Energy barriers at grain boundaries dominate charge carrier transport in an electron-conductive organic semiconductor.

Semiconducting organic films that are at the heart of light-emitting diodes, solar cells and transistors frequently contain a large number of morphological defects, most prominently at the interconnects between crystalline regions. These grain boundaries can dominate the overall (opto-)electronic properties of the entire device and their exact morphological and energetic nature is still under current debate. Here, we explore in detail the energetics at the grain boundaries of a novel electron conductive perylene diimide thin film. Via a combination of temperature dependent charge transport measurements and ab-initio simulations at atomistic resolution, we identify that energetic barriers at grain boundaries dominate charge transport in our system. This novel aspect of physics at the grain boundary is distinct from previously identified grain-boundary defects that had been explained by trapping of charges. We furthermore derive molecular design criteria to suppress such energetic barriers at grain boundaries in future, more efficient organic semiconductors.

High-Mobility, Ultrathin Organic Semiconducting Films Realized by Surface-Mediated Crystallization.

The functionality of common organic semiconductor materials is determined by their chemical structure and crystal modification. While the former can be fine-tuned via synthesis, a priori control over the crystal structure has remained elusive. We show that the surface tension is the main driver for the plate-like crystallization of a novel small organic molecule n-type semiconductor at the liquid-air interface. This interface provides an ideal environment for the growth of millimeter-sized semiconductor platelets that are only few nanometers thick and thus highly attractive for application in transistors. On the basis of the novel high-performance perylene diimide, we show in as-grown, only 3 nm thin crystals electron mobilities of above 4 cm2/(V s) and excellent bias stress stability. We suggest that the established systematics on solvent parameters can provide the basis of a general framework for a more deterministic crystallization of other small molecules.

Metallic carbon nanotubes with metal contacts: electronic structure and transport.

We study quasi-ballistic electron transport in metallic (6, 0) carbon nanotubes (CNTs) of variable length in contact with Al, Cu, Pd, Pt, Ag, and Au electrodes by using the non-equilibrium Green's function formalism in combination with either density functional theory or self-consistent extended Hückel theory. We find good agreement between both. Visualizing the local device density of states of the systems gives a descriptive link between electronic structure and transport properties. In comparison with bare finite and infinite tubes, we show that the electronic structure of short metallic CNTs is strongly modified by the presence of the metallic electrodes, which leads to pronounced size effects in the conductance. The mean conductances and linear response currents allow a ranking of the metals regarding their ability to form low-Ohmic contacts with the nanotube: Ag < or approximately equel to Au < Cu <

Ellipsometric study of the change in the porosity of silica xerogels after chemical modification of the surface with hexamethyldisilazane.

Variable angle spectroscopic ellipsometry (VASE) and ellipsometric porosimetry (EP) have been used to study the effect of treatment with hexamethyldisilazane (HMDS) on the porosity of silica xerogel films. Chemical modification of the surface with HMDS was found to reduce the porosity by approximately 15%. This reduction was connected with changes which occur in the silica network, with further condensation or the reaction between neighbouring trimethylsilyl (TMS) surface groups being possible causes.

The looming maladaptive style: anxiety, danger, and schematic processing.

The importance of cognitive styles as psychological antecedents of psychopathology has gained increasing acceptance over the past 2 decades. Although ample research has explored cognitive styles that confer vulnerability to depression, cognitive styles that confer vulnerability to anxiety have received considerably less attention. In the present investigation, we examined the looming maladaptive style (LMS) as a cognitive style that functions as a danger schema to produce specific vulnerability to anxiety, but not to depression. In 4 studies, we examined the psychometric properties of a revised measure of the LMS, its predictive utility, and its effects on threat-related schematic processing. Results provided evidence for the validity of the LMS and indicated that it predicts anxiety and schematic processing of threat over and above the effects of other cognitive appraisals of threat, even in individuals who are currently nonanxious.

Pediatric admissions by family physicians and pediatricians in a semirural environment: implications for residency training.

