Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “methyl esters”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 145 records · Page 8

Renewable diesel via hydrothermal liquefaction of oleaginous yeast and residual lignin from bioconversion of corn stover

A major barrier to profitable bioconversion of cellulosic biomass to hydrocarbon fuel precursors is the difficulty in breaking down feedstock lignin into carbon substrates that can be easily metabolized by industrial microbes. Hydrothermal liquefaction (HTL) of cellulosic biomass effectively breaks down and converts lignin into biocrude oil products, but provides relatively low yields of biocrude from feedstock carbohydrates. In the present study, bioconversion and HTL were integrated into a new hybrid system that employs the best of both processes to produce high quality fuel in high quantity. Bioreactor cultivation of the oleaginous yeast Lypomyces starkeyi produced dry cell mass yields up to 0.43 g/g of sugar and yields of intracellular triglyceride lipids (measured as fatty acid methyl esters) of up to 0.26 g/g of sugar in pretreated corn stover hydrolysate or simulated hydrolysate media. The lipid-rich bioreactor broth was mixed with pretreated corn stover lignin, and then co-fed to an HTL reactor to produce 0.40 g of biocrude oil per gram of feed on a dry weight basis. Optimizing the separation of HTL biocrude and the HTL aqueous phase could significantly increase the biocrude yield. Hydrotreating of the biocrude produced a high quality, renewable hydrocarbon fuel blendstock, with the majority of the product boiling in the distillate range. The estimated cost of production could be reduced to $3/gasoline gallon equivalent through addressing identified research gaps. Our results provide a proof-of-concept for a new hybrid biorefinery design that could enhance domestic production of renewable diesel, jet, and marine fuel in the United States.

Biomass, Continuous hydrothermal liquefaction, Bio↗

Nebivolol stimulates mitochondrial biogenesis in 3T3-L1 adipocytes

Highlights: •Nebivolol may act as a partial agonist of β3-adrenergic receptor (AR). •Nebivolol stimulates mitochondrial DNA replication and protein expression. •Nebivolol promotes mitochondrial synthesis via activation of eNOS by β3-AR. -- Abstract: Nebivolol is a third-generation β-adrenergic receptor (β-AR) blocker with additional beneficial effects, including the improvement of lipid and glucose metabolism in obese individuals. However, the underlying mechanism of nebivolol’s role in regulating the lipid profile remains largely unknown. In this study, we investigated the role of nebivolol in mitochondrial biogenesis in 3T3-L1 adipocytes. Exposure of 3T3-L1 cells to nebivolol for 24 h increased mitochondrial DNA copy number, mitochondrial protein levels and the expression of transcription factors involved in mitochondrial biogenesis, including PPAR-γ coactivator-1α (PGC-1α), Sirtuin 3 (Sirt3), mitochondrial transcription factor A (Tfam) and nuclear related factor 1 (Nrf1). These changes were accompanied by an increase in oxygen consumption and in the expression of genes involved in fatty acid oxidation and antioxidant enzymes in 3T3-L1 adipocytes, including nebivolol-induced endothelial nitric oxide synthase (eNOS), as well as an increase in the formation of cyclic guanosine monophosphate (cGMP). Pretreatment with NG-nitro-L-arginine methyl ester (l-NAME) attenuated nebivolol-induced mitochondrial biogenesis, as did the soluble guanylate cyclase inhibitor, ODQ. Treatment with nebivolol and β3-AR blocker SR59230A markedly attenuated PGC-1α, Sirt3 and manganese superoxide dismutase (MnSOD) protein levels in comparison to treatment with nebivolol alone. These data indicate that the mitochondrial synthesis and metabolism in adipocytes that is promoted by nebivolol is primarily mediated through the eNOS/cGMP-dependent pathway and is initiated by the activation of β3-AR receptors.

