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Sample records for hydrophobic iminoxyl radicals

  1. Effect of cholesterol on distribution of stable, hydrophobic perchlorotriphenylmethyl triethylester radical incorporated in lecithin liposomal membranes.

    PubMed

    Takeshita, Keizo; Okazaki, Shoko; Kansui, Hisao

    2011-01-01

    Perchlorotriphenylmethyl triethylester radical (PTM-TE) is a hydrophobic, stable radical giving a narrow singlet ESR signal with a small satellite signal for (13)C in organic solvents. In order to use PTM-TE as a label of liposomal membranes, its manner of incorporation into liposomal membranes was studied. Two components, broad and narrow signals, were observed on the ESR spectrum of PTM-TE incorporated into liposomal membranes composed of egg yolk phosphatidylcholine (egg-PC). The broad signal was increased by the presence of cholesterol in the membranes. The spectral anisotropy of the broad signal was very small as analyzed with oriented planar multilamellar membranes. The narrow signal increased with an increase in temperature in the absence of cholesterol, whereas only a small increase in the signal was observed in the presence of cholesterol. The g-value and line width of the narrow signal were very close to those of PTM-TE in mineral oil, whose viscosity is close to the microviscosity in the hydrophobic region of egg-PC membranes. On the other hand, the g-value and line width of the broad signal were close to those of solid PTM-TE. These observations indicate that the broad signal observed in liposomes originates from PTM-TE clusters in the membranes. The clusters were dissolved in egg-PC membranes at a PTM-TE/egg-PC molar ratio of less than 0.017. However, the clusters were hardly dissolved in the presence of cholesterol. PMID:21532201

  2. Method of making a membrane having hydrophilic and hydrophobic surfaces for adhering cells or antibodies by using atomic oxygen or hydroxyl radicals

    NASA Technical Reports Server (NTRS)

    Koontz, Steven L. (Inventor); Spaulding, Glenn F. (Inventor)

    1994-01-01

    A portion of an organic polymer article such as a membrane is made hydrophilic by exposing a hydrophobic surface of the article to a depth of about 50 to about 5000 angstroms to atomic oxygen or hydroxyl radicals at a temperature below 100C., preferably below 40 C, to form a hydrophilic uniform surface layer of hydrophilic hydroxyl groups. The atomic oxygen and hydroxyl radicals are generated by a flowing afterglow microwave discharge, and the surface is outside of a plasma produced by the discharge. A membrane having both hydrophilic and hydrophobic surfaces can be used in an immunoassay by adhering antibodies to the hydrophobic surface. In another embodiment, the membrane is used in cell culturing where cells adhere to the hydrophilic surface. Prior to adhering cells, the hydrophilic surface may be grafted with a compatibilizing compound. A plurality of hydrophilic regions bounded by adjacent hydrophobic regions can be produced such that a maximum of one cell per each hydrophilic region adheres.

  3. Free radical polymerization of poly(ethylene glycol) diacrylate macromers: impact of macromer hydrophobicity and initiator chemistry on polymerization efficiency.

    PubMed

    Dai, Xiaoshu; Chen, Xi; Yang, Laura; Foster, Sarah; Coury, Arthur J; Jozefiak, Thomas H

    2011-05-01

    A series of poly(ethylene glycol)-co-poly(lactide) diacrylate macromers was synthesized with variable PEG molecular weights (10 or 20 kDa) and lactate contents (0 or 6 lactates per end group). These macromers were polymerized to form hydrogels by free radical polymerization using either redox or photochemical initiators. The extent of polymerization was determined by monitoring the compressive modulus of the resulting hydrogels and by quantitative determination of unreacted acrylate after exhaustive hydrolysis of the gel. Polymerization efficiency was found to depend on the lactate content of the macromer, with higher lactate macromers giving more efficient polymerization. For redox-initiated polymerization using ferrous gluconate/t-butyl hydroperoxide initiator, macromers containing approximately six lactate repeats per end group required lower concentrations of initiator to reach high conversion than lactate-free macromers. Photochemical polymerization with α,α-dimethoxy-α-phenylacetophenone (Irgacure 651(®)) was found to be less efficient than redox polymerization, requiring the addition of N-vinyl-2- pyrrolidone (NVP) as a co-monomer to achieve conversions comparable with redox polymerization. When conditions were optimized to provide near complete conversion for all gels, the presence of lactate repeat units in the hydrogel was generally found to reduce swelling and increase the compressive modulus. Calculated values of molecular weight between cross-links (M(c)) and mesh size using Flory-Rehner theory showed that macromer molecular weight had the greatest impact on the network structure of the gel. PMID:21232638

  4. Radical prostatectomy

    MedlinePlus

    Prostatectomy - radical; Radical retropubic prostatectomy; Radical perineal prostatectomy; Laparoscopic radical prostatectomy; LRP; Robotic-assisted laparoscopic prostatectomy; RALP; Pelvic lymphadenectomy; ...

  5. The Hydrophobic Effect.

    ERIC Educational Resources Information Center

    Huque, Entazul M.

    1989-01-01

    Discusses the physical basis and current understanding of hydrophobic effects. The thermodynamic background of the effects, hydrophobic hydration, and hydrophobic interactions are described. Four existing controversies are outlined. (YP)

  6. Toward an Understanding of the Ambiguous Electron Paramagnetic Resonance Spectra of the Iminoxy Radical from o-Fluorobenzaldehyde Oxime: Density Functional Theory and ab Initio Studies.

    PubMed

    Witwicki, Maciej; Jezierska, Julia

    2015-08-27

    Iminoxy radicals (R1R2C═N—O•) possess an inherent ability to exist as E and Z isomers. Although isotropic hyperfine couplings for the species with R1 = H allow one to distinguish between E and Z, unequivocal assignment of the parameters observed in the EPR spectra of the radicals without the hydrogen atom at the azomethine carbon to the right isomer is not a simple task. The iminoxyl derived from o-fluoroacetophenone oxime (R1 = CH3 and R2 = o-FC6H5) appears to be a case in point. Moreover, for its two isomers the rotation of the o-FC6H5 group brings into existence the syn and anti conformers, depending on the mutual orientation of the F atom and C═N—O• group, making a description of hyperfine couplings to structure even more challenging. To accomplish this, a vast array of theoretical methods (DFT, OO-SCS-MP2, QCISD) was used to calculate the isotropic hyperfine couplings. The comparison between experimental and theoretical values revealed that the E isomer is the dominant radical form, for which a fast interconversion between anti and syn conformers is expected. In addition, the origin of the significant AF increase with solvent polarity was analyzed. PMID:26258434

  7. Hydrophobic photonic crystal fibers.

    PubMed

    Xiao, Limin; Birks, T A; Loh, W H

    2011-12-01

    We propose and demonstrate hydrophobic photonic crystal fibers (PCFs). A chemical surface treatment for making PCFs hydrophobic is introduced. This repels water from the holes of PCFs, so that their optical properties remain unchanged even when they are immersed in water. The combination of a hollow core and a water-repellent inner surface of the hydrophobic PCF provides an ultracompact dissolved-gas sensor element, which is demonstrated for the sensing of dissolved ammonia gas. PMID:22139276

  8. Preparation of hydrophobic coatings

    DOEpatents

    Branson, Eric D.; Shah, Pratik B.; Singh, Seema; Brinker, C. Jeffrey

    2009-02-03

    A method for preparing a hydrophobic coating by preparing a precursor sol comprising a metal alkoxide, a solvent, a basic catalyst, a fluoroalkyl compound and water, depositing the precursor sol as a film onto a surface, such as a substrate or a pipe, heating, the film and exposing the film to a hydrophobic silane compound to form a hydrophobic coating with a contact angle greater than approximately 150.degree.. The contact angle of the film can be controlled by exposure to ultraviolet radiation to reduce the contact angle and subsequent exposure to a hydrophobic silane compound to increase the contact angle.

  9. Robust Microcompartments with Hydrophobically Gated Shells.

    PubMed

    Sander, Jonathan S; Steinacher, Mathias; Loiseau, Eve; Demirörs, Ahmet F; Zanini, Michele; Isa, Lucio; Studart, André R

    2015-06-30

    We report on robust synthetic microcompartments with hydrophobically gated shells that can reversibly swell and contract multiple times upon external stimuli. The gating mechanism relies on a hydrophilic-hydrophobic transition of a polymer layer that is grafted on inorganic colloidosomes using atom-transfer radical polymerization. As a result of such a transition, the initially tight hydrophobic shell becomes permeable to the diffusion of hydrophilic solutes across the microcompartment walls. Surprisingly, the microcompartments are strong enough to retain their spherical shape during several swelling and contraction cycles. This provides a powerful alternative platform for the creation of synthetic microreactors and protocells that interact with the surrounding media through a simple gating mechanism and are sufficiently robust for further engineering of increasingly complex compartmentalized structures. PMID:26061672

  10. Prediction of coal hydrophobicity

    SciTech Connect

    Labuschagne, B.C.J.; Wheelock, T.D.; Guo, R.K.; David, H.T.; Markuszewski, R.

    1988-12-31

    Many coals exhibit a certain degree of native hydrophobicity. The more hydrophobic coals (the higher-rank coals) are easily beneficiated by froth flotation or oil agglomeration, while the more hydrophilic coals (the lower-rank coals) are floated or agglomerated with difficulty. Coals of different ranks and often even of the same rank sometimes differ greatly in hydrophobicity as measured by contact angle or natural floatability. Although the degree of hydrophobicity of a coal is related to its rank and has been correlated with other surface properties of the coal , the known information is still not sufficient to allow a good estimation to be made of the hydrophobicity of a given coal and does not explain the variation of coal hydrophobicity as a function of rank. A statistical analysis of previously published data, as well as newly acquired data, shows that coal hydrophobicity correlates better with moisture content than with carbon content, and better with the moisture/carbon molar ratio than with the hydrogen/carbon or oxygen/carbon atomic ratios. These findings indicate that there is a strong association between hydrophobicity and coal moisture content.

  11. Simultaneous Interaction of Hydrophilic and Hydrophobic Solvents with Ethylamino Neurotransmitter Radical Cations: Infrared Spectra of Tryptamine(+)-(H2O)m-(N2)n Clusters (m,n ≤ 3).

    PubMed

    Schütz, Markus; Sakota, Kenji; Moritz, Raphael; Schmies, Matthias; Ikeda, Takamasa; Sekiya, Hiroshi; Dopfer, Otto

    2015-10-01

    Solvation of biomolecules by a hydrophilic and hydrophobic environment strongly affects their structure and function. Here, the structural, vibrational, and energetic properties of size-selected clusters of the microhydrated tryptamine cation with N2 ligands, TRA(+)-(H2O)m-(N2)n (m,n ≤ 3), are characterized by infrared photodissociation spectroscopy in the 2800-3800 cm(-1) range and dispersion-corrected density functional theory calculations at the ωB97X-D/cc-pVTZ level to investigate the simultaneous solvation of this prototypical neurotransmitter by dipolar water and quadrupolar N2 ligands. In the global minimum structure of TRA(+)-H2O generated by electron ionization, H2O is strongly hydrogen-bonded (H-bonded) as proton acceptor to the acidic indolic NH group. In the TRA(+)-H2O-(N2)n clusters, the weakly bonded N2 ligands do not affect the H-bonding motif of TRA(+)-H2O and are preferentially H-bonded to the OH groups of the H2O ligand, whereas stacking to the aromatic π electron system of the pyrrole ring of TRA(+) is less favorable. The natural bond orbital analysis reveals that the H-bond between the N2 ligand and the OH group of H2O cooperatively strengthens the adjacent H-bond between the indolic NH group of TRA(+) and H2O, while π stacking is slightly noncooperative. In the larger TRA(+)-(H2O)m clusters, the H2O ligands form a H-bonded solvent network attached to the indolic NH proton, again stabilized by strong cooperative effects arising from the nearby positive charge. Comparison with the corresponding neutral TRA-(H2O)m clusters illustrates the strong impact of the excess positive charge on the structure of the microhydration network. PMID:26353045

  12. Electrohydrodynamics Near Hydrophobic Surfaces

    NASA Astrophysics Data System (ADS)

    Maduar, S. R.; Belyaev, A. V.; Lobaskin, V.; Vinogradova, O. I.

    2015-03-01

    We show that an electro-osmotic flow near the slippery hydrophobic surface depends strongly on the mobility of surface charges, which are balanced by counterions of the electrostatic diffuse layer. For a hydrophobic surface with immobile charges, the fluid transport is considerably amplified by the existence of a hydrodynamic slippage. In contrast, near the hydrophobic surface with mobile adsorbed charges, it is also controlled by an additional electric force, which increases the shear stress at the slipping interface. To account for this, we formulate electrohydrodynamic boundary conditions at the slipping interface, which should be applied to quantify electro-osmotic flows instead of hydrodynamic boundary conditions. Our theoretical predictions are fully supported by dissipative particle dynamics simulations with explicit charges. These results lead to a new interpretation of zeta potential of hydrophobic surfaces.

  13. Hydrophobic, Porous Battery Boxes

    NASA Technical Reports Server (NTRS)

    Bragg, Bobby J.; Casey, John E., Jr.

    1995-01-01

    Boxes made of porous, hydrophobic polymers developed to contain aqueous potassium hydroxide electrolyte solutions of zinc/air batteries while allowing air to diffuse in as needed for operation. Used on other types of batteries for in-cabin use in which electrolytes aqueous and from which gases generated during operation must be vented without allowing electrolytes to leak out.

  14. Radical Hysterectomy

    MedlinePlus

    ... the base of her partner’s penis during intercourse. Orgasm after radical hysterectomy Women who have had a ... the surgery will affect their ability to have orgasms. This has not been studied a great deal, ...

