Fullerene-capped copolymers for bulk heterojunctions: device stability and efficiency improvements

A fullerene end-capped polymer-compatibilizer based on poly(3-hexylthiophene) (P3HT) was synthesized and demonstrated to have a remarkable effect on both the stability and efficiency of devices made from exemplar P3HT and [6,6]-phenyl C61-butyric acid methyl ester (PCBM). P3HT with ethynyl chain-ends and α-azido-ω-bromo-PS were prepared via Grignard metathesis (GRIM) and atom transfer radical polymerisation, respectively. “Click” chemistry resulted in the preparation of poly(3-hexylthiophene)-block-ω-bromo-polystyrene (P3HT-b-PS-Br), and subsequent atom transfer radical addition chemistry with fullerene (C60) yielded the donor–acceptor block copolymer P3HT-b-PS-C60. Both P3HT-b-PS-Br and P3HT-b-PS-C60 were considered as compatibilizers with P3HT/PCBM blends, with the study detailing effects on active-layer morphology, device efficiency and stability. When used at low concentrations, both P3HT-b-PS-Br (1%) and P3HT-b-PS-C60 (0.5%) resulted in considerable 28% and 35% increases in efficiencies with respect to devices made from P3HT/PCBM alone. Furthermore, P3HT-b-PS-C60 (0.5%) resulted in an important improvement in device stability.

Wireless power and data transfer via a common inductive link using frequency division multiplexing

For wireless power transfer (WPT) systems, communication between the primary side and the pickup side is a challenge because of the large air gap and magnetic interferences. A novel method, which integrates bidirectional data communication into a high-power WPT system, is proposed in this paper. The power and data transfer share the same inductive link between coreless coils. Power/data frequency division multiplexing technique is applied, and the power and data are transmitted by employing different frequency carriers and controlled independently. The circuit model of the multiband system is provided to analyze the transmission gain of the communication channel, as well as the power delivery performance. The crosstalk interference between two carriers is discussed. In addition, the signal-to-noise ratios of the channels are also estimated, which gives a guideline for the design of mod/demod circuits. Finally, a 500-W WPT prototype has been built to demonstrate the effectiveness of the proposed WPT system.

Managing supply chain knowledge in the new product development process:a social network analysis approach

The aim of this paper is to propose a conceptual framework for studying the knowledge transfer problem within the supply chain. The social network analysis (SNA) is presented as a useful tool to study knowledge networks within supply chain, to visualize knowledge flows and to identify the accumulating knowledge nodes of the networks. © 2011 IEEE.

Innovation across the food chain – the Hungarian case

The small and medium sized enterprises (SMEs) in the Hungarian agri-food sector play determining role. The innovation capacity (efforts, activities and results) however of the individual SMEs is very limited. Food production (including SMEs) has to fulfil food safety requirements in a rapidly increasing extent, which implies a continuous innovation and development process from all market players. In Hungary the agri-food chain had to face a suddenly increased competition especially after the EU enlargement. Based on survey data this paper examines the efforts, activities and results in knowledge acquisition, utilisation, coordination and transfer in the Central Hungarian food SMEs. We have found (using ordered logistic regression) that R&D expenditures, achieved innovations, export/import orientation as well as the networking activity of the SMEs play significant role in market development.

Stable isotopes reveal complex changes in trophic relationships following nutrient addition in a coastal marine ecosystem

