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Phenolic benzotriazoles are ultraviolet-light absorbers used in a variety of industrial and consumer applications. We investigated the toxicokinetic behaviour of 9 compounds, covering unsubstituted, monosubstituted, disubstituted, and trisubstituted compounds, following a single gavage (30 and 300 mg/kg) and intravenous (IV) (2.25 mg/kg) administration in male rats.Following IV administration, no distinct pattern in plasma elimination was observed for the compounds with half-lives ranging from 15.4–84.8 h. Systemic exposure parameters, maximum concentration (Cmax) and area under the concentration time curve (AUC), generally increased with the degree of substitution.Following gavage administration, Cmax and AUC of unsubstituted compound were lower compared to the substituted compounds. Cmax and AUC increased ≤7-fold with a 10-fold increase in the dose except for the AUC of the unsubstituted compound where the increase was 30-fold. Plasma elimination half-lives for the class ranged from 1.57 to 192 h with the exception of 30 mg/kg drometrizole.Oral bioavailability was low with ∼ 6% estimated for unsubstituted compound and 12.8–23% for others at 30 mg/kg dose. Bioavailability was lower following administration of the higher dose.Taken collectively, these data point to low oral absorption of phenolic benzotriazoles. The absorption decreased with increasing dose. Substituted compounds may be less metabolized compared to the unsubstituted. Phenolic benzotriazoles are ultraviolet-light absorbers used in a variety of industrial and consumer applications. We investigated the toxicokinetic behaviour of 9 compounds, covering unsubstituted, monosubstituted, disubstituted, and trisubstituted compounds, following a single gavage (30 and 300 mg/kg) and intravenous (IV) (2.25 mg/kg) administration in male rats. Following IV administration, no distinct pattern in plasma elimination was observed for the compounds with half-lives ranging from 15.4–84.8 h. Systemic exposure parameters, maximum concentration (Cmax) and area under the concentration time curve (AUC), generally increased with the degree of substitution. Following gavage administration, Cmax and AUC of unsubstituted compound were lower compared to the substituted compounds. Cmax and AUC increased ≤7-fold with a 10-fold increase in the dose except for the AUC of the unsubstituted compound where the increase was 30-fold. Plasma elimination half-lives for the class ranged from 1.57 to 192 h with the exception of 30 mg/kg drometrizole. Oral bioavailability was low with ∼ 6% estimated for unsubstituted compound and 12.8–23% for others at 30 mg/kg dose. Bioavailability was lower following administration of the higher dose. Taken collectively, these data point to low oral absorption of phenolic benzotriazoles. The absorption decreased with increasing dose. Substituted compounds may be less metabolized compared to the unsubstituted.

Highlights • The kinetics of N-butylbenzenesulfonamide (NBBS) was investigated in rodents. • NBBS was rapidly absorbed following gavage exposure in rodents. • It was rapidly eliminated with a half-life ≤3.5 h. • Bioavailability following gavage administration was high. • Systemic exposure was higher following gavage exposure than following via feed., N-Butylbenzenesulfonamide (NBBS) is a widely used plasticizer and hence there is potential for human exposure via oral routes. This work investigates the toxicokinetic behavior of NBBS in rodents following a single gavage (20, 60, and 200 mg/kg body weight) or multi-day feed administration (500, 1000, and 2000 ppm). In male and female rats following gavage administration, maximum plasma NBBS concentration, Cmax, was reached at ≤0.539 h. Cmax increased proportionally to the dose. Area under the curve (AUC) increased more than proportionally to the dose and was 4- to 5-fold higher in females than in males. In mice, plasma Cmax was reached at ≤0.136 h and increased proportionally to the dose in female mice and more than proportionally to the dose in males. AUC increased more than proportionally to the dose with no apparent sex difference. Elimination of NBBS in plasma was faster in mice (half-life (h); mice ≤0.432, rat ≤3.55). Oral bioavailability was higher in female rats (≥60%) than males (23-52%) with apparent saturation of clearance at ∼200 mg/kg body weight in females. In mice, bioavailability (5-14%) was lower with no apparent sex difference. NBBS was detected in brains of rats and mice but with low brain:plasma ratios (rats, ≤5; mice, ≤1) suggesting low potential to cross the blood brain barrier. Systemic exposure in male rats and mice following a single gavage administration was ≥48-fold higher than multi-day feed exposure. These data demonstrate potential species, sex, dose- and route-related difference in toxicokinetics of NBBS in rodents.

With the addition of reference spectra and 1H 31P cross-polarisation kinetics we have increased the analysis available by 31P NMR of the cheese ageing process. A previous study demonstrated that solid-state 31P NMR can be used to monitor the state of phosphorus in ageing cheeses. It is possible to differentiate between the mobile and immobile phosphorus species present in the cheese casein micelles. In this work, proton to phosphorus cross polarisation (CP) kinetic experiments (1H 31P CP-MAS) (where MAS = magic angle spinning) enable the observation of the state of the colloidal calcium phosphate (CCP) and phosphoserine (PSer) separately in the casein micelles. Also, 1H 31P CP-MAS spectra can be used to indirectly monitor the levels of micellar calcium. From the data gathered, we were able to conclude these points about the ageing process of Mozzarella cheese; in the first 20 days the cheese texture is dependent on the dynamics of free water and immobile calcium and phosphate, the CCP phosphate is mobilised at an exponential rate with the majority mobilised within the first 20 days, the driving force for CCP mobilisation is possibly the migration of water from the cheese serum into the casein proteins and CCP phosphorus is preferentially mobilised while immobile phosphoserine levels remains relatively unchanged during the early (40 days) of Mozzarella cheese ageing.

