Electron-Deficient N-Alkyloyl Derivatives of Thienopyrrole-4,6-dione Yield Efficient Polymer Solar Cells with Open-Circuit Voltages > 1 V

Poly(benzo[1,2-b:4,5-b′]dithiophene–thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymer donors yield some of the highest open-circuit voltages (VOC, ca. 0.9 V) and fill factors (FF, ca. 70%) in conventional bulk-heterojunction (BHJ) solar cells with PCBM acceptors. Recent work has shown that the incorporation of ring substituents into the side chains of the BDT motifs in PBDTTPD can induce subtle variations in material properties, resulting in an increase of the BHJ device VOC to ∼1 V. In this contribution, we report on the synthesis of N-alkyloyl-substituted TPD motifs (TPD(CO)) and show that the electron-deficient motifs can further lower both the polymer LUMO and HOMO levels, yielding device VOC > 1 V (up to ca. 1.1 V) in BHJ solar cells with PCBM. Despite the high VOC achieved (i.e., low polymer HOMO), BHJ devices cast from TPD(CO)-based polymer donors can reach power conversion efficiencies (PCEs) of up to 6.7%, making these promising systems for use in the high-band-gap cell of tandem solar cells

Dependence of Crystallite Formation and Preferential Backbone Orientations on the Side Chain Pattern in PBDTTPD Polymers

Alkyl substituents appended to the π-conjugated main chain account for the solution-processability and film-forming properties of most π-conjugated polymers for organic electronic device applications, including field-effect transistors (FETs) and bulk-heterojunction (BHJ) solar cells. Beyond film-forming properties, recent work has emphasized the determining role that side-chain substituents play on polymer self-assembly and thin-film nanostructural order, and, in turn, on device performance. However, the factors that determine polymer crystallite orientation in thin-films, implying preferential backbone orientation relative to the device substrate, are a matter of some debate, and these structural changes remain difficult to anticipate. In this report, we show how systematic changes in the side-chain pattern of poly(benzo[1,2-b:4,5-b′]dithiophene–alt–thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers can (i) influence the propensity of the polymer to order in the π-stacking direction, and (ii) direct the preferential orientation of the polymer crystallites in thin films (e.g., “face-on” vs “edge-on”). Oriented crystallites, specifically crystallites that are well-ordered in the π-stacking direction, are believed to be a key contributor to improved thin-film device performance in both FETs and BHJ solar cells

Functionalized Carbon Nanotube Adsorption Interfaces for Electron Transfer Studies of Galactose Oxidase

Modified electrodes featuring specific adsorption platforms able to access the electrochemistry of the copper containing enzyme galactose oxidase (GaOx) were explored, including interfaces featuring nanomaterials such as nanoparticles and carbon nanotubes (CNTs). Electrodes modified with various self-assembled monolayers (SAMs) including those with attached nanoparticles or amide-coupled functionalized CNTs were examined for their ability to effectively immobilize GaOx and study the redox activity related to its copper core. While stable GaOx electrochemistry has been notoriously difficult to achieve at modified electrodes, strategically designed functionalized CNT-based interfaces, cysteamine SAM-modified electrode subsequently amide-coupled to carboxylic acid functionalized single wall CNTs, were significantly more effective with high GaOx surface adsorption along with well-defined, more reversible, stable (≥ 8 days) voltammetry and an average ET rate constant of 0.74 s-1 in spite of increased ET distance - a result attributed to effective electronic coupling at the GaOx active site. Both amperometric and fluorescence assay results suggest embedded GaOx remains active. Fundamental ET properties of GaOx may be relevant to biosensor development targeting galactosemia while the use functionalized CNT platforms for adsorption/electrochemistry of electroactive enzymes/proteins may present an approach for fundamental protein electrochemistry and their future use in both direct and indirect biosensor schemes