60 APPLIED LIFE SCIENCES↗

A novel 1-acyl-sn-glycerol-3-phosphate O-acyltransferase homolog for the synthesis of membrane phospholipids with a branched-chain fatty acyl group in Shewanella livingstonensis Ac10

Highlights: • A new 1-acyl-sn-glycerol-3-phosphate O-acyltransferase (PlsC) was discovered. • The enzyme introduces a branched-chain fatty acyl group into membrane phospholipids. • The substrate specificity of the enzyme is unprecedented in the PlsC family enzymes. • Multiple PlsC homologs contribute to generation of membrane phospholipid diversity. 1-Acyl-sn-glycerol-3-phosphate O-acyltransferase (PlsC) plays an essential role in the formation of phosphatidic acid, a precursor of various membrane phospholipids (PLs), in bacteria by catalyzing the introduction of an acyl group into the sn-2 position of lysophosphatidic acid. Various bacteria produce more than one PlsC. However, the physiological significance of the occurrence of multiple PlsCs is poorly understood. A psychrotrophic bacterium, Shewanella livingstonensis Ac10, which produces eicosapentaenoic acid at low temperatures, has five putative PlsCs (PlsC1-5). We previously showed that PlsC1 is responsible for the production of PLs containing an eicosapentaenoyl group. Here, we characterized another putative PlsC of this bacterium named PlsC4. We generated a plsC4-disrupted mutant and found that PLs containing 13:0 found in the parental strain were almost completely absent in the mutant. The loss of these PLs was suppressed by introduction of a plsC4-expression plasmid. PLs containing 15:0 were also drastically decreased by plsC4 disruption. Gas chromatography-mass spectrometry analysis of fatty acyl methyl esters derived from PLs of the parental strain showed that the 13:0 and 15:0 groups were an 11-methyllauroyl group and a 13-methylmyristoyl group, respectively. Phospholipase A2 treatment revealed that these fatty acyl groups were linked to the sn-2 position of PLs. Thus, PlsC4 is a new type of PlsC homolog that is responsible for the synthesis of PLs containing a branched-chain fatty acyl group at the sn-2 position and plays a clearly different role from that of PlsC1 in vivo.

60 APPLIED LIFE SCIENCES↗

Raman-probes for monitoring metabolites and nutrient fate in Yarrowia lipolytica using deuterated glucose

The aim of this study was to explore the application of deuterium (D) labeled glucose-D 7 as Raman-tag in Yarrowia lipolytica to assess triacyl glycerides (TAG) biosynthesis. Cells were grown in N depleted media in: (i) glucose in H 2 O (control), (ii) glucose-D 7 in H 2 O and (iii) glucose-D 7 in D 2 O, and the resulting biomass and lipids quantified. Infrared and Raman spectroscopies showed the incorporation of D with the presence of a C-D stretching bands in the silent region (1800–2600 cm -1 ) for cells grown in glucose-D 7 in H 2 O and glucose-D 7 in D 2 O as compared to the control. Fatty acid methyl ester analysis of cells grown in the three media showed significant differences in lipid profiles. Cells grown on glucose-D 7 in H 2 O and glucose-D 7 in D 2 O showed unequivocally D incorporation in fatty acids and TAG by mass spectrometry. Higher D incorporation was observed when cells were grown in D 2 O than H 2 O. Deuterium was also incorporated into the cell wall polysaccharides.

59 BASIC BIOLOGICAL SCIENCES↗

Tire-derived carbon for catalytic preparation of biofuels from feedstocks containing free fatty acids

The utilization of waste feedstocks rich in free fatty acids (FFAs) improves biofuel production on the basis of economics and sustainability. However, converting these feedstocks to usable biofuel poses inherent problems in terms of the FFA to biofuel conversion yield and the catalyst lifetime. Here, we report novel ferric sulfate impregnated carbon derived from waste tires as highly active catalysts for FFA to biofuel conversion. Our approach takes advantage of facile synthesis methods involving sonication and dehydration processes to create materials that are useful for the efficient catalytic conversion of FFAs to advanced biofuels. Esterification of FFAs to fatty acid methyl esters was achieved at 65 °C and atmospheric pressure with >98% yield even in the presence of triglycerides. These catalysts maintained similar activity after four successive uses, which indicates that the active catalytic sites are effectively supported by the three-dimensional meso/microporous architecture of the tire-derived carbon.