Metal oxide semiconductors, such as amorphous indium gallium zinc oxide (a-IGZO), have made impressive strides as alternatives to amorphous silicon for electronics applications. However, to achieve the full potential of these semiconductors, compatible unconventional gate dielectric materials must also be developed. To this end, solution-processable self-assembled nanodielectrics (SANDs) composed of structurally well-defined and durable nanoscopic alternating organic (e.g., stilbazolium) and inorganic oxide (e.g., ZrO

In this study, novel spore pouches were developed using mashed potato as a food model inoculated with either Geobacillus stearothermophilus or Clostridium sporogenes spores. These spore pouches were used to evaluate the sterilization efficiency of Coaxially induced microwave pasteurization and sterilization (CiMPAS) as a case study. CiMPAS technology combines microwave energy (915 MHz) along with hot water immersion to sterilize food in polymeric packages. The spore pouches were placed at pre-determined specific locations, especially cold spots in each food tray before being processed using two regimes (R-121 and R-65), which consisted of 121 &deg, C and 65 &deg, C at 12 and 22 kW, respectively, followed by recovery and enumeration of the surviving spores. To identify cold spots or the location for inoculation, mashed potato was spiked with Maillard precursors and processed through CiMPAS, followed by measurement of lightness values (*L-values). Inactivation equivalent to of 1&ndash, 2 Log CFU/g and &gt, 6 Log CFU/g for Geobacillus stearothermophilus and Clostridium sporogenes spores, respectively was obtained on the cold spots using R-121, which comprised of a total processing time of 64.2 min. Whereas, inactivation of &lt, 1 and 2&ndash, 3 Log CFU/g for G. stearothermophilus and C. sporogenes spores, respectively on the cold spots was obtained using R-65 (total processing time of 68.3 min), whereas inactivation of 1&ndash, 3 Log CFU/g of C. sporogenes spores was obtained on the sides of the tray. The results were reproducible across three processing replicates for each regime and inactivation at the specific locations were clearly distinguishable. The study indicated a strong potential to use spore pouches as a tool for validation studies of microwave-induced sterilization.

Mozzarella cheese undergoes significant structural rearrangement during maturation. This evolution in structure is critical to the product’s functional performance. Understanding the driving forces responsible for these changes is of significant importance for manufacturers as it allows them to tailor their product and processes to optimise functionality. This investigation took a hierarchical approach to examine structural change and component mobility that occurs following manufacture. This brings together microscopy techniques with both 1 H and 31 P nuclear magnetic resonance. This enabled the observed structural evolution to be coupled with molecular mobility with regards to both water and phosphorous. Two primary drivers for change were proposed from which the other processes cascaded: changing strength in hydrophobic interactions and proteolytic breakdown. Initially the development of the cheese structure was driven primarily by a relaxation in protein matrix (caused by weakening hydrophobic interactions), resulting in the moisture equilibration processes. Further structural changes occurred as a result of the proteolytic breakdown of the casein and a possible relaxation in the protein structure. These proteolytic mechanisms dominated maturation behaviour after the moisture equilibration processes were substantially completed (typically >20 days).

Immediately following manufacture, Mozzarella undergoes significant structural rearrangement. During this maturation process, free water occupying the interstitial area around the fat channels is absorbed into the protein matrix. Magnetic resonance techniques allow the evaluation of molecular mobility within the porous cheese matrix. A 3 week maturation trial was conducted in which the relaxation and diffusion properties of water and fat were assessed at room and elevated temperatures. Relaxation measurements at 20 °C highlighted the progressive change in the mobility of water as it became more associated with the casein gel matrix over the trial period. Heating was found to cause an increase in molecular mobility as the association between the casein and water lessened at elevated temperatures. This work illustrated that the diffusion and relaxation properties of water within Mozzarella on heating changed over a three week maturation period. The data also indicates that the diffusion of water at low temperatures was dominated by free water, while the diffusion at elevated temperatures was likely dictated by the degree of connectivity within the protein matrix.

We report the synthesis and characterization of new alkyl-substituted 1,4-di(thiophen-2-yl)buta-1,3-diyne (R-DTB) donor building blocks, based on the −C≡C–C≡C– conjugative pathway, and their incorporation with thienyl-diketopyrrolopyrrole (R′-TDPP) acceptor units into π-conjugated PTDPP-DTB polymers (P1–P4). The solubility of the new polymers strongly depends on the DTB and DPP solubilizing (R and R′, respectively) substituents. Thus, solution processable and high molecular weight PDPP-DTB polymers are achieved for P3 (R = n-C12H25, R′ = 2-butyloctyl) and P4 (R = 2-ethylhexyl, R′ = 2-butyloctyl). Systematic studies of P3 and P4 physicochemical properties are carried using optical spectroscopy, cyclic voltammetry, and thermal analysis, revealing characteristic features of the dialkynyl motif. For the first time, optoelectronic devices (OFETs, OPVs) are fabricated with 1,3-butadiyne containing organic semiconductors. OFET hole mobilities and record OPV power conversion efficiencies for acetylenic organic ma...