  15. Hydrophobic sugar holograms

    NASA Astrophysics Data System (ADS)

    Mejias-Brizuela, N. Y.; Olivares-Pérez, A.; Páez-Trujillo, G.; Hernández-Garay, M. P.; Fontanilla-Urdaneta, R.; Fuentes-Tapia, I.

    2008-02-01

    The sugar matrix is used to record of phase holograms; it was modified with the purpose of obtaining a hydrophobic material to improve the stability of the registered image and to stimulate the photosensitivity of the sugar. The new material is formed by a sugar, pectin and vanillin dissolution. The diffraction efficiency parameter increases in comparison with only the sugar matrix, obtaining already of 10%.

  16. Investigation on hydrophobic films from a hydrophobic powder

    NASA Astrophysics Data System (ADS)

    Zhu, Liqun; Hao, Guofang; Chen, Yuan; Chen, Yizhi

    2012-11-01

    A hydrophobic powder was prepared based mainly on an organosiloxane and a corrosion inhibitor with the addition of a reaction promoter. Structure and thermal stability of the hydrophobic powder were characterized by FTIR and TG/DSC, respectively. Hydrophobic property and corrosion resistance of the hydrophobic film formed on phosphatized steel by immersion in 3 wt% NaCl aqueous solution were evaluated together with the electrochemical behavior. Results showed that the skeleton of the hydrophobic powder was composed mainly of sbnd Sisbnd Osbnd Sisbnd which comprises longer and more hydrophobic groups of sbnd Sisbnd R compared with the conventional BH-102 water-repellent agent. A thin hydrophobic film with a thickness of 15-20 μm was formed on surface of the phosphatized steel after immersion in the solution of 5 g/L of the hydrophobic powder in ethanol for 5 min. The hydrophobic film exhibited excellent stability at a temperature below 135 °C. Water contact angle on the film is about 117-132° and it was until 30 h later when a corrosion spot occurred on the film covered on steel which revealed better water-repellent and corrosion resistant properties compared to that of the BH-102.

  17. Roaming Radicals

    NASA Astrophysics Data System (ADS)

    Bowman, Joel M.; Shepler, Benjamin C.

    2011-05-01

    Roaming is a recently verified unusual pathway to molecular products from unimolecular dissociation of an energized molecule. Here we present the evidence for this pathway for H2CO and CH3CHO. Theoretical analysis shows that this path visits the plateau region of the potential energy surface near dissociation to radical products. It is not clear whether roaming is a distinct isolated pathway, in addition to the conventional one via the well-known molecular saddle-point transition state. Evidence is presented to suggest that the two pathways may originate from a single, but highly complicated, dividing surface. Other examples of unusual reaction dynamics are also reviewed.

  18. Hydrophobic ionic liquids

    DOEpatents

    Koch, V.R.; Nanjundiah, C.; Carlin, R.T.

    1998-10-27

    Ionic liquids having improved properties for application in non-aqueous batteries, electrochemical capacitors, electroplating, catalysis and chemical separations are disclosed. Exemplary compounds have one of the following formulas shown in a diagram wherein R{sub 1}, R{sub 2}, R{sub 3}, R{sub 4}, R{sub 5}, and R{sub 6} are either H; F; separate alkyl groups of from 1 to 4 carbon atoms, respectively, or joined together to constitute a unitary alkylene radical of from 2 to 4 carbon atoms forming a ring structure converging on N; or separate phenyl groups; and wherein the alkyl groups, alkylene radicals or phenyl groups may be substituted with electron withdrawing groups, preferably F-, Cl-, CF{sub 3}-, SF{sub 5}-, CF{sub 3}S-, (CF{sub 3}){sub 2}CHS- or (CF{sub 3}){sub 3}CS-; and X{sup {minus}} is a non-Lewis acid-containing polyatomic anion having a van der Waals volume exceeding 100 {angstrom}{sup 3}. 4 figs.

  19. Hydrophobic ionic liquids

    DOEpatents

    Koch, Victor R.; Nanjundiah, Chenniah; Carlin, Richard T.

    1998-01-01

    Ionic liquids having improved properties for application in non-aqueous batteries, electrochemical capacitors, electroplating, catalysis and chemical separations are disclosed. Exemplary compounds have one of the following formulas: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are either H; F; separate alkyl groups of from 1 to 4 carbon atoms, respectively, or joined together to constitute a unitary alkylene radical of from 2 to 4 carbon atoms forming a ring structure converging on N; or separate phenyl groups; and wherein the alkyl groups, alkylene radicals or phenyl groups may be substituted with electron withdrawing groups, preferably F--, Cl--, CF.sub.3 --, SF.sub.5 --, CF.sub.3 S--, (CF.sub.3).sub.2 CHS-- or (CF.sub.3).sub.3 CS--; and X.sup.- is a non-Lewis acid-containing polyatomic anion having a van der Waals volume exceeding 100 .ANG..sup.3.

  20. Synthesis of Isoxazoline/Cyclic Nitrone-Featured Methylenes Using Unsaturated Ketoximes: A Dual Role of TEMPO.

    PubMed

    Chen, Fei; Yang, Xiu-Long; Wu, Zhi-Wei; Han, Bing

    2016-04-01

    A novel, metal-free, and regioselective approach for the synthesis of isoxazoline/cyclic nitrone-featured methylenes has been developed by the reaction of readily accessible β,γ- and γ,δ-unsaturated ketoximes with TEMPO via tandem iminoxyl radical-promoted cyclization/TEMPO-mediated Cope-like elimination, respectively. This protocol utilizes commercially available TEMPO as the iminoxyl radical initiator as well as the β-hydrogen acceptor in the Cope-like elimination. PMID:26954339

  1. Voltage-Gated Hydrophobic Nanopores

    SciTech Connect

    Lavrik, Nickolay V

    2011-01-01

    Hydrophobicity is a fundamental property that is responsible for numerous physical and biophysical aspects of molecular interactions in water. Peculiar behavior is expected for water in the vicinity of hydrophobic structures, such as nanopores. Indeed, hydrophobic nanopores can be found in two distinct states, dry and wet, even though the latter is thermodynamically unstable. Transitions between these two states are kinetically hindered in long pores but can be much faster in shorter pores. As it is demonstrated for the first time in this paper, these transitions can be induced by applying a voltage across a membrane with a single hydrophobic nanopore. Such voltage-induced gating in single nanopores can be realized in a reversible manner through electrowetting of inner walls of the nanopores. The resulting I-V curves of such artificial hydrophobic nanopores mimic biological voltage-gated channels.

  2. Air agglomeration of hydrophobic particles

    SciTech Connect

    Drzymala, J.; Wheelock, T.D.

    1995-12-31

    The agglomeration of hydrophobic particles in an aqueous suspension was accomplished by introducing small amounts of air into the suspension while it was agitated vigorously. The extent of aggregation was proportional both to the air to solids ratio and to the hydrophobicity of the solids. For a given air/solids ratio, the extent of aggregation of different materials increased in the following order: graphite, gilsonite, coal coated with heptane, and Teflon. The structure of agglomerates produced from coarse Teflon particles differed noticeably from the structure of bubble-particle aggregates produced from smaller, less hydrophobic particles.

  3. Method for producing hydrophobic aerogels

    SciTech Connect

    Hrubesh, Lawrence W.; Poco, John F.; Coronado, Paul R.

    1999-01-01

    A method for treating a dried monolithic aerogel containing non-dispersed particles, with an organometallic surface modifying agent to produce hydrophobic aerogels. The dried, porous hydrophobic aerogels contain a protective layer of alkyl groups, such as methyl groups, on the modified surfaces of the pores of the aerogel. The alkyl groups at the aerogel surface typically contain at least one carbon-metal bond per group.

  4. 21 CFR 584.700 - Hydrophobic silicas.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Hydrophobic silicas. 584.700 Section 584.700 Food... DRINKING WATER OF ANIMALS Listing of Specific Substances Affirmed as GRAS § 584.700 Hydrophobic silicas. (a) Product. Amorphous fumed hydrophobic silica or precipitated hydrophobic silica (CAS Reg. No....

  5. 21 CFR 584.700 - Hydrophobic silicas.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Hydrophobic silicas. 584.700 Section 584.700 Food... DRINKING WATER OF ANIMALS Listing of Specific Substances Affirmed as GRAS § 584.700 Hydrophobic silicas. (a) Product. Amorphous fumed hydrophobic silica or precipitated hydrophobic silica (CAS Reg. No....

  6. 21 CFR 584.700 - Hydrophobic silicas.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Hydrophobic silicas. 584.700 Section 584.700 Food... DRINKING WATER OF ANIMALS Listing of Specific Substances Affirmed as GRAS § 584.700 Hydrophobic silicas. (a) Product. Amorphous fumed hydrophobic silica or precipitated hydrophobic silica (CAS Reg. No....

  7. 21 CFR 584.700 - Hydrophobic silicas.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Hydrophobic silicas. 584.700 Section 584.700 Food... DRINKING WATER OF ANIMALS Listing of Specific Substances Affirmed as GRAS § 584.700 Hydrophobic silicas. (a) Product. Amorphous fumed hydrophobic silica or precipitated hydrophobic silica (CAS Reg. No....

  8. Water-Mediated Hydrophobic Interactions.

    PubMed

    Ben-Amotz, Dor

    2016-05-27

    Hydrophobic interactions are driven by the combined influence of the direct attraction between oily solutes and an additional water-mediated interaction whose magnitude (and sign) depends sensitively on both solute size and attraction. The resulting delicate balance can lead to a slightly repulsive water-mediated interaction that drives oily molecules apart rather than pushing them together and thus opposes their direct (van der Waals) attraction for each other. As a consequence, competing solute size-dependent crossovers weaken hydrophobic interactions sufficiently that they are only expected to significantly exceed random thermal energy fluctuations for processes that bury more than ∼1 nm(2) of water-exposed area. PMID:27215821

  9. Water-Mediated Hydrophobic Interactions

    NASA Astrophysics Data System (ADS)

    Ben-Amotz, Dor

    2016-05-01

    Hydrophobic interactions are driven by the combined influence of the direct attraction between oily solutes and an additional water-mediated interaction whose magnitude (and sign) depends sensitively on both solute size and attraction. The resulting delicate balance can lead to a slightly repulsive water-mediated interaction that drives oily molecules apart rather than pushing them together and thus opposes their direct (van der Waals) attraction for each other. As a consequence, competing solute size-dependent crossovers weaken hydrophobic interactions sufficiently that they are only expected to significantly exceed random thermal energy fluctuations for processes that bury more than ˜1 nm2 of water-exposed area.

  10. Hydrophobic Solvation: Aqueous Methane Solutions

    ERIC Educational Resources Information Center

    Konrod, Oliver; Lankau, Timm

    2007-01-01

    A basic introduction to concept of a solvation shell around an apolar solute as well as its detection is presented. The hydrophobic solvation of toluene is found to be a good teaching example which connects macroscopic, phenomenological thermodynamic results with an atomistic point of view.

  11. ATOM TRANSFER RADICAL POLYMERIZATION OF N-BUTYL METHACRYLATE IN AQUEOUS DISPERSED SYSTEMS: A MINIEMULSION APPROACH. (R826735)

    EPA Science Inventory

    Ultrasonication was applied in combination with a hydrophobe for the copper-mediated atom transfer radical polymerization of n-butyl methacrylate in an aqueous dispersed system. A controlled polymerization was successfully achieved, as demonstrated by a linear correlation between...

  12. 21 CFR 584.700 - Hydrophobic silicas.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...: (i) Amorphous fumed hydrophobic silica: Not less than 99.0 percent silicon dioxide after ignition... dichlorodimethylsilane. (ii) Precipated hydrophobic silica: Not less than 94.0 percent silicon dioxide after...

  13. Radical prostatectomy - discharge

    MedlinePlus

    ... prostatectomy - discharge; Laparoscopic radical prostatectomy - discharge; LRP - discharge; Robotic-assisted laparoscopic prostatectomy - discharge ; RALP - discharge; Pelvic lymphadenectomy - ...

  14. Intrinsic Hydrophobicity of Rammed Earth

    NASA Astrophysics Data System (ADS)

    Holub, M.; Stone, C.; Balintova, M.; Grul, R.

    2015-11-01

    Rammed earth is well known for its vapour diffusion properties, its ability to regulate humidity within the built environment. Rammed earth is also an aesthetically iconic material such as marble or granite and therefore is preferably left exposed. However exposed rammed earth is often coated with silane/siloxane water repellents or the structure is modified architecturally (large roof overhangs) to accommodate for the hydrophilic nature of the material. This paper sets out to find out optimal hydrophobicity for rammed earth based on natural composite fibres and surface coating without adversely affecting the vapour diffusivity of the material. The material is not required to be waterproof, but should resist at least driving rain. In order to evaluate different approaches to increase hydrophobicity of rammed earth surface, peat fibres and four types of repellents were used.

  15. Dissecting hydrophobic hydration and association.

    PubMed

    Remsing, Richard C; Weeks, John D

    2013-12-12

    We use appropriately defined short-ranged reference models of liquid water to clarify the different roles local hydrogen bonding, van der Waals attractions, and long-ranged electrostatic interactions play in the solvation and association of apolar solutes in water. While local hydrogen bonding interactions dominate hydrophobic effects involving small solutes, longer-ranged electrostatic and dispersion interactions are found to be increasingly important in the description of interfacial structure around large solutes. The hydrogen bond network sets the solute length scale at which a crossover in solvation behavior between these small and large length scale regimes is observed. Unbalanced long-ranged forces acting on interfacial water molecules are also important in hydrophobic association, illustrated here by analysis of the association of model methane and buckminsterfullerene solutes. PMID:23944226

  16. Hydrophobicity of curved microstructured surfaces

    NASA Astrophysics Data System (ADS)

    Cannon, A. H.; King, W. P.

