Crossed molecular beam chemiluminescence study of the metastable mercury reaction: Hg(3P)+Br2 → HgBr(B) + Br

Chemiluminescence from HgBr(B) formed in the reaction of Hg(6³P_o with Br₂ has been observed using a N₂-seeded nozzle beam of metastable Hg³P_o) atoms. The cross section has been estimated to be 3⁺³_?2 at a collission energy of 0.33 eV. This value is smaller by more than an order of magnitude than the corresponding value for Hg(³P₂) atoms measured by Krause et al., in accordance with their inference based on less direct evidence.     

BIOCHEMICAL FACTORS AFFECTING THE QUANTUM EFFICIENCY OF HYDROGEN PRODUCTION BY MEMBRANES OF GREEN PHOTOSYNTHETIC BACTERIA*

Abstract— Photohydrogen production, 200-700 μmol H₂ h^?1 (mg bacteriochlorophyll a)^?1 has been obtained in a system containing unit membrane vesicles (Complex I) from the green photosynthetic bacterium Chiorobium limicola f. thiosulfatophilum, ascorbate, N,N,N′,N′-tetramethyl-p-phenylene-diamine, dithioerythritol, an oxygen scavenging mixture, either methyl viologen (MV) or clostridial ferredoxin (CPS Fd) as electron carrier, and either CPS hydrogenase or platinum asbestos as catalyst. All components are necessary for maximum activity, and spinach Fd cannot be substituted for CPS Fd. Higher rates of photohydrogen production are obtained using MV or CPS Fd with hydrogenase than with MV and Pt asbestos. The highest quantum efficiencies (7–10% at 0.2–0.9 mW absorbed light and over 20% at lower light) were obtained with CPS Fd, hydrogenase and non-saturating 812 nm light. With saturating white light, however, rates of photohydrogen production varied relatively little among the various combinations of electron carrier and catalyst tested. The reaction rate is unaffected by 0.03% Triton X-100, and is insensitive to treatment with antimycin a or m-chloro-carbonyl cyanide phenylhydrazone. This indicates that neither electron flow through an endogenous cyclic chain, nor maintenance of a proton gradient are involved in this process.     

Application of isotopic labeling,and gas chromatography mass spectrometry,to understanding degradation products and pathways in the thermal-oxidative aging of Nylon 6.6

Nylon 6.6 containing ¹³C isotopic labels at specific positions along the macromolecular backbone has been subjected to extensive thermal-oxidative aging at 138 °C for time periods up to 243 days. In complementary experiments, unlabeled Nylon 6.6 was subjected to the same aging conditions under an atmosphere of ¹⁸O₂. Volatile organic degradation products were analyzed by cryofocusing gas chromatography mass spectrometry (cryo-GC/MS) to identify the isotopic labeling. The labeling results, combined with basic considerations of free radical reaction chemistry, provided insights to the origin of degradation species, with respect to the macromolecular structure. A number of inferences on chemical mechanisms were drawn, based on 1) the presence (or absence) of the isotopic labels in the various products, 2) the location of the isotope within the product molecule, and 3) the relative abundance of products as indicated by large differences in peak intensities in the gas chromatogram. The overall degradation results can be understood in terms of free radical pathways originating from initial attacks on three different positions along the nylon chain which include hydrogen abstraction from: the (CH₂) group adjacent to the nitrogen atom, at the (CH₂) adjacent the carbonyl group, and direct radical attack on the carbonyl. Understanding the pathways which lead to Nylon 6.6 degradation ultimately provides new insight into changes that can be leveraged to detect and reduce early aging and minimize problems associated with material degradation.     

Llama-derived single-domain antibodies for the detection of botulinum A neurotoxin

Single-domain antibodies (sdAb) specific for botulinum neurotoxin serotype A (BoNT A) were selected from an immune llama phage display library derived from a llama that was immunized with BoNT A toxoid. The constructed phage library was panned using two methods: panning on plates coated with BoNT A toxoid (BoNT A Td) and BoNT A complex toxoid (BoNT Ac Td) and panning on microspheres coupled to BoNT A Td and BoNT A toxin (BoNT A Tx). Both panning methods selected for binders that had identical sequences, suggesting that panning on toxoided material may be as effective as panning on bead-immobilized toxin for isolating specific binders. All of the isolated binders tested were observed to recognize bead-immobilized BoNT A Tx in direct binding assays, and showed very little cross-reactivity towards other BoNT serotypes and unrelated protein. Sandwich assays that incorporated selected sdAb as capture and tracer elements demonstrated that all of the sdAb were able to recognize soluble (“live”) BoNT A Tx and BoNT Ac Tx with virtually no cross-reactivity with other BoNT serotypes. The isolated sdAb did not exhibit the high degree of thermal stability often associated with these reagents; after the first heating cycle most of the binding activity was lost, but the portion of the protein that did refold and recover antigen-binding activity showed only minimal loss on subsequent heating and cooling cycles. The binding kinetics of selected binders, assessed by both an equilibrium fluid array assay as well as surface plasmon resonance (SPR) using toxoided material, gave dissociation constants (K _D ) in the range 2.2 × 10⁻¹¹ to 1.6 × 10⁻¹⁰ M. These high-affinity binders may prove beneficial to the development of recombinant reagents for the rapid detection of BoNT A, particularly in field screening and monitoring applications.     

Laser desorption VUV postionization MS imaging of a cocultured biofilm

Laser desorption postionization mass spectrometry (LDPI-MS) imaging is demonstrated with a 10.5 eV photon energy source for analysis and imaging of small endogenous molecules within intact biofilms. Biofilm consortia comprised of a synthetic Escherichia coli K12 coculture engineered for syntrophic metabolite exchange are grown on membranes and then used to test LDPI-MS analysis and imaging. Both E. coli strains displayed many similar peaks in LDPI-MS up to m/z 650, although some observed differences in peak intensities were consistent with the appearance of byproducts preferentially expressed by one strain. The relatively low mass resolution and accuracy of this specific LDPI-MS instrument prevented definitive assignment of species to peaks, but strategies are discussed to overcome this shortcoming. The results are also discussed in terms of desorption and ionization issues related to the use of 10.5 eV single-photon ionization, with control experiments providing additional mechanistic information. Finally, 10.5 eV LDPI-MS was able to collect ion images from intact, electrically insulating biofilms at ～100 μm spatial resolution. Spatial resolution of ～20 μm was possible, although a relatively long acquisition time resulted from the 10 Hz repetition rate of the single-photon ionization source.

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.     

Optimising reaction performance in the pharmaceutical industry by monitoring with NMR

Quality assurance and process understanding are assuming increasing importance in the production of Active Pharmaceutical Ingredients (APIs). NMR has the potential to report on physical processes, quantities, structures, and speciation as chemical reactions progress. Following the progression of chemical reactions by placing the sample in an NMR tube, one can perform a large number of useful studies that provide chemical and mechanistic insight. But this simple approach can have limitations, and we have therefore constructed an apparatus comprising a laboratory reactor coupled with an NMR flow cell. The reactor duplicates the exact reaction conditions that will apply with large-scale production. This reaction mixture is sampled and pumped to a high-resolution NMR flow cell where the spectrum is recorded through the course of the reaction. We demonstrate the utility of reaction monitoring using NMR both for simple cases where tubes can be used, and describe the design of the on-flow apparatus and highlight its utility with an example.