Complex links between the top-down and bottomup forces that structure communities can be disrupted by anthropogenic alterations of natural habitats.We used relative abundance and stable isotopes to examine changes in epifaunal food webs in seagrass (Thalassia testudinum) beds following 6 months of experimental nutrient addition at two sites in Florida Bay (USA) with different ambient fertility. At a eutrophic site, nutrient addition did not strongly affect food web structure, but at a nutrient-poor site, enrichment increased the abundances of crustacean epiphyte grazers, and the diets of these grazers became more varied. Benthic grazers did not change in abundance but shifted their diet away from green macroalgae + associated epiphytes and towards an opportunistic seagrass (Halodule wrightii) that occurred only in nutrient addition treatments. Benthic predators did not change in abundance, but their diets were more varied in enriched plots. Food chain length was short and unaffected by site or nutrient treatment, but increased food web complexity in enriched plots was suggested by increasingly mixed diets. Strong bottom-up modifications of food web structure in the nutrient-limited site and the limited top-down influences of grazers on seagrass epiphyte biomass suggest that, in this system, the bottom-up role of nutrient enrichment can have substantial impacts on community structure, trophic relationships, and, ultimately, the productivity values of the ecosystem.

Electroproduction of hyperons at low momentum transfer

A high resolution study of the H(e,e'K+)Λ,Σ 0 reaction was performed at Hall A, TJNAF as part of the hypernuclear experiment E94-107. One important ingredient to the measurement of the hypernuclear cross section is the elementary cross section for production of hyperons, Λ and Σ0. This reaction was studied using a hydrogen (i.e. a proton) target. Data were taken at very low Q2 (∼0.07 (GeV/c) 2) and W∼2.2 GeV. Kaons were detected along the direction of q, the momentum transferred by the incident electron (&thetas;CM∼6°). In addition, there are few data available regarding electroproduction of hyperons at low Q2 and &thetas;CM and the available theoretical models differ significantly in this kinematical region of W. The measurement of the elementary cross section was performed by scaling the Monte Carlo cross section (MCEEP) with the experimental-to-simulated yield ratio. The Monte Carlo cross section includes an experimental fit and extrapolation from the existing data for electroproduction of hyperons. Moreover, the estimated transverse component of the electroproduction cross section of H(e,e'K+)Λ was compared to the different predictions of the theoretical models and exisiting data curves for photoproductions of hyperons. None of the models fully describe the cross-section results over the entire angular range. Furthermore, measurements of the Σ 0/Λ production ratio were performed at &thetas; CM∼6°, where data are not available. Finally, data for the measurements of the differential cross sections and the Σ 0/Λ production were binned in Q2, W and &thetas;CM to understand the dependence on these variables. These results are not only a fundamental contribution to the hypernuclear spectroscopy studies but also an important experimental measurement to constrain existing theoretical models for the elementary reaction.

A Suite of Prey Traits Determine Predator and Nutrient Enrichment Effects in a Tri-Trophic Food Chain

Predation, predation risk, and resource quality affect suites of prey traits that collectively impact individual fitness, population dynamics, and community structure. However, studies of multi-trophic level effects generally focus on a single prey trait, failing to capture trade-offs among suites of covarying traits that govern population responses and emergent community patterns. We used structural equation models (SEM) to summarize the non-lethal and lethal effects of crayfish, Procambarus fallax, and phosphorus (P) addition, which affected prey food quality (periphyton), on the interactive effects of behavioral, morphological, developmental, and reproductive traits of snails, Planorbella duryi. Univariate and multivariate analyses suggested trade-offs between production (growth, reproduction) and defense (foraging behavior, shell shape) traits of snails in response to non-lethal crayfish and P addition, but few lethal effects. SEM revealed that non-lethal crayfish effects indirectly limited per capita offspring standing stock by increasing refuge use, slowing individual growth, and inducing snails to produce thicker, compressed shells. The negative effects of non-lethal crayfish on snails were strongest with P addition; snails increased allocation to shell defense rather than growth or reproduction. However, compared to ambient conditions, P addition with non-lethal crayfish still yielded greater per capita offspring standing stock by speeding individual snail growth enabling them to produce more offspring that also grew faster. Increased refuge use in response to non-lethal crayfish led to a non-lethal trophic cascade that altered the spatial distribution of periphyton. Independent of crayfish effects, snails stimulated periphyton growth through nutrient regeneration. These findings illustrate the importance of studying suites of traits that reveal costs associated with inducing different traits and how expressing those traits impacts population and community level processes.