    2010-02-01

    This paper presents measurements and models for how the macroscopic curvature of microstructured polymers affects hydrophobicity. Flexible polymer substrates were fabricated with arrays of regular microstructures. The interaction of liquid drops with these surfaces was analyzed for flat substrates and substrates flexed into either positive or negative cylindrical shapes. Liquid droplet static contact angle and dynamic slide angle were measured for a range of surfaces. An increase in substrate curvature corresponded with decreased slide angle for liquid droplets suspended on the surface asperities. This phenomenon is investigated in terms of solid-liquid contact line and the periodicity of surface microstructures. We present a model that can be used to understand the observed phenomena and to design microstructure geometries for hydrophobicity.

  17. Sunlight and free radicals

    NASA Astrophysics Data System (ADS)

    Tidwell, Thomas

    2013-08-01

    Thomas Tidwell reflects on the overlooked -- but prescient -- proposal by the British chemists Arthur Downes and Thomas Blunt for photochemical free-radical formation, decades before Moses Gomberg launched the field of radical chemistry by preparing triphenylmethyl, the first stable organic radical.

  18. Hydrophobic effect at aqueous interfaces

    NASA Technical Reports Server (NTRS)

    Pohorille, Andrew

    2005-01-01

    Conceptual basis for hydrophobic effects in bulk water and at aqueous interfaces have similar conceptual basis but often manifests itself differently. Using a wide range of computer simulations as the basis, I will review different forms of hydrophobic effects at a variety of interfaces starting from simple liquid-vapor and water-oil interfaces and progressing to water-membrane interfaces. I will start with discussing how water is organized at different interfaces, stressing both similarities and differences. The main thread is that, as in the bulk liquid, hydrophobic effects have profound influence on conformational equilibria and organization of both small molecules and macromolecules, but the result of this influence is quite different. Specifically, it will be shown that many small, but not necessarily amphiphilic molecules tend to accumulate at the interface and, and this tendency will be explained. Furthermore, I will show that many short peptides that are disordered in water spontaneously fold into well-defined structures in the interfacial environment. Biological implications of this self-organizing effect will be discussed.

  19. Hydrophobic-Core Microcapsules and Their Formation

    NASA Technical Reports Server (NTRS)

    Calle, Luz M. (Inventor); Li, Wenyan (Inventor); Buhrow, Jerry W. (Inventor); Jolley, Scott T. (Inventor)

    2016-01-01

    Hydrophobic-core microcapsules and methods of their formation are provided. A hydrophobic-core microcapsule may include a shell that encapsulates a hydrophobic substance with a core substance, such as dye, corrosion indicator, corrosion inhibitor, and/or healing agent, dissolved or dispersed therein. The hydrophobic-core microcapsules may be formed from an emulsion having hydrophobic-phase droplets, e.g., containing the core substance and shell-forming compound, dispersed in a hydrophilic phase. The shells of the microcapsules may be capable of being broken down in response to being contacted by an alkali, e.g., produced during corrosion, contacting the shell.

  20. Reversible Hydrophobic to Hydrophilic Transition in Graphene via Water Splitting Induced by UV Irradiation

    PubMed Central

    Xu, Zhemi; Ao, Zhimin; Chu, Dewei; Younis, Adnan; Li, Chang Ming; Li, Sean

    2014-01-01

    Although the reversible wettability transition between hydrophobic and hydrophilic graphene under ultraviolet (UV) irradiation has been observed, the mechanism for this phenomenon remains unclear. In this work, experimental and theoretical investigations demonstrate that the H2O molecules are split into hydrogen and hydroxyl radicals, which are then captured by the graphene surface through chemical binding in an ambient environment under UV irradiation. The dissociative adsorption of H2O molecules induces the wettability transition in graphene from hydrophobic to hydrophilic. Our discovery may hold promise for the potential application of graphene in water splitting. PMID:25245110

  1. Contemporary Radical Prostatectomy

    PubMed Central

    Fu, Qiang; Moul, Judd W.; Sun, Leon

    2011-01-01

    Purpose. Patients diagnosed with clinically localized prostate cancer have more surgical treatment options than in the past. This paper focuses on the procedures' oncological or functional outcomes and perioperative morbidities of radical retropubic prostatectomy, radical perineal prostatectomy, and robotic-assisted laparoscopic radical prostatectomy. Materials and Methods. A MEDLINE/PubMed search of the literature on radical prostatectomy and other new management options was performed. Results. Compared to the open procedures, robotic-assisted radical prostatectomy has no confirmed significant difference in most literatures besides less blood loss and blood transfusion. Nerve sparing is a safe means of preserving potency on well-selected patients undergoing radical prostatectomy. Positive surgical margin rates of radical prostatectomy affect the recurrence and survival of prostate cancer. The urinary and sexual function outcomes have been vastly improved. Neoadjuvant treatment only affects the rate of positive surgical margin. Adjuvant therapy can delay and reduce the risk of recurrence and improve the survival of the high risk prostate cancer. Conclusions. For the majority of patients with organ-confined prostate cancer, radical prostatectomy remains a most effective approach. Radical perineal prostatectomy remains a viable approach for patients with morbid obesity, prior pelvic surgery, or prior pelvic radiation. Robot-assisted laparoscopic prostatectomy (RALP) has become popular among surgeons but has not yet become the firmly established standard of care. Long-term data have confirmed the efficacy of radical retropubic prostatectomy with disease control rates and cancer-specific survival rates. PMID:22110994

  2. Designed metalloprotein stabilizes a semiquinone radical

    NASA Astrophysics Data System (ADS)

    Ulas, Gözde; Lemmin, Thomas; Wu, Yibing; Gassner, George T.; Degrado, William F.

    2016-04-01

    Enzymes use binding energy to stabilize their substrates in high-energy states that are otherwise inaccessible at ambient temperature. Here we show that a de novo designed Zn(II) metalloprotein stabilizes a chemically reactive organic radical that is otherwise unstable in aqueous media. The protein binds tightly to and stabilizes the radical semiquinone form of 3,5-di-tert-butylcatechol. Solution NMR spectroscopy in conjunction with molecular dynamics simulations show that the substrate binds in the active site pocket where it is stabilized by metal-ligand interactions as well as by burial of its hydrophobic groups. Spectrochemical redox titrations show that the protein stabilized the semiquinone by reducing the electrochemical midpoint potential for its formation via the one-electron oxidation of the catechol by approximately 400 mV (9 kcal mol-1). Therefore, the inherent chemical properties of the radical were changed drastically by harnessing its binding energy to the metalloprotein. This model sets the basis for designed enzymes with radical cofactors to tackle challenging chemistry.

  3. Designed metalloprotein stabilizes a semiquinone radical

    PubMed Central

    Ulas, Gözde; Lemmin, Thomas; Wu, Yibing; Gassner, George T.; DeGrado, William F.

    2016-01-01

    Enzymes use binding energy to stabilize their substrates in high-energy states that are otherwise inaccessible at ambient temperature. Here we show that a de novo designed Zn(ii) metalloprotein stabilizes a chemically reactive organic radical that is otherwise unstable in aqueous media. The protein binds tightly to and stabilizes the radical semiquinone form of 3,5-di-tert-butylcatechol. Solution NMR spectroscopy in conjunction with molecular dynamics simulations show that the substrate binds in the active site pocket where it is stabilized by metal–ligand interactions as well as by burial of its hydrophobic groups. Spectrochemical redox titrations show that the protein stabilized the semiquinone by reducing the electrochemical midpoint potential for its formation via the one-electron oxidation of the catechol by approximately 400 mV (9 kcal mol−1). Therefore, the inherent chemical properties of the radical were changed drastically by harnessing its binding energy to the metalloprotein. This model sets the basis for designed enzymes with radical cofactors to tackle challenging chemistry. PMID:27001731

  4. Designed metalloprotein stabilizes a semiquinone radical.

    PubMed

    Ulas, Gözde; Lemmin, Thomas; Wu, Yibing; Gassner, George T; DeGrado, William F

    2016-04-01

    Enzymes use binding energy to stabilize their substrates in high-energy states that are otherwise inaccessible at ambient temperature. Here we show that a de novo designed Zn(II) metalloprotein stabilizes a chemically reactive organic radical that is otherwise unstable in aqueous media. The protein binds tightly to and stabilizes the radical semiquinone form of 3,5-di-tert-butylcatechol. Solution NMR spectroscopy in conjunction with molecular dynamics simulations show that the substrate binds in the active site pocket where it is stabilized by metal-ligand interactions as well as by burial of its hydrophobic groups. Spectrochemical redox titrations show that the protein stabilized the semiquinone by reducing the electrochemical midpoint potential for its formation via the one-electron oxidation of the catechol by approximately 400 mV (9 kcal mol(-1)). Therefore, the inherent chemical properties of the radical were changed drastically by harnessing its binding energy to the metalloprotein. This model sets the basis for designed enzymes with radical cofactors to tackle challenging chemistry. PMID:27001731

  5. Preparation of hydrophobic organic aeorgels

    DOEpatents

    Baumann, Theodore F.; Satcher, Jr., Joe H.; Gash, Alexander E.

    2007-11-06

    Synthetic methods for the preparation of hydrophobic organics aerogels. One method involves the sol-gel polymerization of 1,3-dimethoxybenzene or 1,3,5-trimethoxybenzene with formaldehyde in non-aqueous solvents. Using a procedure analogous to the preparation of resorcinol-formaldehyde (RF) aerogels, this approach generates wet gels that can be dried using either supercritical solvent extraction to generate the new organic aerogels or air dried to produce an xerogel. Other methods involve the sol-gel polymerization of 1,3,5 trihydroxy benzene (phloroglucinol) or 1,3 dihydroxy benzene (resorcinol) and various aldehydes in non-aqueous solvents. These methods use a procedure analogous to the one-step base and two-step base/acid catalyzed polycondensation of phloroglucinol and formaldehyde, but the base catalyst used is triethylamine. These methods can be applied to a variety of other sol-gel precursors and solvent systems. These hydrophobic organics aerogels have numerous application potentials in the field of material absorbers and water-proof insulation.

  6. Preparation of hydrophobic organic aeorgels

    DOEpatents

    Baumann, Theodore F.; Satcher, Jr., Joe H.; Gash, Alexander E.

    2004-10-19

    Synthetic methods for the preparation of hydrophobic organics aerogels. One method involves the sol-gel polymerization of 1,3-dimethoxybenzene or 1,3,5-trimethoxybenzene with formaldehyde in non-aqueous solvents. Using a procedure analogous to the preparation of resorcinol-formaldehyde (RF) aerogels, this approach generates wet gels that can be dried using either supercritical solvent extraction to generate the new organic aerogels or air dried to produce an xerogel. Other methods involve the sol-gel polymerization of 1,3,5 trihydroxy benzene (phloroglucinol) or 1,3 dihydroxy benzene (resorcinol) and various aldehydes in non-aqueous solvents. These methods use a procedure analogous to the one-step base and two-step base/acid catalyzed polycondensation of phloroglucinol and formaldehyde, but the base catalyst used is triethylamine. These methods can be applied to a variety of other sol-gel precursors and solvent systems. These hydrophobic organics aerogels have numerous application potentials in the field of material absorbers and water-proof insulation.

  7. Micelle Structure and Hydrophobic Hydration.

    PubMed

    Long, Joshua A; Rankin, Blake M; Ben-Amotz, Dor

    2015-08-26

    Despite the ubiquity and utility of micelles self-assembled from aqueous surfactants, longstanding questions remain regarding their surface structure and interior hydration. Here we combine Raman spectroscopy with multivariate curve resolution (Raman-MCR) to probe the hydrophobic hydration of surfactants with various aliphatic chain lengths, and either anionic (carboxylate) or cationic (trimethylammonium) head groups, both below and above the critical micelle concentration. Our results reveal significant penetration of water into micelle interiors, well beyond the first few carbons adjacent to the headgroup. Moreover, the vibrational C-D frequency shifts of solubilized deuterated n-hexane confirm that it resides in a dry, oil-like environment (while the localization of solubilized benzene is sensitive to headgroup charge). Our findings imply that the hydrophobic core of a micelle is surrounded by a highly corrugated surface containing hydrated non-polar cavities whose depth increases with increasing surfactant chain length, thus bearing a greater resemblance to soluble proteins than previously recognized. PMID:26222042

  8. Stability of proteins inside a hydrophobic cavity

    NASA Astrophysics Data System (ADS)

    Radhakrishna, Mithun; Sharma, Sumit; Kumar, Sanat K.

    2011-03-01

    Previous studies have shown that enclosing a protein in an athermal cavity stabilizes the protein against reversible unfolding by virtue of eliminating many open chain conformations. Examples of such confined spaces include pores in chromatographic columns, Anfinsen's cage in Chaperonins, interiors of Ribosomes or regions of steric occlusion inside cells. However, the situation is more complex inside a hydrophobic cavity. The protein has a tendency to adsorb on the surface of the hydrophobic cavity, but at the same time it loses conformational entropy because of confinement. We study this system using a simple Hydrophobic Polar (HP) lattice protein model. Canonical Monte Carlo (MC) simulations at different temperatures and surface hydrophobicity show that proteins are stabilized at low and moderate hydrophobicity upon adsorption. The range of surface hydrophobicity over which a protein is stable increases with a decrease in radius of the cavity.

