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Heterocyclic dimers consisting of combinations of butterfly-shaped phenothiazine (PTZ) and its chemically oxidized form phenothiazine-5,5-dioxide (PTZ(SO2)) have been synthesized. A twist is imposed across the dimers by ortho-substituents including methyl ethers, sulfides and sulfones. X-ray crystallography, cyclic voltammetry and optical spectroscopy, underpinned by computational studies, have been employed to study the interplay between the oxidation state, conformational restriction, and emission mechanisms including thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP). While the PTZ(SO2) dimers are simple fluorophores, the presence of PTZ induces triplet-mediated emission with a mixed PTZ-PTZ(SO2) dimer displaying concentration dependent hallmarks of both TADF and RTP.

Narrow bandgap conjugated polymers are a heavily studied class of organic semiconductors, but their excited states usually have a very short lifetime, limiting their scope for applications. One approach to overcome the short lifetime is to populate long-lived triplet states for which relaxation to the ground state is forbidden. However, the triplet lifetime of narrow bandgap polymer films is typically limited to a few microseconds. Here, we investigated the effect of film morphology on triplet dynamics in red-emitting conjugated polymers based on the classic benzodithiophene monomer unit with the solubilizing alkyl side chains C16 and C2C6 and then used Pd porphyrin sensitization as a further strategy to change the triplet dynamics. Using transient absorption spectroscopy, we demonstrated a 0.45 ms triplet lifetime for the more crystalline nonsensitized polymer C2C6, 2-3 orders of magnitude longer than typically reported, while the amorphous C16 had only a 5 μs lifetime. The increase is partly due to delaying bimolecular electron-hole recombination in the more crystalline C2C6, where a higher energy barrier for charge recombination is expected. A triplet lifetime of 0.4 ms was also achieved by covalently incorporating 5% of Pd porphyrin into the C16 polymer, which introduced extra energy transfer steps between the polymer and porphyrin that delayed triplet dynamics and increased the polymer triplet yield by 7.9 times. This work demonstrates two synthetic approaches to generate the longest-lived triplet excited states in narrow bandgap conjugated polymers, which is of necessity in a wide range of fields that range from organic electronics to sensors and bioapplications.

Molecular size and shape have a commanding influence on the electronic structure and photophysical properties of organic optoelectronic molecules. Small changes in, for example, the dihedral angles between two rings in a molecule can be used to fine tune frontier orbital distributions, and make the difference between efficient or poor absorbance, luminescence, charge transport etc. as well as impacting on mechanical and thermal properties to improve processability. Recent works have made it clear that structural changes which enforce homoconjugation, the through-space overlap of frontier π-orbitals across a shared non-conjugating group, can exert even more dramatic changes on these useful functional properties. Triptycene is an archetypical homoconjugated molecule with a rigid 3D structure which presents an ideal substrate from which to learn how best to employ homoconjugation to optimise functional molecular properties. This review demonstrates this by highlighting triptycene-based molecules in the context of organic electronic materials, where homoconjugation has resulted in markedly enhanced optoelectronic properties, and provides comment on the performance and future potential of these materials in devices where possible.

A series of four heterocyclic dimers has been synthesized, with twisted geometries imposed across the central linking bond by ortho‐alkoxy chains. These include two isomeric bicarbazoles, a bis(dibenzothiophene‐S,S‐dioxide) and a bis(thioxanthene‐S,S‐dioxide). Spectroscopic and electrochemical methods, supported by density functional theory, have given detailed insights into how para‐ vs. meta‐ vs. broken conjugation, and electron‐rich vs. electron‐poor heterocycles impact the HOMO–LUMO gap and singlet and triplet energies. Crucially for applications as OLED hosts, the triplet energy (E T) of these molecules was found to vary significantly between dilute polymer films and neat films, related to conformational demands of the molecules in the solid state. One of the bicarbazole species shows a variation in E T of 0.24 eV in the different media—sufficiently large to “make‐or‐break” an OLED device—with similar discrepancies found between neat films and frozen solution measurements of other previously reported OLED hosts. From consolidated optical and optoelectronic investigations of different host/dopant combinations, we identify that only the lower E T values measured in neat films give a reliable indicator of host/guest compatibility. This work also provides new molecular design rules for obtaining very high E T materials and controlling their HOMO and LUMO energies., A new series of high E T heterocyclic dimers has been synthesized with large dihedral angles enforced by steric hindrance. A meta‐conjugated carbazole dimer displays the highest E T of 3.07 eV in dilute polymer film, however in a neat film this falls to 2.83 eV. Similar variation is observed across the series. This work highlights that to reliably estimate host/guest compatibility, E T determined from phosphorescence of neat films must be reported for new host materials. The currently accepted practice of reporting values from frozen solution or polymer films is no substitute.