Electroproduction of hyperons at low momentum transfer

A high resolution study of the H(e,e'K+)Λ,Σ0 reaction was performed at Hall A, TJNAF as part of the hypernuclear experiment E94-107. One important ingredient to the measurement of the hypernuclear cross section is the elementary cross section for production of hyperons, Λ and Σ0. This reaction was studied using a hydrogen (i.e. a proton) target. Data were taken at very low Q2 (∼0.07 (GeV/c)2) and W∼2.2 GeV. Kaons were detected along the direction of q, the momentum transferred by the incident electron (θCM~6°). In addition, there are few data available regarding electroproduction of hyperons at low Q2 and θCM, and the available theoretical models differ significantly in this kinematical region of W. The measurement of the elementary cross section was performed by scaling the Monte Carlo cross section (MCEEP) with the experimental-to-simulated yield ratio. The Monte Carlo cross section includes an experimental fit and extrapolation from the existing data for electroproduction of hyperons. Moreover, the estimated transverse component of the electroproduction cross section of H(e,e'K+)Λ was compared to the different predictions of the theoretical models and exisiting data curves for photoproductions of hyperons. None of the models fully describe the cross-section results over the entire angular range. Furthermore, measurements of the Σ0/Λ production ratio were performed at θCM, where data are not available. Finally, data for the measurements of the differential cross sections and the Σ0/Λ production were binned in Q2, W and θCM to understand the dependence on these variables. These results are not only a fundamental contribution to the hypernuclear spectroscopy studies but also an important experimental measurement to constrain existing theoretical models for the elementary reaction.

Characterization of Juvenile Hormone Biosynthetic Enzymes in the Mosquito, Aedes aegypti

The juvenile hormones (JHs) are sesquiterpenoid compounds that play a central role in insect reproduction, development and behavior. They are synthesized and secreted by a pair of small endocrine glands, the corpora allata (CA), which are intimately connected to the brain. The enzymes involved in the biosynthesis of JH are attractive targets for the control of mosquito populations. This dissertation is a comprehensive functional study of five Aedes aegypti CA enzymes, HMG-CoA synthase (AaHMGS), mevalonate kinase (AaMK), phosphomevalonate kinase (AaPMK), farnesyl diphosphate synthase (AaFPPS) and farnesyl pyrophosphate phosphatase (AaFPPase). The enzyme AaHMGS catalyzes the condensation of acetoacetyl-CoA and acetyl-CoA to produce HMG-CoA. The enzyme does not require any co-factor, although its activity is enhanced by addition of Mg2+. The enzyme AaMK is a class I mevalonate kinase that catalyzes the ATP-dependent phosphorylation of mevalonic acid to form mevalonate 5-phosphate. Activity of AaMK is inhibited by isoprenoids. The enzyme AaPMK catalyzes the cation-dependent reversible reaction of phosphomevalonate and ATP to form diphosphate mevalonate and ADP. The enzyme AaFPPS catalyzes the condensation of isopentenyl diphosphate (IPP) and dimethylallyl pyrophosphate (DMAPP) to form geranyl diphosphate (GPP) and farnesyl pyrophosphate (FPP). The enzyme AaFPPS shows an unusual product regulation mechanism, with chain length final product of 10 or 15 C depending on the metal cofactor present. The enzymes AaFPPase-1 and AaFPPase-2 efficiently hydrolyze FPP into farnesol, although RNAi experiments demonstrate that only AaFPPase-1 is involved in the catalysis of FPP into FOL in the CA of A. aegypti. This dissertation also explored the inhibition of the activity of some of the JH biosynthesis enzymes as tools for insect control. We described the effect of N-acetyl-S-geranylgeranyl-L-cysteine as a potent inhibitor of AaFPPase 1 and AaFPPase-2. In addition, inhibitors of AaMK and AaHMGS were also investigated using purified recombinant proteins. The present study provides an important contribution to the characterization of recombinant proteins, the analysis of enzyme kinetics and inhibition constants, as well as the understanding of the importance of these five enzymes in the control of JH biosynthesis rates.

