427 resultados para pyrene
Resumo:
The efficient collection of solar energy relies on the design and construction of well-organized light-harvesting systems. Herein we report that supramolecular phenanthrene polymers doped with pyrene are effective collectors of light energy. The linear polymers are formed through the assembly of short amphiphilic oligomers in water. Absorption of light by phenanthrene residues is followed by electronic energy transfer along the polymer over long distances (>100 nm) to the accepting pyrene molecules. The high efficiency of the energy transfer, which is documented by large fluorescence quantum yields, suggests a quantum coherent process.
Resumo:
DNA can serve as a versatile scaffold for chromophore assemblies. For example, light-harvesting antennae have been realized by incorporating phenanthrene and pyrene building blocks into DNA strands. It was shown that by exciting at 320 nm (absorption of phenanthrene), an emission at 450 nm is observed which corresponds to a phenanthrene-pyrene exciplex. The more phenanthrenes are added into the DNA duplex, the higher is the fluorescence intensity with no significant change in quantum yield. This shows that phenanthrene acts as a donor and efficiently transfers the excitation energy to the pyrene. Up to now, the mechanism of this energy transfer and exciplex formation is not known. Therefore, we first aim at studying the photo-cycle of such DNA assemblies through transient absorption spectroscopy. Based on the results, we will explore ways to manipulate the energy transfer by application of intense THz fields. Ground as well as excited state Stark effect dynamics will be investigated.
Resumo:
Measured rates of intrinsic clearance determined using cryopreserved trout hepatocytes can be extrapolated to the whole animal as a means of improving modeled bioaccumulation predictions for fish. To date, however, the intra- and interlaboratory reliability of this procedure has not been determined. In the present study, three laboratories determined in vitro intrinsic clearance of six reference compounds (benzo[a]pyrene, 4-nonylphenol, di-tert-butyl phenol, fenthion, methoxychlor and o-terphenyl) by conducting substrate depletion experiments with cryopreserved trout hepatocytes from a single source. O-terphenyl was excluded from the final analysis due to nonfirst-order depletion kinetics and significant loss from denatured controls. For the other five compounds, intralaboratory variability (% CV) in measured in vitro intrinsic clearance values ranged from 4.1 to 30%, while interlaboratory variability ranged from 27 to 61%. Predicted bioconcentration factors based on in vitro clearance values exhibited a reduced level of interlaboratory variability (5.3-38% CV). The results of this study demonstrate that cryopreserved trout hepatocytes can be used to reliably obtain in vitro intrinsic clearance of xenobiotics, which provides support for the application of this in vitro method in a weight-of-evidence approach to chemical bioaccumulation assessment.
Resumo:
If quantum interference patterns in the hearts of polycyclic aromatic hydrocarbons (PAHs) could be isolated and manipulated, then a significant step towards realizing the potential of single-molecule electronics would be achieved. Here we demonstrate experimentally and theoretically that a simple, parameter-free, analytic theory of interference patterns evaluated at the mid-point of the HOMO-LUMO gap (referred to as M-functions) correctly predicts conductance ratios of molecules with pyrene, naphthalene, anthracene, anthanthrene or azulene hearts. M-functions provide new design strategies for identifying molecules with phase-coherent logic functions and enhancing the sensitivity of molecular-scale interferometers.