BACKGROUND: The 3-year family practice residency curriculum includes longitudinal care of children in the family health center and a 4-month experience dedicated to the care of children. This study was designed to compare the diseases of hospitalized children cared for by family physicians and pediatricians and to examine the use of pediatricians as consultants by family physicians. METHODS: The study included all patients younger than 18 years who were discharged by a family physician or a pediatrician from this semirural hospital during a 3-year period. The primary discharge diagnosis, physician, consultations, and transfer status were recorded. RESULTS: Family physicians cared for 37 percent of the 4169 pediatric patients discharged during the study. Infectious diseases and their complications were the most common conditions for patients who were discharged beyond the newborn period. The 15 most frequent discharge diagnoses were identical for family physicians and pediatricians, accounting for about 86 percent of all discharge diagnoses. Pediatricians, however, cared for 86 percent of the newborns with major complications and were responsible for 80 percent of the infants and children who were transferred. The overall inpatient consultation rate of pediatricians by family physicians was 8 percent, whereas the consultation rate for nonneonatal-related discharges was 20 percent. CONCLUSION: In this semirural environment, family physicians and pediatricians care for a very similar mix of hospitalized pediatric patients. Pediatricians, however, care for a greater proportion of newborns with major complications.

Resistance to blood flow in microvessels in vivo.

Resistance to blood flow through peripheral vascular beds strongly influences cardiovascular function and transport to tissue. For a given vascular architecture, flow resistance is determined by the rheological behavior of blood flowing through microvessels. A new approach for calculating the contribution of blood rheology to microvascular flow resistance is presented. Morphology (diameter and length), flow velocity, hematocrit, and topological position were determined for all vessel segments (up to 913) of terminal microcirculatory networks in the rat mesentery by intravital microscopy. Flow velocity and hematocrit were also predicted from mathematical flow simulations, in which the assumed dependence of flow resistance on diameter, hematocrit, and shear rate was optimized to minimize the deviation between measured and predicted values. For microvessels with diameters below approximately 40 microns, the resulting flow resistances are markedly higher and show a stronger dependence on hematocrit than previously estimated from measurements of blood flow in narrow glass tubes. For example, flow resistance in 10-microns microvessels at normal hematocrit is found to exceed that of a corresponding glass tube by a factor of approximately 4. In separate experiments, flow resistance of microvascular networks was estimated from direct measurements of total pressure drop and volume flow, at systemic hematocrits intentionally varied from 0.08 to 0.68. The results agree closely with predictions based on the above-optimized resistance but not with predictions based on glass-tube data. The unexpectedly high flow resistance in small microvessels may be related to interactions between blood components and the inner vessel surface that do not occur in smooth-walled tubes.

Differential effect of growth- and differentiation-inducing factors on the release of eicosanoids and phospholipids from ML-1 human myeloblastic leukemia cells.

In the absence of serum, growth of ML-1 human myeloblastic leukemia cells is induced by the insulin-like growth factor-1 (IGF1) together with transferrin (Tf), whereas monocytic differentiation is initiated by the transforming growth factor-beta (TGF-beta) in combination with Tf. Initiation of growth was followed by the rapid release of arachidonic acid (AA), hydroxyeicosatetraenoic acids (HETEs) and phospholipids into the culture medium. In contrast, induction of differentiation occurred without the release of these lipids beyond the level present in control. Inhibitors of enzymes involved in the formation of AA and of HETEs, including phospholipase A2 and lipoxygenases, caused interference with growth but not with differentiation, and an inhibitor of the cyclooxygenase path affected neither growth nor differentiation. These results indicate that the initiation of ML-1 cell growth but not of cell differentiation is dependent upon the increased formation of AA and its derivatives formed primarily via the lipoxygenase path.

Effects of photodynamic treatment of platelets or endothelial cells in vitro on platelet aggregation.

The purpose of this work was to gain insight into the role played by platelets and endothelial cells in the development of thrombogenic vascular events, observed after in vivo photodynamic therapy (PDT), by studying the in vitro effects of PDT on isolated human platelets and cultured human and bovine endothelial cells. Exposure to Photofrin II (PII) and light caused platelets to rapidly lose their ability to aggregate. Photofrin II alone at high concentrations also exerted inhibitory effects on aggregation. Endothelial cells exposed to PII- and phthalocyanine (GaCl-PcS2,3 or Zn-PCS1,2)-mediated PDT released potent platelet anti- and disaggregating activity which could be identified as prostacyclin by the following criteria: a close correlation between the time and dose dependent anti-aggregating effects and released 6-keto-PGF1 alpha (the spontaneous hydrolysis product of PGI2, determined by radioimmunoassay), the inhibition of these effects by indomethacin, accumulation of 6-keto-PGF1 alpha metabolite in the media of cells treated with PDT (as determined by HPLC analysis), and the absence of evidence for significant nitric oxide production. This prostacyclin release occurred following plasma membrane damage. Although no pro-aggregating activity was observed, endothelial cells were found to release considerable amounts of arachidonic acid and prostaglandin F2 alpha in response to PDT. These data, which indicate powerful anti-thrombogenic effects in vitro, are in sharp contrast to the vascular effects of PDT in vivo which are characterized by severe platelet aggregation, and imply that the in vivo effects involve additional components of the vascular system.