09 BIOMASS FUELS↗

Improving biodiesel monoglyceride determination by ASTM method D6584-17

Biodiesels produced from commercial and non-traditional feedstocks were analyzed by ASTM D6584-17 for monoglyceride (monoacylglycerol, or MG) content. It was found that D6584-17 as currently written may not accurately determine MGs from conventional feedstocks due to significant differences in retention time using modern instrumentation. For biodiesel from non-traditional feedstocks, D6584-17 did not sufficiently account for MGs containing fatty acids outside of C16 and C18 species. This led to under- and over-reporting of MGs, as critical components were not accurately measured. Improvements to the method were made through a three-step process. First, a standard mixture of MGs was run to determine the retention time of individual MGs that could be present in the samples from C10 to C24. An additional analysis for the fatty acid methyl ester (FAME) profile was used to determine the major MG species present in the biodiesel samples, using the assumption that the MG profile was proportional to the FAME profile. The biodiesel samples were analyzed by D6584-17, and the MGs were identified using retention time matching, based on the major species expected from measuring the FAME profile. Here, by combining these two methods, the accuracy of MG determination by D6584-17 was improved for biodiesels prepared from all feedstocks.

30 DIRECT ENERGY CONVERSION↗

Enhanced performance of P3HT/(PCBM:ZnO:TiO{sub 2}) blend based hybrid organic solar cells

Highlights: • We fabricated hybrid bulk heterojunction organic solar cells. • TiO{sub 2} and ZnO nanoparticles replace PCBM with fixed amount of P3HT in active layer • PCE was significantly improved by the introduction of TiO{sub 2} and ZnO. • A possible route toward low-cost OPV. • To the best of my knowledge, this work is the first time going to report. - Abstract: Quaternary blend hybrid organic solar cells enjoy both an increased light absorption range and an easy method to fabricate because of the simple structure. In this study effects of mixing inorganic metal oxides (ZnO and TiO{sub 2}) nanoparticles to the active layer of organic photovoltaics devices were investigated. The active layer primarily consists of various ratios of electron donor poly (3-hexylthiophene) (P3HT) and an electron acceptor [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) together with nanostructured ZnO and TiO{sub 2} dispersed in chlorobenzene (CB) and 1,2-dichlorobenzene (DCB). The ratio of PCBM to nanoparticles was varied keeping the ratio of P3HT to acceptor material constant. Mixing of nanoparticle plays a significant role in the resulting power conversion efficiency (PCE) of the devices. An increased PCE for ZnO/TiO{sub 2} doped devices can be attributed to increased absorption in the visible region and enhanced charge collection due to the percolation networks formed by metal oxides nanoparticles.

36 MATERIALS SCIENCE↗

Effect of nano particle sizes on the third-order optical non-linearities and nanostructure of copolymer P3HT:PCBM thin film for organic photovoltaics

Highlights: • Active layer (P3HT:PCBM) has been deposited on substrate type by spin coating at 1000 rpm. • The device was completed by evaporating a 60 nm thick, circular gold electrodes onto the P3HT:PCBM. • Nonlinear refractive indices of the three particle sizes are found to be of the order of 10{sup −7} cm{sup 2}/W - Abstract: Organic solar cells are based on (3-hexylthiophene):[6,6]-phenyl C61-butyric acid with methyl ester Bulk Heterojunction. An inverted structure has been fabricated using nano-anatase crystalline titanium dioxide, as the electron transport layer, which was prepared on either the Indium Tin Oxide coated glass (ITO—glass), or Silicon wafer, as well as on glass substrates by the sol–gel method, at different spin speed, using the spin-coating system. The effect of thickness on the surface morphology and on the optical properties of TiO{sub 2} layer, was investigated using the Atomic Force Microscopy (AFM), X-ray diffraction, and UV–visible spectrophotometer. The samples were examined to feature currents and voltages, in the darkness and light extraction efficiency of the solar cell. The highest open-circuit voltage, V{sub oc}, and power conversion efficiency were 0.66% and 0.39%, fabricated with 90 nm, respectively. The non-linear optical properties of nano-anatase TiO{sub 2} sol–gel, were investigated at different particle sizes, using the z-scan technique.

