Theoretical studies of the energetics and dynamics of chemical reactions

Computational studies of basic chemical processes not only provide numbers for comparison with experiment or for use in modeling complex chemical phenomena such as combustion, but also provide insight into the fundamental factors that govern molecular structure and change which cannot be obtained from experiment alone. We summarize the results of three case studies, on HCO, OH + H(2), and O + C(2)H(2), which illustrate the range of problems that can be addressed by using modern theoretical techniques. In all cases, the potential energy surfaces were characterized by using ab initio electronic structure methods. Collisions between molecules leading to reaction or energy transer were described with quantum dynamical methods (HCO), classical trajectory techniques (HCO and OH + H(2)), and statistical methods (HCO, OH + H(2), and O + C(2)H(2)). We can anticipate dramatic increases in the scope of this work as new generations of computers are introduced and as new chemistry software is developed to exploit these computers.     

Kinetic isotope effects for the reactions of muonic helium and muonium with H2

The neutral muonic helium atom may be regarded as the heaviest isotope of the hydrogen atom, with a mass of ~4.1 atomic mass units ((4.1)H), because the negative muon almost perfectly screens one proton charge. We report the reaction rate of (4.1)H with (1)H(2) to produce (4.1)H(1)H + (1)H at 295 to 500 kelvin. The experimental rate constants are compared with the predictions of accurate quantum-mechanical dynamics calculations carried out on an accurate Born-Huang potential energy surface and with previously measured rate constants of (0.11)H (where (0.11)H is shorthand for muonium). Kinetic isotope effects can be compared for the unprecedentedly large mass ratio of 36. The agreement with accurate quantum dynamics is quantitative at 500 kelvin, and variational transition-state theory is used to interpret the extremely low (large inverse) kinetic isotope effects in the 10(-4) to 10(-2) range.     

Measurement of Faecal Cortisol Metabolites in Cats and Dogs: A Non-invasive Method for Evaluating Adrenocortical Function

The aim of this comparative study was to gain more information about the metabolism and excretion of glucocorticoids in cats and dogs in order to establish non-invasive methods for evaluating stressful conditions. Therefore, in a first experiment, [¹⁴C]cortisol was administered intravenously to 8 animals (two of each sex and species). Over a period of 6 days, faeces and urine were collected immediately after spontaneous defecation and urination. Marked species differences were found, as cats mainly excreted cortisol in the faeces (82%±4% of the total recovered radioactivity), whereas in dogs only a small portion was found there (23%±4%). The highest urinary radioactivity was observed after 9±3 h in cats and 3±1 h in dogs. Peak concentrations in the faeces occurred after 22±6 h in cats and after 24±4 h in dogs. Most of the radioactivity was not extractable with diethyl ether, indicating that the metabolites excreted in urine and faeces were mainly of the conjugated or polar unconjugated types. This was confirmed by RP-HPLC, which also revealed marked differences between cats and dogs concerning the metabolites formed. In addition, the immunoreactivity of the metabolites was tested in cortisol, corticosterone and 11-oxoaetiocholanolone EIAs. The latter, measuring 11,17-dioxoandrostanes (11,17-DOA) detected the highest quantities of immunoreactive metabolites in cats, but not in dogs. In a second experiment, the adrenal cortex of both species was stimulated by ACTH and, three weeks later, suppressed by dexamethasone. In this study, only faeces were collected over a period of 7 days. In both species, inter-animal variability in the basal and maximal/minimal faecal cortisol metabolite concentrations and the time course was observed. The 11-oxoaetiocholanolone EIA in cats and the cortisol EIA in dogs proved best suited for monitoring changes in adrenocortical activity. ACTH injections resulted in an increase above baseline values of 355% (median) in 11,17-DOA concentrations in cats and of 702% in the concentrations of cortisol equivalents in dogs by about 25 h and 22 h (median) after injection, respectively. Minimal concentrations after dexamethasone administration were about 17% in cats and 31% in dogs (in relation to baseline values) and were reached in 66 h and 72 h, respectively. It was concluded that measuring cortisol metabolites in faeces should be a useful non-invasive tool for monitoring stress in carnivores.     

Detection of European bat lyssavirus 2 (EBLV-2) in a Daubenton's bat (Myotis daubentonii) from Magdeburg, Germany

In Europe bat rabies in Daubenton's bats (Myotisdaubentonii) and in Pond bats (Myotis dasycneme) caused by the European bat lyssavirus 2 (EBLV-2) has been confirmed in less than 20 cases to date. Here we report the second encounter of this virus species in Germany. A Daubenton's bat found grounded in the zoological garden in Magdeburg died shortly after. In the frame of a retrospective study the bat carcass was eventually transferred to the national reference laboratory for rabies at the Friedrich-Loeffler-Institute for rabies diagnosis. Lyssavirus was isolated and characterized as EBLV-2.     

Nanoparticle superlattice engineering with DNA

A current limitation in nanoparticle superlattice engineering is that the identities of the particles being assembled often determine the structures that can be synthesized. Therefore, specific crystallographic symmetries or lattice parameters can only be achieved using specific nanoparticles as building blocks (and vice versa). We present six design rules that can be used to deliberately prepare nine distinct colloidal crystal structures, with control over lattice parameters on the 25- to 150-nanometer length scale. These design rules outline a strategy to independently adjust each of the relevant crystallographic parameters, including particle size (5 to 60 nanometers), periodicity, and interparticle distance. As such, this work represents an advance in synthesizing tailorable macroscale architectures comprising nanoscale materials in a predictable fashion.     

NCSA Mosaic and the World Wide Web: Global Hypermedia Protocols for the Internet

Network information systems reached the public consciousness this year as a result of the phenomenal growth in the use of the Internet. In particular, the software constituting NCSA (National Center for Supercomputing Applications) Mosaic and the World Wide Web have made global hypermedia a widespread reality for the first time. The technology underlying this software is described to explain the protocols behind information spaces. These include the historical predecessors, the current protocols with examples, future directions for the software, and discussion of research systems with different architectures. Reasons for its popularity are given, with the goal of illuminating successful services for the National Information Infrastructure.