Improved understanding of fundamental structure–property relationships, particularly the effects of molecular shape and intermolecular packing on film morphology and active layer charge transport characteristics, enables more rational synthesis of new p-type small molecules. Here we investigate a series of small molecules consisting of an acene-based electron-rich core flanked by one or two electron-deficient diketopyrrolopyrrole (DPP) moieties. Through minor changes in the molecule structures, measurable variations in the crystal structure and sizable differences in macroscopic properties are achieved. The molecular symmetry as well as the conformation of the side chains affects the unit cell packing density and strength of the intermolecular electronic coupling in single crystals of all molecules in this series. The addition of a second DPP unit to the benzodithiophene (BDT) core increases molecular planarity leading to decreased reorganization energy, strong cofacial coupling, and moderate hole mobility (2.7 × 10−4 cm2 V−1 s−1). Increasing the length of the acene core from benzodithiophene to naphthodithiophene (NDT) results in a further reduction in reorganization energy and formation of smaller crystalline domains (∼11 nm) when mixed with PCBM. Decreasing the aspect ratio of the core using a “zig-zag” naphthodithiophene (zNDT) isomer results in the highest hole mobility of 1.3 × 10−3 cm2 V−1 s−1 due in part to tight lamellar (d = 13.5 A) and π–π stacking (d = 3.9 A). The hole mobility is directly correlated with the short-circuit current (11.7 mA cm−2) and solar cell efficiency (4.4%) of the highest performing zNDT:PCBM device. For each of these small molecules the calculated π-coupling constant is correlated with the hole mobility as a function of crystal structure and orientation indicating the importance of designing molecules that create extended crystalline networks with maximal π-orbital overlap.

The metabolic series approach has successfully linked internal dosimetries of metabolically related compounds reducing cost and time for chemical risk assessments. Here, we developed a physiologically based pharmacokinetic (PBPK) model in rats and humans for the propyl metabolic series including propyl acetate, 1-propanol, propionaldehyde, and propionic acid. Manufacturers use these compounds as organic solvents and intermediates during chemical synthesis. Public exposures can occur through using consumer products containing propyl compounds like cosmetics, aerosol sprays, or foods, and occupational exposures can occur at manufacturing facilities. To develop the PBPK model, we measured in vitro metabolism of propyl acetate in blood and liver S9 fractions. We measured concentrations of propyl compounds in blood following intravenous (iv) infusion of 13C-propanol or 13C-propionic acid and closed chamber inhalation exposures to propyl acetate or propanol in rats. Using these studies and other published data, we modified an existing PBPK model for the butyl metabolic series to simulate time course concentrations of propyl compounds in rats and humans. Consistent with measured in vitro and in vivo data, the optimized propyl series model predicts rapid clearance of propyl acetate, higher concentrations of propanol in blood from propyl acetate inhalation compared to propanol inhalation in rats but not in humans, and low concentrations of propionic acid in blood from exposures to propyl acetate or propanol. Regulators can use this model as a tool for propyl compound risk assessment by linking internal dosimetries under various exposure scenarios.

High-throughput patterning and enhanced mechanical stability are key to enabling large-area applications of metal nanowire mesh transparent electrodes. In this work, hybrid transparent conductors based on silver nanowires embedded in an indium zinc oxide matrix were prepared by high-speed gravure-printing (1.0 m s−1) from a single, stable liquid precursor. These gravure-printed films demonstrate excellent conductivity (9.3 Ω □−1) and transparency (T550nm ∼ 91%), as well as robust mechanical properties. The encapsulating indium zinc oxide matrix dramatically improves adhesion, surface roughness (Rq < 5 nm), film uniformity, and thermal stability (up to 350 °C) of the embedded silver nanowires. These properties of the hybrid films make them a suitable electrode material for a variety of printed electronic devices, such as flexible OLEDs and solar cells.

