Reversible acetonitrile-induced inactivation/activation of thermolysin

Thermolysin is catalytically inactive in mixtures of 10-15 % acetonitrile in aqueous buffer. Unexpectedly, dilution of the inactive enzyme with acetonitrile leads to complete recovery of the catalytic activity in a similar way to dilution with aqueous buffer. Circular dichroism and fluorescence studies of thermolysin in the same solvent mixtures reveal discontinuous changes in the overall secondary and tertiary protein structure that correlate well with the reversible differences in catalytic activity. The spectra on either side of the minimum activity point are different from each other, a fact indicating that the enzyme may be able to access two active conformations which are thermodynamically stable in different solvent environments.     

Quasi-probability distributions for the simplest dynamical groups

We prove that the Wigner-Stratonovich-Agarwal operator that defines the quasi-probability distribution on the sphere [for the SU(2) dynamical group] can be written as an integral of the SU(2) (irreducible unitary) representation element with respect to a single variable that labels the orbits in the coadjoint representation. This allows us to consider contractions of the SU(2) quasi-probability distribution to the cases of the Heisenberg-Weyl group and the two-dimensional Euclidean group.     

Finding minimal herbicide concentrations in ground water? Try looking for their degradates

Extensive research has been conducted regarding the occurrence of herbicides in the hydrologic system, their fate, and their effects on human health and the environment. Few studies, however, have considered herbicide transformation products (degradates). In this study of Iowa ground water, herbicide degradates were frequently detected. In fact, herbicide degradates were eight of the 10 most frequently detected compounds. Furthermore, a majority of a herbicide's measured concentration was in the form of its degradates--ranging from 55 to over 99%. The herbicide detection frequencies and concentrations varied significantly among the major aquifer types sampled. These differences, however, were much more pronounced when herbicide degradates were included. Aquifer types presumed to have the most rapid recharge rates (alluvial and bedrock/karst region aquifers) were those most likely to contain detectable concentrations of herbicide compounds. Two indirect estimates of ground-water age (depth of well completion and dissolved-oxygen concentration) were used to separate the sampled wells into general vulnerability classes (low, intermediate, and high). The results show that the herbicide detection frequencies and concentrations varied significantly among the vulnerability classes regardless of whether or not herbicide degradates were considered. Nevertheless, when herbicide degradates were included, the frequency of herbicide compound detection within the highest vulnerability class approached 90%, and the median total herbicide residue concentration increased over an order of magnitude, relative to the parent compounds alone, to 2 microg/l. The results from this study demonstrate that obtaining data on herbicide degradates is critical for understanding the fate of herbicides in the hydrologic system. Furthermore, the prevalence of herbicide degradates documented in this study suggests that to accurately determine the overall effect on human health and the environment of a specific herbicide its degradates should also be considered.     

Electrostrictive ceramics for low-frequency active transducers

Electrostrictive ceramics based on Pb(Mg(1/3)Nb(2/3 ))O(3) have demonstrated promise as low-frequency active materials. They broaden the range of design options by providing a mix of properties unavailable in traditional piezoceramics. Typical properties are: 1000 microstrain on the interval 0-1 MV/m with a k(33) of 0.5; high-field electrical impedance ~5 times that of traditional piezoelectrics; graceful, predictable, and repeatable property variation with temperature, frequency, and prestress; recoverable change of properties with temperature. Unipolar excitation at fields less than 1 MV/m is typical to provide direct frequency conversion and prevent corona discharge and reliability issues within transducers. Although electrostrictive ceramics are not direct replacements for traditional piezoceramics, they have many similarities in physical and chemical properties. The differences are most obvious in the electromechanical response behavior with changes in bias field, drive level, frequency, and prestress. In addition, the "rules-of-thumb" for traditional piezoceramics, both processing and use, do not wholly apply to electrostrictive ceramics. The development and present state of the art in electrostrictive ceramics for low-frequency uses are detailed.     

Effect of sintering parameters on the density and microstructure of carbonate hydroxyapatite

This work documents an investigation into the effect of water on the density and microstructure of carbonate hydroxyapatite in carbon dioxide sintering atmospheres. Carbonate apatites with carbonate contents of between 3.2 and 7.8 wt % were precipitated and the precipitates were formed into dry gels. Isothermal and isochronal sintering experiments were performed under dry carbon dioxide and wet carbon dioxide (containing 3 wt % water) atmospheres. The effect of carbonate content was studied by using two gels both with a green density of 37% and with carbonate contents of 5.8 and 7.8 wt %. Both isothermal and isochronal experiments demonstrated that bloating of the apatite occurred and this behavior was associated with the loss of carbonate from the apatite. It was found that only in wet carbon dioxide atmospheres fully dense translucent carbonate apatite could be formed. 93% dense carbonate apatite was formed after 4 h sintering at temperatures as low as 700 °C. © 2000 Kluwer Academic Publishers     

Evaluation of binding selectivities of caged crown ligands toward heavy metals by electrospray ionization/quadrupole ion trap mass spectrometry