Restructuring nursing care delivery systems.

Job design and system redesign theory are applied to elucidate costs and benefits of alternative restructuring schemes. Strategies are outlined for nurse executives to use for successful reconceptualization of nursing positions.

Elevated pentose cycle and glucuronyltransferase in daunorubicin-resistant P388 cells.

Anthracycline resistance of P388 daunorubicin-resistant cells cannot be accounted for merely by differences in drug uptake and retention; protection against intracellular drug was also indicated. Cytotoxicity of daunorubicin may be partially due to the formation of free radicals and reactive oxygen species (hydrogen peroxide, hydroxyl radical, singlet oxygen, and superoxide anion radical). Protection against free radicals and peroxides is largely dependent upon the availability of reduced glutathione, which in turn requires NADPH for its continual regeneration. Pentose phosphate cycle (also called hexose monophosphate shunt) is known to provide NADPH for maintenance of glutathione. Activities of the two NADPH-producing dehydrogenases of the cycle, glucose-6-phosphate and 6-phosphogluconate dehydrogenase, were 40% higher (P less than 0.05) and activity of the cycle in intact cells was 2-fold higher in the resistant than the sensitive cells. The cycle was as active in these cells as it is known to be in macrophages, indicating a very effective protection against oxidative stress, free radicals, and alkylating electrophiles. Elevated activity of the pentose phosphate pathway in drug-resistant cells can represent a mechanism of resistance against multiple structurally unrelated drugs. Efflux of daunorubicin may be aided by further metabolism to glucuronides. Daunorubicinol, a known active metabolite of daunorubicin, can be metabolized to a glucuronide by the cells and eliminated into the surrounding medium. Glucuronidation of daunorubicinol was evidenced by (a) release of daunorubicinol following glucuronidase hydrolysis of media from cell incubations with 1.8 microM daunorubicin and (b) production of radioactive glucuronide when cell homogenates were incubated with UDP-[14C]glucuronic acid plus daunorubicinol. Glucuronyltransferase activity with a broad substrate specificity was found in the cells. Using model substrates, 1-naphthol and o-aminophenol, it was determined that glucuronyltransferase activity was 4 times higher in daunorubicin-resistant than -sensitive P388 cells. Elevated glucuronyltransferase could contribute to daunorubicin and multidrug resistance.

The principle of additivity and its relation to clinical decision making.

Clients (N = 178) with varying degrees of organic indicators were administered a psychological battery including the Memory for Designs Test (MFD; Graham & Kendall, 1960) to assess the extent to which joint presence of organic indicators affected the sensitivity of the MFD in identifying organicity. Joint presence failed to add to the discriminability of the MFD, although individual instruments such as the PIAT (Arithmetic) and WAIS-R (PIQ less than VIQ) clearly discriminated across the MFD.

Effects of inhibition of NADPH: cytochrome P-450 reductase on benzo(a)pyrene metabolism in mouse liver microsomes.

1. Effects of antioxidants (butylated hydroxytoluene and nor-dihydroguaiaretic acid), vitamin K-related quinones (vitamin K1 and coenzyme Q10) and inorganic copper (CuSO4), in concentrations inhibiting NADPH: cytochrome P-450 reductase, were re-examined on benzo(a)pyrene metabolism in mouse liver uninduced microsomes. 2. It was found that all these compounds decrease production of the two-electron oxygenation products of benzo(a)pyrene (monophenoles, diols) and the amounts of glucuronides in a manner parallel to their inhibitory potency against NADPH: cytochrome P-450 reductase. 3. No correlation was found between amounts of one-electron oxidation products of benzo(a)pyrene and inhibition of NADPH: cytochrome P-450 reductase. 4. Without added UDPGA the compounds studied decreased protein associated benzo(a)pyrene metabolites in parallel to the decreased overall metabolism of this polyaromatic hydrocarbon. 5. The mode of action of the studied compounds is discussed.