  9. How specific halide adsorption varies hydrophobic interactions.

    PubMed

    Stock, Philipp; Müller, Melanie; Utzig, Thomas; Valtiner, Markus

    2016-03-01

    Hydrophobic interactions (HI) are driven by the water structure around hydrophobes in aqueous electrolytes. How water structures at hydrophobic interfaces and how this influences the HI was subject to numerous studies. However, the effect of specific ion adsorption on HI and hydrophobic interfaces remains largely unexplored or controversial. Here, the authors utilized atomic force microscopy force spectroscopy at well-defined nanoscopic hydrophobic interfaces to experimentally address how specific ion adsorption of halide ions as well as NH4 (+), Cs(+), and Na(+) cations alters interaction forces across hydrophobic interfaces. Our data demonstrate that iodide adsorption at hydrophobic interfaces profoundly varies the hydrophobic interaction potential. A long-range and strong hydration repulsion at distances D > 3 nm, is followed by an instability which could be explained by a subsequent rapid ejection of adsorbed iodides from approaching hydrophobic interfaces. In addition, the authors find only a weakly pronounced influence of bromide, and as expected no influence of chloride. Also, all tested cations do not have any significant influence on HI. Complementary, x-ray photoelectron spectroscopy and quartz-crystal-microbalance with dissipation monitoring showed a clear adsorption of large halide ions (Br(-)/I(-)) onto hydrophobic self-assembled monolayers (SAMs). Interestingly, iodide can even lead to a full disintegration of SAMs due to specific and strong interactions of iodide with gold. Our data suggest that hydrophobic surfaces are not intrinsically charged negatively by hydroxide adsorption, as it was generally believed. Hydrophobic surfaces rather interact strongly with negatively charged large halide ions, leading to a surface charging and significant variation of interaction forces. PMID:26753786

  10. Site-directed analysis on protein hydrophobicity.

    PubMed

    Chong, Song-Ho; Ham, Sihyun

    2014-07-01

    Hydrophobicity of a protein is considered to be one of the major intrinsic factors dictating the protein aggregation propensity. Understanding how protein hydrophobicity is determined is, therefore, of central importance in preventing protein aggregation diseases and in the biotechnological production of human therapeutics. Traditionally, protein hydrophobicity is estimated based on hydrophobicity scales determined for individual free amino acids, assuming that those scales are unaltered when amino acids are embedded in a protein. Here, we investigate how the hydrophobicity of constituent amino acid residues depends on the protein context. To this end, we analyze the hydration free energy-free energy change on hydration quantifying the hydrophobicity-of the wild-type and 21 mutants of amyloid-beta protein associated with Alzheimer's disease by performing molecular dynamics simulations and integral-equation calculations. From detailed analysis of mutation effects on the protein hydrophobicity, we elucidate how the protein global factor such as the total charge as well as underlying protein conformations influence the hydrophobicity of amino acid residues. Our results provide a unique insight into the protein hydrophobicity for rationalizing and predicting the protein aggregation propensity on mutation, and open a new avenue to design aggregation-resistant proteins as biotherapeutics. PMID:24817476

  11. Method for making nanoporous hydrophobic coatings

    DOEpatents

    Fan, Hongyou; Sun, Zaicheng

    2013-04-23

    A simple coating method is used to form nanoporous hydrophobic films that can be used as optical coatings. The method uses evaporation-induced self-assembly of materials. The coating method starts with a homogeneous solution comprising a hydrophobic polymer and a surfactant polymer in a selective solvent. The solution is coated onto a substrate. The surfactant polymer forms micelles with the hydrophobic polymer residing in the particle core when the coating is dried. The surfactant polymer can be dissolved and selectively removed from the separated phases by washing with a polar solvent to form the nanoporous hydrophobic film.

  12. Reassessing Radical Pedagogy.

    ERIC Educational Resources Information Center

    Sweet, Stephen

    1998-01-01

    Responds to comments about, and critiques of, his own article on radical pedagogy. Outlines major points of contention raised by other commentators and responds to them, including matters of definition, power relations in the classroom, and tempering radical theory with pragmatism. (DSK)

  13. [Alchemists' humid radical].

    PubMed

    Lafont, Olivier

    2007-01-01

    The term radical has been used by chemists since the beginnings and even when they still were alchemists. The term "humid radical" is present in numerous alchemists' texts. It was used to represent a kind of "humid", which was considered as different from what is nowadays called "humid", but was a sort of principle necessary for life. PMID:17575839

  14. Hydrophobically Modified Keratin Vesicles for GSH-Responsive Intracellular Drug Release.

    PubMed

    Curcio, Manuela; Blanco-Fernandez, Barbara; Diaz-Gomez, Luis; Concheiro, Angel; Alvarez-Lorenzo, Carmen

    2015-09-16

    Redox-responsive polymersomes were prepared by self-assembly of a hydrophobically modified keratin and employing a water addition/solvent evaporation method. Polyethylene glycol-40 stearate (PEG40ST) was chosen as hydrophobic block to be coupled to keratin via radical grafting. The amphiphilic polymer exhibited low critical aggregation concentration (CAC; 10 μg/mL), indicating a good thermodynamic stability. The polymeric vesicles loaded both hydrophilic methotrexate and hydrophobic curcumin with high entrapment efficiencies, and showed a GSH-dependent drug release rate. Confocal studies on HeLa cells revealed that the obtained polymersomes were efficiently internalized. Biocompatibility properties of the proposed delivery vehicle were assessed in HET-CAM test and Balb-3T3 mouse fibroblasts. Polymersomes loaded with either methotrexate or curcumin inhibited HeLa and CHO-K1 cancer cells proliferation. Overall, the proposed keratin polymersomes could be efficient nanocarriers for chemotherapeutic agents. PMID:26287808

  15. Exploring Hydrophobic Binding Surfaces Using Comfa and Flexible Hydrophobic Ligands

    NASA Astrophysics Data System (ADS)

    Thakkar, Shraddha; Sanchez, Rosa. I.; Bhuveneswaran, Chidambaram; Compadre, Cesar M.

    2011-06-01

    Cysteine proteinases are a very important group of enzymes involved in a variety of physiological and pathological processes including cancer metastasis and rheumatoid arthritis. In this investigation we used 3D-Quantitative Structure Activity Relationships (3D-QSAR) techniques to model the binding of a variety of substrates to two cysteine proteinases, papain, and cathepsin B. The analysis was performed using Comparative Molecular Field Analysis (CoMFA). The molecules were constructed using standard bond angles and lengths, minimized and aligned. Charges were calculated using the PM3 method in MOPAC. The CoMFA models derived for the binding of the studied substrates to the two proteinases were compared with the expected results from the experimental X-ray crystal structures of the same proteinases. The results showed the value of CoMFA modeling of flexible hydrophobic ligands to analyze ligand binding to protein receptors, and could also serve as the basis to design specific inhibitors of cysteine proteinases with potential therapeutic value.

  16. Composite, nanostructured, super-hydrophobic material

    DOEpatents

    D'Urso, Brian R.; Simpson, John T.

    2007-08-21

    A hydrophobic disordered composite material having a protrusive surface feature includes a recessive phase and a protrusive phase, the recessive phase having a higher susceptibility to a preselected etchant than the protrusive phase, the composite material having an etched surface wherein the protrusive phase protrudes from the surface to form a protrusive surface feature, the protrusive feature being hydrophobic.

  17. Dynamics of Wetting of Ultra Hydrophobic Surfaces

    NASA Astrophysics Data System (ADS)

    Mohammad Karim, Alireza; Kim, Jeong-Hyun; Rothstein, Jonathan; Kavehpour, Pirouz; Mechanical and Industrial Engineering, University of Massachusetts, Amherst Collaboration

    2013-11-01

    Controlling the surface wettability of hydrophobic and super hydrophobic surfaces has extensive industrial applications ranging from coating, painting and printing technology and waterproof clothing to efficiency increase in power and water plants. This requires enhancing the knowledge about the dynamics of wetting on these hydrophobic surfaces. We have done experimental investigation on the dynamics of wetting on hydrophobic surfaces by looking deeply in to the dependency of the dynamic contact angles both advancing and receding on the velocity of the three-phase boundary (Solid/Liquid/Gas interface) using the Wilhelmy plate method with different ultra-hydrophobic surfaces. Several fluids with different surface tension and viscosity are used to study the effect of physical properties of liquids on the governing laws.

  18. Radical chemistry of artemisinin

    NASA Astrophysics Data System (ADS)

    Denisov, Evgenii T.; Solodova, S. L.; Denisova, Taisa G.

    2010-12-01

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  19. Recovering Magnetic Fe3O4-ZnO Nanocomposites from Algal Biomass Based on Hydrophobicity Shift under UV Irradiation.

    PubMed

    Ge, Shijian; Agbakpe, Michael; Zhang, Wen; Kuang, Liyuan; Wu, Zhiyi; Wang, Xianqin

    2015-06-01

    Magnetic separation, one of the promising bioseparation technologies, faces the challenges in recovery and reuse of magnetic agents during algal harvesting for biofuel extraction. This study synthesized a steric acid (SA)-coated Fe3O4-ZnO nanocomposite that could shift hydrophobicity under UV365 irradiation. Our results showed that with the transition of surface hydrophobicity under UV365 irradiation, magnetic nanocomposites detached from the concentrated algal biomass. The detachment was partially induced by the oxidation of SA coating layers due to the generation of radicals (e.g., •OH) by ZnO under UV365 illumination. Consequently, the nanocomposite surface shifted from hydrophobic to hydrophilic, which significantly reduced the adhesion between magnetic particles and algae as predicted by the extended Derjaguin and Landau, Verwey, and Overbeek (EDLVO) theory. Such unique hydrophobicity shift may also find many other potential applications that require recovery, recycle, and reuse of valuable nanomaterials to increase sustainability and economically viability. PMID:25965291

  20. Effect of hydrophobicity of cationic carbocyanine dyes DiOC n on their binding to anionic surfactant micelles

    NASA Astrophysics Data System (ADS)

    Lebed, A. S.; Yefimova, S. L.; Guralchuk, G. Ya.; Sorokin, A. V.; Borovoy, I. A.; Malyukin, Yu. V.

    2010-05-01

    The interaction of a series of cationic dialkyloxacarbocyanine perchlorate (DiOC n ) dyes of different degrees of hydrophobicity with micelles of an anionic surfactant, sodium dodecylsulfate (SDS), has been studied spectrophotometrically in aqueous solutions. The Benesi-Hildebrand equation was used to calculate binding constants ( K b ) of the dyes to surfactant micelles, the fraction of dye bound to the micelles ( f mic ), and the standard free-energy change (Δ G 0) for the transfer of dye from the aqueous to micellar phase. It has been shown that the interaction of oppositely charged dye molecules and surfactant micelles is controlled by both electrostatic and hydrophobic interactions. A small increase in dye hydrophobicity due to lengthening of the hydrocarbon radical has been shown to cause an abrupt nonlinear increase of the fmic value. This points to a key role of hydrophobic interactions in the binding of dye molecules with the micelles.

  1. Quantification of hydrophobic interaction affinity of colloids

    NASA Astrophysics Data System (ADS)

    Saini, G.; Nasholm, N.; Wood, B. D.

    2009-12-01

    Colloids play an important role in a wide variety of disciplines, including water and wastewater treatment, subsurface transport of metals and organic contaminants, migration of fines in oil reservoirs, biocolloid (virus and bacteria) transport in subsurface, and are integral to laboratory transport studies. Although the role of hydrophobicity in adhesion and transport of colloids, particularly bacteria, is well known; there is scarcity of literature regarding hydrophobicity measurement of non-bacterial colloids and other micron-sized particles. Here we detail an experimental approach based on differential partitioning of colloids between two liquid phases (hydrocarbon and buffer) as a measure of the hydrophobic interaction affinity of colloids. This assay, known as Microbial adhesion to hydrocarbons or MATH, is frequently used in microbiology and bacteriology for quantifying the hydrophobicity of microbes. Monodispersed colloids and particles, with sizes ranging from 1 micron to 33 micron, were used for the experiments. A range of hydrophobicity values were observed for different particles. The hydrophobicity results are also verified against water contact angle measurements of these particles. This liquid-liquid partitioning assay is quick, easy-to-perform and requires minimal instrumentation. Estimation of the hydrophobic interaction affinity of colloids would lead to a better understanding of their adhesion to different surfaces and subsequent transport in porous media.

  2. Hydroxyl radicals in indoor environments

    NASA Astrophysics Data System (ADS)

    Sarwar, Golam; Corsi, Richard; Kimura, Yosuke; Allen, David; Weschler, Charles J.

    Indoor hydroxyl radical concentrations were estimated using a new indoor air quality model which employs the SAPRC-99 atmospheric chemistry model to simulate indoor homogenous reactions. Model results indicate that typical indoor hydroxyl radical concentrations are lower than typical outdoor summertime urban hydroxyl radical levels of 5-10×10 6 molecules cm -3; however, indoor levels can be similar to or greater than typical nighttime outdoor hydroxyl radical levels of approximately 5×10 4 molecules cm -3. Effects of selected parameters on indoor hydroxyl radical concentrations are presented herein. Indoor hydroxyl radical concentrations are predicted to increase non-linearly with increasing outdoor ozone concentrations, indoor alkene emission rates, and air exchange rates. Indoor hydroxyl radical concentrations decrease with increasing outdoor nitric oxide concentrations. Indoor temperature and indoor light intensity have moderate impacts on indoor hydroxyl radical concentrations. Outdoor hydroxyl radical concentrations, outdoor nitrate (NO 3rad ) radical concentrations, outdoor hydroperoxy radical concentrations, and hydroxyl radical removal by indoor surfaces are predicted to have no appreciable impact on indoor hydroxyl radical concentrations. Production of hydroxyl radicals in indoor environments appears to be controlled primarily by reactions of alkenes with ozone, and nitric oxide with hydroperoxy radical. Estimated indoor hydroxyl radical levels may potentially affect indoor air quality. Two examples are presented in which reactions of d-limonene and α-pinene with indoor hydroxyl radicals produce aldehydes, which may be of greater concern than the original compounds.

  3. Molecular Shape and the Hydrophobic Effect

    NASA Astrophysics Data System (ADS)

    Hillyer, Matthew B.; Gibb, Bruce C.

    2016-05-01

    This review focuses on papers published since 2000 on the topic of the properties of solutes in water. More specifically, it evaluates the state of the art of our understanding of the complex relationship between the shape of a hydrophobe and the hydrophobic effect. To highlight this, we present a selection of references covering both empirical and molecular dynamics studies of small (molecular-scale) solutes. These include empirical studies of small molecules, synthetic hosts, crystalline monolayers, and proteins, as well as in silico investigations of entities such as idealized hard and soft spheres, small solutes, hydrophobic plates, artificial concavity, molecular hosts, carbon nanotubes and spheres, and proteins.

