Near-IR Capturing N-Methylbenzene Sulfonamide-Phenothiazine Incorporating Strong Electron Acceptor Push-Pull Systems: Photochemical Ultrafast Carrier Dynamics.

Unraveling the intriguing aspects of the intramolecular charge transfer (ICT) phenomenon of multi-modular donor-acceptor-based push-pull systems are of paramount importance considering their promising applications, particularly in solar energy harvesting and light-emitting devices. Herein, a series of symmetrical and unsymmetrical donor-acceptor chromophores 1-6, are designed and synthesized by the Corey-Fuchs reaction via Evano's condition followed by [2+2] cycloaddition retroelectrocyclic ring-opening reaction with strong electron acceptors TCNE and TCNQ in good yields (~60-85 %). The photophysical, electrochemical, and computational studies are investigated to explore the effect of incorporation of strong electron acceptors 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) and dicyanoquinodimethane (DCNQ) with phenothiazine (PTZ) donor. An additional low-lying broad absorption band extended towards the near-infrared (NIR) region suggests charge polarization after the introduction of the electron acceptors in both symmetrical and asymmetrical systems, leading to such strong ICT bands. The electrochemical properties reveal that reduction potentials of 3 and 6 are lower than those of 2 and 5, suggesting DCNQ imparts more on the electronic properties and hence largely contributes to the stabilization of LUMO energy levels than TCBD, in line with theoretical observations. Relative positions of the frontier orbitals on geometry-optimized structures further support accessing donor-acceptor sites responsible for the ICT transitions. Eventually, ultrafast carrier dynamics of the photoinduced species are investigated by femtosecond transient absorption studies to identify their spectral characteristics and target analysis further provides information about different excited states photophysical events including ICT and their associated time profiles. The key findings obtained here related to excited state dynamical processes of these newly synthesized systems are believed to be significant in advancing their prospect of utilization in solar energy conversion and related photonic applications.

Improving the optical properties of [5] circulene with different electron donors and acceptor substitutions (push-pull system).

In this research, the circulene molecule was selected, and the electron donor and acceptor groups were attached to improve its optical properties. Large negative values of enthalpies, Gibbs free energies, and exothermic energies of formation for these molecules, especially for the CN-CIR-NHLi molecule, show that their formation is highly reasonable. It was illustrated that the Eg of the circulene molecule was lowered in the electron donor and acceptor groups' presence, while the CN-CIR-NHLi and CF3-CIR-NHLi molecules have the lowest values of Eg. It was observed that the optical properties of circulene molecules were improved in electron donor and acceptor groups' presence. Between these groups, the -CN and -CF3 as electron acceptors and -NHLi substituents, as electron donor groups, yield higher enhancements on the optical properties of circulene, which is in agreement with the results obtained for Eg values. Graphical abstract.

The potential of trap and barrier cropping to decrease densities of the whitefly Bemisia tabaci MED on cotton in China.

BACKGROUND: The whitefly, Bemisia tabaci (Gennadius) MED, is a destructive insect pest in many countries of the world. Although the use of insecticides for controlling B. tabaci has been effective to a certain extent, pesticides are not an acceptable long-term control method, and alternatives should be sought. This paper focuses on the possibility of controlling B. tabaci on cotton using trap and barrier crops. We performed field experiments using cantaloupe (Cucumis melo) and sunflower (Helianthus annuus) as trap crops, and maize (Zea mays) as a barrier crop in various configurations in Hebei Province, North China. RESULTS: The main activity periods were shortest on cantaloupe and ranged between 16-32 days for immatures and 14-33 days for adults. Adult whitefly densities were not significantly reduced by any treatment. During the main activity period, maize intercropping reduced densities of immature whiteflies from 24.2 individuals (ind.) 100 cm-2 to 4.0 ind.100 cm-2 , but all treatments were successful in significantly reducing immature B. tabaci densities. This resulted in a significant yield premium. CONCLUSIONS: Intercropping reduced B. tabaci densities on cotton more than perimeter planting. Maize was more effective to reduce densities of immature whiteflies on cotton than cantaloupe. The results will contribute to the development of more effective and practical approaches for protecting cotton from B. tabaci and lowering chemical pressure on this crop. © 2019 Society of Chemical Industry.