The isolated rat heart (Langendorff) assay combined with NMR spectroscopy and histology were used to elucidate functional, metabolic, and histological signs of cardiotoxicity resulting from acute exposure to clinically relevant concentrations of doxorubicin and its metabolite dox-ol. Doxorubicin blood concentrations and pharmacokinetic parameters were assessed following a clinically relevant dose of 2 mg/kg in order to select concentrations for isolated heart perfusions. Isolated rat hearts were exposed to 1 or 10 μM of doxorubicin or 0.3 μM dox-ol for at least 60 min using the Langendorff perfusion method. Effects on heart function were monitored using ECGs, left ventricular contraction parameters, and microscopic histology. Cardiac energetics (PCr, ATP, and Pi) were evaluated before, during, and after exposure to doxorubicin/dox-ol in perfused hearts using NMR spectroscopy. Cardiac effects were evident following clinically relevant concentrations of doxorubicin and dox-ol in isolated rat hearts demonstrated by altered heart function, energetic reserve, and microscopic lesions. A cardiac stress test utilizing isoproterenol resulted in enhanced functional response and reductions in PCr in doxorubicin versus vehicle treated hearts indicating possible alterations in the isoproterenol mediated pathway. Dox-ol treated hearts were similar to control with regard to function, but exhibited histologic findings. The use of combined Langendorff/NMR/histology methodologies allowed for comparison of multiple indices of cardiac function at one time in which cardiac effects were evident in multiple parameters. Short abstract The isolated rat heart assay combined with NMR spectroscopy and histology was used to elucidate functional, metabolic, and histological signs of cardiotoxicity resulting from acute exposure to clinically relevant concentrations of doxorubicin and its metabolite dox-ol. Heart function was altered and microscopic signs of toxicity were evident with dox and dox-ol exposures. The use of combined Langendorff/NMR/histology assays allowed for comparison of multiple indices of cardiac function at one time in which cardiac effects were evident in multiple parameters.

Recent findings suggest that secondary organic aerosols (SOA) formed from aqueous-phase reactions of some organic species, including phenols, contribute significantly to particulate mass in the atmosphere. In this study, we employ a Fourier transform infrared (FT-IR) spectroscopic technique to identify and quantify the functional group makeup of phenolic SOA. Solutions containing an oxidant (hydroxyl radical or 3,4-dimethoxybenzaldehyde) and either one phenol (phenol, guaiacol, or syringol) or a mixture of phenols mimicking softwood or hardwood emissions were illuminated to make SOA, atomized, and collected on a filter. We produced laboratory standards of relevant organic compounds in order to develop calibrations for four functional groups: carbonyls (CO), saturated C–H, unsaturated C–H and O–H. We analyzed the SOA samples with transmission FT-IR to identify and determine the amounts of the four functional groups. The carbonyl functional group accounts for 3–12% of the SOA sample mass in single phenolic SOA samples and 9–14% of the SOA sample mass in mixture samples. No carbonyl functional groups are present in the initial reactants. Varying amounts of each of the other functional groups are observed. Comparing carbonyls measured by FT-IR (which could include aldehydes, ketones, esters, and carboxylic acids) with eight small carboxylic acids measured by ion chromatography indicates that the acids only account for an average of 20% of the total carbonyl reported by FT-IR.

In oxide semiconductors, such as those based on indium zinc oxide (IXZO), a strong oxygen binding metal ion ("oxygen getter"), X, functions to control O vacancies and enhance lattice formation, hence tune carrier concentration and transport properties. Here we systematically study, in the IXZO series, the role of X = Ga(3+) versus the progression X = Sc(3+) → Y(3+) → La(3+), having similar chemical characteristics but increasing ionic radii. IXZO films are prepared from solution over broad composition ranges for the first time via low-temperature combustion synthesis. The films are characterized via thermal analysis of the precursor solutions, grazing incidence angle X-ray diffraction (GIAXRD), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and scanning transmission electron microscopy (STEM) with high angle annular dark field (HAADF) imaging. Excellent thin-film transistor (TFT) performance is achieved for all X, with optimal compositions after 300 °C processing exhibiting electron mobilities of 5.4, 2.6, 2.4, and 1.8 cm(2) V(-1) s(-1) for Ga(3+), Sc(3+), Y(3+), and La(3+), respectively, and with I(on)/I(off) = 10(7)-10(8). Analysis of the IXZO TFT positive bias stress response shows X = Ga(3+) to be superior with mobilities (μ) retaining95% of the prestress values and threshold voltage shifts (ΔV(T)) of1.6 V, versus85% μ retention and ΔV(T) ≈ 20 V for the other trivalent ions. Detailed microstructural analysis indicates that Ga(3+) most effectively promotes oxide lattice formation. We conclude that the metal oxide lattice formation enthalpy (ΔH(L)) and metal ionic radius are the best predictors of IXZO oxygen getter efficacy.

Reduction in the operating voltage of organic field-effect transistors (OFETs) is sought for their successful implementation into future portable and low-power electronic applications. Here we demonstrate OFETs with operation below 2 V enabled by the use of self-assembled monolayer (SAM) gate dielectrics with high geometrical capacitances. A high surface energy monolayer is chosen to allow processing of small molecule semiconductors from solution. Impedance spectroscopy measurements of metal-insulator-semiconductor devices suggest the geometrical capacitance of the alumina-SAM dielectric can reach ~1 P F/cm 2 when accumulating charge at the semiconductor-insulator interface. Atomic force microscopy images reveal that the glass substrates and the SAM-functionalized aluminum gate electrode display significant roughness. Despite this, mobilities of 0.02 cm 2 /Vs are demonstrated. These results represent an important step towards low-power solution processable electronics. Keywords: organic semiconductor, organic field-effect transistor, organic thin-film transistor, self-assembled monolayer, low-voltage, metal-insulator-semiconductor, atomic force microscopy

