Molecular structure and puckering potential of gas-phase 1-pyrroline as determined by microwave and infrared spectroscopy

The microwave spectrum of 1-pyrroline has been measured from 8 to 48 GHz. The transitions have been assigned to those of the ground state and the four lowest excited states of the ring-puckering vibration of monomer, which is a five-membered ring molecule with one CN double bond. The trimer, which exists in the liquid phase, has not been detected in the gas phase. The geometrical structure of the monomer has been estimated by an ab initio calculation and the trimer by a molecular mechanics calculation. The former is consistent with the experimental rotational constants. A gas-phase infrared spectrum has also been measured, and the ring-puckering potential has been determined by an analysis of the combination bands of the ring-puckering mode and the ring-stretching modes. The potential is described using a puckering coordinate, z, as V(z) = az² + bz⁴, where $\text{a = ?3.358(16) × 10}{}^4\text{cm}{}^{\mathrm{?1}}\text{A}\text{?}{}^{\mathrm{?2}}$ and $\text{b = 1.345(9) × 10}{}^6\text{cm}{}^{\mathrm{?1}}\text{A}\text{?}{}^{\mathrm{?4}}$; these values are intermediate of the corresponding values for cyclopentene and 1-pyrazoline. The nuclear quadrupole coupling constants, χ_aa = ?4.39(10), χ_bb = 1.04(10), and χ_cc = 3.35(10) MHz, have been determined by an analysis of well-resolved hyperfine splittings. These constants have been reproduced by an ab initio calculation with a 4-31G(N¹) basis set.     

Some Experiences with the Teaching of Decision Support Systems to Management Students

There are essentially two schools of thought regarding the function of decision support systems. One is that the main purpose is to support the decision-maker in whatever style of decision-making he or she wishes. The other is that the support, while suiting the decision-maker's individual style, must also be based on an appropriate theoretical paradigm. The work with students of decision support systems reported here suggests that the latter, normative, view is not one which comes naturally to many of the students, even when working on an example where it seemed relatively easy to incorporate. Other conclusions are also presented, relating to the choice of software for decision support system development, the process of teaching about decision support systems, and group formation.     

Production of 13C labelled pea flour for use in human digestion and fermentation studies

Stable isotope breath tests offer a new approach to the study of digestion and fermentation of carbohydrates in man. In this study, 13C labelled peas were grown by pulsing 250 ml 13CO2 into a sealed growth chamber. A second pulse was added to a portion of the peas to increase the 13C enrichment. This generated pea flour with an enrichment of 2.36 at.% excess (range 2.09-2.71 n = 3) and 8.64 atom % excess (range 7.37-9.78 n = 3) respectively. This represented incorporation of an absolute yield of 3.8% of the 13CO2 into peas in the 'once-labelled' treatment and 7.5% in the 'twice-labelled' treatment. Ingestion of a mixture of the labelled pea flour (300 mg) by two volunteers generated measurable 13CO2 excretion for breath test analysis. The profile of breath 13CO2 enrichment increased to a maximum within three hours after consuming the pea flour followed by a decrease almost back to baseline by 13 hours. Breath 13CO2 appeared to rise again after this apparent nadir at 13 hours until the end of the sampling period. Mathematical analysis of the data suggested that two peaks best described the profile of breath 13CO2 up to 13 hours. A third peak was necessary to describe the late rise in breath 13CO2 enrichment. This use of 13C enriched pea flour may provide a useful non invasive method for measurement of digestion and fermentation in vivo.     

A method for calculating rheological and morphological properties of constant-volume polymer blend models in inhomogeneous shear fields

We show how to formulate two-point boundary-value problems in order to compute fully-developed laminar channel and tube flow profiles for viscoelastic fluid models. The formulation is applied to Couette and pressure-driven flows separately, or a combination of both. The application of this methodology is illustrated analytically for the Upper-Convected Maxwell Model, and it is applied computationally for the Phan-Thien/Tanner and Giesekus Models. Numerical solutions exist for the last two models [J.Y. Yoo, H.C. Choi, On the steady simple shear flows of the one-mode Giesekus fluid, Rheol. Acta 28 (1989) 13–24; P.J. Oliveira, F.T. Pinho, Analytical solution for fully developed channel and pipe flow of Phan-Thien–Tanner fluids, J. Fluid Mech. 387 (1999) 271–280; M.A. Alves, F.T. Pinho, P.J. Oliveira, Study of steady pipe and channel flows of a single-mode Phan-Thien–Tanner fluid, J. Non-Newtonian Fluid Mech. 101 (2001) 55–76], allowing verification of the computational technique. Subsequently, the computational algorithm is applied to the constant-volume polymer blend models of Maffettone and Minale [P.L. Maffettone, M. Minale, Equation of change for ellipsoidal drops in viscous flow, J. Non-Newtonian Fluid Mech. 84 (1999) 105–106 (Erratum), J. Non-Newtonian Fluid Mech. 78 (1998) 227–241] and Dressler and Edwards [M. Dressler, B.J. Edwards, The influence of matrix viscoelasticity on the rheology of polymer blends, Rheol. Acta 43 (2004) 257–282; M. Dressler, B.J. Edwards, Rheology of polymer blends with matrix-phase viscoelasticity and a narrow droplet size distribution, J. Non-Newtonian Fluid Mech. 120 (2004) 189–205]. Rheological and morphological properties of the model blends are thus obtained as functions of the spatial position within the channel, applied pressure drop, and shear rate at the wall.     