A critical challenge facing thermally activated delayed fluorescence (TADF) is to facilitate rapid and efficient electronic transitions while ensuring a narrow singlet-triplet energy gap (ΔEST) in a single luminophore. We present a TADF-active iptycene that clearly demonstrates that homoconjugation can be harnessed as a viable design strategy towards answering this challenge. A homoconjugated analogue of an established quinoxaline-based TADF luminophore has been produced by fusing three of these luminophores together across a shared triptycene core. Homoconjugation was confirmed by electrochemistry, and as a direct consequence of this phenomenon we observed synergistic improvements to photoluminescence quantum yield (ΦPL), radiative rate of singlet decay (kSr), delayed fluorescence lifetime (τTADF), and rate of reverse intersystem crossing (krISC), all while narrowing the ΔEST. The enhancement is rationalised with TD-DFT calculations including spin-orbit coupling (SOC). A facile synthesis, the ubiquity of the pyrazine motif in state-of-the-art TADF materials of all colours, and the extent of the overall performance enhancement leads to a great potential for generality.

La conduite de la plupart des troupeaux de vaches allaitantes, basée sur l’utilisation de l’herbe pâturée ou conservée, est déjà extensive. Modifier la date de vêlage permet d’adapter la conduite du troupeau aux ressources fourragères. Lorsque la production d’herbe est suffisante pour satisfaire les besoins alimentaires du couple vache-veau, faire vêler les vaches au début de la période de végétation accroît la part de l’herbe pâturée dans l’alimentation du troupeau et limite ainsi les besoins en fourrages récoltés. Inversement, si la production des prairies est insuffisante, les vaches peuvent vêler pendant l’hivernage et être taries au pâturage. Leurs performances de reproduction sont alors préservées. Dans ces conditions plus difficiles, la durée de lactation peut être raccourcie, ce qui dissocie les besoins de la mère et du jeune. Les troupeaux de bovins allaitants peuvent contribuer à l’entretien des espaces herbagers avec des ajustements de la conduite du pâturage, par exemple en allongeant la durée de pâturage au-delà de la période de végétation active. Une augmentation du chargement à certaines périodes clés limite l’extension de végétations indésirables. Les races adaptées aux conditions extensives se caractérisent par leurs bonnes aptitudes maternelles et leur aptitude à mobiliser puis reconstituer leurs réserves corporelles et à ingérer des fourrages grossiers., Suckler herd management, based on the maximal use of grazed or harvested grass, is already extensive in most situations. Appropriate change of calving date fits herd management to seasonal variations in food supply, When grass production is sufficient, spring calving increases the proportion of grazed grass in the annual feed and reduces the need for harvested forages. If good forages are available for only a short time, the lactation period can also be shortened, which splits up the requirements of the dam and the calf. On the other hand, when grass production is low and/for grassland of poor quality, cows can calve in early wintering and be dried off when turned out at pasture. Their reproductive performance is thus maintained at an acceptable level. Suckler herds can contribute to the control and the maintenance of vegetation, for example by lengthening the grazing season far beyond the period of active vegetation growth. An increase in stocking rate at certain key periods can be used to control undesirable species efficiently. The genotypes adapted to extensive management conditions are characterized by their good maternal abilities, their relatively high intake capacity on roughages and low quality grass, and their ability to mobilise then recover body reserves.

The construction of carboxylic acid compounds in a selective fashion from low value materials such as alkenes remains a long-standing challenge to synthetic chemists. In particular, β-addition to styrenes is underdeveloped. Herein we report a new electrosynthetic approach to the selective hydrocarboxylation of alkenes that overcomes the limitations of current transition metal and photochemical approaches. The reported method allows unprecedented direct access to carboxylic acids derived from β,β-trisubstituted alkenes, in a highly regioselective manner.

A fundamental problem facing thermally activated delayed fluorescence (TADF) is to overcome the paradox of efficient electronic transitions and a narrow singlet-triplet energy gap (ΔEST) in a single luminophore. We present a quinoxaline-based TADF iptycene as the first clear example that homoconjugation can be harnessed as a viable design strategy toward this objective. Homoconjugation was introduced in an established TADF luminophore by trimerization through an iptycene core. This homoconjugation was confirmed by electrochemistry. As a direct consequence of homoconjugation we observed synergistic improvements to photoluminescence quantum yield (ΦPL), radiative rate of singlet decay (krS), delayed fluorescence lifetime (τTADF), and rate of reverse intersystem crossing (krISC), while narrowing the ΔEST. The cooperative enhancement is rationalised with TD-DFT calculations including spin-orbit coupling (SOC). A facile synthesis of this system, and the ubiquity of the pyrazine motif in state-of-the-art TADF materials across the electromagnetic spectrum, leads to a great potential for generality.

Thermally activated delayed fluorescence (TADF) is a current promising route for generating highly efficient light-emitting devices. However, the design process of new chromophores is hampered by the complicated underlying photophysics that requires a number of different pathways to be optimised simultaneously. In this work, four closely related donor-pi-acceptor-pi-donor systems have been investigated, two of which were synthesised previously, with the aim of elucidating their varying effectiveness for TADF. We, first, outline that neither the frontier orbitals nor the singlet-triplet gaps are sufficient in discriminating between the molecules. Subsequently, a detailed analysis of the excited states, performed at a correlated ab initio level, is shown highlighting the presence of a number of closely spaced singlet and triplet states of varying character. Five density functionals are benchmarked against this reference revealing dramatic changes in, both, excited state energies and wavefunctions following variations in the amount of Hartree-Fock exchange included. Excited-state minima are optimised in solution showing the crucial role of structural variations for stabilising locally excited and CT states and of symmetry breaking for producing a strongly emissive S1 state. More generally, this work shows how a detailed analysis of excited-state wavefunctions can provide critical new insight into excited-state electronic structure, helping to reveal the photophysics of existing push-pull chromophores and ultimately guiding the design of new ones.

