Semiochemicals such as pheromones play a major role in communication between insects, influencing their spatial orientation, aggregation, defense, and mating. The rational chemical design of precision pheromone-releasing materials are increased the efficiency of pheromone-based plant protection agents. Decades of research is begun to unravel the complex communication structures regulated by semiochemicals, from the neuronal perception of specific chemical substances to the behavioral responses in hundreds of species, including many devastating pest insects. This article summarizes the most effective uses of semiochemicals in agriculture, the behavioral responses of selected target species, and controlled-release strategies based on formulations such as novel fibrous polymer carriers. This study helps scientists, decision-makers, farmers, and the public understand the importance of appropriate mating disruption techniques that reduce the need for broad-spectrum insecticides and limit their impact on non-target and beneficial insects.

Freeform growth of multiwalled carbon nanotubes (MWCNTs) is demonstrated on stainless steel AISI 304 (EN AW 1.4301) modified by pulsed laser irradiation. A nanosecond pulsed laser is utilized as a fast and facile tool for the generation of transition metal oxide precursors that promote spatially selective CNT growth upon chemical vapor deposition at 800 °C in an atmosphere comprising n‐hexane and forming gas (5% H2/95% N2). Investigations on a set of 12 precursor oxides indicate that iron‐rich transition metal oxides with high granularity provide best conditions for CNT growth. The laser‐induced generation of specific oxide precursors facilitates the fabrication of complex CNT microarchitectures. High levels of control over CNT location and height as well as the option to influence CNT alignment provide great flexibilities in design. The introduced technique displays a high degree of automatability and the potential for upscaling thus meeting the increasing demand for large scale fabrication of CNT‐enhanced devices.

Concurrence of the vibrational coherence and ultrafast electron transfer has been observed in polymer/fullerene blends. However, it is difficult to experimentally investigate the role that the excited-state vibrational coherence plays during the electron transfer process since vibrational coherence from the ground- and excited-electronic states is usually temporally and spectrally overlapped. Here, we performed 2-dimensional electronic spectroscopy (2D ES) measurements on poly(3-hexylthiophene) (P3HT) films. By Fourier transforming the whole 2D ES datasets (S(λ1,T̃2,λ3)) along the population time (T̃2) axis, we develop and propose a protocol capable of separating vibrational coherence from the ground- and excited-electronic states in 3D rephasing and nonrephasing beating maps (S(λ1,ν̃2,λ3)). We found that the vibrational coherence from pure excited electronic states appears at positive frequency (+ν̃2) in the rephasing beating map and at negative frequency (-ν̃2) in the nonrephasing beating map. Furthermore, we also found that vibrational coherence from excited electronic state had a long dephasing time of 244 fs. The long-lived excited-state vibrational coherence indicates that coherence may be involved in the electron transfer process. Our findings not only shed light on the mechanism of ultrafast electron transfer in organic photovoltaics but also are beneficial for the study of the coherence effect on photoexcited dynamics in other systems.

ABSTRACTIt has been demonstrated that the 0‐0 absorption transition of poly(3‐hexylthiophene) (P3HT) in blends with poly(ethylene oxide) (PEO) could be rationally tuned through the control of the liquid–liquid phase separation process during solution deposition. Pronounced J‐like aggregation behavior, characteristic for systems of a low exciton band width, was found for blends where the most pronounced liquid–liquid phase separation occurred in solution, leading to domains of P3HT and PEO of high phase purity. Since liquid–liquid phase separation could be readily manipulated either by the solution temperature, solute concentration, or deposition temperature, to name a few parameters, our findings promise the design from the out‐set of semiconductor:insulator architectures of pre‐defined properties by manipulation of the interaction parameter between the solutes as well as the respective solute:solvent system using classical polymer science principles. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 304–310

In polymeric semiconductors, charge carriers are polarons, which means that the excess charge deforms the molecular structure of the polymer chain that hosts it. This results in distinctive signatures in the vibrational modes of the polymer. Here, we probe polaron photogeneration dynamics at polymer:fullerene heterojunctions by monitoring its time-resolved resonance-Raman spectrum following ultrafast photoexcitation. We conclude that polarons emerge within 300 fs. Surprisingly, further structural evolution on ≲ 50-ps timescales is modest, indicating that the polymer conformation hosting nascent polarons is not significantly different from that near equilibrium. We interpret this as suggestive that charges are free from their mutual Coulomb potential because we would expect rich vibrational dynamics associated with charge-pair relaxation. We address current debates on the photocarrier generation mechanism at molecular heterojunctions, and our work is, to our knowledge, the first direct probe of molecular conformation dynamics during this fundamentally important process in these materials.