Clustering Attitudes and Behaviors of High/Low Involvement Grocery Shopper

The purpose of this exploratory and quantitative study was to examine the attitudes and behaviors of 14,807 grocery shop- pers. These respondents across the US were asked to answer attitudinal, behavioral, and demographic related questions. Shoppers were profiled by analyzing their responses to 16 relevant attitudinal and behavioral questions. A cluster analysis was performed followed by a discriminant analysis to deter- mine attitudinal and behavioral variables explaining cluster membership. A cross-tabulation analysis assessed demo- graphic variables that correlated with cluster membership. Two clusters were identified: high and low involvement grocery shoppers. In an event that has long been perceived as low involvement, a large percentage (53%) can be categorized as high involvement grocery shoppers. These shoppers tend to be younger. They were more likely to enjoy the hunt of finding products/deals, seek the advice of others and perceive that the products they buy reflect upon them. Grocery stores have a significant opportunity to target this high involvement shop- per. Grocery stores will need to create an integrative, engaging online and in-store experience to attract high involvement shoppers and ultimately increase store loyalty. The results of this research has significant communication, branding and digital marketing implications

Ring Substituents Mediate the Morphology of PBDTTPD-PCBM Bulk-Heterojunction Solar Cells

Among π-conjugated polymer donors for efficient bulk-heterojunction (BHJ) solar cell applications, poly(benzo[1,2-b:4,5-b′]dithiophene–thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers yield some of the highest open-circuit voltages (VOC, ca. 0.9 V) and fill-factors (FF, ca. 70%) in conventional (single-cell) BHJ devices with PCBM acceptors. In PBDTTPD, side chains of varying size and branching affect polymer self-assembly, nanostructural order, and impact material performance. However, the role of the polymer side-chain pattern in the intimate mixing between polymer donors and PCBM acceptors, and on the development of the BHJ morphology is in general less understood. In this contribution, we show that ring substituents such as furan (F), thiophene (T) and selenophene (S)—incorporated into the side chains of PBDTTPD polymers—can induce significant and, of importance, very different morphological effects in BHJs with PCBM. A combination of experimental and theoretical (via density functional theory) characterizations sheds light on how varying the heteroatom of the ring substituents impacts (i) the preferred side-chain configurations and (ii) the ionization, electronic, and optical properties of the PBDTTPD polymers. In parallel, we find that the PBDT(X)TPD analogs (with X = F, T, or S) span a broad range of power conversion efficiencies (PCEs, 3–6.5%) in optimized devices with improved thin-film morphologies via the use of 1,8-diiodooctane (DIO), and discuss that persistent morphological impediments at the nanoscale can be at the origin of the spread in PCE across optimized PBDT(X)TPD-based devices. With their high VOC ∼1 V, PBDT(X)TPD polymers are promising candidates for use in the high-band gap cell of tandem solar cells

The influence of delayed light curing on the degree of conversion and polymerization contraction stress in dual-cured resin luting agents

The aim of the study was to assess the effect of delayed photo-initiation on the polymerization contraction stress (PCS) and degree of conversion (DC) of a dual-cure resin-luting agent. Thirty-five disk (6 mm × 1 mm) samples (n = 10 each group) of dual cure resin luting agent for PCS assessment were fabricated and polymerized using two illuminated quartz rods. Based on the delay in photo-initiation, 30 disks were divided among six groups [group A-0 min (min) delay, group B-2 min, group C-4 min, group D-6 min, group E-8 min and group F-10 min]. A non-photoinitiated group (group G – chemical cure – n = 5) was included as control. The PCS for all specimens was assessed using a Tensometer. For DC evaluation thirty-five specimens were divided into seven groups with delays in photo-initiation (group H-0 min, group I-2 min, group J-4 min, group K-6 min, group L-8 min and group M-10 min, group N-chemical cure). DC was assessed using attenuated total reflectance spectroscopic technique. Statistical comparison among groups was performed using analysis of variance (α = 0.05). The maximum and minimum PCS and DC values with delayed photo-initiation was observed in group-C (3.34 MPa) & group-F (2.44 MPa); and group-M (0.78 MPa) and group-H (0.55 MPa) respectively. Chemically cured samples showed the least PCS (group-G, 1.94) and DC (group-N, 0.53) values in their respective categories. PCS significantly decreased with delayed photo-initiation. A significant increase in DC was noticed when photo-initiation was delayed in the dual cure resin luting agent