Authors thank the EPSRC for funding under grants EP/L012200/1 and EP/L012294/1. A new dual-chain oligothiophene-based organic semiconductor, EH-5T-TTC, is presented. The molecule contains two conjugated chains linked by a fused tetrathiocin core. X-ray crystallography reveals a boat conformation within the 8-membered sulfur heterocycle core and extensive π–π and intermolecular sulfur–sulfur interactions in the bulk, leading to a 2-dimensional structure. This unusual molecule has been studied as a ternary component in organic solar cell blends containing the electron donor PTB7-Th and both fullerene (PC71BM) and non-fullerene acceptors ITIC and EH-IDTBR. By incorporating EH-5T-TTC as a ternary component, the power conversion efficiency of the binary blends containing non-fullerene acceptor increases by 17% (from 7.8% to 9.2%) and by 85% for the binary blend with fullerene acceptor (from 3.3% to 6.3%). Detailed characterisation of the ternary blend systems implies that the ternary small molecule EH-5T-TTC functions differently in polymer:fullerene and polymer:non-fullerene blends and has dual functions of morphology modification and complementary spectral absorption. Publisher PDF

A new structural class of 3D molecule capable of intramolecular charge transfer (ICT) is introduced, based upon an electron poor ring-fused triptycene core. Its photophysical and electrochemical properties are evaluated in comparison with an analogous molecule, representative of a single fin of the iptycene. Homoconjugation through the delocalised LUMO of the iptycene facilitates a great increase in transition probability both to and from the ICT state, while the deep blue photoluminescence of the single fin is retained. The peripherally distributed HOMO of the iptycene also permits reversible access to a tricationic state in a single step and at an oxidation potential lower than that of the single fin. This first example demonstrates great potential for this 3D design concept in producing new optoelectronic molecular materials.

Bulk heterojunction (BHJ) solar cells have been developed intensively over the last two decades due to the cheap, flexible devices which may be obtained, although their efficiency remains below that of other emerging solar cell technologies such as dye-sensitized and perovskite solar cells. Molecular organometallic phosphors are noted for their triplet harvesting ability which has produced highly efficient organic light-emitting devices. However, triplet harvesting presents an equally appealing route to enhance the photovoltaic properties of BHJ devices. The results of studies which have used the triplet sensitizing properties of metal complexes towards increasing the efficiency of BHJ solar cells are presented here. By using small quantities of molecular phosphors as dopants, large improvements in short circuit current and power conversion efficiency may be obtained.

The synthesis is reported of twelve new symmetrical carbazole dimers in which the carbazole units are linked via 1,4-phenylene spacers. There are two distinct series of compounds based on the position on the carbazole ring where the phenylene spacer is attached: this is either at carbazole C(3) (series 1a–1f) or at C(2) (series 2a–2f). The central phenylene ring is substituted with either two methyl, two methoxy or two cyano substituents which impart an intramolecular torsional angle between the phenylene and carbazole rings, thereby limiting the extent of π-conjugation between the carbazole units, and raising the triplet energies of the molecules to ET 2.6–3.0 eV, as determined from their phosphorescence spectra at 80 K. Structure–property relationships were studied by UV-vis and fluorescence spectroscopy, cyclic voltammetry and theoretical calculations. A notable observation is that substitution at the 2-position of carbazole (linear conjugation) exerts control over the position of the HOMO, while substitution at the 3-position of carbazole (meta conjugation) allows greater control over the LUMO. X-ray crystal structures are reported for two of the bicarbazoles. Compound 2d is shown to be a suitable host for the sky-blue emitter FIrpic in PhOLEDs, with improved device performance compared to CBP as host.

Employing the thiophene based quinone, benzo[1,2-b:4,5-b']dithiophene-4,8-dione, as the electron-accepting moiety alongside N-phenylcarbazole donors to produce a donor-π-acceptor-π-donor (D-π-A-π-D) molecule has yielded a new red emitter displaying delayed fluorescence. This new molecule shows strongly (over 100 nm) red-shifted emission when compared to an anthraquinone based analogue. Cyclic voltammetry complemented by computational insights prove that this red-shift is due to the significantly stronger electron-accepting ability of the thiophene quinone compared to anthraquinone. Photophysical and computational studies of this molecule have revealed that while the presence of the thiophene containing acceptor facilitates rapid intersystem crossing which is comparable to anthraquinone analogues, the reverse intersystem crossing rate is slow and non-radiative decay is rapid which we can attribute to low-lying locally excited states. This limits the total photoluminescence quantum efficiency to less than 10% in both solution and the solid state. These results provide a useful example of how very minor structural variations can have a defining impact on the photophysical properties of new molecular materials.