Blending of small-molecule organic semiconductors (OSCs) with amorphous polymers is known to yield high performance organic thin film transistors (OTFTs). Vertical stratification of the OSC and polymer binder into well-defined layers is crucial in such systems and their vertical order determines whether the coating is compatible with a top and/or a bottom gate OTFT configuration. Here, we investigate the formation of blends prepared via spin-coating in conditions which yield bilayer and trilayer stratifications. We use a combination of in situ experimental and computational tools to study the competing effects of formulation thermodynamics and process kinetics in mediating the final vertical stratification. It is shown that trilayer stratification (OSC/polymer/OSC) is the thermodynamically favored configuration and that formation of the buried OSC layer can be kinetically inhibited in certain conditions of spin-coating, resulting in a bilayer stack instead. The analysis reveals here that preferential loss of the OSC, combined with early aggregation of the polymer phase due to rapid drying, inhibit the formation of the buried OSC layer. The fluid dynamics and drying kinetics are then moderated during spin-coating to promote trilayer stratification with a high quality buried OSC layer which yields unusually high mobility >2 cm2 V−1 s−1 in the bottom-gate top-contact configuration.

We report the synthesis of two novel cyclopenta[2,1-b:3,4-b′]dithiophen-4-one monomers containing solubilizing alkyl groups in the peripheral 3,5 positions. Polymerization with (E)-1,2-bis(tributylstannyl)-ethylene under Stille coupling conditions afforded the first reported examples of soluble poly(cyclopentadithiophen-4-one)vinylenes. The resulting polymers absorb in the near-infrared, with a maximum thin film absorbance around 815 nm and have optical band gaps of 1.25 eV. The polymers exhibit promising ambipolar field effect transistor performance, with average saturated mobilities of 0.5 cm2 V–1 s–1 for holes and 0.12 cm2 V–1 s–1 for electrons. The ambipolar transistors operate in both the hole and electron transport regimes in ambient air. Prolonged exposure to ambient atmosphere leads to a gradual loss of the electron transport behavior, with little change observed in the p-type mobility.

Using phase-separated organic semiconducting blends containing a small molecule, as the hole transporting material, and a conjugated amorphous polymer, as the binder material, we demonstrate solution-processed organic thin-film transistors with superior performance characteristics that include; hole mobility >5 cm(2) /Vs, current on/off ratio ≥10(6) and narrow transistor parameter spread. These exceptional characteristics are attributed to the electronic properties of the binder polymer and the advantageous nanomorphology of the blend film.

We report the synthesis of a novel class of low band gap copolymers based on anacenaphtho[1,2-b]quinoxaline core and oligothiophene derivatives acting as the acceptor and the donor moieties, respectively. The optical properties of the copolymers were characterized by ultraviolet-visible spectroscopy while the electrochemical properties were determined by cyclic voltammetry. The band gap of these polymers was found to be in the range 1.8-2.0 eV as calculated from the optical absorption band edge. X-ray diffraction measurements show weak pi-pi stacking interactions between the polymer chains. The hole mobility of the copolymers was evaluated using field-effect transistor measurements yielding values in the range 10(-5)-10(-3) cm(2)/Vs.

We present a new soluble pentacene derivative with ethyl substitutions in the 1,13,14,22 backbone positions to modulate the solubility and film forming properties of this material compared to triisopropylsilylethynyl (TIPS) pentacene. This permits reproducible production of molecularly highly ordered structures that feature average transistor mobilities in excess of 1 cm 2 V -1 s -1 depending on crystal orientation by careful selection of casting conditions. © 2012 The Royal Society of Chemistry.

Here we report a simple methodology for the synthesis of dithienosilole and dithienogermole monomers in which the necessary solubilizing long chain alkyl groups are incorporated into the peripheral 3,5-positions of the fused ring. We report four novel monomers in which methyl or butyl groups are attached to the bridging Si and Ge atom. Copolymers with bithiophene were synthesized by a Stille polymerization in high molecular weight. We report the optical, electrical, electrochemical and morphological properties of the resulting polymers. We find that the nature of the bridging heteroatom (Si or Ge) has only a minor influence on these properties, whereas the nature of the alkyl chain attached to the bridging atom is found to have a much larger effect.

The successful design and synthesis of two novel benzo[1,2-b:3,4-b′:5,6-d′]trithiophene-containing polymers is presented. The planar benzotrithiophene core induces strong aggregation effects in alternating co-polymers with both thiophene and thieno[3,2-b]thiophene. Co-monomer choice is found to play a crucial role in determining the backbone conformation, the interchain interactions, and the polymer solubility. Despite molecular disorder introduced by a branched solubilizing alkyl chain and a regiorandom polymerization of the asymmetric benzotrithiophene unit, these co-polymers exhibit hole mobilities as high as 0.24 cm2/(V s).

