Isomeric effects in the gas-phase reactions of dichloroethene, C2H2Cl2, with a series of cations

A study of the reactions of a series of gas-phase cations (NH$_4^+$, H$_3$O$^+$, SF$_3^+$, CF$_3^+$, CF$^+$, SF5$^+$, SF$_2^+$, SF$^+$, CF$_2^+$, SF$_4^+$, O$_2^+$, Xe$^+$, N$_2$O$^+$, CO$_2^+$, Kr$^+$, CO$^+$, N$^+$, N$_2^+$, Ar$^+$, F$^+$ and Ne$^+$) with the three structural isomers of dichloroethene, i.e. 1,1-C$_2$H$_2$Cl$_2$, cis-1,2-C$_2$H$_2$Cl$_2$ and trans-1,2-C$_2$H$_2$Cl$_2$ is reported. The recombination energy of these ions spans the range 4.7-21.6 eV. Reaction rate coefficients and product branching ratios have been measured at 298 K in a selected ion flow tube. Collisional rate coefficients are calculated by modified average dipole orientation theory and compared with experimental data. Thermochemistry and mass balance have been used to predict the most feasible neutral products. Threshold photoelectron-photoion coincidence spectra have also been obtained for the three isomers of C$_2$H$_2$Cl$_2$ with photon energies in the range 10-23 eV. The fragment ion branching ratios have been compared with those of the flow tube study to determine the importance of long-range charge transfer. A strong influence of the isomeric structure of dichloroethene on the products of ion-molecule reactions has been observed for H$_3$O$^+$, CF$_3^+$, and CF$^+$. For 1,1-C$_2$H$_2$Cl$_2$ the reaction with H$_3$O$^+$ proceeds at the collisional rate with the only ionic product being 1,1-C$_2$H$_2$Cl$_2$H$^+$. However, the same reaction yields two more ionic products in the case of cis-1,2- and trans-1,2-C$_2$H$_2$Cl$_2$, but only proceeds with 14 % and 18 % efficiency, respectively. The CF$_3^+$ reaction proceeds with 56-80 % efficiency, the only ionic product for 1,1-C$_2$H$_2$Cl$_2$ being C$_2$H$_2$Cl$^+$ formed via Cl- abstraction, whereas the only ionic product for both 1,2-isomers is CHCl$_2^+$ corresponding to a breaking of the C=C double bond. Less profound isomeric effects, but still resulting in different products for 1,1- and 1,2-C$_2$H$_2$Cl$_2$ isomers, have been found in the reactions of SF$^+$, CO$_2^+$, CO$^+$, N$_2^+$, and Ar$^+$. Although these five ions have recombination energies above the ionization energy of any of the C$_2$H$_2$Cl$_2$ isomers and hence the threshold for long-range charge transfer, the results suggest that the formation of a collision complex at short range between these ions and C$_2$H$_2$Cl$_2$ is responsible for the observed effects

Threshold photoelectron photoion coincidence spectroscopy and selected ion flow tube reactions of CHF3: comparison of product branching ratios

The threshold photoelectron and threshold photoelectron photoion coincidence spectra of CHF$_3$ in the range 13.5 – 24.5 eV have been recorded. Ion yields and branching ratios have been determined for the three fragments CF$_3^+$, CHF2$^+$ and CF$^+$. The mean kinetic energy releases into fragment ions involving either C-H or C-F bond cleavage have been measured, and compared with statistical and impulsive models. CHF$_3^+$ behaves in a non-statistical manner characteristic of the small-molecule limit, with the ground electronic state and low-lying excited states of CHF$_3^+$ being largely repulsive along the C-H and C-F coordinates, respectively. The rate coefficients and product ion branching ratios have been measured at 298 K in a selected ion flow tube for the reactions of CHF$_3$ with a large number of gas-phase cations whose recombination energies span the range 6.3 through 21.6 eV. A comparison between the branching ratios from the two experiments, together with an analysis of the threshold photoelectron spectrum of CHF$_3$, shows that long-range charge transfer probably occurs for the Ar$^+$ and F$^+$ atomic ions whose recombination energies lie above ca. 15 eV. Below this energy, the mechanism involves a combination of short-range charge transfer and chemical reactions involving a transition state intermediate