Triply fused 1,3-diazepine derivatives have been obtained by acidic reduction of rotationally locked and sterically hindered nitro groups in the presence of an aldehyde or ketone. The nitro groups are sited on adjacent rings of a dicyanodibenzothiophene-5,5-dioxide, which also displays fully reversible two-electron-accepting behavior. The synthesis, crystallographically determined molecular structures, and aspects of the electronic properties of these new molecules are presented.

Ion-sensitive field-effect transistors based on silicon nanowires are promising candidates for the detection of chemical and biochemical species. These devices have been established as pH sensors thanks to the large number of surface hydroxyl groups at the gate dielectrics which makes them intrinsically sensitive to protons. To specifically detect species other than protons, the sensor surface needs to be modified. However, the remaining hydroxyl groups after functionalization may still limit the sensor response to the targeted species. Here, we describe the influence of competing reactions on the measured response using a general site-binding model. We investigate the key features of the model with a real sensing example based on gold-coated nanoribbons functionalized with a self-assembled monolayer of calcium-sensitive molecules. We identify the residual pH response as the key parameter limiting the sensor response. The competing effect of pH or any other relevant reaction at the sensor surface has therefore to be included to quantitatively understand the sensor response and prevent misleading interpretations.

Two 2,2′:6′,2′′-terpyridine ligands (9 and 10) incorporating second-generation diphenylamino-dendrons have been synthesized and characterized; one ligand contains chromophoric benzothiadiazole domains. Using the ‘surface-as-ligand, surface-as-complex’ strategy, zinc(II)-containing sensitizers [Zn(Lanchor)(Lancillary)]2+ with carboxylic or phosphonic acid anchors (1 and 2, respectively) have been assembled and tested in n-type DSCs. The solid-state absorption spectra of dye-functionalized electrodes show a broad spectral response for all the dyes with enhanced intensity for those containing the benzothiadiazole units. However, the [Zn(Lanchor)(Lancillary)]2+ dyes perform poorly, exhibiting very low values of the short-circuit current density (JSC) and open-circuit voltage (VOC). The external quantum efficiency (EQE) spectra confirm that electron injection occurs, but EQEmax is ≤3%. Non-optimal positioning of the thiadiazole domain in the dye probably contributes to the poor performances. Screening of DSCs containing FTO/TiO2 photoanodes without adsorbed dye shows that they generate small short-circuit current densities and open-circuit voltages which contribute significantly to parameters reported for badly performing dyes. An organic dye 11, structurally similar to 10 and containing a 2-cyanoacrylic acid anchor, is also reported. This exhibits a broad and intense spectral response between 300 and 600 nm, and shows efficient electron injection over a broad wavelength range. DSCs containing 11 are stable over a 17 day period and show global efficiencies of 3.93–4.57% (ca. 70% with respect to N719 set at 100%). Ground state DFT calculations reveal that the HOMO in each of [Zn(1)(9)]2+, [Zn(2)(9)]2+, [Zn(1)(10)]2+, [Zn(2)(10)]2+ and 11 is localized on the peripheral diphenylamino units, allowing for hole-transfer to the reduced electrolyte. In 11, a major contribution from the 2-cyanoacrylic acid anchoring group appears in the LUMO manifold; however, while the LUMO in each zinc(II) dye is localized on anchoring ligand 1 or 2, it is concentrated close to the metal centre which may contribute to poor electron injection.

Five ruthenium(II) complexes [Ru(bpy)2(L)][PF6]2 in which L is a 6-substituted 2,2′-bipyridine ligand (ligands 1–3), 5-(2-picoloyl) (4), or an N,O-donor (5) have been prepared and characterized to investigate the role of the intramolecular caging effect of pendant aryl-substituents on the electronic and photophysical properties. The single crystal structures of three of the complexes are reported; in [Ru(bpy)2(L)][PF6]2 where L = 6-(selenophen-2-yl)-2,2′-bipyridine, intra-cation face-to-face π-stacking of the selenophenyl unit and one pyridine ring of an adjacent ligand is observed. In comparison to [Ru(bpy)3]2+, the energy of the MLCT band in [Ru(bpy)2(L)]2+ for L = 1, 2, 3 or 4 is little affected, but a red-shift of 35 nm is observed for [Ru(bpy)2(5)]2+. The new complexes are emissive at room temperature in degassed MeCN solution; values of λmaxem range from 613 to 689 nm for [Ru(bpy)2(L)]2+ (L = 1 to 5). The electrochemical behaviour of [Ru(bpy)2(L)][PF6]2 for L = 1, 2 and 3 is similar; in contrast, [Ru(bpy)2(4)][PF6]2 exhibits more complicated ligand-based redox behaviour, and for [Ru(bpy)2(5)][PF6]2, the presence of the N,O-donor shifts the metal-based oxidation to lower potential.