  4. Super-hydrophobic fluorine containing aerogels

    SciTech Connect

    Coronado, Paul R.; Poco, John F.; Hrubesh, Lawrence W.

    2007-05-01

    An aerogel material with surfaces containing fluorine atoms which exhibits exceptional hydrophobicity, or the ability to repel liquid water. Hydrophobic aerogels are efficient absorbers of solvents from water. Solvents miscible with water are separated from it because the solvents are more volatile than water and they enter the porous aerogel as a vapor across the liquid water/solid interface. Solvents that are immisicble with water are separated from it by selectively wetting the aerogel. The hydrophobic property is achieved by formulating the aerogel using fluorine containing molecules either directly by addition in the sol-gel process, or by treating a standard dried aerogel using the vapor of fluorine containing molecules.

  5. Molecular Shape and the Hydrophobic Effect.

    PubMed

    Hillyer, Matthew B; Gibb, Bruce C

    2016-05-27

    This review focuses on papers published since 2000 on the topic of the properties of solutes in water. More specifically, it evaluates the state of the art of our understanding of the complex relationship between the shape of a hydrophobe and the hydrophobic effect. To highlight this, we present a selection of references covering both empirical and molecular dynamics studies of small (molecular-scale) solutes. These include empirical studies of small molecules, synthetic hosts, crystalline monolayers, and proteins, as well as in silico investigations of entities such as idealized hard and soft spheres, small solutes, hydrophobic plates, artificial concavity, molecular hosts, carbon nanotubes and spheres, and proteins. PMID:27215816

  6. Free Radical Reactions in Food.

    ERIC Educational Resources Information Center

    Taub, Irwin A.

    1984-01-01

    Discusses reactions of free radicals that determine the chemistry of many fresh, processed, and stored foods. Focuses on reactions involving ascorbic acid, myoglobin, and palmitate radicals as representative radicals derived from a vitamin, metallo-protein, and saturated lipid. Basic concepts related to free radical structure, formation, and…

  7. Chemistry of carotenoid neutral radicals.

    PubMed

    Ligia Focsan, A; Magyar, Adam; Kispert, Lowell D

    2015-04-15

    Proton loss from the carotenoid radical cations (Car(+)) to form neutral radicals (#Car) was investigated by numerous electrochemical, EPR, ENDOR and DFT studies described herein. The radical cation and neutral radicals were formed in solution electrochemically and stabilized on solid silica-alumina and MCM-41 matrices. Carotenoid neutral radicals were recently identified in Arabidopsis thaliana plant and photosystem II samples. Deprotonation at the terminal ends of a zeaxanthin radical cation could provide a secondary photoprotection pathway which involves quenching excited state chlorophyll by the long-lived zeaxanthin neutral radicals formed. PMID:25687648

  8. Hydrophobic character of pretreated coal surfaces

    SciTech Connect

    Jin, R.; Ye, Y.; Miller, J.D.

    1988-01-01

    Increased hydrophobicity and hence the flotability of coals of different rank has been observed for CO/sub 2/ pretreatment and/or controlled thermal pretreatment. DRIFT- and ATR-FTIR and XPS techniques have been used to determine the surface chemical characteristics in order to evaluate coal hydrophobicity. These results agree very well with those determined by traditional methods. The enhanced hydrophobicity of CO/sub 2/-treated coal is attributed to the high specific affinity of coal for CO/sub 2/ which results in the displacement of pore water and hydration water by CO/sub 2/ and on pressure release leads to nanobubble formation at the coal surface in aqueous suspension. Increased hydrophobicity of lignite by thermal treatment arises from the removal of pore water, hydration water and some organic OH functional groups as well as the diffusion of volatile matter to the surface and the reorientation of surface functional groups.

  9. SORPTION OF HYDROPHOBIC POLLUTANTS ON NATURAL SEDIMENTS

    EPA Science Inventory

    The sorption of hydrophobic compounds (aromatic hydrocarbons and chlorinated hydrocarbons) spanning a concentration range in water solubility from 500 parts per trillion (ppt) to 1800 parts per million (ppm) on local (North Georgia) pond and river sediments was investigated. The ...

  10. Preparation and characterization of hydrophobic superparamagnetic gel.

    SciTech Connect

    Liu, X.; Kaminski, M. D.; Guan, Y.; Chen, H.; Liu, H.; Rosengart, A. J.; Chemical Engineering; Univ. of Chicago; Pritzker School of Medicine; Chinese Academy of Sciences

    2006-01-01

    The present study describes the preparation and analysis of a highly concentrated hydrophobic oleic acid-coated magnetite gel. By contrast to conventional techniques to prepare magnetic fluids, herein the oleic acid was introduced as a reactant during the initial crystallization phase of magnetite that was obtained by the co-precipitation of Fe(II) and Fe(III) salts by addition of ammonium hydroxide. The resulting gelatinous hydrophobic magnetite was characterized in terms of morphology, particle size, magnetic properties, crystal structure, and hydrophobicity/hydrophilicity. This magnetic gel exhibited superparamagnetism with a saturation magnetization of 46.0 emu/g at room temperature and could be well dispersed both in polar and nonpolar carrier liquids. This protocol produced highly concentrated hydrophobic magnetic gel for biopolymer encapsulations.

  11. Erosion and flow of hydrophobic granular materials

    NASA Astrophysics Data System (ADS)

    Utter, Brian; Benns, Thomas; Mahler, Joseph

    2013-11-01

    We experimentally investigate submerged granular flows of hydrophobic and hydrophilic grains both in a rotating drum geometry and under erosion by a surface water flow. While slurry and suspension flows are common in nature and industry, effects of surface chemistry on flow behavior have received relatively little attention. In the rotating drum , we use varying concentrations of hydrophobic and hydrophilic grains of sand submerged in water rotated at a constant angular velocity. Sequential images of the resulting avalanches are taken and analyzed. High concentrations of hydrophobic grains result in an effectively cohesive interaction between the grains forming aggregates, with aggregate size and repose angle increasing with hydrophobic concentration. However, the formation and nature of the aggregates depends significantly on the presence of air in the system. We present results from a related experiment on erosion by a surface water flow designed to characterize the effects of heterogeneous granular surfaces on channelization and erosion. Supported by NSF CBET Award 1067598.

  12. Erosion and flow of hydrophobic granular materials

    NASA Astrophysics Data System (ADS)

    Utter, Brian; Benns, Thomas; Foltz, Benjamin; Mahler, Joseph

    2015-03-01

    We experimentally investigate submerged granular flows of hydrophobic and hydrophilic grains both in a rotating drum geometry and under erosion by a surface water flow. While slurry and suspension flows are common in nature and industry, effects of surface chemistry on flow behavior have received relatively little attention. In the rotating drum, we use varying concentrations of hydrophobic and hydrophilic grains of sand submerged in water rotated at a constant angular velocity. Sequential images of the resulting avalanches are taken and analyzed. High concentrations of hydrophobic grains result in an effectively cohesive interaction between the grains forming aggregates, with aggregate size and repose angle increasing with hydrophobic concentration. However, the formation and nature of the aggregates depends significantly on the presence of air in the system. We present results from a related experiment on erosion by a surface water flow designed to characterize the effects of heterogeneous granular surfaces on channelization and erosion.

  13. Surface analysis of selected hydrophobic materials

    NASA Astrophysics Data System (ADS)

    Wisniewska, Sylwia Katarzyna

    This dissertation contains a series of studies on hydrophobic surfaces by various surface sensitive techniques such as contact angle measurements, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and atomic force microscopy (AFM). Hydrophobic surfaces have been classified as mineral surfaces, organic synthetic surfaces, or natural biological surfaces. As a model hydrophobic mineral surface, elemental sulfur has been selected. The sulfur surface has been characterized for selected allotropic forms of sulfur such as rhombic, monoclinic, plastic, and cyclohexasulfur. Additionally, dextrin adsorption at the sulfur surface was measured. The structure of a dextrin molecule showing hydrophobic sites has been presented to support the proposed hydrophobic bonding nature of dextrin adsorption at the sulfur surface. As a model organic hydrophobic surface, primary fatty amines such as dodecylamine, hexadecylamine, and octadecylamine were chosen. An increase of hydrophobicity, significant changes of infrared bands, and surface topographical changes with time were observed for each amine. Based on the results it was concluded that hydrocarbon chain rearrangement associated with recrystallization took place at the surface during contact with air. A barley straw surface was selected as a model of biological hydrophobic surfaces. The differences in the contact angles for various straw surfaces were explained by the presence of a wax layer. SEM images confirmed the heterogeneity and complexity of the wax crystal structure. AFM measurements provided additional structural details including a measure of surface roughness. Additionally, straw degradation as a result of conditioning in an aqueous environment was studied. Significant contact angle changes were observed as soon as one day after conditioning. FTIR studies showed a gradual wax layer removal due to straw surface decomposition. SEM and AFM images revealed topographical changes and biological

  14. Enhanced Permeation of a Hydrophobic Fluid through Particles with Hydrophobic and Hydrophilic Patterned Surfaces

    PubMed Central

    Zhang, Renliang; Xu, Yousheng; Wen, Binghai; Sheng, Nan; Fang, Haiping

    2014-01-01

    The wetting properties of solid surfaces are significant in oil/gas and liquid displacement processes. It is difficult for hydrophobic fluids to permeate channels filled with hydrophilic particles and an aqueous phase, and this is thought to be the primary cause of low yields in low permeability reservoir operations. Using three-dimensional lattice Boltzmann simulations, we show that particles with hydrophobic and hydrophilic patterned surfaces can greatly improve hydrophobic fluid permeation. Specifically, a hydrophobic fluid can easily access micro-channels in the hydrophobic regions, which extend rapidly even to the hydrophilic regions and accelerate hydrophobic fluid escape. This work enriches understanding of multiphase flow in porous media at the pore scale and fracture conductivity and is expected to have great significance in the exploitation of low permeability reservoirs and shale gas. PMID:25033709

  15. Enhanced permeation of a hydrophobic fluid through particles with hydrophobic and hydrophilic patterned surfaces.

    PubMed

    Zhang, Renliang; Xu, Yousheng; Wen, Binghai; Sheng, Nan; Fang, Haiping

    2014-01-01

    The wetting properties of solid surfaces are significant in oil/gas and liquid displacement processes. It is difficult for hydrophobic fluids to permeate channels filled with hydrophilic particles and an aqueous phase, and this is thought to be the primary cause of low yields in low permeability reservoir operations. Using three-dimensional lattice Boltzmann simulations, we show that particles with hydrophobic and hydrophilic patterned surfaces can greatly improve hydrophobic fluid permeation. Specifically, a hydrophobic fluid can easily access micro-channels in the hydrophobic regions, which extend rapidly even to the hydrophilic regions and accelerate hydrophobic fluid escape. This work enriches understanding of multiphase flow in porous media at the pore scale and fracture conductivity and is expected to have great significance in the exploitation of low permeability reservoirs and shale gas. PMID:25033709

  16. Radiolysis of Potassium Picrate in 77 K

    NASA Astrophysics Data System (ADS)

    Yakubik, D. G.; Pak, V. Kh; Anan'ev, V. A.; Ghyngazov, S. A.

    2016-02-01

    The formation of paramagnetic centers in potassium picrate under irradiation at low temperature was investigated. The heating irradiated at 77 K potassium picrate crystal to room temperature results in paramagnetic centers - 2,6-dinitro-para-quinone radicals, ortho- and para-iminoxyl radicals and atomic oxygen. These products are formed under irradiation at room temperature.

  17. Contribution of Hydrophobic Interactions to Protein Stability

    PubMed Central

    Pace, C. Nick; Fu, Hailong; Fryar, Katrina Lee; Landua, John; Trevino, Saul R.; Shirley, Bret A.; Hendricks, Marsha McNutt; Iimura, Satoshi; Gajiwala, Ketan; Scholtz, J. Martin; Grimsley, Gerald R.