Differential effects on verbal-performance achievement levels on the WAIS-R as a function of progressive error rate on the Memory for Designs Test (MFD).

One hundred seventy-eight subjects participated in a study to measure the degree of selective subtest decline on the WAIS-R as a function of increased error rate on the Memory-for-Designs Test. The data show that there is an initial, significant decline in the verbal knowledge component of the verbal scale as error rate on the MFD progresses. Performance factors are only significantly related to error rate on the MFD when the latter are maximized.

Qualitative and quantitative differences in the induction and inhibition of hepatic benzo[a]pyrene metabolism in the rat and hamster.

The present study compared the induction and inhibition of the metabolism of the prototype polycyclic aromatic hydrocarbon, benzo[a]pyrene (BaP), in rat and hamster liver microsomes. The production of total polar metabolites was quantitated by separating 3H-metabolites from [3H]-BaP using reverse-phase thin-layer chromatography. The rate of hepatic microsomal BaP metabolism was similar in the rat and hamster (0.81 vs 0.72 nmol/min/nmol cytochrome P-450 respectively). In the rat, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD; 5 micrograms/kg, i.p.) and 3-methylcholanthrene (3-MC; 50 mg/kg, i.p., X 3 days) pretreatments doubled the rate of BaP metabolism, whereas phenobarbital pretreatment (PB; 80 mg/kg, i.p., X 3 days) had no effect. In contrast, hamster hepatic microsomal BaP metabolism was elevated 2.3-fold by PB pretreatment, whereas TCDD and 3-MC pretreatments had no effect. Isosafrole pretreatment (ISO; 150 mg/kg, i.p., X 3 days) elevated the rate by almost 2-fold in each species. Another cytochrome P-448-mediated activity, 7-ethoxyresorufin O-deethylase (EROD), was induced by the same compounds that induced BaP metabolism in the rat. In hamster liver microsomes, in contrast to BaP metabolism, EROD was induced by TCDD and 3-MC but not PB or ISO pretreatments. The results suggest differences in the substrate specificity of the cytochromes P-448-450 induced by TCDD, 3-MC and PB in these species. This was supported by the different selectivity of the in vitro inhibitors, metyrapone and 7,8-benzoflavone, towards BaP metabolism and EROD in hepatic microsomes from TCDD- or PB-pretreated rats and hamsters. Reverse-phase HPLC analysis indicated that, while 3-hydroxy-BaP was the major metabolite formed by the untreated rat, untreated hamster liver microsomes formed predominantly BaP-4,5-diol. Microsomes from TCDD-treated rats generated elevated levels of all BaP-diols, diones and 3-hydroxy-BaP, with the major metabolites being BaP-9,10- and BaP-7,8-diols. In contrast, the metabolite profile from TCDD-pretreated hamsters was unchanged from the control. PB-treated hamster microsomes produced elevated levels of BaP-diones and 3-hydroxy-BaP. However, the major hepatic metabolite formed by PB-pretreated hamsters was BaP-4,5-diol, while BaP-9,10- and BaP-7,8-diols were not detected. The results of the study indicate differences in the induced cytochrome P-450s and the generation of toxic BaP metabolites in the liver of the rat and hamster.

Inhibition of the redox cycling of vitamin K3 (menadione) in mouse liver microsomes.

1. Concentration-dependent effects of vitamin K1, coenzyme Q10, butylated hydroxytoluene, nor-dihydroguaiaretic acid and Fe-initiated lipid peroxidation on redox cycling of vitamin K3 were studied in mouse liver microsomes in vitro. 2. The antioxidants (butylated hydroxytoluene, nor-dihydroguaiaretic acid) caused apparent non-competitive inhibition of vitamin K3 redox cycling. 3. Vitamin K1 and coenzyme Q10 caused competitive inhibition of the redox cycling (Ki = 33 and 46 microM, respectively). 4. Fe-initiated microsomal lipid peroxidation caused irreversible decrease of one-electron reduction of vitamin K3. 5. The role of NADPH:cytochrome P-450 reductase along with mechanisms of these inhibitions are discussed.