Ion-sensitive field-effect transistors based on silicon nanowires with high dielectric constant gate oxide layers (e.g., Al2O3 or HfO2) display hydroxyl groups which are known to be sensitive to pH variations but also to other ions present in the electrolyte at high concentration. This intrinsically nonselective sensitivity of the oxide surface greatly complicates the selective sensing of ionic species other than protons. Here, we modify individual nanowires with thin gold films as a novel approach to surface functionalization for the detection of specific analytes. We demonstrate sodium ion (Na(+)) sensing by a self-assembled monolayer (SAM) of thiol-modified crown ethers in a differential measurement setup. A selective Na(+) response of ≈-44 mV per decade in a NaCl solution is achieved and tested in the presence of protons (H(+)), potassium (K(+)), and chloride (Cl(-)) ions, by measuring the difference between a nanowire with a gold surface functionalized by the SAM (active) and a nanowire with a bare gold surface (control). We find that the functional SAM does not affect the unspecific response of gold to pH and background ionic species. This represents a clear advantage of gold compared to oxide surfaces and makes it an ideal candidate for differential measurements.

Ionic gradients play a crucial role in the physiology of the human body, ranging from metabolism in cells to muscle contractions or brain activities. To monitor these ions, inexpensive, label-free chemical sensing devices are needed. Field-effect transistors (FETs) based on silicon (Si) nanowires or nanoribbons (NRs) have a great potential as future biochemical sensors as they allow for the integration in microscopic devices at low production costs. Integrating NRs in dense arrays on a single chip expands the field of applications to implantable electrodes or multifunctional chemical sensing platforms. Ideally, such a platform is capable of detecting numerous species in a complex analyte. Here, we demonstrate the basis for simultaneous sodium and fluoride ion detection with a single sensor chip consisting of arrays of gold-coated SiNR FETs. A microfluidic system with individual channels allows modifying the NR surfaces with self-assembled monolayers of two types of ion receptors sensitive to sodium and fluoride ions. The functionalization procedure results in a differential setup having active fluoride- and sodium-sensitive NRs together with bare gold control NRs on the same chip. Comparing functionalized NRs with control NRs allows the compensation of non-specific contributions from changes in the background electrolyte concentration and reveals the response to the targeted species.

This study investigates the status, estimates the cost, and identifies the determinants of compliance with food safety measures in milk production in India. The study is based on the cross section primary data collected at the farm level in 3 states of India, namely, Bihar, Punjab, and Uttar Pradesh, in the year 2007. These states capture the geographical and institutional diversity of milk production and marketing in the country. The study shows that the status of compliance with food safety measures at the dairy farm level is not encouraging and a lot of efforts are needed to bridge this gap. The adoption intensity of food safety practices shows wide inter- and intraregional variations. This intensity depicts a positive relationship with herd size. The additional cost of compliance with food milk safety measures reveals an inverse relationship with herd size. The adoption intensity of food safety practices has been found to be influenced by the dairy farmers' characteristics. Herd size, education level,...

As the demand for livestock products increases, and is expected to continue to increase over the next few decades, especially in developing countries, smallholder mixed systems are becoming more intensive. However, with limited land and water resources and concern about the environmental impact of agricultural practices and climate change, the challenge is to find ways of increasing productivity that do not compromise household food security, but rather increase incomes equitably and sustain or enhance the natural resource base. In developed countries there has been increased specialisation of crop and livestock production. In contrast, the majority of livestock in developing countries is kept in mixed crop/livestock systems. Crops (cereal grains and pulses) and crop residues provide the basis of the diet for animals, e.g. cereal straw fed to dairy cattle or sweet potato vines fed to pigs. Animal manure can provide significant nutrient inputs to crops. Water productivity is higher in mixed crop/livestock systems compared with growing crops alone. Mixed systems allow for a more flexible and profitable use of family labour where employment opportunities are limited. They also spread risks across several enterprises, a consideration in smallholder systems that may become even more important under certain climate change scenarios. Integrated crop/livestock systems can play a significant role in improving global food security but will require appropriate technological developments, institutional arrangements and supportive policy environments if they are to fulfil that potential in the coming decades.

A hybrid tetrathiafulvalene–oligothiophene compound has been synthesised, in which the fulvalene unit is fused on both sides to an end-capped septithiophene oligomer. The compound (1) has been studied by cyclic voltammetry, UV-vis spectroelectrochemistry and X-ray crystallography. The properties of this material are compared to the half-unit (9), which lacks the TTF core and contains only one septithiophene chain. In the case of the larger molecule, there are multiple and complex redox processes leading to the loss of 6–8 electrons per molecule. Charge generation layer time-of-flight measurements give maximum hole mobilities of ca. 1 × 10−5 cm2 V−1 s−1.

There is growing interest in the environmental benefits of grazing by cattle, yet little information is available regarding the levels of production that might be achieved on semi-natural rough grazing (SNRG). The overall aim of this research was to assess the performance of native and ‘improved’ breeds of cattle when grazing grass/clover swards and SNRG in order to explore potential genotype × nutritional environment interactions. This paper reports the findings of three experiments conducted over three years. The first experiment assessed the performance of autumn-born Welsh Black (WB) and Charolais cross (CX) cattle aged approximately 9 months when grazing ryegrass/white clover-dominated improved permanent pasture (PP) and Molinia caerulea-dominated SNRG. Both genotype and pasture type had significant effects on liveweight gain, with growth rates higher for WB steers than CX steers (P

Fraser, M. D., Davies, D. A., Wright, I. A., Vale, J. E., Nute, G. R., Hallett, K. G., Richardson, R. I. (2007). Effect on upland beef production of incorporating winter feeding of red clover or summer grazing of Molinia-dominated semi-natural pastures. Grass and Forage Science, 62, (3), 284-300

Fraser, M. D., Davies, D. A., Vale, J. E., Hirst, W. M., Wright, I. A. (2007). Effects on animal performance and sward composition of mixed and sequential grazing of permanent pasture by cattle and sheep. Livestock Science, 110, (3), 251-266. Sponsorship: UK Department for Environment, Food and Rural Affairs and the Scottish Executive Environment and Rural Affairs Department.