Genetic variability, stability and heritability for quality and yield characteristics in provitamin A cassava varieties

Open Access Article; Published online: 25 Jan 2020Cassava is widely consumed in many areas of Africa, including Ghana, and is a major part of most household diets. These areas are characterized by rampant malnutrition, because the tuberous roots are low in nutritional value. Provitamin A biofortified cassava varieties have been developed by the International Institute for Tropical Agriculture, but adoption of these varieties in Ghana will largely depend on their agronomic performance, including fresh root yield, dry matter content, resistance to major pests and diseases, mealiness, starch content and the stability of these traits. Eight provitamin A varieties with two white checks were planted in three environments for two seasons to determine stability and variability among the varieties for important traits. There were significant variations in performance between varieties and between environments for cassava mosaic disease, root number, fresh root yield and starch content. High broad-sense heritability and genetic advance were observed in all traits, except for storage root number, and could be exploited through improvement programs. This study identified the best performing enhanced provitamin A varieties for traits that are key drivers of variety adoption in Ghana. In view of this, some varieties can be recommended for varietal release after on-farm testing. The study also showed the possibility of tapping heterosis after careful selection of parents

Test Facility and Preliminary Performance of a 100 kW Class MPD Thruster

A 260 kW magnetoplasmadynamic (MPD) thruster test facility was assembled and used to characterize thrusters at power levels up to 130 kW using argon and helium propellants. Sensitivities of discharge characteristics to arc current, mass flow rate, and applied magnetic field were investigated. A thermal efficiency correlation developed by others for low power MPD thrusters defined parametric guidelines to minimize electrode losses in MPD thrusters. Argon and helium results suggest that a parameter defined as the product of arc voltage and the square root of the mass flow rate must exceed 0.7 V/kg(sup 1/2)/sec(sup 1/2) in order to obtain thermal efficiencies in excess of 60 percent

A selected ion flow tube study of the ion-molecule reactions of monochloroethene, trichloroethene and tetrachloroethene

Data for the rate coefficients and product cations of the reactions of a large number of atomic and small molecular cations with monochloroethene, trichloroethene and tetrachloroethene in a selected ion flow tube at 298 K are reported. The recombination energy of the ions range from 6.27 eV (H$_3$O$^+$) through to 21.56 eV (Ne$^+$). Collisional rate coefficients are calculated by modified average dipole orientation theory and compared with experimental values. Thermochemistry and mass balance predict the most feasible neutral products. Together with previously reported results for the three isomers of dichloroethene (J. Phys. Chem. A., 2006, 110, 5760), the fragment ion branching ratios have been compared with those from threshold photoelectron photoion coincidence spectroscopy over the photon energy range 9-22 eV to determine the importance or otherwise of long-range charge transfer. For ions with recombination energy in excess of the ionisation energy of the chloroethene, charge transfer is energetically allowed. The similarity of the branching ratios from the two experiments suggest that long-range charge transfer is dominant. For ions with recombination energy less than the ionisation energy, charge transfer is not allowed; chemical reaction can only occur following formation of an ion-molecule complex, where steric effects are more significant. The products that are now formed and their percentage yield is a complex interplay between the number and position of the chlorine atoms with respect to the C=C bond, where inductive and conjugation effects can be important