In this study, a generally applicable strategy is described to manipulate the optical properties of a wide range of polymer semiconductors in the solid state. Blending these materials with a non-conjugated, polar polymer matrix is found to be the processing key to a drastic change and red-shift of the absorption characteristics.

The synthesis and characterization of a series of poly(3-allcyltellurophene)s are described. Polymers are prepared by both electrochemical and Kumada catalyst transfer polymerization methods. These polymers have reasonably high molecular weights (M-n = 5.4-11.3 kDa) and can be processed in a manner analogous to that of their lighter atom analogues. All examples exhibit red-shifted optical absorption, as well as solid-state organization, as evidenced by absorption spectroscopy and atomic force microscopy. Overall, the synthesis and characterization of these materials open up a wide range of future studies involving tellurium-based polyheterocycles.

Beginning fifty years ago, the search for suitable dispensers containing insect pheromones grew with the availability of these synthetic biotechnical tools. Many economic entomologists and application engineers dearly wish they had the "smart, intelligent and ideal dispenser". More or less suitable approximations are available commercially, but none so far meets all demands. Under economic strictures, novel inexpensive systems would be advantageous with release characteristics tailored to the specific life histories of pest insects, the plants considered and the numerous requirements of growers alike. Simultaneously, their field distribution should be mechanizable and be accomplished by one (or very few) application runs. The dispensers should be biodegradable, biocompatible, sustainably applicable, and they should be based on renewable resources. This report presents first results of a novel organic, electrospun nanofiber dispenser with dimensions in the upper nanometer range. Its load of pheromone can be adjusted to be sufficient for 7 weeks of constant disruptive action in vineyards and can be directed against the European Grape Vine Moth Lobesia botrana (Lepidoptera: Tortricidae) which here serves as a readily available model. Mating disruption in L. botrana and the related Eupoecilia ambiguella is a well studied and developed engineering process. Equally, nanofiber production by electrospinning (for a comprehensive review see Greiner and Wendorff, 2007A, B) is well known and already has numerous applications in filtration technology, air conditioning, and medical wound dressing. Our goal was to bring together and successfully mate these (partly incompatible) technologies via technical tricks of a proprietary nature. Even though the lifetime and effectiveness of currently available nanofibers still must be doubled, the rather complicated system of their production and analysis is known well enough to identify the parameters that need future adjustment. Another challenge is the mechanical distribution of the fibers in the vineyards by suitable machinery. Also, in this respect, certain technical leads are available for future development.

Organic nanofibers have a history of technical application in various independent fields, including medical technology, filtration technology, and applications of pharmaceuticals via inhalation into the lungs. Very recently, in a joint effort with polymer chemists, agricultural applications have been added to this list of priorities. The aim is finding novel approaches to insect control. Pheromones, dispensed in a quantifiable way, are being used here in disrupting the mating communication between male and female pest insects, e.g. the European grapevine moth Lobesia botrana (Lepidoptera: Tortricidae), where current dispenser technology does not fully meet the high expectations of growers and environmentalists with respect to longevity of constant release, self decomposition, mechanical distribution, renewability as well as sustainability of resources. The methodology of electrospinning is exhaustively covered by Greiner and Wendorff (2007), with technical details reported by Hellmann et al. (2009), Hein et al. (2011), and Hummel et al. (2010). Wind tunnel studies were run within a tunnel with adjustable laminar flow and 0.5 m/sec air velocity. Mass losses of the electrospun fiber bundles were determined with a sensitive analytical balance 2-3 times per week and recorded as time vs. mass change. CLSA experiments were performed with a self developed glass apparatus (Lindner, 2010) based on various suggestions of previous authors. Microgram quantities of volatile pheromone (E,Z)-7,9-Dodecadienylacetate were absorbed on a filter of rigorously purified charcoal and desorbed by repeated micro extraction with a suitable solvent mixture. Aliquots of the solution were subjected to temperature programmed capillary GLC. Retention times were used for identification, whereas the area covered by the pheromone peak originating from a FID detector signal was integrated and compared with a carefully calibrated standard peak. Since these signals were usually in the low nanogram range, several replications were averaged for statistical improvement. - Thermogravimetric analysis between ambient temperature and 500 degrees C provided a series of degradation curves where the diagram contained information on the evaporation of pheromone alone, polymer fiber alone and pheromone included in the fiber.- Microscopic investigations resulted in pictures of nanofibers from which the overall morphology and the fiber dimensions could be quantified. Organic nanofibers loaded with the grapevine moth pheromone have been well characterized by 5 different lab methods, followed by field bioassays reported elsewhere in these communications volumes (HUMMEL et al., 2011). This comprehensive analytical approach to fiber characterization is new and will be further refined. The federal agency JKI Berlin subjected the pheromone loaded organic fibers to various independent toxicological and ecotoxicological tests and found no adverse side effects.

