Theory has established the importance of geometric phase (GP) effects in the adiabatic dynamics of molecular systems with a conical intersection connecting the ground- and excited-state potential energy surfaces, but direct observation of their manifestation in chemical reactions remains a major challenge. Here, we report a high-resolution crossed molecular beams study of the H + HD → H2+ D reaction at a collision energy slightly above the conical intersection. Velocity map ion imaging revealed fast angular oscillations in product quantum state–resolved differential cross sections in the forward scattering direction for H2products at specific rovibrational levels. The experimental results agree with adiabatic quantum dynamical calculations only when the GP effect is included.
The high frequency of single nucleotide polymorphisms (SNPs) in the human genome makes them a valuable source of genetic markers for identity testing, genome mapping, and medical diagnostics. Conventional technologies for detecting SNPs are laborious and time‐consuming, often prohibiting large‐scale analysis. A rapid, accurate, and cost‐effective method is needed to meet the demands of a high‐throughput DNA assay. We demonstrate here that analysis of these genetic markers can now be performed routinely in a rapid, automated, and high‐throughput fashion using time‐of‐flight mass spectrometry and a primer extension assay with a novel cleavable primer. SNP genotyping by mass spectrometry involves detection of single‐base extension products of a primer immediately adjacent to the SNP site. Measurement of the mass difference between the SNP primer and the extension peak reveals which nucleotide is present at the polymorphic site. The primer is designed such that its extension products can be purified and chemically released from the primer in an automated format. The reduction in size of the products as a result of this chemical cleavage allows more accurate identification of the polymorphic base, especially in samples from a heterozygotic population. All six possible heterozygotes are resolved unambiguously, including an A/T heterozygote with extension products differing by only 9 Da. Multiplex SNP determination is demonstrated by simultaneously probing multiple SNP sites from a single polymerase chain reaction (PCR) product as well as from multiplexed PCR amplicons. Samples are processed in parallel on a robotic workstation, and analyzed serially in an automated mass spectrometer with analysis times of only a few seconds per sample, making it possible to process thousands of samples per day.
The spatial and temporal variability of North Atlantic hurricane tracks and its possible association with the annual hurricane landfall frequency along the U.S. East Coast are studied using principal component analysis (PCA) of hurricane track density function (HTDF). The results show that, in addition to the well-documented effects of the El Niño–Southern Oscillation (ENSO) and vertical wind shear (VWS), North Atlantic HTDF is strongly modulated by the dipole mode (DM) of Atlantic sea surface temperature (SST) as well as the North Atlantic Oscillation (NAO) and Arctic Oscillation (AO). Specifically, it was found that Atlantic SST DM is the only index that is associated with all top three empirical orthogonal function (EOF) modes of the Atlantic HTDF. ENSO and tropical Atlantic VWS are significantly correlated with the first and the third EOF of the HTDF over the North Atlantic Ocean. The second EOF of North Atlantic HTDF, which represents the “zonal gradient” of North Atlantic hurricane track density, showed no significant correlation with ENSO or with tropical Atlantic VWS. Instead, it is associated with the Atlantic SST DM, and extratropical processes including NAO and AO. Since for a given hurricane season, the preferred hurricane track pattern, together with the overall basinwide hurricane activity, collectively determines the hurricane landfall frequency, the results provide a foundation for the construction of a statistical model that projects the annual number of hurricanes striking the eastern seaboard of the United States.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.