The synthesis of cyclic polymers by olefin metathesis: Achievements and challenges

Cyclic polymers have drawn considerable interest for their peculiar physical properties in comparison to linear polymers, despite their equivalent compositions. Synthetically, cyclic polymers can be accessed through either macrocyclic ring‐closure or by ring‐expansion polymerization, but the main challenge with either method is the production of highly pure cyclic polymer samples. This highlight describes advances in the area of cyclic polymer synthesis, with a particular focus on ring‐expansion metathesis polymerization. Methods for characterizing cyclic polymers and assessing their purity are also discussed in order to emphasize the need for additional robust and reliable methods for synthesizing and studying topologically complex macromolecules. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 228–242     

Evidence for the decay D0-->K(-)pi(+)pi(-)e(+)nu(e)

Using a 281 pb{-1} data sample collected at the psi(3770) with the CLEO-c detector, we present the first absolute branching fraction measurement of the decay D0-->K(-)pi(+)pi(-)e(+)nu(e) at a statistical significance of about 4.0 standard deviations. We find 10 candidates consistent with the decay D0-->K(-)pi(+)pi(-)e(+)nu(e). The probability that a background fluctuation accounts for this signal is less than 4.1 x 10{-5}. We find B(D0-->K(-)pi(+)pi(-)e(+)nu(e)) = [2.8{-1.1}{+1.4}(stat)+/-0.3(syst)]x10{-4}. By restricting the invariant mass of the hadronic system to be consistent with K1(1270), we obtain the product of branching fractions B(D{0}-->K{1}{-}(1270)e{+}nu{e})xB(K1-(1270)-->K{-}pi{+}pi{-})=[2.5{-1.0}{+1.3}(stat)+/-0.2(syst)]x10{-4}. Using B(K1-(1270)-->K{-}pi{+}pi{-})=(33+/-3)%, we obtain B(D{0}-->K{1}{-}(1270)e{+}nu{e})=[7.6{-3.0}{+4.1}(stat)+/-0.6(syst)+/-0.7]x10{-4}. The last error accounts for the uncertainties in the measured K1-(1270)-->K{-}pi{+}pi{-} branching fractions.     

Language specificity in the perception of voiceless sibilant fricatives in Japanese and English: implications for cross-language differences in speech-sound development

Both English and Japanese have two voiceless sibilant fricatives, an anterior fricative /s/ contrasting with a more posterior fricative /∫/. When children acquire sibilant fricatives, English children typically substitute [s] for /∫/, whereas Japanese children typically substitute [∫] for /s/. This study examined English- and Japanese-speaking adults' perception of children's productions of voiceless sibilant fricatives to investigate whether the apparent asymmetry in the acquisition of voiceless sibilant fricatives reported previously in the two languages was due in part to how adults perceive children's speech. The results of this study show that adult speakers of English and Japanese weighed acoustic parameters differently when identifying fricatives produced by children and that these differences explain, in part, the apparent cross-language asymmetry in fricative acquisition. This study shows that generalizations about universal and language-specific patterns in speech-sound development cannot be determined without considering all sources of variation including speech perception.     

Force localization in contracting cell layers

Epithelial cell layers on soft elastic substrates or pillar arrays are commonly used as model systems for investigating the role of force in tissue growth, maintenance, and repair. Here we show analytically that the experimentally observed localization of traction forces to the periphery of the cell layers does not necessarily imply increased local cell activity, but follows naturally from the elastic problem of a finite-sized contractile layer coupled to an elastic foundation. For homogeneous contractility, the force localization is determined by one dimensionless parameter interpolating between linear and exponential force profiles for the extreme cases of very soft and very stiff substrates, respectively. If contractility is sufficiently increased at the periphery, outward directed displacements can occur at intermediate positions. We also show that anisotropic extracellular stiffness can lead to force localization in the stiffer direction, as observed experimentally.     

Synthesis of 3-methoxy-quinoxalin-2-ones from methyl trimethoxyacetate and phenylenediamines

Treatment of phenylenediamines with methyl trimethoxyacetate led to the formation of 3-methoxy-quinoxalin-2-ones with the assistance of lanthanide-based Lewis acids.