Interest in organic semiconductors is motivated by their promise to offer a viable route to fabricating low-cost electronic devices on arbitrary substrates, and by the versatility of their chemical structures and physical properties, accomplished by means of molecular engineering. [ 1–3 ] Molecular modifi cations can yield soluble semiconductors that allow reduced complexity device fabrication using methods such as spin-coating, ink-jet printing, roll-to-roll processing and spray-deposition. [ 4–7 ]

The functional properties of a food are determined by the composition and arrangement of the components (the microstructure). In general as the microstructure of a food changes, the dielectric properties of the food change as well. Cheese is an excellent example of a food system which undergoes significant structural rearrangement both during shelf life (maturation) and in applications involving heating. The purpose of this study was to see if dielectric spectroscopy could be used to assess the microstructure of cheese with a view to predicting its functionality. The first task was to create a model cheese system where the composition could be systematically varied and the resulting changes in dielectric properties measured. We were also interested in how the dielectric properties (and thus the arrangement of components) changed with temperature. We developed a model system and samples were prepared with varying levels of calcium. We then measured the dielectric properties over a frequency range of 200 MHz to 1.3 GHz and between the temperatures of 5 and 85 °C. The samples were also examined using a confocal laser scanning microscope as well being subjected to texture profile analysis. We found that the dielectric constant and dielectric loss factors decreased as frequency increased. The dielectric properties were also found to be temperature dependent. The texture of the system was influenced by the addition of calcium which influenced the emulsification. The results from this initial study support the concept of dielectric spectroscopy as a tool for studying the microstructure of cheese. This suggests that dielectric spectroscopy could aid in the development of a better understanding of changes occurring in food systems. The next stage of this study will investigate the changes to the dielectric properties during cheese maturation as well as examining aspects of component mobility within cheese.

Organic field-effect transistors (OFETs) based upon blends of small molecular semiconductor and polymers show promise for high performance organic electronics applications. Here the charge transport characteristics of high mobility p-channel organic transistors based on 2,8-difluoro-5,11-bis(triethylsilyiethynyl) anthradithiophene:poly(triarylamine) blend films are investigated. By simple alteration of the film processing conditions two distinct film microstructures can be obtained: one characterized by small spherulitic grains (SG) and one by large grains (LG). Charge transport measurements reveal thermally activated hole transport in both SG and LG film microstructures with two distinct temperature regimes. For temperatures >115 K, gate voltage dependent activation energies (E A ) in the range of 25―60 meV are derived. At temperatures

A study was conducted to demonstrate the fabrication of high-performance zinc oxide (ZnO) transistors and circuits using spray pyrolysis (SP) deposition technique in ambient atmosphere. The method was found to be compatible with large-area deposition and potentially addressed the issues of manufacturing cost and high operating voltages. High mobility n-channel thin-film transistors (TFTs) based on ZnO deposited at substrate temperatures in the range of 200-500 °C were realized to demonstrate the method. Semiconductor deposition was performed entirely in ambient atmosphere without the need for special precautions. It was demonstrated that the as-deposited ZnO films were of high quality and uniformity, while the SP was compatible with a number of solution-processible self-assembled monolayer (SAM) dielectrics. ZnO transistors operating at significantly low voltages were demonstrated by combining SP with soluble SAM dielectrics.

We report the first soluble poly(3-dodecyl tellurophenylenevinylene) and compare its properties to the analogous thiophene and selenophene containing polymers., We report the first soluble poly(3-dodecyl tellurophenylene-vinylene) polymer (P3TeV) by Stille copolymerization and compare its properties to the analogous thiophene and selenophene containing polymers. The optical band gap of the polymers is shown to systematically decrease as the size of the heteroatom is increased, mainly as a result of a stabilization of the LUMO energy, resulting in a small band gap of 1.4 eV for P3TeV. Field effect transistors measurements in variety of architectures demonstrate that the selenophene polymer exhibits the highest mobility, highlighting that increasing the size of the heteroatom is not always beneficial for charge transport.

Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants – the triplet excited state of an aromatic carbonyl (3C∗) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ∼ 2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures (C∗) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C∗ values is observed, varying from −20 µg m−3 for functionalized phenolic oligomers to > 10 µg m−3 for small open-ring species. The detection of abundant extremely low-volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere.

Solubilizing alkyl chains play a crucial role in the design of semiconducting polymers because they define the materials solubility and process-ability as well as both the crystallinity and solid-state microstructure. In this paper, we present a scarcely explored design approach by attaching the alkyl side chains on one side (cis-) or on both sides (trans-) of the conjugated backbone. We further investigate the effects of this structural modification on the solid-state properties of the polymers and on the charge-carrier mobilities in organic thin-film transistors.

Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C6H5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV–visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.

Mercury (Hg) is a major global pollutant arising from both natural and anthropogenic sources. Defining the factors that determine the relative affinities of different ligands for the mercuric ion, Hg2+, is critical to understanding its speciation, transformation, and bioaccumulation in the environment. Here, we used quantum chemistry to dissect the relative binding free energies for a series of inorganic anion complexes of Hg2+. The results show that, whereas in the gas phase the binding affinity of two identical anionic ligands (forming HgL2) increases with ligand (L–) hardness, in contrast, in the aqueous phase the affinity increases with ligand softness. This switch in affinity upon hydration is shown to result mostly from interactions with only a small number (e.g. one or two) of water molecules. The results yield a clear, robust periodic trend within the chalcogenide and halide groups and are in agreement with the well-known experimentally observed preference of Hg2+ for soft ligands. By comparing the Hg2+ binding of one with two anions, the gas phase preferences are found to arise from the enhancement of reactivity of the cationic complex (HgL+) with the hardness of L–. The approach establishes a theoretical basis for understanding Hg speciation in the biosphere.