    2011-01-01

    Our goal was to gain a better understanding of the contribution of hydrophobic interactions to protein stability. We measured the change in conformational stability, Δ(ΔG), for hydrophobic mutants of four proteins: villin head piece subdomain (VHP) with 36 residues, a surface protein from Borrelia burgdorferi (VlsE) with 341 residues, and two proteins previously studied in our laboratory, ribonucleases Sa and T1. We compare our results with previous studies and reach the following conclusions. 1. Hydrophobic interactions contribute less to the stability of a small protein, VHP (0.6 ± 0.3 kcal/mole per –CH2– group), than to the stability of a large protein, VlsE (1.6 ± 0.3 kcal/mol per –CH2– group). 2. Hydrophobic interactions make the major contribution to the stability of VHP (40 kcal/mol) and the major contributors are (in kcal/mol): Phe 18 (3.9), Met 13 (3.1), Phe 7 (2.9), Phe 11 (2.7), and Leu 21 (2.7). 3. Based on Δ(ΔG) values for 148 hydrophobic mutants in 13 proteins, burying a –CH2– group on folding contributes, on average, 1.1 ± 0.5 kcal/mol to protein stability. 4. The experimental Δ(ΔG) values for aliphatic side chains (Ala, Val, Ile, and Leu) are in good agreement with their ΔGtr values from water to cyclohexane. 5. For 22 proteins with 36 to 534 residues, hydrophobic interactions contribute 60 ± 4% and hydrogen bonds 40 ± 4% to protein stability. 6. Conformational entropy contributes about 2.4 kcal/mol per residue to protein instability. The globular conformation of proteins is stabilized predominately by hydrophobic interactions. PMID:21377472

  18. Contribution of hydrophobic interactions to protein stability.

    PubMed

    Pace, C Nick; Fu, Hailong; Fryar, Katrina Lee; Landua, John; Trevino, Saul R; Shirley, Bret A; Hendricks, Marsha McNutt; Iimura, Satoshi; Gajiwala, Ketan; Scholtz, J Martin; Grimsley, Gerald R

    2011-05-01

    Our goal was to gain a better understanding of the contribution of hydrophobic interactions to protein stability. We measured the change in conformational stability, Δ(ΔG), for hydrophobic mutants of four proteins: villin headpiece subdomain (VHP) with 36 residues, a surface protein from Borrelia burgdorferi (VlsE) with 341 residues, and two proteins previously studied in our laboratory, ribonucleases Sa and T1. We compared our results with those of previous studies and reached the following conclusions: (1) Hydrophobic interactions contribute less to the stability of a small protein, VHP (0.6±0.3 kcal/mol per -CH(2)- group), than to the stability of a large protein, VlsE (1.6±0.3 kcal/mol per -CH(2)- group). (2) Hydrophobic interactions make the major contribution to the stability of VHP (40 kcal/mol) and the major contributors are (in kilocalories per mole) Phe18 (3.9), Met13 (3.1), Phe7 (2.9), Phe11 (2.7), and Leu21 (2.7). (3) Based on the Δ(ΔG) values for 148 hydrophobic mutants in 13 proteins, burying a -CH(2)- group on folding contributes, on average, 1.1±0.5 kcal/mol to protein stability. (4) The experimental Δ(ΔG) values for aliphatic side chains (Ala, Val, Ile, and Leu) are in good agreement with their ΔG(tr) values from water to cyclohexane. (5) For 22 proteins with 36 to 534 residues, hydrophobic interactions contribute 60±4% and hydrogen bonds contribute 40±4% to protein stability. (6) Conformational entropy contributes about 2.4 kcal/mol per residue to protein instability. The globular conformation of proteins is stabilized predominantly by hydrophobic interactions. PMID:21377472

  19. [Aging and free radicals].

    PubMed

    Manso, C

    1992-02-01

    Several theories on aging are presented. All of them give important contributions but none explains all the aspects of the problem. Oxygen radicals produced during cellular combustion contribute to aging through multiple cumulative microlesions throughout life. The importance of glucose is emphasized; it forms early and late Maillard compounds. Other causes of aging are discussed. PMID:1595373

  20. Radical School Reform.

    ERIC Educational Resources Information Center

    Gross, Beatrice, Ed.; Gross, Ronald, Ed.

    This book provides a comprehensive examination of the nature of the school crisis and the ways in which radical thinkers and educators are dealing with it. Excerpts from the writings of Jonathan Kozol, John Holt, Kenneth Clark, and others are concerned with the realities of education in ghettos and suburbs. Paul Goodman, Marshall McLuhan, Sylvia…

  1. Tyrosyl Radicals in Dehaloperoxidase

    PubMed Central

    Dumarieh, Rania; D'Antonio, Jennifer; Deliz-Liang, Alexandria; Smirnova, Tatyana; Svistunenko, Dimitri A.; Ghiladi, Reza A.

    2013-01-01

    Dehaloperoxidase (DHP) from Amphitrite ornata, having been shown to catalyze the hydrogen peroxide-dependent oxidation of trihalophenols to dihaloquinones, is the first oxygen binding globin that possesses a biologically relevant peroxidase activity. The catalytically competent species in DHP appears to be Compound ES, a reactive intermediate that contains both a ferryl heme and a tyrosyl radical. By simulating the EPR spectra of DHP activated by H2O2, Thompson et al. (Thompson, M. K., Franzen, S., Ghiladi, R. A., Reeder, B. J., and Svistunenko, D. A. (2010) J. Am. Chem. Soc. 132, 17501–17510) proposed that two different radicals, depending on the pH, are formed, one located on either Tyr-34 or Tyr-28 and the other on Tyr-38. To provide additional support for these simulation-based assignments and to deduce the role(s) that tyrosyl radicals play in DHP, stopped-flow UV-visible and rapid-freeze-quench EPR spectroscopic methods were employed to study radical formation in DHP when three tyrosine residues, Tyr-28, Tyr-34, and Tyr-38, were replaced either individually or in combination with phenylalanines. The results indicate that radicals form on all three tyrosines in DHP. Evidence for the formation of DHP Compound I in several tyrosine mutants was obtained. Variants that formed Compound I showed an increase in the catalytic rate for substrate oxidation but also an increase in heme bleaching, suggesting that the tyrosines are necessary for protecting the enzyme from oxidizing itself. This protective role of tyrosines is likely an evolutionary adaptation allowing DHP to avoid self-inflicted damage in the oxidative environment. PMID:24100039

  2. Thickness-Dependent Hydrophobicity of Epitaxial Graphene.

    PubMed

    Munz, Martin; Giusca, Cristina E; Myers-Ward, Rachael L; Gaskill, D Kurt; Kazakova, Olga

    2015-08-25

    This article addresses the much debated question whether the degree of hydrophobicity of single-layer graphene (1LG) is different from that of double-layer graphene (2LG). Knowledge of the water affinity of graphene and its spatial variations is critically important as it can affect the graphene properties as well as the performance of graphene devices exposed to humidity. By employing chemical force microscopy with a probe rendered hydrophobic by functionalization with octadecyltrichlorosilane (OTS), the adhesion force between the probe and epitaxial graphene on SiC has been measured in deionized water. Owing to the hydrophobic attraction, a larger adhesion force was measured on 2LG Bernal-stacked domains of graphene surfaces, thus showing that 2LG is more hydrophobic than 1LG. Identification of 1LG and 2LG domains was achieved through Kelvin probe force microscopy and Raman spectral mapping. Approximate values of the adhesion force per OTS molecule have been calculated through contact area analysis. Furthermore, the contrast of friction force images measured in contact mode was reversed to the 1LG/2LG adhesion contrast, and its origin was discussed in terms of the likely water depletion over hydrophobic domains as well as deformation in the contact area between the atomic force microscope tip and 1LG. PMID:26218503

  3. Electron relaxation of DNP free radicals BDPA and DPPH at W-band

    NASA Astrophysics Data System (ADS)

    Khamoshi, Armin; Kaur, Pavanjeet; Song, Likai; Lumata, Lloyd

    2015-03-01

    The stable, spin-1/2 organic free radicals BDPA and DPPH are efficient polarizing agents for dissolution dynamic nuclear polarization (DNP). Despite the hydrophobic nature of these two free radicals, BDPA and DPPH can be dissolved in specialized solvents such as sulfolane or dimethyl sulfoxide. In this work, we have investigated the temperature dependence of the spin-lattice relaxation rate 1/T1 of these two DNP free radicals at W-band from 250 K down to 4 K. We have found that at high temperature above 40 K the relaxation rates of these free radicals (at optimum DNP concentration) behave closely according to the Raman process prediction. At lower temperature below 40 K, the relaxation rate slows down according to the direct process behavior. The results obtained here may elucidate the correlation between the relaxation of electrons and the efficiency of these free radicals in DNP.

  4. Enzymatic Hydrophobic Modification of Jute Fibers via Grafting to Reinforce Composites.

    PubMed

    Liu, Ruirui; Dong, Aixue; Fan, Xuerong; Yu, Yuanyuan; Yuan, Jiugang; Wang, Ping; Wang, Qiang; Cavaco-Paulo, Artur

    2016-04-01

    Horseradish peroxidase (HRP)/H2O2 system catalyzes the free-radical polymerization of aromatic compounds such as lignins and gallate esters. In this work, dodecyl gallate (DG) was grafted onto the surfaces of lignin-rich jute fabrics by HRP-mediated oxidative polymerization with an aim to enhance the hydrophobicity of the fibers. The DG-grafted jute fibers and reaction products of their model compounds were characterized by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOF MS), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The results clearly indicated the grafting of DG to the jute fiber by HRP. Furthermore, the hydrophobicity of jute fabrics was determined by measuring the wetting time and static contact angle. Compared to the control sample, the wetting time and static contact angle of the grated fabrics changed from ~1 s to 1 h and from ~0° to 123.68°, respectively. This clearly proved that the hydrophobicity of jute fabrics improved considerably. Conditions of the HRP-catalyzed DG-grafting reactions were optimized in terms of the DG content of modified jute fabrics. Moreover, the results of breaking strength and elongation of DG-grafted jute/polypropylene (PP) composites demonstrated improved reinforcement of the composite due to enzymatic hydrophobic modification of jute fibers. PMID:26754422

  5. Magnetic hydrophobic nanocomposites: Silica aerogel/maghemite

    NASA Astrophysics Data System (ADS)

    Mendoza Zélis, P.; Fernández van Raap, M. B.; Socolovsky, L. M.; Leyva, A. G.; Sánchez, F. H.

    2012-08-01

    Magnetic hydrophobic aerogels (MHA) in the form of nanocomposites of silica and maghemite (γ-Fe2O3) were prepared by one step sol-gel procedure followed by supercritical solvent extraction. Silica alcogels were obtained from TEOS, MTMS, methanol and H2O, and Fe(III) nitrate as magnetic precursor. The hydrophobic property was achieved using the methytrimethoxysilane (MTMS) as co-precursor for surface modification. The so produced nanocomposite aerogels are monolithic, hydrophobic and magnetic. The interconnected porous structure hosts ∼6 nm size γ-Fe2O3 particles, has a mean pore diameter of 5 nm, and a specific surface area (SSA) of 698 m²/g. Medium range structure of MHA is determined by SAXS, which displays the typical fractal power law behavior with primary particle radius of ∼1 nm. Magnetic properties of the nanoparticle ensembles hosted in them are studied by means of dc-magnetometry.

  6. Toward Radicalizing Community Service Learning

    ERIC Educational Resources Information Center

    Sheffield, Eric C.

    2015-01-01

    This article advocates a radicalized theoretical construction of community service learning. To accomplish this radicalization, I initially take up a discussion of traditional understandings of CSL rooted in pragmatic/progressive thought. I then suggest that this traditional structural foundation can be radicalized by incorporating Deborah…

  7. Free radical explosive composition

    DOEpatents

    Walker, Franklin E.; Wasley, Richard J.

    1979-01-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a getter additive comprising a compound or mixture of compounds capable of capturing or deactivating free radicals or ions under mechanical or electrical shock conditions and which is not an explosive. Exemplary getter additives are isocyanates, olefins and iodine.

  8. Free radical propulsion concept

    NASA Technical Reports Server (NTRS)

    Hawkins, C. E.; Nakanishi, S.

    1981-01-01

    The concept of a free radical propulsion system, utilizing the recombination energy of dissociated low molecular weight gases to produce thrust, is analyzed. The system, operating at a theoretical impulse with hydrogen, as high as 2200 seconds at high thrust to power ratio, is hypothesized to bridge the gap between chemical and electrostatic propulsion capabilities. A comparative methodology is outlined by which characteristics of chemical and electric propulsion for orbit raising mission can be investigated. It is noted that free radicals proposed in rockets previously met with difficulty and complexity in terms of storage requirements; the present study proposes to eliminate the storage requirements by using electric energy to achieve a continuous-flow product of free radicals which are recombined to produce a high velocity propellant. Microwave energy used to dissociate a continuously flowing gas is transferred to the propellant via three-body-recombination for conversion to propellant kinetic energy. Microwave plasma discharge was found in excess of 90 percent over a broad range of pressure in preliminary experiments, and microwave heating compared to electrothermal heating showed much higher temperatures in gasdynamic equations.

  9. Laparoscopic radical cystectomy

    PubMed Central

    Fergany, Amr

    2012-01-01

    Objective Laparoscopic radical cystectomy (LRC) has emerged as a minimally invasive alternative to open radical cystectomy (ORC). This review focuses on patient selection criteria, technical aspects and postoperative outcomes of LRC. Methods Material for the review was obtained by a PubMed search over the last 10 years, using the keywords ‘laparoscopic radical cystectomy’ and ‘laparoscopic bladder cancer’ in human subjects. Results Twenty-two publications selected for relevance and content were used for this review from the total search yield. The level of evidence was IIb and III. LRC results in comparable short- and intermediate-range oncological outcomes to ORC, with generally longer operative times but decreased blood loss, postoperative pain and hospital stay. Overall operative and postoperative morbidity are equivalent. Conclusion In experienced hands, LRC is an acceptable minimally invasive alternative to ORC in selected patients, with the main advantage of decreased blood loss and postoperative pain, as well as a shorter hospital stay and recovery. PMID:26558003

  10. THERMOCHEMISTRY OF HYDROCARBON RADICALS

    SciTech Connect

    Kent M. Ervin, Principal Investigator

    2004-08-17

    Gas phase negative ion chemistry methods are employed to determine enthalpies of formation of hydrocarbon radicals that are important in combustion processes and to investigate the dynamics of ion-molecule reactions. Using guided ion beam tandem mass spectrometry, we measure collisional threshold energies of endoergic proton transfer and hydrogen atom transfer reactions of hydrocarbon molecules with negative reagent ions. The measured reaction threshold energies for proton transfer yield the relative gas phase acidities. In an alternative methodology, competitive collision-induced dissociation of proton-bound ion-molecule complexes provides accurate gas phase acidities relative to a reference acid. Combined with the electron affinity of the R {center_dot} radical, the gas phase acidity yields the RH bond dissociation energy of the corresponding neutral molecule, or equivalently the enthalpy of formation of the R{center_dot} organic radical, using equation: D(R-H) = {Delta}{sub acid}H(RH) + EA(R) - IE(H). The threshold energy for hydrogen abstraction from a hydrocarbon molecule yields its hydrogen atom affinity relative to the reagent anion, providing the RH bond dissociation energy directly. Electronic structure calculations are used to evaluate the possibility of potential energy barriers or dynamical constrictions along the reaction path, and as input for RRKM and phase space theory calculations. In newer experiments, we have measured the product velocity distributions to obtain additional information on the energetics and dynamics of the reactions.