36 MATERIALS SCIENCE↗

Open-air spray deposition of PCBM/BCP electron transport layer for inverted perovskite solar cells

A [6,6]-phenyl C61 butyric acid methyl ester (PCBM) and bathocuproine (BCP) electron transport layer (ETL) is spray deposited in open air directly on top of a perovskite at linear speeds of 9 m/min. The PCBM precursor ink contains a binary mixture of 1:1 chlorobenzene:chloroform, which optimizes spray wettability on the perovskite surface and allows quick solvent evaporation. A near-infrared heating module additionally provides a flash cure (<5 s) for the formation of smooth, large-area PCBM films (∼20 cm 2 ). A BCP solution in isopropanol is subsequently sprayed to form an ultrathin (<5 nm) film and characterized with a suite of high-resolution metrologies. The spray-deposition processing and near-infrared treatment do not damage the underlying perovskite. Inverted architecture devices containing the sprayed ETL achieve a champion efficiency of 20.3% and demonstrate stable performance without additional interlayers or surface treatments. Here, the technoeconomic cost of the open-air spray process is compared against traditional vacuum-based evaporation, resulting in a decrease in manufacturing costs by 26%.

14 SOLAR ENERGY↗

Critical role of domain crystallinity, domain purity and domain interface sharpness for reduced bimolecular recombination in polymer solar cells

In this study, inverted bulk heterojunction solar cells were fabricated using poly(3-hexylthiophene) (P3HT) blended with two different fullerene derivatives namely phenyl-C61-butyric acid methyl ester (PC 60 BM) and indene-C 60 bis-adduct (IC 60 BA). The effects of annealing temperatures on the morphology, optical and structural properties were studied and correlated to differences in photovoltaic device performance. It was observed that annealing temperature significantly improved the performance of P3HT:IC 60 BA solar cells while P3HT:PC 60 BM cells showed relatively less improvement. The performance improvement is attributed to the extent of fullerene mixing with polymer domains. Energy filtered transmission electron microscopy (EFTEM) and x-ray diffraction (XRD) results showed that ICBA mixes with disordered P3HT much more readily than PC 60 BM which leads to lower short circuit current density and fill factor for P3HT:IC 60 BA cells annealed below 120°C. Annealing above 120°C improves the crystallinity of P3HT in case of P3HT:IC 60 BA whereas in P3HT:PC 60 BM films, annealing above 80°C leads to negligible change in crystallinity. Crystallization of P3HT also leads to higher domain purity as seen EFTEM. Further it is seen that cells processed with additive nitrobenzene (NB) showed enhanced short circuit current density and power conversion efficiency regardless of the fullerene derivative used. Addition of NB led to nanoscale phase separation between purer polymer and fullerene domains. Kelvin probe force microscopy (KPFM) images showed that enhanced domain purity in additive casted films led to a sharper interface between polymer and fullerene. Lastly, enhanced domain purity and interfacial sharpness led to lower bimolecular recombination and higher mobility and charge carrier lifetime in NB modified devices.

14 SOLAR ENERGY↗

Monitoring the dynamics of miscible P3HT:PCBM blends: A quasi elastic neutron scattering study of organic photovoltaic active layers

Our work reports on the detailed molecular dynamic behavior of miscible blends of Poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and their pure counterparts by quasi-elastic neutron scattering measurements (QENS). The study provides the measure of relaxation processes on pico-to-nanosecond time scales. A single relaxation process was observed in pure P3HT and PCBM while two relaxation processes, one fast and one slow, were observed in the blends. The fast process was attributed to the dynamics of P3HT while the slow process was correlated to the dynamics of PCBM. The results show that the relaxation process is a balance between two opposing effects: increased mobility due to thermal activation of P3HT molecules and decrease mobility due to the presence of PCBM which is correlated to the percent crystallinity of P3HT and local packing density of PCBM in the amorphous phase. The threshold for the domination of the thermally activated relaxation is between 5 and 9 vol.% of PCBM loading. Two distinct spatial dependences of the relaxation processes, in which the crossover length scale depends neither on temperature nor composition, were observed for all the samples. They were attributed to the collective motions of the hexyl side chains and the rotational motions of the C-C single bonds of the side chains. Finally, these results provide an understanding of the effects of PCBM loading and temperature on the dynamics of the polymer-fullerene blends which provides a tool to optimize the efficiency of charge carrier and exciton transport within the organic photovoltaic (OPV) active layer to improve the high performance of organic solar cells.