The photoionization dynamics of the three structural isomers of dichloroethene

Using tunable vacuum-UV radiation from a synchrotron, the threshold photoelectron spectrum, threshold photoelectron photoion coincidence spectrum and ion breakdown diagram of the 1,1, cis-1,2 and trans-1,2 isomers of C$_2$H$_2$Cl$_2$ have been recorded in the range 9-23 eV. The energies of the peaks in the threshold photoelectron spectrum are in good agreement with outer-valence Greens function caculations. The major difference between the isomers, both predicted and observed experimentally is that the F and G states of C$_2$H$_2$Cl$_2^+$ are approximately degenerate for 1,1 and trans-1,2, but well separated for the cis-1,2 isomer. The ground and low-lying valence states of C$_2$H$_2$Cl$_2^+$ are bound, with higher-lying states dissociating to C$_2$H$_2$Cl$^+$ or C$_2$H$_2^+$. The translational kinetic energy release into C$_2$H$_2$Cl$^+$ + Cl is determined as a function of energy. Isolated-state behaviour for the low-lying electronic states of C$_2$H$_2$Cl$_2^+$ becomes more statistical as the energy increases

Popular biofortified cassava cultivars are heavily impacted by plant parasitic nematodes, especially Meloidogyne Spp.

Open Access Journal; Published online: 26 June 2020The development of new biofortified cassava cultivars, with higher micronutrient contents, offers great potential to enhance food and nutrition security prospects. Among the various constraints affecting cassava production are plant parasitic nematodes (PPN), especially root-knot nematodes. In this study, six popular biofortified cultivars were field-evaluated for their response to PPN in Nigeria. A field naturally infested with a diversity of PPN but dominated by root-knot nematodes was used. Application of the nematicide carbofuran significantly reduced PPN densities, and at harvest, no root galling damage was observed, compared with untreated plots, which had heavy galling damage. Plant height, stem girth, plant weight, marketable storage root number and weight were significantly lower for most cultivars in untreated plots. Percentage yield losses in the range of 21.3–63.7% were recorded from two separate trials conducted for 12 months each. Lower total carotenoid and dry matter contents were associated with higher PPN densities in some biofortified cultivars, resulting in a loss of as much as 63% of total carotenoid and 52% of dry matter contents. The number and weight of rotted storage roots were significantly greater in untreated plots across cultivars, reducing in-field and post-harvest storability. This study demonstrates that natural field populations of PPN can substantially affect yield, quality and nutritional value of released biofortified cassava cultivar

In situ hybridisation and S1 mapping show that the presence of infiltrating plasma cells is associated with poor prognosis in breast cancer.

In order to identify potential markers of prognosis in breast cancer, representative cDNA libraries were constructed using RNA isolated from primary breast tumour tissue associated with good and poor prognosis. Cross-screening of these libraries repeatedly identified cloned mRNA species associated with the immune system, in particular B-cells, in libraries derived from tumours of poor prognosis. We have used one of these a kappa IV light chain cDNA probe, in two complementary studies to investigate the relationship between immunoglobin gene expression and prognosis. The results obtained using a combination of S1 mapping, RNA blotting and in situ hybridisation demonstrate that the presence of plasma cells, as defined by infiltrating cells which express high levels of immunoglobulin kappa-chain mRNA, is associated with a poor prognosis

Subject-oriented plural method meets BPMN: a case study

Subject-oriented approach to business process management focuses on the subjects and their interactions with the aim to capture more accurate process information with increased fidelity. In a common setting, business processes are modeled by process engineers or modeling experts who often create their processes in a top-down fashion. However, this may pose risks to the acceptance and adoption of these models in practice, particularly in knowledge-centric environments. The Plural method follows a subject-oriented approach and allows process participants, rather than a centralized group of process engineers, to model and maintain their processes in a decentralized way. It guides process participants to focus on the roles and their interactions in terms of message exchanges. This study investigates the use of BPMN 2.0 for the Plural method. With the aim to show the applicability of the notation for a subject-oriented approach and report on the benefits and limitations of the new edition of the Plural method in general, we performed a case study in an industry company. Guided by a coordinator, 11 process participants modeled four processes that they participate by following the Plural method. These models were also compared with the classical models developed prior to the application of the Plural method to better understand the influence. Analyses showed that the application of the Plural resulted in more complete process models. However, there are concerns regarding the understandability of these models when compared with their classical counterparts. It has been shown that the Plural method is a powerful tool for process discovery and modeling, but an improvement on its models is needed to obtain full value of the framework