Managing supply chain knowledge-based linkages for improving operational performance

Purpose: This paper aims to explore the role of internal and external knowledgebased linkages across the supply chain in achieving better operational performance. It investigates how knowledge is accumulated, shared, and applied to create organization-specific knowledge resources that increase and sustain the organization's competitive advantage. Design/methodology/approach: This paper uses a single case study with multiple, embedded units of analysis, and the social network analysis (SNA) to demonstrate the impact of internal and external knowledge-based linkages across multiple tiers in the supply chain on the organizational operational performance. The focal company of the case study is an Italian manufacturer supplying rubber components to European automotive enterprises. Findings: With the aid of the SNA, the internal knowledge-based linkages can be mapped and visualized. We found that the most central nodes having the most connections with other nodes in the linkages are the most crucial members in terms of knowledge exploration and exploitation within the organization. We also revealed that the effective management of external knowledge-based linkages, such as buyer company, competitors, university, suppliers, and subcontractors, can help improve the operational performance. Research limitations/implications: First, our hypothesis was tested on a single case. The analysis of multiple case studies using SNA would provide a deeper understanding of the relationship between the knowledge-based linkages at all levels of the supply chain and the integration of knowledge. Second, the static nature of knowledge flows was studied in this research. Future research could also consider ongoing monitoring of dynamic linkages and the dynamic characteristic of knowledge flows. Originality/value: To the best of our knowledge, the phrase 'knowledge-based linkages' has not been used in the literature and there is lack of investigation on the relationship between the management of internal and external knowledge-based linkages and the operational performance. To bridge the knowledge gap, this paper will show the importance of understanding the composition and characteristics of knowledge-based linkages and their knowledge nodes. In addition, this paper will show that effective management of knowledge-based linkages leads to the creation of new knowledge and improves organizations' operational performance.

A Molecular-scale Programmable Stochastic Process Based On Resonance Energy Transfer Networks: Modeling And Applications

While molecular and cellular processes are often modeled as stochastic processes, such as Brownian motion, chemical reaction networks and gene regulatory networks, there are few attempts to program a molecular-scale process to physically implement stochastic processes. DNA has been used as a substrate for programming molecular interactions, but its applications are restricted to deterministic functions and unfavorable properties such as slow processing, thermal annealing, aqueous solvents and difficult readout limit them to proof-of-concept purposes. To date, whether there exists a molecular process that can be programmed to implement stochastic processes for practical applications remains unknown.

In this dissertation, a fully specified Resonance Energy Transfer (RET) network between chromophores is accurately fabricated via DNA self-assembly, and the exciton dynamics in the RET network physically implement a stochastic process, specifically a continuous-time Markov chain (CTMC), which has a direct mapping to the physical geometry of the chromophore network. Excited by a light source, a RET network generates random samples in the temporal domain in the form of fluorescence photons which can be detected by a photon detector. The intrinsic sampling distribution of a RET network is derived as a phase-type distribution configured by its CTMC model. The conclusion is that the exciton dynamics in a RET network implement a general and important class of stochastic processes that can be directly and accurately programmed and used for practical applications of photonics and optoelectronics. Different approaches to using RET networks exist with vast potential applications. As an entropy source that can directly generate samples from virtually arbitrary distributions, RET networks can benefit applications that rely on generating random samples such as 1) fluorescent taggants and 2) stochastic computing.

By using RET networks between chromophores to implement fluorescent taggants with temporally coded signatures, the taggant design is not constrained by resolvable dyes and has a significantly larger coding capacity than spectrally or lifetime coded fluorescent taggants. Meanwhile, the taggant detection process becomes highly efficient, and the Maximum Likelihood Estimation (MLE) based taggant identification guarantees high accuracy even with only a few hundred detected photons.