The novel phosphotyrosine (pTyr) mimetic 4′-carboxymethyloxy-3′-phosphonophenylalanine (Cpp) has been designed and incorporated into a series of nonpeptide inhibitors of the SH2 domain of pp60 c-Src (Src) tyrosine kinase. A 2.2 A X-ray crystal structure of 1a bound to a mutant form of Lck SH2 domain provides insight regarding the structure–activity relationships and supports the design concept of this new pTyr mimetic.

We report here a bilayer metal oxide thin film transistor concept (bMO TFT) where the channel has the structure: dielectric/semiconducting indium oxide (In2O3) layer/semiconducting indium gallium oxide (IGO) layer. Both semiconducting layers are grown from solution via a low-temperature combustion process. The TFT mobilities of bottom-gate/top-contact bMO TFTs processed at T = 250 °C are ~5tmex larger (~2.6 cm(2)/(V s)) than those of single-layer IGO TFTs (~0.5 cm(2)/(V s)), reaching values comparable to single-layer combustion-processed In2O3 TFTs (~3.2 cm(2)/(V s)). More importantly, and unlike single-layer In2O3 TFTs, the threshold voltage of the bMO TFTs is ~0.0 V, and the current on/off ratio is significantly enhanced to ~1 × 10(8) (vs ~1 × 10(4) for In2O3). The microstructure and morphology of the In2O3/IGO bilayers are analyzed by X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy, revealing the polycrystalline nature of the In2O3 layer and the amorphous nature of the IGO layer. This work demonstrates that solution-processed metal oxides can be implemented in bilayer TFT architectures with significantly enhanced performance.

A benzotrithiophene polymer with a new thermally cleavable ketal substituent is reported. It is shown how this functional group can be used to facilitate solvent processing and, subsequently, how it can be removed by a thermal annealing process to generate a structurally ordered and crystalline thin film with significantly improved field-effect transistor properties.

Using existing experimental data taken over a period of roughly 12 years that documents the concentrations of dieldrin levels in the environment and fatty tissue of the fish, we construct a model of the total dieldrin concentration decline. Comparisons between the experimental data and speculative data can be made using calculus and elements of statistics in order to better understand the movement of dieldrin in the reservoir. Because of the potentially harmful exposure effects of dieldrin to humans as well as the environment, it is important to be able to predict when stability has been restored to the ecosystem.

Using impedance spectroscopy, we demonstrate that the low fill factor (FF) typically observed in small molecule solar cells is due to hindered carrier transport through the active layer and hindered charge transfer through the anode interfacial layer (IFL). By carefully tuning the active layer thickness and anode IFL in BDT(TDPP)2 solar cells, the FF is increased from 33 to 55% and the PCE from 1.9 to 3.8%. These results underscore the importance of simultaneously optimizing active layer thickness and IFL in small molecule solar cells.

One of the most inspiring and puzzling developments in the organic electronics community in the last few years has been the emergence of solution-processable semiconducting polymers that lack significant long-range order but outperform the best, high-mobility, ordered semiconducting polymers to date. Here we provide new insights into the charge-transport mechanism in semiconducting polymers and offer new molecular design guidelines by examining a state-of-the-art indacenodithiophene-benzothiadiazole copolymer having field-effect mobility of up to 3.6 cm(2) V(-1) s(-1) with a combination of diffraction and polarizing spectroscopic techniques. Our results reveal that its conjugated planes exhibit a common, comprehensive orientation in both the non-crystalline regions and the ordered crystallites, which is likely to originate from its superior backbone rigidity. We argue that charge transport in high-mobility semiconducting polymers is quasi one-dimensional, that is, predominantly occurring along the backbone, and requires only occasional intermolecular hopping through short π-stacking bridges.

Silaindacenodithiophene is copolymerized with benzo[c][1,2,5]thiadiazole (BT) and 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (DTBT), respectively their fluorinated counter parts 5,6-difluorobenzo[c][1,2,5]thiadiazole (2FBT) and 5,6-difluoro-4,7-di(thiophen-2-yl) benzo[c][1,2,5]thiadiazole (2FDTBT). The influence of the thienyl spacers and fluorine atoms on molecular packing and active layer morphology is investigated with regard to device performances. bulk heterojunction (BHJ) solar cells based on silaindacenodithiophene donor-acceptor polymers achieved PCE's of 4.5% and hole mobilities of as high as 0.28 cm2/(V s) are achieved in an organic field-effect transistor (OFET).