The Relationship Between Physical Activity and Perceived Health Status in Older Women: Findings from the Woman’s College Alumni Study

Using data collected from the Woman’s College (WC) Alumni Study, the purpose of this study was to determine whether perceived health status is related to physical activity in older women. A multiple linear regression analysis was conducted to examine the relationship between amounts of physical activity and self-reported health status. The results of the current study reveal that the level of physical activity is significantly correlated with perceived health status. The findings of this study have implications for the assessment of older individuals’ health and may lead to interventions that are tailored to increase physical activity among older women

Hydrodynamic Analysis of a Wave Energy Converter (WEC)

Honorable Mention Winner The UNF CREW competing in the U.S. Department of Energy 2021 Marine Energy Collegiate Competition developed a Wave Energy Converter (WEC) for quick deployment in disaster relief areas. When natural disasters disable coastal power grids, a WEC can be easily deployed close to shore and serve as a source of electricity. The ocean waves move magnets through a coil wired within the WEC to generate electricity. To initiate the design process, ANSYS AQWA software simulated both the oceanic environment and the device’s response in the WEC’s testing conditions. AQWA allows the user to change device dimensions easily and optimize the design ahead of physical construction. The resulting WEC proof of concept minimized prototype manufacturing waste and cost by eliminating poor designs in advance. The simulated geometry neglected hollow sections and used unidirectional, regular waves to account for software limitations. The software simulated the WEC for 20 seconds in an oceanic environment with a 40-meter depth and a 0.25-meter amplitude regular wave. Simulations produced graphs and animations describing the forces acting on the WEC as well as the WEC’s movement. The animation proved that the WEC reacts well in similar physical testing conditions. Based on the simulation results, the team constructed a 3D model for small-scale testing. Future investigations will involve more complex designs. Research conducted onward will focus on mass-damper systems and contact surfaces provided in the software

Cost Analysis of Osprey C.R.E.W.

Renewable energy adoption is on the rise in the U.S. and abroad. More than ever, energy sourcing needs to shift away from harmful fossil fuels and towards fully renewable energy sources. Adapting from traditional fossil fuel energy sources to renewable energy sources is paramount for environmental health and public health. Fossil fuels emit harmful pollutants, which have led to changing weather conditions and exasperated natural disasters. Existing renewable sources are not ideal, either. For instance, solar cannot run continuously and wind turbines are subject to weather changes. The recent energy debacle in Texas shows the need for alternative renewable energy sources. The Osprey C.R.E.W. wave energy converter (WEC) alleviates many of the current problems existing renewable energy systems cannot solve. First, it provides reliable and constant service. With other renewable energy services, there will be stops in production. However, there are no stops in wave energy because the waves are constant. Another positive of the WEC device is that their deployments are flexible and scalable. This means that energy production levels can be changed rapidly and without delay. The average cost per device falls significantly with seamless scalability, making large increments of devices procured in a relatively cost-effective manner. Cost comparisons between competing energy sources show that the WEC is very cost-efficient as well. The cost of producing wave energy is found to be more efficient than solar energy and wind alternatives. Our cost figures also show that Osprey C.R.E.W provides a very competitive alternative to the primary fossil fuel producers such as coal and fuel

Optimization of Power Performance of a Wave Energy Converter

With climate change on the rise, unprecedented dependence on electricity, and an increased incidence of extreme weather, the UNF team participating in the U.S. Department of Energy 2021 Marine Energy Collegiate Competition: Powering the Blue Economy wants to give an alternative solution to provide renewable energy in areas that lose electricity as a result of a natural disaster, or that due to their isolated location cannot use traditional renewable energy sources. This led to the creation of the Osprey C.R.E.W (Cheap Reliable Energy from Waves). The Osprey C.R.E.W. is a wave energy converter that uses the vertical motion of the ocean waves to generate electricity. The principle of energy conversion is Faraday’s Law of Electromagnetic Induction, which states that a magnetic field moving past a conductor will generate electricity. The UNF team has developed a numerical simulation to test how different parameters influence the output and has built three small-scale prototypes that have been tested in a wave tank. A medium-sized prototype and a wave pool are being constructed, with the expectation that the size will also increase the output