Meanwhile, RET-based sampling units (RSU) can be constructed to accelerate probabilistic algorithms for wide applications in machine learning and data analytics. Because probabilistic algorithms often rely on iteratively sampling from parameterized distributions, they can be inefficient in practice on the deterministic hardware traditional computers use, especially for high-dimensional and complex problems. As an efficient universal sampling unit, the proposed RSU can be integrated into a processor / GPU as specialized functional units or organized as a discrete accelerator to bring substantial speedups and power savings.

An assessment of the influence of the industry distribution chain on the oxygen levels in commercial modified atmosphere packaged cheddar cheese using non-destructive oxygen sensor technology

The establishment and control of oxygen levels in packs of oxygen-sensitive food products such as cheese is imperative in order to maintain product quality over a determined shelf life. Oxygen sensors quantify oxygen concentrations within packaging using a reversible optical measurement process, and this non-destructive nature ensures the entire supply chain can be monitored and can assist in pinpointing negative issues pertaining to product packaging. This study was carried out in a commercial cheese packaging plant and involved the insertion of 768 sensors into 384 flow-wrapped cheese packs (two sensors per pack) that were flushed with 100% carbon dioxide prior to sealing. The cheese blocks were randomly assigned to two different storage groups to assess the effects of package quality, packaging process efficiency, and handling and distribution on package containment. Results demonstrated that oxygen levels increased in both experimental groups examined over the 30-day assessment period. The group subjected to a simulated industrial distribution route and handling procedures of commercial retailed cheese exhibited the highest level of oxygen detected on every day examined and experienced the highest rate of package failure. The study concluded that fluctuating storage conditions, product movement associated with distribution activities, and the possible presence of cheese-derived contaminants such as calcium lactate crystals were chief contributors to package failure.

Long chain diols and diol indices of surface sediments of the Iberian Atlantic margin

Long chain diols are lipids that have gained interest over the last years due to their high potential to serve as biomarkers and diol indices have been proposed to reconstruct upwelling conditions and sea surface temperature (SST). However, little is known about the sources of the diols and the mechanisms impacting their distribution. Here we studied the factors controlling diol distributions in the Iberian Atlantic margin, which is characterized by a dynamic continental shelf under the influence of upwelling of nutrient-rich cold deep waters, and fluvial input. We analyzed suspended particulate matter (SPM) of the Tagus river, marine SPM and marine surface sediments along five transects off the Iberian margin, as well as riverbank sediments and soil from the catchment area of the Tagus river. Relatively high fractional abundances of the C32 1,15-diol (normalized with respect to the 1,13- and 1,15-diols) were observed in surface sediments in front of major river mouths and this abundance correlates strongly with the BIT index, a tracer for continental input of organic carbon. Together with an even higher fractional abundance of the C32 1,15-diol in the Tagus river SPM, and the absence of long chain diols in the watershed riverbank sediments and soils, we suggest that this long chain diol is produced in-situ in the river. Further support for this hypothesis comes from the small but distinct stable carbon isotopic difference of 1.3? with the marine C28 1,13-diol. The 1,14-diols are relatively abundant in surface sediments directly along the northern part of the coast, close to the upwelling zone, suggesting that Diol Indices based on 1,14-diols would work well as upwelling tracers in this region. Strikingly, we observed a significant difference in stable carbon isotopic composition between the monounsaturated C30:1 1,14- and the saturated C28 1,14-diol (3.8±0.7 per mil), suggesting different sources, in accordance with their different distributions. In addition, the Long chain Diol Index (LDI), a proxy for sea surface temperature, was applied for the surface sediments. The results correlate well with satellite SSTs offshore but reveal a significant discrepancy with satellite-derived SSTs in front of the Tagus and Sado rivers. This suggests that river outflow might compromise the applicability of this proxy.