Resumo:
Conjugation of functional entities with a specific set of optical, mechanical or biological properties to DNA strands allows engineering of sophisticated DNA-containing architectures. Among various hybrid systems, DNA-grafted polymers occupy an important place in modern materials science. In this contribution we present the non-covalent synthesis and properties of DNA-grafted linear supramolecular polymers (SPs), which are assembled in a controllable manner from short chimeric DNA-pyrene oligomers. The synthetic oligomers consist of two parts: a 10 nucleotides long DNA chain and a covalently attached segment of variable number of phosphodiester-linked pyrenes. The temperature-dependent formation of DNA-grafted SPs is described by a nucleation-elongation mechanism. The high tendency of pyrenes to aggregate in water, leads to the rapid formation of SPs. The core of the assemblies consists of stacked pyrenes. They form a 1D platform, to which the DNA chains are attached. Combined spectroscopic and microscopic studies reveal that the major driving forces of the polymerization are π-stacking of pyrenes and hydrophobic interactions, and DNA pairing contributes to a lesser extent. AFM and TEM experiments demonstrate that the 1D SPs appear as elongated ribbons with a length of several hundred nanometers. They exhibit an apparent helical structure with a pitch-to-pitch distance of 50±15 nm. Since DNA pairing is a highly selective process, the ongoing studies are aimed to utilize DNA-grafted SPs for the programmable arrangement of functional entities. For example, the addition of non-modified complementary DNA strands to the DNA-grafted SPs leads to the cooperative formation of higher-order assemblies. Also, our experiments suggest that the fluorescent pyrene core of 1D ribbons serves as an efficient donor platform for energy transfer applications.
Resumo:
Conjugation of functional entities with a specific set of optical, mechanical or biological properties to DNA strands allows engineering of sophisticated DNA-containing architectures. Among various hybrid systems, DNA-grafted polymers occupy an important place in modern materials science. In this contribution we present the non-covalent synthesis and properties of DNA-grafted linear supramolecular polymers (SPs), which are assembled in a controllable manner from short chimeric DNA-pyrene oligomers. The synthetic oligomers consist of two parts: a 10 nucleotides long DNA chain and a covalently attached segment of variable number of phosphodiester-linked pyrenes. The temperature-dependent formation of DNA-grafted SPs is described by a nucleation-elongation mechanism. The high tendency of pyrenes to aggregate in water, leads to the rapid formation of SPs. The core of the assemblies consists of stacked pyrenes. They form a 1D platform, to which the DNA chains are attached. Combined spectroscopic and microscopic studies reveal that the major driving forces of the polymerization are π-stacking of pyrenes and hydrophobic interactions, and DNA pairing contributes to a lesser extent. AFM and TEM experiments demonstrate that the 1D SPs appear as elongated ribbons with a length of several hundred nanometers. They exhibit an apparent helical structure with a pitch-to-pitch distance of 50±15 nm. Since DNA pairing is a highly selective process, the ongoing studies are aimed to utilize DNA-grafted SPs for the programmable arrangement of functional entities. For example, the addition of non-modified complementary DNA strands to the DNA-grafted SPs leads to the cooperative formation of higher-order assemblies. Also, our experiments suggest that the fluorescent pyrene core of 1D ribbons serves as an efficient donor platform for energy transfer applications.
Resumo:
DNA-grafted supramolecular polymers (SPs) allow the programmed organization of DNA in a highly regular, one-dimensional array. Oligonucleotides are arranged along the edges of pyrene-based helical polymers. Addition of complementary oligonucleotides triggers the assembly of individual nanoribbons resulting in the development of extended supramolecular networks. Network formation is enabled by cooperative coaxial stacking interactions of terminal GC base pairs. The process is accompanied by structural changes in the pyrene polymer core that can be followed spectroscopically. Network formation is reversible, and disassembly into individual ribbons is realized either via thermal denaturation or by addition of a DNA separator strand.