  11. Anionic surfactant with hydrophobic and hydrophilic chains for nanoparticle dispersion and shape memory polymer nanocomposites.

    PubMed

    Iijima, Motoyuki; Kobayakawa, Murino; Yamazaki, Miwa; Ohta, Yasuhiro; Kamiya, Hidehiro

    2009-11-18

    An anionic surfactant comprising a hydrophilic poly(ethylene glycol) (PEG) chain, hydrophobic alkyl chain, and polymerizable vinyl group was synthesized as a capping agent of nanoparticles. TiO(2) nanoparticles modified by this surfactant were completely dispersible in various organic solvents with a wide range of polarities, such as nitriles, alcohols, ketones, and acetates. Furthermore, these particles were found to be dispersible in various polymers with different properties, such as thermosetting epoxy resins and radical polymerized poly(methylmethacrylate) (PMMA). A polymer composite of surface-modified TiO(2) nanoparticles in epoxy resins prepared by using the developed surfactant also possessed temperature-induced shape memory properties. PMID:19852463

  12. Surface topography dependence of biomolecular hydrophobic hydration

    NASA Astrophysics Data System (ADS)

    Cheng, Yuen-Kit; Rossky, Peter J.

    1998-04-01

    Many biomolecules are characterized by surfaces containing extended nonpolar regions, and the aggregation and subsequent removal of such surfaces from water is believed to play a critical role in the biomolecular assembly in cells. A better understanding of the hydrophobic hydration of biomolecules may therefore yield new insights into intracellular assembly. Conventional views hold that the hydration shell of small hydrophobic solutes is clathrate-like, characterized by local cage-like hydrogen-bonding structures and a distinct loss in entropy. The hydration of extended nonpolar planar surfaces, however, appears to involve structures that are orientationally inverted relative to clathrate-like hydration shells,, with unsatisfied hydrogen bonds that are directed towards the hydrophobic surface. Here we present computer simulations of the interaction between the polypeptide melittin and water that demonstrate that the two different hydration structures also exist near a biomolecular surface. We find that the two structures are distinguished by a substantial difference in the water-water interaction enthalpy, and that their relative contributions depend strongly on the surface topography of the melittin molecule: clathrate-like structures dominate near convex surface patches, whereas the hydration shell near flat surfaces fluctuates between clathrate-like and less-ordered or inverted structures. The strong influence of surface topography on the structure and free energy of hydrophobic hydration is likely to hold in general, and will be particularly important for the many biomolecules whose surfaces contain convex patches, deep or shallow concave grooves and roughly planar areas.

  13. COSOLVENCY AND SOPRTION OF HYDROPHOBIC ORGANIC CHEMICALS

    EPA Science Inventory

    Sorption of hydrophobic organic chemicals (HOCs) by two soils was measured from mixed solvents containing water plus completely miscible organic solvents (CMOSs) and partially miscible organic solvents (PMOSs). The utility of the log-linear cosolvency model for predicting HOC sor...

  14. Energy Conversion over Super-hydrophobic Surfaces

    NASA Astrophysics Data System (ADS)

    Zhao, Hui; Zhai, Shengjie

    2015-11-01

    The streaming potential generated by a pressure-driven flow over a charged slip-stick surface with an arbitrary double layer thickness is both theoretically and experimentally studied. To understand the impact of the slip, the streaming potential is compared against that over a homogenously charged smooth surface. Our results indicate that the streaming potential over a super-hydrophobic surface only can be enhanced under certain conditions. In addition, the Onsager relation which directly relates the magnitude of electro-osmotic effect to that of the streaming current effect has been explicitly proved to be valid for thin and thick double layers and homogeneously charged super-hydrophobic surfaces. Comparisons between the streaming current and electro-osmotic mobility for an arbitrary electric double layer thickness under various conditions indicate that the Onsager relation seems applicable for arbitrary weakly charged super-hydrophobic surfaces though there is no general proof. Knowledge of the streaming potential over a slip-stick surface can provide guidance for designing novel and efficient microfluidic energy-conversion devices using super-hydrophobic surfaces. The work was supported by the NSF Grant No. ECCS-1509866.

  15. Charges in the hydrophobic interior of proteins

    PubMed Central

    Isom, Daniel G.; Castañeda, Carlos A.; Cannon, Brian R.; Velu, Priya D.; García-Moreno E., Bertrand

    2010-01-01

    Charges are inherently incompatible with hydrophobic environments. Presumably for this reason, ionizable residues are usually excluded from the hydrophobic interior of proteins and are found instead at the surface, where they can interact with bulk water. Paradoxically, ionizable groups buried in the hydrophobic interior of proteins play essential roles, especially in biological energy transduction. To examine the unusual properties of internal ionizable groups we measured the pKa of glutamic acid residues at 25 internal positions in a stable form of staphylococcal nuclease. Two of 25 Glu residues titrated with normal pKa near 4.5; the other 23 titrated with elevated pKa values ranging from 5.2–9.4, with an average value of 7.7. Trp fluorescence and far-UV circular dichroism were used to monitor the effects of internal charges on conformation. These data demonstrate that although charges buried in proteins are indeed destabilizing, charged side chains can be buried readily in the hydrophobic core of stable proteins without the need for specialized structural adaptations to stabilize them, and without inducing any major conformational reorganization. The apparent dielectric effect experienced by the internal charges is considerably higher than the low dielectric constants of hydrophobic matter used to represent the protein interior in electrostatic continuum models of proteins. The high thermodynamic stability required for proteins to withstand the presence of buried charges suggests a pathway for the evolution of enzymes, and it underscores the need to mind thermodynamic stability in any strategy for engineering novel or altered enzymatic active sites in proteins. PMID:20798341

  16. Pathways to dewetting in hydrophobic confinement

    PubMed Central

    Remsing, Richard C.; Xi, Erte; Vembanur, Srivathsan; Sharma, Sumit; Debenedetti, Pablo G.; Garde, Shekhar; Patel, Amish J.

    2015-01-01

    Liquid water can become metastable with respect to its vapor in hydrophobic confinement. The resulting dewetting transitions are often impeded by large kinetic barriers. According to macroscopic theory, such barriers arise from the free energy required to nucleate a critical vapor tube that spans the region between two hydrophobic surfaces—tubes with smaller radii collapse, whereas larger ones grow to dry the entire confined region. Using extensive molecular simulations of water between two nanoscopic hydrophobic surfaces, in conjunction with advanced sampling techniques, here we show that for intersurface separations that thermodynamically favor dewetting, the barrier to dewetting does not correspond to the formation of a (classical) critical vapor tube. Instead, it corresponds to an abrupt transition from an isolated cavity adjacent to one of the confining surfaces to a gap-spanning vapor tube that is already larger than the critical vapor tube anticipated by macroscopic theory. Correspondingly, the barrier to dewetting is also smaller than the classical expectation. We show that the peculiar nature of water density fluctuations adjacent to extended hydrophobic surfaces—namely, the enhanced likelihood of observing low-density fluctuations relative to Gaussian statistics—facilitates this nonclassical behavior. By stabilizing isolated cavities relative to vapor tubes, enhanced water density fluctuations thus stabilize novel pathways, which circumvent the classical barriers and offer diminished resistance to dewetting. Our results thus suggest a key role for fluctuations in speeding up the kinetics of numerous phenomena ranging from Cassie–Wenzel transitions on superhydrophobic surfaces, to hydrophobically driven biomolecular folding and assembly. PMID:26100866

  17. Charges in the hydrophobic interior of proteins.

    PubMed

    Isom, Daniel G; Castañeda, Carlos A; Cannon, Brian R; Velu, Priya D; García-Moreno E, Bertrand

    2010-09-14

    Charges are inherently incompatible with hydrophobic environments. Presumably for this reason, ionizable residues are usually excluded from the hydrophobic interior of proteins and are found instead at the surface, where they can interact with bulk water. Paradoxically, ionizable groups buried in the hydrophobic interior of proteins play essential roles, especially in biological energy transduction. To examine the unusual properties of internal ionizable groups we measured the pK(a) of glutamic acid residues at 25 internal positions in a stable form of staphylococcal nuclease. Two of 25 Glu residues titrated with normal pK(a) near 4.5; the other 23 titrated with elevated pK(a) values ranging from 5.2-9.4, with an average value of 7.7. Trp fluorescence and far-UV circular dichroism were used to monitor the effects of internal charges on conformation. These data demonstrate that although charges buried in proteins are indeed destabilizing, charged side chains can be buried readily in the hydrophobic core of stable proteins without the need for specialized structural adaptations to stabilize them, and without inducing any major conformational reorganization. The apparent dielectric effect experienced by the internal charges is considerably higher than the low dielectric constants of hydrophobic matter used to represent the protein interior in electrostatic continuum models of proteins. The high thermodynamic stability required for proteins to withstand the presence of buried charges suggests a pathway for the evolution of enzymes, and it underscores the need to mind thermodynamic stability in any strategy for engineering novel or altered enzymatic active sites in proteins. PMID:20798341

  18. Site reactivity in the free radicals induced damage to leucine residues: a theoretical study.

    PubMed

    Medina, M E; Galano, A; Alvarez-Idaboy, J R

    2015-02-21

    Several recent computational studies have tried to explain the observed selectivity in radical damage to proteins. In this work we use Density Functional Theory and Transition State Theory including tunnelling corrections, reaction path degeneracy, the effect of diffusion, and the role of free radicals to get further insights into this important topic. The reaction between a leucine derivative and free radicals of biological significance, in aqueous and lipid media, has been investigated. Both thermochemical and kinetic analyses, in both hydrophilic and hydrophobic environments, have been carried out. DPPH, ˙OOH, ˙OOCH3, ˙OOCH2Cl, ˙OOCHCl2 and ˙OOCHCH2 radicals do not react with the target molecule. The reactions are proposed to be kinetically controlled. The leucine gamma site was the most reactive for the reactions with ˙N3, ˙OOCCl3, ˙OCH3, ˙OCH2Cl, and ˙OCHCl2 radicals, with rate constants equal to 1.97 × 10(5), 3.24 × 10(4), 6.68 × 10(5), 5.98 × 10(6) and 8.87 × 10(8) M(-1) s(-1), respectively, in aqueous solution. The ˙Cl, ˙OH and ˙OCCl3 radicals react with leucine at the beta, gamma, and delta positions at rates close to the diffusion limit with the alpha position which is the slowest path and the most thermodynamically favored. The presented results confirm that the Bell-Evans-Polanyi principle does not apply for the reactions between amino acid residues and free radicals. Regarding the influence of the environment on the reactivity of the studied series of free radicals towards leucine residues, it is concluded that hydrophilic media slightly lower the reactivity of the studied radicals, compared to hydrophobic ones, albeit the trends in reactivity are very similar. PMID:25592549

  19. Oligorotaxane Radicals under Orders.

    PubMed

    Wang, Yuping; Frasconi, Marco; Liu, Wei-Guang; Sun, Junling; Wu, Yilei; Nassar, Majed S; Botros, Youssry Y; Goddard, William A; Wasielewski, Michael R; Stoddart, J Fraser

    2016-02-24

    A strategy for creating foldameric oligorotaxanes composed of only positively charged components is reported. Threadlike components-namely oligoviologens-in which different numbers of 4,4'-bipyridinium (BIPY(2+)) subunits are linked by p-xylylene bridges, are shown to be capable of being threaded by cyclobis(paraquat-p-phenylene) (CBPQT(4+)) rings following the introduction of radical-pairing interactions under reducing conditions. UV/vis/NIR spectroscopic and electrochemical investigations suggest that the reduced oligopseudorotaxanes fold into highly ordered secondary structures as a result of the formation of BIPY(•+) radical cation pairs. Furthermore, by installing bulky stoppers at each end of the oligopseudorotaxanes by means of Cu-free alkyne-azide cycloadditions, their analogous oligorotaxanes, which retain the same stoichiometries as their progenitors, can be prepared. Solution-state studies of the oligorotaxanes indicate that their mechanically interlocked structures lead to the enforced interactions between the dumbbell and ring components, allowing them to fold (contract) in their reduced states and unfold (expand) in their fully oxidized states as a result of Coulombic repulsions. This electrochemically controlled reversible folding and unfolding process, during which the oligorotaxanes experience length contractions and expansions, is reminiscent of the mechanisms of actuation associated with muscle fibers. PMID:27163033

  20. Oligorotaxane Radicals under Orders

    PubMed Central

    2016-01-01

    A strategy for creating foldameric oligorotaxanes composed of only positively charged components is reported. Threadlike components—namely oligoviologens—in which different numbers of 4,4′-bipyridinium (BIPY2+) subunits are linked by p-xylylene bridges, are shown to be capable of being threaded by cyclobis(paraquat-p-phenylene) (CBPQT4+) rings following the introduction of radical-pairing interactions under reducing conditions. UV/vis/NIR spectroscopic and electrochemical investigations suggest that the reduced oligopseudorotaxanes fold into highly ordered secondary structures as a result of the formation of BIPY•+ radical cation pairs. Furthermore, by installing bulky stoppers at each end of the oligopseudorotaxanes by means of Cu-free alkyne–azide cycloadditions, their analogous oligorotaxanes, which retain the same stoichiometries as their progenitors, can be prepared. Solution-state studies of the oligorotaxanes indicate that their mechanically interlocked structures lead to the enforced interactions between the dumbbell and ring components, allowing them to fold (contract) in their reduced states and unfold (expand) in their fully oxidized states as a result of Coulombic repulsions. This electrochemically controlled reversible folding and unfolding process, during which the oligorotaxanes experience length contractions and expansions, is reminiscent of the mechanisms of actuation associated with muscle fibers. PMID:27163033

  1. Radically innovative steelmaking technologies

    NASA Astrophysics Data System (ADS)

    Szekely, Julian

    1980-09-01

    The steel industry is faced with serious problems caused by the increasing cost of energy, labor and capital and by tough overseas competition, employing new highly efficient process plants. The very high cost of capital and of capital equipment renders the construction of new green field site plants, exemplifying the best available technology economically unattractive. For this reason, over the long term the development radically innovative steelmaking technologies appears to be the only satisfactory resolution of this dilemma. The purpose of this article is to present a critical review of some of the radically innovative steelmaking technologies that have been proposed during the past few years and to develop the argument that these indeed do deserve serious consideration at the present time. It should be stressed, however, that these innovative technologies can be implemented only as part of a carefully conceived long range plan, which contains as a subset short term solutions, such as trigger prices improved investment credits, and so forth and intermediate term solutions, such as more extensive use of continuous casting, external desulfurization and selective modernization in general.