Novel tetrathiafulvalene (TTF) containing compounds (III) are obtained by four-fold Stille coupling between tetrabromo-dithieno TTF (I) and stannylated thiophene (IIa) or thiazole (IIb).

Two novel tetrathiafulvalene (TTF) containing compounds 1 and 2 have been synthesised via a four-fold Stille coupling between a tetrabromo-dithienoTTF 5 and stannylated thiophene 6 or thiazole 4. The optical and electrochemical properties of compounds 1 and 2 have been measured by UV–vis spectroscopy and cyclic voltammetry and the results compared with density functional theory (DFT) calculations to confirm the observed properties. Organic field effect transistor (OFET) devices fabricated from 1 and 2 demonstrated that the substitution of thiophene units for thiazoles was found to increase the observed charge transport, which is attributed to induced planarity through S–N interactions of adjacent thiazole nitrogen atoms and TTF sulfur atoms and better packing in the bulk.

10 pages, 7 tables.-- Printed version published Nov 2006., The Northern Areas of Pakistan form a mountainous, semi-arid region in which subsistence mixed farming is the predominant economic activity for the majority of the population, which numbers around 1 million. Following a period of relative isolation, construction of the Karakoram Highway and the ensuing development activity have been catalysts for rapid infrastructural and social change over the last two decades. In the study reported here, feed resources for the livestock enterprise, which is largely made up of cattle, goats and sheep, were studied in detail over the course of a single winter feeding season. Productive outputs including liveweight change, milk production and reproductive performance were also quantified over a full year. The aim of the study was to provide a quantitative description of the system and to assess the extent to which proximity to a major highway influenced livestock husbandary. Six villages across the region were selected for study as part of a 2 × 3 factorial design with one village per cell of the study design. Factors consisted of two geographical transects and three agro-ecological zones. Transects were the Karakoram Highway (KKH) transect which enjoyed relatively good transport infrastructure and the Gilgit Ghizer Region (GGR) transect where infrastructure was more limited. Agro-ecological zones were the single, transitional and double cropping zones. One village per transect from each of the three main agro-ecological zones was chosen for study with 6–7 households within each village studied. Results showed that feed resources per household did not vary significantly according to transect or zone but cattle numbers per household were higher in the GGR transect than in the KKH transect indicating a heavier reliance on subsistence livestock production in this transect. Live weight and body condition of livestock in the Northern Areas changed markedly over the annual cycle. Losses of live weight were in the order of 10% over winter while summer gains during the summer season averaged 35% of initial live weight. There were differences between transects, with animals in the KKH gaining less weight in summer but showing higher milk yield (in cattle) and better reproductive performance. The results indicate a typical system of smallholder livestock production with heavy reliance on cereal by-products, a mix of livestock species and a relative scarcity of stored feed resources relative to overall livestock holdings. This study also suggests that proximity to the main highway running through the Northern Areas is associated with a reduced but more feed-efficient livestock production system., The research reported here was funded by the European Union under the Framework 5 INCO-DC Programme.

This paper presents a scenario-based analysis of the impacts of Common Agricultural Policy (CAP) reform for upland agriculture using a Welsh case-study. Specifically the paper examines the impacts of the introduction of the single-farm payment (SFP), the modulation of direct payments under Pillar I of the CAP and the increase in agri-environment payments under Pillar II. Three enterprises are examined, upland sheep rearing with lamb finishing, spring- and autumn-calving suckler-cattle with calf rearing. These enterprises are modelled under conditions in 2002/3, 2004/5 and for the reformed CAP in 2005/6. To support this analysis a livestock system model (LSM) was implemented. The model assesses alternative management regimen using a flexible state-transition approach. This simplifies the realisation and parameterisation of potentially complex management regimen. The model tracks fodder requirements to achieve targets based on defined diets. The LSM underpins whole-farm analyses of stocking-rates, labour and other resource requirements and net-farm income. From the case study the paper concludes that the impacts of the introduction of the CAP reform on the financial performance of the systems are small but negative (a net reduction of around 5% in support). The larger reduction in direct payments (15–18%) is partially offset by agri-environment measures. The paper concludes that while SFP encourages a more market-oriented outlook, the adaptive capacity within systems as they stand is very limited. There are a range of possible adaptation strategies, but for the uplands the extensification of cattle systems by reducing stock numbers and cutting back on labour seems most probable.