14 SOLAR ENERGY↗

Production of lipid and carbohydrate from microalgae without compromising biomass productivities: Role of Ca and Mg

We report the cultivation of Chlorella sorokiniana str. SLA-04 in media containing trace amounts of Ca and Mg. The differences in productivities of biomass, lipids and carbohydrates were assessed relative to cultures grown in standard media (BG-11) that contain approximately 8 × higher concentration of Ca and 30 × higher concentration of Mg. Culture performance in N-limited standard media was also investigated. In addition to growth and accumulation of storage products (lipid and carbohydrate), we measured the utilization of N, Ca and Mg and monitored changes in cell size and photosynthetic activity. Our results showed that limitation of Ca or Mg did not inhibit cell replication and culture growth. On the contrary, Ca-limited (Ca L ) cultures had ~30% higher biomass productivity relative to the control with excessive nutrients possibly due to improvement in cell wall flexibility and cell division. We also observed that Ca L and Mg-limited (Mg L ) cultures had nearly 3-fold higher lipid concentration (measured as fatty acid methyl ester) and 50% higher carbohydrate concentration than the nutrient excess control cultures. Simultaneous culture growth and lipid accumulation in Ca L and Mg L cultures suggest that de novo synthesis was the primary mechanism for lipid accumulation in Ca/Mg-limited media. Overall, our study demonstrates that micronutrient optimization, in addition to optimization of macronutrients, could significantly improve microalgal biorefinery yields.

09 BIOMASS FUELS↗

Gas expanded polymer process to anneal nanoparticle dispersion in thin films

A spin-coating solution comprising poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) nanoparticles used to create organic photovoltaic (OPV) active layers have been shown to adopt a non-uniform concentration profile across the thin film dimension. This inhomogeneous distribution can reduce the efficiency of the device. For our new process, gas expanded polymer (GXP) annealing, is applied to P3HT/PCBM thin film blends, enabling the distribution of the PCBM nanoparticles to be manipulated by varying the GXP processing conditions. Films of 50 nm thickness (nominally) created by spin casting a blend of P3HT mixed with PCBM were annealed by oscillatory GXP and GXP at constant pressure using high pressure CO 2 . An increase in P3HT crystallinity (detected by X-ray diffraction and UV-vis spectroscopy) along with a more uniform distribution of PCBM nanoparticles in the thickness dimension, as interpreted from neutron reflectivity measurements, were observed after oscillatory GXP annealing. In addition, static water contact angles suggest that the film/air interface is enriched in PCBM relative to the as-cast film. Finally, these results demonstrate that GXP annealing, which is commercially scalable, can be successfully used to create a uniform distribution of PCBM nanoparticles across the thickness dimension in a P3HT thin film.

36 MATERIALS SCIENCE↗

Hepatic lipid profiling of deer mice fed ethanol using {sup 1}H and {sup 31}P NMR spectroscopy: A dose-dependent subchronic study