Tuning the Optical Properties of Sulfonylaniline Derivatives: Degeneracy Breaking of Benzene Orbitals and Linkage through Nodal Planes.

The orbital degeneracy of benzene rings is resolved by an asymmetric push-pull system in 2,6-bis(methylsulfonyl)aniline (BMeSA), in which the highest occupied molecular orbital (HOMO) is located at the 4-position, while the lowest unoccupied molecular orbital (LUMO) is located at a different position and has a nodal plane through the carbon atoms at the 1- and 4-positions. Therefore, the π-extension of BMeSA at the 4-position reveals a strong overlap in the HOMO and a minimal overlap in the LUMO. Consequently, π-extended BMeSA derivatives exhibit longer absorbance and emission wavelengths in the order of the electron-donating abilities of their substituents at the 4-position, which is based on a decrease in an absolute HOMO-level-dependent HOMO-LUMO gap in accordance with the nodal arrangement. Positive fluorescent solvatochromism with polarity-dependent decrease in fluorescent intensity was also observed. The biaryls exhibited more planar geometries in the excited state than in the ground state. The charge transfer mechanism, which can be described as node-induced intramolecular charge transfer (NICT), differs from the planar intramolecular charge transfer (PICT) and twisted intramolecular charge transfer (TICT).

Small-scale field evaluation of push-pull system against early- and outdoor-biting malaria mosquitoes in an area of high pyrethroid resistance in Tanzania.

Background: Despite high coverage of indoor interventions like insecticide-treated nets, mosquito-borne infections persist, partly because of outdoor-biting, early-biting and insecticide-resistant vectors. Push-pull systems, where mosquitoes are repelled from humans and attracted to nearby lethal targets, may constitute effective complementary interventions. Methods: A partially randomized cross-over design was used to test efficacy of push-pull in four experimental huts and four local houses, in an area with high pyrethroid resistance in Tanzania. The push-pull system consisted of 1.1% or 2.2% w/v transfluthrin repellent dispensers and an outdoor lure-and-kill device (odour-baited mosquito landing box). Matching controls were set up without push-pull. Adult male volunteers collected mosquitoes attempting to bite them outdoors, but collections were also done indoors using exit traps in experimental huts and by volunteers in the local houses. The collections were done hourly (1830hrs-0730hrs) and mosquito catches compared between push-pull and controls. An. gambiae s.l. and An. funestus s.l. were assessed by PCR to identify sibling species, and ELISA to detect Plasmodium falciparum and blood meal sources. Results: Push-pull in experimental huts reduced outdoor-biting for An. arabiensis and Mansonia species by 30% and 41.5% respectively. However, the reductions were marginal and insignificant for An. funestus (12.2%; p>0.05) and Culex (5%; p>0.05). Highest protection against all species occurred before 2200hrs. There was no significant difference in number of mosquitoes inside exit traps in huts with or without push-pull. In local households, push-pull significantly reduced indoor and outdoor-biting of An. arabiensis by 48% and 25% respectively, but had no effect on other species. Conclusion: This push-pull system offered modest protection against outdoor-biting An. arabiensis, without increasing indoor mosquito densities. Additional experimentation is required to assess how transfluthrin-based products affect mosquito blood-feeding and mortality in push-pull contexts. This approach, if optimised, could potentially complement existing malaria interventions even in areas with high pyrethroid resistance.

Design of push-pull system to control diesel particular matter inside a dead-end entry.

Diesel particulate matter (DPM) is considered to be carcinogenic after prolonged exposure. With more diesel-powered equipment used in underground mines, miners' exposure to DPM has become an increasing concern. This paper used computational fluid dynamics method to study the DPM dispersion in a dead-end entry with loading operation. The effects of different push-pull ventilation systems on DPM distribution were evaluated to improve the working conditions for underground miners. The four push-pull systems considered include: long push and short pull tubing; short push and long pull tubing, long push and curved pull tubing, and short push and curved pull tubing. A species transport model with buoyancy effect was used to examine the DPM dispersion pattern with unsteady state analysis. During the 200 s of loading operation, high DPM levels were identified in the face and dead-end entry regions. This study can be used for mining engineer as guidance to design and setup local ventilation, select DPM control strategies and for DPM annual training for underground miners.