Resumo:
The hydroxylation of N- and O-methyl drugs and a polycyclic hydrocarbon has been demonstrated in microsomes prepared from two transplantable Morris hepatomas (i.e., 7288C. t.c. and 5123 t.c.(H). The hydroxylation rates of the drug benzphetamine and the polycyclic hydrocarbon benzo {(alpha)} pyrene by tumor microsomes were inducible 2 to 3-fold and 2-fold, respectively by pretreatment of rats with phenobarbital/hydrocortisone. Hepatoma 5123t.c.(h) microsomal hydroxylation activities were more inducible after these pretreatments than hepatoma 7288C.t.c. Two chemotherapeutic drugs (cyclophosphamide and isophosphamide) were shown to be mutagenic after activation by the tumor hemogenate with the TA100 strain of Salmonella typhimurium bacteria. NADPH-cytochrome P-450 was purified from phenobarbital/hydrocortisone treated rat hepatoma 5123t.c.(H) microsomes 353-fold with a specific activity 63.6 nmol of cytochrome c reduced per min per mg of protein. The purified enzyme, has an apparent molecular weight of 79,500 daltons, and contained an equal molar ratio of FMN and FAD, with a total flavin content of 16.4 nmol per mg of protein. The purified enzyme also catalyzed electron transfer to artificial electron acceptors with the K(,m) values of the hepatoma reductase similar to those of purified liver reductase. The K(,m) value of the hepatoma reductase (13 uM) for NADPH was similar to that of purified liver reductase (5.0 uM). In addition the purified hepatoma reductase was immunochemically similar to the liver reductase.^ Hepatoma cytochrome P-450, the hemeprotein component of the hepatoma microsomes of rats pretreated with phenobarbital/hydrocortisone. The resolution of the six forms was achieved by the DE-53 ion-exchange chromatography, and further purified by hydroxyapatite. The six different fractions that contained P-450 activity, had specific contents from 0.47 to 1.75 nmol of cytochrome P-450 per mg of protein, and indicated a 2 to 9-fold purification as compared to the original microsomes. In addition, difference spectra, molecular weights and immunological results suggest there are at least six different forms of cytochrome P-450 in hepatoma 5123 t.c.(H). ^
Resumo:
Non-pregnant, female adult rats pretreated with either phenobarbital (PB) or (beta)-naphthoflavone ((beta)NF) through short-course intraperitoneal injections were shown by sodium dithionite-reduced carbon monoxide difference spectroscopy and NADPH-cytochrome c in vitro assay to contain cytochrome P-450 and NADPH-dependent reductase associated with the microsomal fraction of colon mucosa. These two protein components of the mixed function oxidase system were released from the microsomal membrane, resolved from each other, and partially purified by using a combination of techniques including solubilization in nonionic detergent followed by ultracentrifugation, anion exchange and adsorption column chromatographies, native gel electrophoresis, polyethylene glycol fractionation and ultrafiltration.^ In vitro reconstitution assays demonstrated the cytochrome P-450 fraction as the site of substrate and molecular oxygen binding. By the use of immunochemical techniques including radial immunodiffusion, Ouchterlony double diffusion and protein electroblotting, the cytochrome P-450 fraction was shown to contain at least 5 forms of the protein, having molecular weights as determined by SDS gel electrophoresis identical to the corresponding hepatic cytochrome P-450. Estimation of total cytochrome P-450 content confirmed the preferential induction of particular forms in response to the appropriate drug pretreatment.^ The colonic NADPH-dependent reductase was isolated from native gel electrophoresis and second dimensional SDS gel electrophoresis was performed in parallel to that for purified reductase from liver. Comparative electrophoretic mobilities together with immunochemical analysis, as with the cytochrome P-450s, reconstitution assays, and kinetic characterization using artificial electron acceptors, gave conclusive proof of the structural and functional homology between the colon and liver sources of the enzyme.^ Drug metabolism was performed in the reconstituted mixed function oxidase system containing a particular purified liver cytochrome P-450 form or partially pure colon cytochrome P-450 fraction plus colon or liver reductase and synthetic lipid vesicles. The two drugs, benzo{(alpha)}pyrene and benzphetamine, which are most representative of the action of system in liver, lung and kidney, were tested to determine the specificity of the reconstituted system. The kinetics of benzo{(alpha)}pyrene hydroxylation were followed fluorimetrically for 3-hydroxybenzo{(alpha)}pyrene production. . . . (Author's abstract exceeds stipulated maximum length. Discontinued here with permission of author.) UMI ^
