Analysis of isomeric mixtures by molecular rotational resonance spectroscopy

Recent developments in molecular rotational resonance (MRR) spectroscopy that have enabled its use as an analytical technique for the precise determination of molecular structure are reviewed. In particular, its use in the differentiation of isomeric compounds—including regioisomers, stereoisomers and isotopic variants—is discussed. When a mixture of isomers, such as resulting from a chemical reaction, is analyzed, it is highly desired to be able to unambiguously identify the structures of each of the components present, as well as quantify them, without requiring complex sample preparation or reference standards. MRR offers unique capabilities for addressing this analytical challenge, owing to two factors: its high sensitivity to a molecule's structure and its high spectral resolution, allowing mixtures to be resolved without separation of components. This review introduces core theoretical principles, an introduction to MRR instrumentation and the methods by which spectra can be interpreted with the aid of computational chemistry to correlate the observed patterns to molecular structures. Recent articles are discussed in which this technique was applied to help chemists complete challenging isomer analyses. Developments in the use of MRR for chiral analysis and in the measurement of isotopically labeled compounds are also highlighted

Production/maintenance cooperative scheduling using multi-agents and fuzzy logic

Within companies, production is directly concerned with the manufacturing schedule, but other services like sales, maintenance, purchasing or workforce management should also have an influence on this schedule. These services often have together a hierarchical relationship, i.e. the leading function (most of the time sales or production) generates constraints defining the framework within which the other functions have to satisfy their own objectives. We show how the multi-agent paradigm, often used in scheduling for its ability to distribute decision-making, can also provide a framework for making several functions cooperate in the schedule performance. Production and maintenance have been chosen as an example: having common resources (the machines), their activities are actually often conflicting. We show how to use a fuzzy logic in order to model the temporal degrees of freedom of the two functions, and show that this approach may allow one to obtain a schedule that provides a better compromise between the satisfaction of the respective objectives of the two functions

Viewgraph preparation made easier

Rolls of color-reversal film permit exposure of over 200 viewgraphs on one film loading. Time is saved in film development as roll film lends itself readily to automatic processing

Competition between In-Plane vs Above-Plane Configurations of Water with Aromatic Molecules: Non-Covalent Interactions in 1,4-Naphthoquinone-(H2O)1-3Complexes

Non-covalent interactions between aromatic molecules and water are fundamental in many chemical and biological processes, and their accurate description is essential to understand molecular relative configurations. Here we present the rotational spectroscopy study of the water complexes of the polycyclic aromatic hydrocarbon 1,4-naphthoquinone (1,4-NQ). In 1,4-NQ-(H2O)1,2, water molecules bind through O-H···O and C-H···O hydrogen bonds and are located on the plane of 1,4-NQ. For 1,4-NQ-(H2O)3, in-plane and above-plane water configurations are observed exhibiting O-H···O, C-H···O, and lone pair···π-hole interactions. The observation of different water arrangements for 1,4-NQ-(H2O)3 allows benchmarking theoretical methods and shows that they have great difficulty in predicting energy orderings due to the strong competition of C-H···O binding with πand π-hole interactions. This study provides important insight into water interactions with aromatic systems and the challenges in their modeling

Accuracy of quantum chemistry structures of chiral tag complexes and the assignment of absolute configuration

The absolute configuration of a molecule can be established by analysis of molecular rotational spectra of the analyte complexed with a small chiral molecule of known configuration. This approach of converting the analyte enantiomers, with identical rotational spectra, into diastereomers that can be distinguished spectroscopically is analogous to chiral derivatization in nuclear magnetic resonance (NMR) spectroscopy. For the rotational chiral tag method, the derivatization uses noncovalent interactions to install the new chiral center and avoids complications due to possible racemization of the analyte when covalent chemistry is used. The practical success of this method rests on the ability to attribute assigned rotational spectra to specific geometries of the diastereomeric homochiral and heterochiral tag complexes formed in the pulsed jet expansion that is used to introduce samples into the microwave spectrometer. The assignment of a molecular structure to an experimental rotational spectrum uses quantum chemistry equilibrium geometries to provide theoretical estimates of the spectrum parameters that characterize the rotational spectrum. This work reports the results of a high-sensitivity rotational spectroscopy study of the complexes formed between (3)-butyn-2-ol and verbenone. The rotational spectra of four homochiral and four heterochiral complexes are assigned. In addition, the 14 distinct, singly-substituted 13C isotopomer spectra of five of these species are assigned in natural abundance. Analysis of these spectra provides direct structural characterization of the complexes through determination of the carbon atom position coordinates. This data set is used to benchmark quantum chemistry calculations of candidate equilibrium geometries of the chiral tag complexes. The quantum chemistry calculations are limited to methods commonly used in the field of rotational spectroscopy. It is shown that the accuracy of the structures from quantum chemistry provides a high-confidence assignment of cluster geometries to the observed spectra. As a result, a high-confidence determination of the analyte (verbenone) absolute configuration is achieved

The Role of Non-Covalent Interactions on Cluster Formation: Pentamer, Hexamers and Heptamer of Difluoromethane

The role of non-covalent interactions (NCIs) has broadened with the inclusion of new types of interactions and a plethora of weak donor/acceptor partners. This work illustrates the potential of chirped-pulse Fourier transform microwave technique, which has revolutionized the field of rotational spectroscopy. In particular, it has been exploited to reveal the role of NCIs’ in the molecular self-aggregation of difluoromethane where a pentamer, two hexamers and a heptamer were detected. The development of a new automated assignment program and a sophisticated computational screening protocol was essential for identifying the homoclusters in conditions of spectral congestion. The major role of dispersion forces leads to less directional interactions and more distorted structures than those found in polar clusters, although a detailed analysis demonstrates that the dominant interaction energy is the pairwise interaction. The tetramer cluster is identified as a structural unit in larger clusters, representing the maximum expression of bond between dimers

Total Cross Section for p+p → p+p+pi0 Close to Threshold

This research was sponsored by the National Science Foundation Grant NSF PHY-931478

Interaction of Cooled Ion Beams with Internal Fiber Targets

This research was sponsored by the National Science Foundation Grant NSF PHY-931478

Physical and Social Contexts of Physical Activities Among Adolescent Girls

Background: With limited opportunities for physical activity during school hours, it is important to understand the contexts of physical activities done outside of school time. Given the importance of physical and social aspects of environments, the purpose of this study was to describe where and with whom girls participate in physical activities outside of school. Methods: Participants were 1925 sixth-grade girls in the Trial of Activity for Adolescent Girls (TAAG). At baseline, they completed a 3-day physical activity recall (3DPAR), reporting the main activity performed during 30-minute intervals and the physical and social contexts of physical activities. Results: The most frequently reported physical activities done outside of school time were house chores, walking (for transportation or exercise), dance, basketball, playing with younger children, and running or jogging. The most common location for these activities was at home or in the neighborhood. With the exception of household chores, these activities were typically done with at least one other person. Conclusions: Interventions that promote physical activities that can be done at or around home or developing supportive social networks for physical activity would be consistent with the current physical activity contexts of adolescent girls

Pionic Atoms as Compound States in Nucleon-Nucleus Collisons: Status Report on the Cooler Experiment CE02

This research was sponsored by the National Science Foundation Grant NSF PHY-931478