Plants tend to attract diseases quite similar to human beings. Pesticides tend to be used to control such diseases. An alternative route, at least as far as damages from insects is concerned, envisions the application of pheromones. These cause a disorientation of male insects so that they are no longer able to locate the females, which finally gives rise to suppression of reproduction. The approach considered in this paper is based on the release of pheromones from polymer carriers, in particular, from nanofibers webs as obtained by electrospinning. These may be distributed across the field quite similar to spider webs. The pheromones are required to be incorporated in sufficiently high concentrations in the nanofibers via electrospinning and to be released from the nanofibers for a sufficiently long time expanding over several weeks to months. Polyamide 6 as well as cellulose acetate was used as a polymer carrier in the investigations reported in this contribution. Studies reveal that fluid pheromones can, in fact, be incorporated in the nanofibers to more than 33 wt%. They may undergo a nanoscalar phase separation within the fibers during electrospinning. Furthermore, thermogravimetric studies revealed via in vitro release studies that the pheromones are released from the nanofibers in a nearly linear fashion over a period covering many weeks. Copyright (C) 2009 John Wiley & Sons, Ltd.

Elektrogesponnene, organische Nanofasern sind neuartige Trager fur fluchtige Signalstoffe zur biotechnischen Regulierung von Schadinsekten im integrierten und okologischen Landbau. Der Einsatz von Pheromonen im Pflanzenschutz ist als eine umweltvertragliche Alternative zur Verwendung von chemisch-synthetischen Insektiziden oder als dessen Erganzung bekannt. Die pheromonbeladenen Nanofasern wirken als Dispenser und sollten vom Konzept her eine moglichst kontinuierliche, raumlich und zeitlich gleichmasige Abgaberate der fluchtigen Signalstoffe ermoglichen. Anforderungen sind, dass die Fasern wetterstabil sind, lang anhaltend funktionieren, einfach und kostengunstig ausgebracht sowie ruckstandsfrei abgebaut werden konnen. Es werden Ergebnisse von Halb-Freilandversuchen prasentiert, die den Nachweis der prinzipiellen Funktionsfahigkeit von pheromonbeladenen, elektrogesponnenen Polymerfaserdispensern zur Insektenverwirrung erbringen. Der in unseren Versuchen eingesetzte Bekreuzte Traubenwickler, Lobesia botrana, dient uns lediglich als Modellorganismus. Eine Ausweitung dieser Technik auf andere Schadorganismen ist geplant.

Using nanofibers as dispensers for pheromones and kairomones in plant protection for disrupting insect chemical communication is a novel approach aiming at popularizing this technique in organic and integrated plant production. Expected advantages of the nanofibers are highly controlled spatiotemporal release rates of pheromones / kairomones, improved climatic stability, and mechanized application. Dispenser types used so far show deficiencies in one or more of these requirements. Mechanical application of pheromones is a new approach to reduce the costs of manual labour and therefore the environmentally compatible, highly specific and efficient technique of mating disruption may become an alternative to the use of synthetic pesticides in integrated pest management. The nanofibers are highly elastic, which prevents breakoff of smaller pieces, and polymers used are biocompatible. Due to the scale of nanofibers the mass input both for pheromones and for polymeric nanofibers is very low. Major environmental benefits are high control specificity, very low concentrations of residues and reduced risk of development towards insect resistance.