Chronic alcohol abuse is a 2nd major cause of liver disease resulting in significant morbidity and mortality. Alcoholic liver disease (ALD) is characterized by a wide spectrum of pathologies starting from fat accumulation (steatosis) in early reversible stage to inflammation with or without fibrosis and cirrhosis in later irreversible stages. Previously, we reported significant steatosis in the livers of hepatic alcohol dehydrogenase (ADH)-deficient (ADH{sup −}) vs. hepatic ADH-normal (ADH{sup +}) deer mice fed 4% ethanol daily for 2 months [Bhopale et al., 2006, Alcohol 39, 179–188]. However, ADH{sup −} deer mice fed 4% ethanol also showed a significant mortality. Therefore, a dose-dependent study was conducted to understand the mechanism and identify lipid(s) involved in the development of ethanol-induced fatty liver. ADH{sup −} and ADH{sup +} deer mice fed 1, 2 or 3.5% ethanol daily for 2 months and fatty infiltration in the livers were evaluated by histology and by measuring dry weights of extracted lipids. Lipid metabolomic changes in extracted lipids were determined by proton ({sup 1}H) and {sup 31}phosphorus ({sup 31}P) nuclear magnetic resonance (NMR) spectroscopy. The NMR data was analyzed by hierarchical clustering (HC) and principle component analysis (PCA) for pattern recognition. Extensive vacuolization by histology and significantly increased dry weights of total lipids found only in the livers of ADH{sup −} deer mice fed 3.5% ethanol vs. pair-fed controls suggest a dose-dependent formation of fatty liver in ADH{sup −} deer mouse model. Analysis of NMR data of ADH{sup −} deer mice fed 3.5% ethanol vs. pair-fed controls shows increases for total cholesterol, esterified cholesterol, fatty acid methyl esters (FAMEs), triacylglycerides and unsaturation, and decreases for free cholesterol, phospholipids and allylic and diallylic protons. Certain classes of neutral lipids (cholesterol esters, fatty acyl chain (-COCH{sub 2}-) and FAMEs) were also mildly increased in ADH{sup −} deer mice fed 1 or 2% ethanol. Only small increases were observed for allylic and diallylic protons, FAMEs and unsaturations in ADH{sup +} deer mice fed 3.5% ethanol vs. pair-fed controls. PCA of NMR data showed increased clustering by gradual separation of ethanol-fed ADH{sup −} deer mice groups from their respective pair-fed control groups and corresponding ethanol-fed ADH{sup +} deer mice groups. Our data indicate that dose of ethanol and hepatic ADH deficiency are two key factors involved in initiation and progression of alcoholic fatty liver disease. Further studies on characterization of individual lipid entities and associated metabolic pathways altered in our deer mouse model after different durations of ethanol feeding could be important to delineate mechanism(s) and identify potential biomarker candidate(s) of early stage ALD. -- Highlights: ► Dose-dependent ethanol-induced fatty liver was studied in deer mouse model. ► A NMR-based lipidomic approach with histology and dry lipid weights was used. ► We used principal component analysis (PCA) to analyze the NMR lipidomic data. ► Dose-dependent clustering patterns by PCA were compared among the groups.

60 APPLIED LIFE SCIENCES↗

The estrogen-dependent baroreflex dysfunction caused by nicotine in female rats is mediated via NOS/HO inhibition: Role of sGC/PI3K/MAPK{sub ERK}

We have previously reported that estrogen (E2) exacerbates the depressant effect of chronic nicotine on arterial baroreceptor activity in female rats. Here, we tested the hypothesis that this nicotine effect is modulated by nitric oxide synthase (NOS) and/or heme oxygenase (HO) and their downstream soluble guanylate cyclase (sGC)/phosphatidylinositol 3-kinase (PI3K)/mitogen-activated protein kinases (MAPKs) signaling. We investigated the effects of (i) inhibition or facilitation of NOS or HO on the interaction of nicotine (2 mg/kg/day i.p., 2 weeks) with reflex bradycardic responses to phenylephrine in ovariectomized (OVX) rats treated with E2 or vehicle, and (ii) central pharmacologic inhibition of sGC, PI3K, or MAPKs on the interaction. The data showed that the attenuation by nicotine of reflex bradycardia in OVXE2 rats was abolished after treatment with hemin (HO inducer) or L-arginine (NOS substrate). The hemin or L-arginine effect disappeared after inhibition of NOS (Nω-Nitro-L-arginine methyl ester hydrochloride, L-NAME) and HO (zinc protoporphyrin IX, ZnPP), respectively, denoting the interaction between the two enzymatic pathways. E2-receptor blockade (ICI 182,780) reduced baroreflexes in OVXE2 rats but had no effect on baroreflex improvement induced by hemin or L-arginine. Moreover, baroreflex enhancement by hemin was eliminated following intracisternal (i.c.) administration of wortmannin, ODQ, or PD98059 (inhibitors of PI3K, sGC, and extracellular signal-regulated kinases, MAPK{sub ERK}, respectively). In contrast, the hemin effect was preserved after inhibition of MAPK{sub p38} (SB203580) or MAPK{sub JNK} (SP600125). Overall, NOS/HO interruption underlies baroreflex dysfunction caused by nicotine in female rats and the facilitation of NOS/HO-coupled sGC/PI3K/MAPK{sub ERK} signaling might rectify the nicotine effect. - Highlights: • Hemin or L-arginine blunts baroreflex dysfunction caused by nicotine in OVXE2 rats. • NO/CO crosstalk mediates favorable baroreflex effect of hemin or L-arginine. • Central sGC/PI3K/MAPK{sub ERK} is required for hemin facilitation of baroreflexes. • The favorable baroreflex action of hemin is independent of estrogen receptors.