An experiment was conducted to examine the effects of mixed grazing of sheep plus cattle under continuous stocking of permanent pasture at different sward heights. The experiment had a 2×3 factorial design, with two sward surface heights (4–5 and 8–10 cm) and three combinations of animal species viz., sheep only, cattle only and sheep plus cattle. There were two replicate plots of each treatment combination and the experiment was conducted over 2 years consecutively. The sheep were Beulah Speckled Face ewes and their single Suffolk-cross lambs while the cattle were yearling Charolais-cross steers. Six ‘core’ steers and six ‘core’ ewes and their lambs grazed plots, as appropriately, while additional, non-experimental steers and ewes and their lambs were used to maintain sward heights. Each year the steers and the ewes grazed the pastures from May to October, while lambs were weaned and removed each year from the experiment in July. There was no significant effect of mixed grazing on live-weight gain of steers, but ewes had significantly higher live-weight gains on the sheep plus cattle treatment than on the sheep-only treatment (82 v. 61 g/day;Pv. 212 g/day;Pv. 250 g/day;P>0·05). The total output of live-weight gain per ha from steers, ewes and lambs was not significantly affected by animal species combination. It is concluded that while output per ha is not enhanced by mixed grazing by sheep and cattle when sward height is controlled, the live-weight gain of ewes is increased and the live-weight gain of lambs can be increased on taller swards.

We present a model of household decision-making in Kazakhstan. Traditionally, long-distance livestock migration of livestock occurred in Kazakhstan's rangelands, exploiting seasonal differences in forage availability. After independence, the rural economy collapsed and migrations stopped. We use multi-agent system modelling to examine trade-offs in allocation of wealth between capital and flocks. Winter forage availability is the key determinant of overall livestock numbers, while availability and price of winter fodder is an important determinant of livestock sector productivity. Seasonal migrations are only likely to reestablish if distant pastures have very poor winter forage. Otherwise, as total flock size increases, larger herds are predicted to settle away from villages. These predictions match field observations.

A series of hybrid tetrathiafulvalene-oligothiophene compounds has been synthesised, where the tetrathiafulvalene unit is fused at each side to an end-capped oligothiophene chain of varying length (terthiophene, quinquithiophene and septithiophene). Each hybrid structure (1-3) has been studied by cyclic voltammetry and triple EPR-UV-Vis-NIR spectroelectrochemistry in the case of the quinquithiophene compound (2). Comparison is made with the corresponding half-units, which lack the fulvalene core and contain just one oligothiophene chain. The highest hole mobility of quinquithiophene-TTF 2 was obtained from field effect transistors (8.61 × 10-3 cm 2 V-1 s-1); its surface morphology was characterised by tapping mode atomic force microscopy and a power conversion of 2.5% was achieved from a bulk heterojunction organic solar cell device using PC71BM as the acceptor.

Charge transport has been studied in a germanium-centred oligothiophene cruciform featuring 2-D close packing in the bulk. The morphology has been found to play a significant role in charge carrier transport, evidenced by time-of-flight and field effect transistor measurements. Thermal step-annealing leads to the formation of smaller crystalline domains which are favourable for charge transport in device applications.

The examination of surface charges within dye-sensitized solar cells containing copper(I)-based dyes has proved to be difficult due to the instability of these systems compared with existing commercial dyes. We report the use of scanning electrochemical microscopy in a setup in which homoleptic [Cu(Lancillary)2]+ complexes are used as the electrolyte to investigate a series of [Cu(Lanchor)(Lancillary)]+ sensitizers. The ligands Lanchor and Lancillary are 6,6′-disubstituted 2,2′-bipyridines. By incorporating sensitizers and electrolytes containing the same ligands, changes in the diffusion layer around the scanning electrode have been used to map the substrate surface both in the dark and under controlled illumination. Examination of the changes in current as a constant potential is applied shows the formation of stable surface charge as the cell components equilibrate. Comparison of the time taken for this stabilization to occur as ancillary or anchoring ligands within the dye and electrolyte are varied shows a significant dependence upon the aliphatic substituents in the 6,6′-positions of the ligands that surround the copper(I) center.

The solubility of luminescent quantum dots in solvents from hexane to water can be finely tuned by the choice of the countercations associated with carboxylate residues present on the nanocrystal surface. The resulting nanocrystals exhibit long term colloidal and chemical stability and maintain their photophysical properties.

Methods for high-throughput validation of cell components for use in dye sensitized solar cells (DSCs) are needed as the global production of such cells becomes widespread. We have carried out preliminary investigations into the use of scanning electrochemical microscopy (SECM) for high-throughput screening of materials. By coupling the technique of SECM with a light source, we have examined the surface charge of non-earthed pseudo-DSCs under variable light conditions and screened substrates by varying the working electrode potential. By studying the surface currents in a series of tests in which one or more component of a DSC were varied, the effect of TiO2, dye and iodide/triiodide electrolyte on the surface characteristics have been examined.

