheral nerve. Direct sequencing of the connexin32 gene showed seven different mutations in affected persons from eight CMTX families. These findings, a demonstration of inherited defects in a gap junction protein, suggest that connexin32 plays an important role in peripheral nerve.     

Insulin, ketone bodies, and mitochondrial energy transduction

Addition of insulin or a physiological ratio of ketone bodies to buffer with 10 mM glucose increased efficiency (hydraulic work/energy from O2 consumed) of working rat heart by 25%, and the two in combination increased efficiency by 36%. These additions increased the content of acetyl CoA by 9- to 18-fold, increased the contents of metabolites of the first third of the tricarboxylic acid (TCA) cycle 2- to 5-fold, and decreased succinate, oxaloacetate, and aspartate 2- to 3-fold. Succinyl CoA, fumarate, and malate were essentially unchanged. The changes in content of TCA metabolites resulted from a reduction of the free mitochondrial NAD couple by 2- to 10-fold and oxidation of the mitochondrial coenzyme Q couple by 2- to 4-fold. Cytosolic pH, measured using 31P-NMR spectra, was invariant at about 7.0. The total intracellular bicarbonate indicated an increase in mitochondrial pH from 7.1 with glucose to 7.2, 7.5 and 7.4 with insulin, ketones, and the combination, respectively. The decrease in Eh7 of the mitochondrial NAD couple, Eh7NAD+/NADH, from -280 to -300 mV and the increase in Eh7 of the coenzyme Q couple, Eh7Q/QH2, from -4 to +12 mV was equivalent to an increase from -53 kJ to -60 kJ/2 mol e in the reaction catalyzed by the mitochondrial NADH dehydrogenase multienzyme complex (EC 1.6.5.3). The increase in the redox energy of the mitochondrial cofactor couples paralleled the increase in the free energy of cytosolic ATP hydrolysis, delta GATP. The potential of the mitochondrial relative to the cytosolic phases, Emito/cyto, calculated from delta GATP and delta pH on the assumption of a 4 H+ transfer for each ATP synthesized, was -143 mV during perfusion with glucose or glucose plus insulin, and decreased to -120 mV on addition of ketones. Viewed in this light, the moderate ketosis characteristic of prolonged fasting or type II diabetes appears to be an elegant compensation for the defects in mitochondrial energy transduction associated with acute insulin deficiency or mitochondrial senescence.