MEDIUM-CHAIN-LENGTH POLY(3-HYDROXYALKANOATE) NANOPARTICLE SUSPENSIONS

The main goal of this thesis was to prepare medium-chain-length poly-3-hydroxyalkanoate (mcl-PHA) nanoparticle suspensions at high solids content (≥ 10 % w/v). A two-stage emulsification-solvent evaporation process was employed to produce poly-3-hydroxydecanoate (PHD) suspensions. The formulation and processing conditions including ultrasonication time and amplitude, selection of solvent, and selection of surfactants and their concentrations were investigated to make concentrated suspensions (10 and 30 % (w/v)) of PHD with particles less than 300 nm. Among the ionic surfactants tested to stabilize the suspension, the anionic, sodium dodecyl sulphate (SDS), and the cationic, dodecyltrimethylammonium bromide (DTAB) surfactants produced the smallest particle sizes (~100 nm). However, more stabilized nanoparticles were obtained when the ionic surfactant, SDS, was combined with any of the non-ionic surfactants tested, with polyoxyethylene octyl phenyl ether (Triton X-100) or polyoxyethylene (20) sorbitan monooleate (Tween 80) resulting in a slight increase in zeta potential over 30 days while the zeta potential with other non-ionic surfactants decreased. Mcl-PHA containing 11 and 18 % of carboxyl groups was synthesized via free radical addition reaction of 11-mercaptoundecanoic acid to the pendant double bonds of unsaturated poly-3-hydroxynonanoate (PHNU). Colloidal suspensions prepared by ultrasonication needed a surfactant to maintain stability, even at 0.4 % solids of mcl-PHA containing 11 % carboxylation (PHNC-1) unlike the stable suspensions prepared without surfactants by the titration method. Similar particle sizes (155.6 ± 8.4 to 163.4 ± 11.3 nm) and polydispersity indices (0.42 ± 0.03 to 0.49 ± 0.04) were obtained when several non-ionic surfactants were tested to minimize particle agglomeration, with the smallest particles obtained with Triton X-100. When Triton X-100 was combined with a variety of ionic surfactants, smaller nanoparticles (97.1 ± 1.1 to 121.7 ± 5.7 nm) with a narrower particle size distribution (0.21 ± 0.001 to 0.25 ± 0.003) were produced. The SDS and Triton X-100 combination was chosen to evaluate other mcl-PHAs at 10 % (w/v) solids content. Slightly smaller nanoparticles were formed with carboxylated mcl-PHAs compared to mcl-PHAs having aliphatic pendant side chains. Mcl-PHA consisting of 18 % carboxylation (PHNC-2) formed a much smaller nanoparticles and higher zeta potential.

Point-and-shoot: rapid quantitative detection methods for on-site food fraud analysis – moving out of the laboratory and into the food supply chain

Major food adulteration and contamination events occur with alarming regularity and are known to be episodic, with the question being not if but when another large-scale food safety/integrity incident will occur. Indeed, the challenges of maintaining food security are now internationally recognised. The ever increasing scale and complexity of food supply networks can lead to them becoming significantly more vulnerable to fraud and contamination, and potentially dysfunctional. This can make the task of deciding which analytical methods are more suitable to collect and analyse (bio)chemical data within complex food supply chains, at targeted points of vulnerability, that much more challenging. It is evident that those working within and associated with the food industry are seeking rapid, user-friendly methods to detect food fraud and contamination, and rapid/high-throughput screening methods for the analysis of food in general. In addition to being robust and reproducible, these methods should be portable and ideally handheld and/or remote sensor devices, that can be taken to or be positioned on/at-line at points of vulnerability along complex food supply networks and require a minimum amount of background training to acquire information rich data rapidly (ergo point-and-shoot). Here we briefly discuss a range of spectrometry and spectroscopy based approaches, many of which are commercially available, as well as other methods currently under development. We discuss a future perspective of how this range of detection methods in the growing sensor portfolio, along with developments in computational and information sciences such as predictive computing and the Internet of Things, will together form systems- and technology-based approaches that significantly reduce the areas of vulnerability to food crime within food supply chains. As food fraud is a problem of systems and therefore requires systems level solutions and thinking.