Wright, I. A., Jones, J. R., Parsons, A. J. (2001). Effects of grazing by sheep or cattle on sward structure and subsequent performance of weaned lambs. Grass and Forage Science, 56, (2), 138-150. Sponsorship: MAFF/SEERAD

Four groups of six spring-calving beef cows and their calves were allocated to two replicated grazing treatments on a Nardus stricta-dominated hill pasture in the UK during six consecutive summer grazing seasons. Treatments were applied by continuous variable stocking to maintain a sward height of either 4–5 cm (short) or 6–7 cm (tall) between tussocks of N. stricta. Cows on both treatments ingested a greater proportion of N. stricta than was present in the sward. The short treatment reduced the herbage intake of cows proportionally by 0·35 (P

An experiment was conducted to examine how variation in the composition and structure of mixed grass/white clover swards affected diet selection by sheep and goats. Sward composition in a mixed perennial ryegrass/white clover sward was manipulated by continuous grazing from 28 May to 28 July (pre-experimental phase) with cattle, sheep or goats, and then from 29 July to 2 September (experimental phase) with sheep or goats in a factorial design replicated twice. Sward surface height was maintained at 6 cm by regular adjustment of stocking density. Grazing by different sequences of animal species resulted in significant differences in the proportions of white clover in the sward, and especially in the proportion of clover lamina and petiole. Grazing by goats in the pre-experimental phase led to greater proportions of clover lamina and petiole in the whole sward and the sward surface. The proportion of white clover in the diet selected by sheep in the experimental phase was consistently higher than that in the sward as a whole, but was closely related to that near to the sward surface (approximately the top 2 cm). For goats there was no significant relationship between the proportion of clover in the diet and in the whole sward, and they generally selected a diet with a lower proportion of white clover than was present in approximately the top 2 cm of the sward. It is concluded that on mixed grass/white clover swards goats do not graze as deeply into the sward as sheep and that this results in a lower proportion of white clover in their diet and therefore allows higher proportions of white clover to develop under grazing by goats than by sheep.

Ligands containing first and second generation hole-transport triphenylamino-dendrons have been evaluated as ancillary ligands in copper(I) DSCs yielding an optimal efficiency of 3.77% in unmasked cells. The effects of masking the DSCs on measured parameters are discussed.

An experiment was conducted to assess the effects of grazing a perennial ryegrass (Lolium perenne)/ white clover (Trifolium repens) sward by sheep or goats on sward composition and structure and on subsequent diet selection, herbage intake and liveweight gain by weaned lambs. From mid-May to late July (phase 1), ewes with twin lambs or yearling Scottish Cashmere goats grazed continuously swards maintained at 4- or 8-cm sward surface height. From mid-August to the end of September (phase 2), weaned lambs continuously grazed the same swards maintained at 4 cm (treatment 4–4) or at 8 cm (treatment 8–8) or which had been allowed to increase from 4 cm to 8 cm (treatment 4–8). By the end of phase 1, swards grazed by goats had higher proportions of white clover in the whole sward (0.377 vs. 0.181; s.e.d 0.0382; P< 0.001) than those grazed by sheep, irrespective of sward height treatment. This resulted in phase 2 in a higher proportion of white clover selected (P

An experiment was conducted to test the hypothesis that postpartum anoestrus in beef cows is prolonged in cows in low body condition (BC) because they have a reduced LH pulse frequency compared with cows in high BC. Thirty-six multiparous Blue-Grey (White Shorthorn × Galloway) cows were fed so that they calved in either low (L) (BC score 2.07; SE 0.05; n = 24) or high (H) (BC score 2.81; SE 0.08; n = 12) body condition. They were then fed to maintain BC after calving. Twelve L cows were infused (i.v.) with 2 μg GnRH in 2 ml saline every 2 h from 5 to 7 weeks postpartum (LG) while the remaining L cows and all H cows were infused with saline only (LS and HS). Ovulations, as indicated by the presence of a morphologically normal corpus luteum, were recorded in one, one and ten of the cows of the LS, HS and LG groups, respectively. Mean LH concentrations and pulse frequencies were not affected by either GnRH treatment or BC but mean LH pulse amplitudes were lower (P < 0.05) in LG and LS cows than in HS cows at Week 5 and in LG cows at Week 6. At Week 7 postpartum, the numbers of small (3–7.9 mm diameter) and large (≥ 8 mm diameter) ovarian follicles, mean granulosa cell numbers per follicle and mean concentrations of LH receptors (pg per mg thecal and granulosa tissue) were not affected by GnRH treatment or BC. Granulosa cells from oestrogen active follicles of HS and LG cows secreted more oestradiol in vitro (P < 0.01) than cells from LS cows. However, there were no significant differences with treatment in the intrafollicular concentrations of oestradiol, testosterone or insulin-like growth factor-1. It was concluded that, since infusion of GnRH pulses enhanced both follicular steroidogenesis and the incidence of ovulation in low BC cows, the frequency of GnRH pulses is one determinant of follicle development in the postpartum cow. While H cows also exhibited a degree of enhancement of oestradiol synthesis by the granulosa cells of oestrogenic follicles, compared with L cows there was no difference in the LH pulse frequency or in the incidence of ovulation. It is concluded that there may be a threshold level of oestrogen synthesis by granulosa cells below which the final stages of follicle maturation and ovulation cannot be initiated, or that a high rate of oestradiol synthesis by this tissue is not the only factor mediating the effects of body condition on follicle development in the postpartum cow.