60 APPLIED LIFE SCIENCES↗

Mixing Behavior in Small Molecule: Fullerene Organic Photovoltaics [On the Mixing Behavior in Small Molecule: Fullerene Organic Photovoltaics]

Here, we report a novel method to determine the amount of pure, aggregated phase of donor and acceptor in organic photovoltaic (OPV) bulk heterojunctions. By determination of the diffraction intensity per unit volume for both donor and acceptor, the volume content of pure, aggregated donor and acceptor in the blend can be determined. We find that for the small molecule X2:[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) system, in contrast to most polymer systems, all the PCBM is aggregated, indicating there is negligible miscibility of PCBM with X2. This provides an explanation why the performance of OPV devices of X2:PCBM are high over a large range of PCBM concentrations. This is in contrast to many other OPV blends, where PCBM forms a mixed phase with the donor and does not provide sufficient transport for electrons when the PCBM concentration is low. This study demonstrates that a mixed phase is not necessarily a requirement for good OPV device performance.

14 SOLAR ENERGY↗

Engineering Two-Phase and Three-Phase Microstructures from Water-Based Dispersions of Nanoparticles for Eco-Friendly Polymer Solar Cell Applications

Nanoparticle organic photovoltaics, a subfield of organic photovoltaics (OPV), has attracted increasing interest in recent years due to the eco-friendly fabrication of solar modules afforded by colloidal ink technology. Importantly, using this approach it is now possible to engineer the microstructure of the light absorbing/charge generating layer of organic photovoltaics; decoupling film morphology from film deposition. In this study, single-component nanoparticles of poly(3-hexylthiophene) (P3HT) and phenyl-C 61 butyric acid methyl ester (PC 61 BM) were synthesized and used to generate a two-phase microstructure with control over domain size prior to film deposition. Scanning transmission X-ray microscopy (STXM) and electron microscopy were used to characterize the thin film morphology. Uniquely, the measured microstructure was a direct input for a nanoscopic kinetic Monte Carlo (KMC) model allowing us to assess exciton transport properties that are experimentally inaccessible in these single-component particles. Photoluminescence, UV-vis spectroscopy measurements, and KMC results of the nanoparticle thin films enabled the calculation of an experimental exciton dissociation efficiency (η ED ) of 37% for the two-phase microstructure. The glass transition temperature (T g ) of the materials was characterized with dynamic mechanical thermal analysis (DMTA) and thermal annealing led to an increase in ηED to 64% due to an increase in donor-acceptor interfaces in the thin film from both sintering of neighboring opposite-type particles in addition to the generation of a third mixed phase from diffusion of PC 61 BM into amorphous P3HT domains. Finally, this study demonstrates the higher level of control over donor-acceptor film morphology enabled by customizing nanoparticulate colloidal inks, where the optimal three-phase film morphology for an OPV photoactive layer can be designed and engineered.

36 MATERIALS SCIENCE↗