Resumo:
Cytochrome P450s, a superfamily of heme enzymes found in most living organisms. They are responsible for metabolism of many therapeutic drugs, industrial pollutants, carcinogens, and additives to foodstuffs, as well as some endogenous compounds including fatty acids and steroids. First pass drug metabolism studies represent mainly liver and small intestine elimination, and are viewed as the standard to predict therapeutic outcome. However, drug plasma levels determined after administration do not always correlate with therapeutic efficacy of the drug. Therefore, a possible explanation may come by understanding drug metabolism in extrahepatic tissues and/or at the site of drug action. Identification and characterization of novel tissue specific isoforms of P450 generated by alternative splicing of known P450 genes or as yet unidentified genes is essential to predict pharmacological outcome of drugs or the fate of a carcinogen that act at sites remote from liver. ^ Using RT-PCR, brain-specific cytochrome P450s were detected in samples of human autopsy brain. So far, we have identified two human brain variants including P450 2D7 and P450 1A1. We have shown the presence of the P450 1A1 brain specific splice variant in African Americans, Caucasians and Indians albeit different patterns of liver to brain variant ratio were seen distributed throughout each population. Interestingly, the splice variant was detected only in the brain but not in any other tissues from the same individual. Homology modeling was used to compare the variant 3D structure to the liver form structure and differences in the substrate access channels and substrate binding sites were noticed. Automated computational docking was used to predict the metabolic fate of the potent carcinogenic substrate, benzo[a]pyrene. P450 1A1 brain variant showed no binding orientations that could produce the active metabolite, whereas P450 1A1 liver form did reveal orientations capable of generating active carcinogenic product. In vitro P32 labeling studies verified the docking predictions. Therefore, the data support the hypothesis that P450 brain splice variants mediate the metabolism of xenobiotics by mechanisms distinct from the well-studied liver counterparts. ^
Resumo:
There is scant evidence regarding the associations between ambient levels of combustion pollutants and small for gestational age (SGA) infants. No studies of this type have been completed in the Southern United States. The main objective of the project presented was to determine associations between combustion pollutants and SGA infants in Texas using three different exposure assessments. ^ Birth certificate data that contained information on maternal and infant characteristics were obtained from the Texas Department of State Health Services (TX DSHS). Exposure assessment data for the three aims came from: (1) U.S. Environmental Protection Agency (EPA) National Air Toxics Assessment (NATA), (2) U.S. EPA Air Quality System (AQS), and (3) TX Department of Transportation (DOT), respectively. Multiple logistic regression models were used to determine the associations between combustion pollutants and SGA. ^ For the first study looked at annual estimates of four air toxics at the census tract level in the Greater Houston Area. After controlling for maternal race, maternal education, tobacco use, maternal age, number of prenatal visits, marital status, maternal weight gain, and median census tract income level, adjusted ORs and 95% confidence intervals (CI) for exposure to PAHs (per 10 ng/m3), naphthalene (per 10 ng/m3), benzene (per 1 µg/m3), and diesel engine emissions (per 10 µg/m3) were 1.01 (0.97–1.05), 1.00 (0.99–1.01), 1.01 (0.97–1.05), and 1.08 (0.95–1.23) respectively. For the second study looking at Hispanics in El Paso County, AORs and 95% confidence intervals (CI) for increases of 5 ng/m3 for the sum of carcinogenic PAHs (Σ c-PAHs), 1 ng/m3 of benzo[a]pyrene, and 100 ng/m3 in naphthalene during the third trimester of pregnancy were 1.02 (0.97–1.07), 1.03 (0.96–1.11), and 1.01 (0.97–1.06), respectively. For the third study using maternal proximity to major roadways as the exposure metric, there was a negative association with increasing distance from a maternal residence to the nearest major roadway (Odds Ratio (OR) = 0.96; 95% CI = 0.94–0.97) per 1000 m); however, once adjusted for covariates this effect was no longer significant (AOR = 0.98; 95% CI = 0.96–1.00). There was no association with distance weighted traffic density (DWTD). ^ This project is the first to look at SGA and combustion pollutants in the Southern United States with three different exposure metrics. Although there was no evidence of associations found between SGA and the air pollutants mentioned in these studies, the results contribute to the body of literature assessing maternal exposure to ambient air pollution and adverse birth outcomes. ^
Resumo:
The 24th Biochemical Engineering Symposium was held 9-10 September 1994 at the YMCA of the Rockies conference center in Estes Park, Colorado, under the sponsorship of the Department of Chemical Engineering at the University of Colorado. Previous symposia in this series have been hosted by Kansas State University (1st, 3rd, 5th, 9th, 12th, 16th, 20th), University of Nebraska-Lincoln (2nd, 4th), Iowa State University (6th, 7th, 10th, 13th, 17th, 22nd), University of Missouri-Columbia (8th, 14th, 19th), Colorado State University (11th, 15th, 21st), University of Colorado (18th), and the University of Oklahoma (23rd). The next symposium is scheduled to be held at the University of Missouri-Columbia. The symposia are devoted to talks by students about their ongoing research. Because final publication usually takes place elsewhere, the papers included in the proceedings are brief, and often cover work in progress. ContentsIn-Well Aeration: An Innovative Subsurface Remediation TechnologyPrashant Gandhi, X. Yang, L.E. Erickson, and L. T. Fan; Kansas State University Expression of an Antimicrobial Peptide Analog in Eacherlchill coliChris Haught and Roger G. Harrison; University of Oklahoma Using High-frequency Backpulaing to Maximize Croasflow Filtration PerformanceSanjeev G. Redkar and Robert H. Davis; University of Colorado Low Molecular Weight Organic Compositions of Acid Waters from Vegetable Oil SoapstocksSteven L. Johansen, Arunthathi Sivasothy, Peter J. Reilly, and Earl G. Hammond; Iowa State University; Michael K. Dowd; U.S. Department of Agriculture Gas Phase Composition Effects on Suspension Cultures of Taxus cuspidata Noushin Mirjalili and James C. Linden; Colorado State University Cybernetic Modeling of Spontaneous Oscillations in Continuous Cultures of Ssccharomyces cerevisiaeKenneth D. Jones and Dhinakar S. Kompala; University of Colorado The Effect of Turbulent Shear on Calcium Mobilization in Mammalian CellsChristopher M. Cannizzaro, Pradyumna K. Namdev, and Eric H. Dunlop; Colorado State University Experimental Studies of Droplet Ejection at the Free Surface In Sparged ReactorsT. Y. Yiin, L A. Glasgow, and L. E. Erickson; Kansas State University The Role of Domain E (Starch-Binding Region) on the Activity of a Bacillus macersns Cyclodextrln GlucanotransferaseHai-yin Chang, Trang Le, and Zivko L. Nikolov; Iowa State University Use of the Rotating Wall Vessel for Study of Plant Cell Suspension CulturesXinzhi Sun and James C. Linden; Colorado State University A Novel Counter-Current Distribution Apparatus for the Study of Multi-Stage Aqueous Two-Phase Extraction of Biomolecules and Cell ParticlesMartin R. Guinn and Paul Todd; University of Colorado The Dynamics of Unhooking and Contraction of a Polyelectrolyte Chain Around an Isolated PostLin Zhang and Edith M. Sevick; University of Colorado A Laboratory Study of the Fate of Trichloroathylene and 1,1,1-Trlchloroathane In the Presence of Alfalfa PlantsMuralidharan Narayanan, Ryan M. Green, Lawrence C. Davis, and Larry E. Erickson; Kansas State University Modeling the Fate of Pyrene In the RhIzosphereS.K. Santharam, LE. Erickson, and L. T. Fan; Kansas State University Derivatization of MaltooligosaccharidesDaniela Prinz, Peter J. Reilly, and Zivko L. Nikolov; Iowa State University Probing Surfactant-Protein Binding by EPA SpectroscopyNarendra B. Bam, Yale University; Theodore W. Randolph; University of Colorado Optimization of a Stir-Cell Bioreactor for In Vitro Production of RNANeal T. Williams, Kim A. Wicklund, and Robert H. Davis; University of Colorado