Electrospray ionization (ESI)/quadrupole ion trap mass spectrometry is used to evaluate the heavy metal binding selectivities of five caged crown ethers and two polyether reference compounds in methanol solution. The binding preferences for Hg2+, Pb2+, Cd2+, and Cu2+ were analyzed by comparison of ESI mass spectral intensities with the aim of developing this method for the rapid screening of binding selectivities of new synthetic ligands. The cage compounds preferentially bind Hg2+, except for the cage cryptand derivative, which favors Pb2+. The preference for Hg2+ stems from the favorable positioning of the nitrogen or sulfur atoms for linear coordination of Hg2+, whereas the cryptand derivative favors Pb2+ because of its larger cavity size. The counterions of the metal salts influence the type of complexes observed in the ESI mass spectra because the strengths of the metal-anion bonds affect retention of the anion in the complexes.     

Focal-plane processing architectures for real-time hyperspectral image processing

Real-time image processing requires high computational and I/O throughputs obtained by use of optoelectronic system solutions. A novel architecture that uses focal-plane optoelectronic-area I/O with a fine-grain, low-memory, single-instruction-multiple-data (SIMD) processor array is presented as an efficient computational solution for real-time hyperspectral image processing. The architecture is evaluated by use of realistic workloads to determine data throughputs, processing demands, and storage requirements. We show that traditional store-and-process system performance is inadequate for this application domain, whereas the focal-plane SIMD architecture is capable of supporting real-time performances with sustained operation throughputs of 500-1500 gigaoperations/s. The focal-plane architecture exploits the direct coupling between sensor and parallel-processor arrays to alleviate data-bandwidth requirements, allowing computation to be performed in a stream-parallel computation model, while data arrive from the sensors.     

Fast imaging of hard x rays with a laboratory microscope

An improved x-ray microscope with a fully electronic CCD detector system has been constructed that allows improved laboratory-based microstructural investigations of materials with hard x rays. It uses the Kirkpatrick-Baez multilayer mirror design to form an image that has a demonstrated resolution of 4 mum at 8 keV (Cu K(alpha) radiation). This microscope performs well with standard sealed-tube laboratory x-ray sources, producing digital images with 20-s exposure times for a 5-mum Au grid (a thickness of two absorption lengths).     

Analytic validation of an infrared milk urea assay and effects of sample acquisition factors on milk urea results

The objective of this study was to determine if milk samples, as they are routinely collected by Ontario Dairy Herd Improvement, would yield accurate milk urea results with an infrared assay. This investigation involved analytic validation of the infrared assay and assessment of the effect of DHI routine sample acquisition factors on milk urea results. Analytic validation of an automated milk urea assay was performed by assessing the relative accuracy and precision of milk urea results produced by the Fossomatic 4000 Milk Analyzer, an infrared method of analysis, compared with the Eurochem test, an accepted reference method. Results indicated that, when interpreted at the group level, milk urea results between the infrared method and the reference test were in good agreement. The two tests shared a similar and high level of precision. Milk urea concentrations obtained from composite (metered) milk samples, and not quarter stripping samples, were most representative of concurrent serum urea concentrations. The addition of bronopol preservative did not result in a numerically important change in milk urea concentrations. Storage of preserved metered milk samples for up to 4 d at either room temperature or by refrigeration, or for up to 3 d by freezing, did not result in changes in milk urea concentrations. We concluded that milk samples, as they are routinely collected and handled by DHI, are suitable for measurement of milk urea concentrations with the infrared method of analysis if data are interpreted at the group level.     

Mixed-mode anion-cation exchange/hydrophilic interaction liquid chromatography-electrospray mass spectrometry as an alternative to reversed phase for small molecule drug discovery

Within pharmaceutical drug discovery, significant needs currently exist for the analysis and purification of structurally diverse samples prior to or immediately following high-throughput screening. These processes are required to facilitate rapid and accurate biological profiling, structural determination, and resupply of new drug candidates. Reversed-phase high-performance liquid chromatography (RP-HPLC) coupled with electrospray ionization mass spectrometry (ESI-MS) for both analytical and preparative applications has become the small molecule separation/detection tool of choice for meeting many of these needs. However, the separation selectivity provided by RP-HPLC has been limited to the hydrophobicity-based resolution of relatively nonpolar sample components, and for high-throughput drug discovery applications, no sufficient alternative procedures have been identified. In this investigation, a mixed-mode anion-cation exchange/hydrophilic interaction chromatography (ACE-HILIC) method has been developed to provide both direct compatibility with ESI-MS and evaporative light-scattering detection (ELSD) and separation selectivity highly orthogonal to RP-HPLC. The technique employed silica-based small-pore weak ion exchange resins eluted with a combined aqueous and pH gradient. A diverse set of dipeptide probes was employed for the elucidation of the relative contributions of three retention mechanisms. ACE-HILIC-ESI-MS-ELSD should prove useful for the analysis and purification of compounds from both biological (e.g., natural products) and synthetic (e.g., combinatorial chemistry) sources of molecular diversity.