Use of a carefully designed small-molecule organic semiconductor based on an oxidized diketopyrrolopyrrole core enables the fabrication by solution processing of electron-transporting (n-channel) blend-based organic thin-film transistors with high electron mobility (0.5 cm(2)/Vs) and high operating stability even when the devices are exposed to ambient air for prolonged periods of time.

We describe a series of highly soluble diketo pyrrolo-pyrrole (DPP)-bithiophene copolymers exhibiting field effect hole mobilities up to 0.74 cm(2) V(-1) s(-1), with a common synthetic motif of bulky 2-octyldodecyl side groups on the conjugated backbone. Spectroscopy, diffraction, and microscopy measurements reveal a transition in molecular packing behavior from a preferentially edge-on orientation of the conjugated plane to a preferentially face-on orientation as the attachment density of the side chains increases. Thermal annealing generally reduces both the face-on population and the misoriented edge-on domains. The highest hole mobilities of this series were obtained from edge-on molecular packing and in-plane liquid-crystalline texture, but films with a bimodal orientation distribution and no discernible in-plane texture exhibited surprisingly comparable mobilities. The high hole mobility may therefore arise from the molecular packing feature common to the entire polymer series: backbones that are strictly oriented parallel to the substrate plane and coplanar with other backbones in the same layer.

New silaindacenodithiophene (SiIDT) semiconducting polymers were reported. Two repeat units were selected for copolymerization. Polymers P-1 and P-2 were both synthesized by Stille cross coupling, using microwave heating conditions. Polymerizations proceeded in good yield when the stannyl groups were located on the electron rich SiIDT, with sufficiently high molecular weights obtained. Both polymers show evidence of crystallinity when evaluated by differential scanning calorimetry (DSC). By replacing the BT unit (P-1) with DPP (P-2), a redshifted absorption spectrum with more defined vibronic structure is obtained. The deep HOMO level ensures that the P-1 is stable against electrochemical oxidization, and thus good device life times can be expected. Both as-spun and annealed P-2 FET devices show clear ambipolar characteristics. These polymers can exhibit either high solar cell efficiencies of greater than 4% PCE, or high ambipolar charge transport, with holes and electrons exhibiting mobilities of greater than 0.1 cm2/(V s)., SCOPUS: ar.j, info:eu-repo/semantics/published

High-performance, solution-processed transistors fabricated from semiconducting polymers containing indacenodithiohene repeat units are described. The bridging functions on the backbone contribute to suppressing large-scale crystallization in thin films. However, charge carrier mobilities of up to 1 cm(2)/(V s) for a benzothiadiazole copolymer were reported and, coupled with both ambient stability and long-wavelength absorption, make this family of polymers particularly attractive for application in next-generation organic optoelectronics.

An alternative approach for the development of high-performance unipolar and ambipolar thin-film transistors and integrated circuits based on hybrid heterostructures comprising a phase-separated solution processed p-type organic small-molecule:polymer semicondcutor blend and a spray-coated n-type ZnO semiconductor layer is demonstrated.

Water is widely assumed to be essential for life 1, although the exact molecular basis of this requirement is unclear 2-4. Water facilitates protein motions 5-9 and although enzyme activity has been demonstrated at low hydrations in organic solvents 10-13, such non-aqueous solvents may allow the necessary motions for catalysis. To examine enzyme function in the absence of solvation and bypass diffusional constraints we have tested the ability of an esterase to catalyse alcoholysis as an anhydrous powder, using a closed reaction system in which the substrates and products of the enzyme reaction are gaseous 14-15, and where the water content can be well defined 16. At hydrations equivalent to 3 (±2) molecules of water per molecule of enzyme, activity is observed that is several orders of magnitude greater than non-enzymatic catalysis. Neutron spectroscopy indicates that the fast (≤nanosecond) global anharmonic dynamics of the anhydrous functional enzyme are heavily suppressed. The results indicate that neither hydration water nor the solvent-activated fast anharmonic dynamics are required for enzyme function. An implication of these results is that one of the essential requirements of water for life may lie with its role as a diffusion medium rather than any of its more specific properties.

The nature of charge transport and local structure are investigated in amorphous indium oxide-based thin fi lms fabricated by spin-coating. The In–X–O series where X = Sc, Y, or La is investigated to understand the effects of varying both the X cation ionic radius (0.89–1.17 A) and the fi lm processing temperature (250–300 °C). Larger cations in particular are found to be very effective amorphosizers and enable the study of high mobility (up to 9.7 cm 2 V −1 s −1 ) amorphous oxide semiconductors without complex processing. Electron mobilities as a function of temperature and gate voltage are measured in thin-fi lm transistors, while X-ray absorption spectroscopy and ab initio molecular dynamics simulations are used to probe local atomic structure. It is found that trap-limited conduction and percolation-type conduction mechanisms convincingly model transport for low- and high-temperature processed fi lms, respectively. Increased cation size leads to increased broadening of the tail states (10–23 meV) and increased percolation barrier heights (24–55 meV) in the two cases. For the fi rst time in the amorphous In–X–O system, such effects can be explained by local structural changes in the fi lms, including decreased In–O and In–M (M = In, X) coordination numbers, increased bond length disorder, and changes in the MO x polyhedra interconnectivity.