  2. Radical-radical interactions among oxidized guanine bases including guanine radical cation and dehydrogenated guanine radicals.

    PubMed

    Zhao, Jing; Wang, Mei; Yang, Hongfang; Zhang, Meng; Liu, Ping; Bu, Yuxiang

    2013-09-19

    We present here a theoretical investigation of the structural and electronic properties of di-ionized GG base pairs (G(•+)G(•+),G(-H1)(•)G(•+), and G(-H1)(•)G(-H1)(•)) consisting of the guanine cation radical (G(•+)) and/or dehydrogenated guanine radical (G(-H1)(•)) using density functional theory calculations. Different coupling modes (Watson-Crick/WC, Hoogsteen/Hoog, and minor groove/min hydrogen bonding, and π-π stacking modes) are considered. We infer that a series of G(•+)G(•+) complexes can be formed by the high-energy radiation. On the basis of density functional theory and complete active space self-consistent (CASSCF) calculations, we reveal that in the H-bonded and N-N cross-linked modes, (G(•+)G(•+))WC, (G(-H1)(•)G(-H1)(•))WC, (G(-H1)(•)G(-H1)(•))minI, and (G(-H1)(•)G(-H1)(•))minIII have the triplet ground states; (G(•+)G(•+))HoogI, (G(-H1)(•)G(•+))WC, (G(-H1)(•)G(•+))HoogI, (G(-H1)(•)G(•+))minI, (G(-H1)(•)G(•+))minII, and (G(-H1)(•)G(-H1)(•))minII possess open-shell broken-symmetry diradical-characterized singlet ground states; and (G(•+)G(•+))HoogII, (G(•+)G(•+))minI, (G(•+)G(•+))minII, (G(•+)G(•+))minIII, (G(•+)G(•+))HoHo, (G(-H1)(•)G(•+))minIII, (G(-H1)(•)G(•+))HoHo, and (G(-H1)(•)G(-H1)(•))HoHo are the closed-shell systems. For these H-bonded diradical complexes, the magnetic interactions are weak, especially in the diradical G(•+)G(•+) series and G(-H1)(•)G(-H1)(•) series. The magnetic coupling interactions of the diradical systems are controlled by intermolecular interactions (H-bond, electrostatic repulsion, and radical coupling). The radical-radical interaction in the π-π stacked di-ionized GG base pairs ((G(•+)G(•+))ππ, (G(-H1)(•)G(•+))ππ, and (G(-H1)(•)G(-H1)(•))ππ) are also considered, and the magnetic coupling interactions in these π-π stacked base pairs are large. This is the first theoretical prediction that some di

  3. Curvature Dependence of Hydrophobic Hydration Dynamics

    NASA Astrophysics Data System (ADS)

    Weiß, R. Gregor; Heyden, Matthias; Dzubiella, Joachim

    2015-05-01

    We investigate the solute curvature dependence of water dynamics in the vicinity of hydrophobic spherical solutes using molecular dynamics simulations. For both the lateral and perpendicular diffusivity, as well as for H-bond kinetics of water in the first hydration shell, we find a nonmonotonic solute-size dependence, exhibiting extrema close to the well-known structural crossover length scale for hydrophobic hydration. Additionally, we find an apparent anomalous diffusion for water moving parallel to the surface of small solutes, which, however, can be explained by topology effects. Our findings regarding the intimate connection between solute curvature and water dynamics has implications for our understanding of hydration dynamics at heterogeneous biomolecular surfaces.

  4. Dewetting-induced collapse of hydrophobic particles

    PubMed Central

    Huang, X.; Margulis, C. J.; Berne, B. J.

    2003-01-01

    A molecular dynamics study of the depletion of water (drying) around a single and between two hydrophobic nanoscale oblate plates in explicit water as a function of the distance of separation between them, their size, and the strength of the attraction between the plates and the water molecules is presented. A simple macroscopic thermodynamic model based on Young's law successfully predicts drying between the stacked plates and accounts for the free-energy barriers to this drying. However, because drying around a single plate is not macroscopic, a molecular theory is required to describe it. The data are consistent with the rate-determining step in the hydrophobic collapse of the two plates being a large-scale drying fluctuation, characterized by a free-energy barrier that grows with particle size. PMID:14507993

  5. Oxygen radicals and renal diseases.

    PubMed

    Klahr, S

    1997-01-01

    Reactive oxygen metabolites (superoxide, hydrogen peroxide, hydroxyl radical, and hypochlorous acid) are important mediators of renal damage in acute renal failure and glomerular and tubulointerstitial diseases. The role of these oxygen metabolites in the above entities is discussed, and the effects of antioxidants and scavengers of O2 radicals are considered. The role of oxygen radicals in the regulation of gene transcription is also considered. PMID:9387104

  6. Temperature dependence of amino acid hydrophobicities

    PubMed Central

    Wolfenden, Richard; Lewis, Charles A.; Yuan, Yang; Carter, Charles W.

    2015-01-01

    The hydrophobicities of the 20 common amino acids are reflected in their tendencies to appear in interior positions in globular proteins and in deeply buried positions of membrane proteins. To determine whether these relationships might also have been valid in the warm surroundings where life may have originated, we examined the effect of temperature on the hydrophobicities of the amino acids as measured by the equilibrium constants for transfer of their side-chains from neutral solution to cyclohexane (Kw>c). The hydrophobicities of most amino acids were found to increase with increasing temperature. Because that effect is more pronounced for the more polar amino acids, the numerical range of Kw>c values decreases with increasing temperature. There are also modest changes in the ordering of the more polar amino acids. However, those changes are such that they would have tended to minimize the otherwise disruptive effects of a changing thermal environment on the evolution of protein structure. Earlier, the genetic code was found to be organized in such a way that—with a single exception (threonine)—the side-chain dichotomy polar/nonpolar matches the nucleic acid base dichotomy purine/pyrimidine at the second position of each coding triplet at 25 °C. That dichotomy is preserved at 100 °C. The accessible surface areas of amino acid side-chains in folded proteins are moderately correlated with hydrophobicity, but when free energies of vapor-to-cyclohexane transfer (corresponding to size) are taken into consideration, a closer relationship becomes apparent. PMID:26034278

  7. Bacterial Interaction with Hydrophobic and Hydrophilic Interfaces

    NASA Astrophysics Data System (ADS)

    Pedri, Laura; Itier, Sophie; Schraft, Heidi; Hawton, Margaret

    2004-03-01

    Bacterial adhesion is believed to be governed by physical-chemical laws in the initial stages of attachment. We calculate the free energy of adhesion for a Pseudomonas putida bacterium interacting with either mercaptoundecanol or dodecanethiol self-assembled monolayers using the Young-Dupré equation and experimentally measured contact angles. We then compare our model with preliminary biological studies involving the analysis of real-time laser scanning confocal microscopy images of bacteria attaching to hydrophobic and hydrophilic substrates.

  8. DNA Hairpin Stabilization on a Hydrophobic Surface

    PubMed Central

    Kastantin, Mark

    2013-01-01

    DNA hybridization in the vicinity of surfaces is a fundamental process for self-assembled nanoarrays, nanocrystal superlattices, and biosensors. It is widely recognized that solid surfaces alter molecular forces governing hybridization relative to bulk solution, and these effects can either favor or disfavor the hybridized state depending on the specific sequence and surface. Results presented here provide new insights into the dynamics of DNA hairpin-coil conformational transitions in the vicinity of hydrophilic oligo(ethylene glycol) (OEG) and hydrophobic trimethylsilane (TMS) surfaces. Single-molecule methods are used to observe the forward and reverse hybridization hairpin-coil transition of adsorbed species while simultaneously measuring molecular surface diffusion in order to gain insight into surface interactions with individual DNA bases. At least 35,000 individual molecular trajectories are observed on each type of surface. We find that unfolding slows and the folding rate increases on TMS relative to OEG despite stronger attractions between TMS and unpaired nucleobases. These rate differences lead to nearly complete hairpin formation on hydrophobic TMS and significant unfolding on hydrophilic OEG, resulting in the surprising conclusion that hydrophobic surface coatings are preferable for nanotechnology applications that rely on DNA hybridization near surfaces. PMID:23184340

  9. Diameter-dependent hydrophobicity in carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Kyakuno, Haruka; Fukasawa, Mamoru; Ichimura, Ryota; Matsuda, Kazuyuki; Nakai, Yusuke; Miyata, Yasumitsu; Saito, Takeshi; Maniwa, Yutaka

    2016-08-01

    Single-wall carbon nanotubes (SWCNTs) are a good model system that provides atomically smooth nanocavities. It has been reported that water-SWCNTs exhibit hydrophobicity depending on the temperature T and the SWCNT diameter D. SWCNTs adsorb water molecules spontaneously in their cylindrical pores around room temperature, whereas they exhibit a hydrophilic-hydrophobic transition or wet-dry transition (WDT) at a critical temperature Twd ≈ 220-230 K and above a critical diameter Dc ≈ 1.4-1.6 nm. However, details of the WDT phenomenon and its mechanism remain unknown. Here, we report a systematic experimental study involving X-ray diffraction, optical microscopy, and differential scanning calorimetry. It is found that water molecules inside thick SWCNTs (D > Dc) evaporate and condense into ice Ih outside the SWCNTs at Twd upon cooling, and the ice Ih evaporates and condenses inside the SWCNTs upon heating. On the other hand, residual water trapped inside the SWCNTs below Twd freezes. Molecular dynamics simulations indicate that upon lowering T, the hydrophobicity of thick SWCNTs increases without any structural transition, while the water inside thin SWCNTs (D < Dc) exhibits a structural transition, forming an ordered ice. This ice has a well-developed hydrogen bonding network adapting to the cylindrical pores of the SWCNTs. Thus, the unusual diameter dependence of the WDT is attributed to the adaptability of the structure of water to the pore dimension and shape.

  10. Nonflammable, Hydrophobic Aerogel Composites for Insulation

    NASA Technical Reports Server (NTRS)

    Redouane, Begag

    2005-01-01

    Aerogel composites that are both nonflammable and hydrophobic have been developed for use as lightweight thermal- insulation materials for cryogenic systems. Aerogels are well known in the industry for their effectiveness as thermal insulators under cryogenic conditions, but the treatments used heretofore to render them hydrophobic also make them flammable. Nonflammability would make it safer to use aerogel insulation, especially in oxygen-rich environments and on cryogenic systems that contain liquid oxygen. A composite of this type is a silica aerogel reinforced with fibers. In comparison with unreinforced aerogels, the aerogel composite is about ten times as stiff and strong, better able to withstand handling, and more amenable to machining to required shapes. The composite can be made hydrophobic and nonflammable by appropriate design of a sol-gel process used to synthesize the aerogel component. In addition to very low thermal conductivity needed for insulation, aerogel composites of this type have been found to exhibit high resistance to moisture and nonflammability in oxygen-rich atmospheres: Samples floating on water for months gained no weight and showed no signs of deterioration. Samples were found to be nonflammable, even in pure oxygen at atmospheric pressure [14.7 psia (0.10 MPa)

  11. Exposure of hydrophobic moieties promotes the selective degradation of hydrogen peroxide-modified hemoglobin by the multicatalytic proteinase complex, proteasome.

    PubMed

    Giulivi, C; Pacifici, R E; Davies, K J

    1994-06-01

    between Hb hydrophobicity and proteolytic susceptibility for both Fraction II and proteasome. Inhibitor studies and SDS activation experiments indicate that proteasome is responsible for most of the Hb degradation during exposure of RBC to H2O2. Previous work yielded essentially identical conclusions for Hb exposed to hydroxyl radicals (R. E. Pacifici, Y. Kono, and K. J. A. Davies, J. Biol. Chem. 268, 15405-15411, 1993). Thus, nonspecific oxidation by .OH and site-specific (metal-catalyzed) oxidation by H2O2 both yield a more hydrophobic Hb molecule with increased proteolytic susceptibility. We propose that increased exposure of hydrophobic, and perhaps basic, amino acids is the general common cause for degradation of oxidized proteins.(ABSTRACT TRUNCATED AT 400 WORDS) PMID:8203895

  12. Free radical propulsion concept

    NASA Technical Reports Server (NTRS)

    Hawkins, C. E.; Nakanishi, S.

    1981-01-01

    A free radical propulsion concept utilizing the recombination energy of dissociated low molecular weight gases to produce thrust was examined. The concept offered promise of a propulsion system operating at a theoretical impulse, with hydrogen, as high as 2200 seconds at high thrust to power ratio, thus filling the gas existing between chemical and electrostatic propulsion capabilities. Microwave energy used to dissociate a continuously flowing gas was transferred to the propellant via three body recombination for conversion to propellant kinetic energy. Power absorption by the microwave plasma discharge was in excess of 90 percent over a broad range of pressures. Gas temperatures inferred from gas dynamic equations showed much higher temperatures from microwave heating than from electrothermal heating. Spectroscopic analysis appeared to corroborate the inferred temperatures of one of the gases tested.

  13. Radicals in Berkeley?

    PubMed Central

    Linn, Stuart

    2015-01-01

    In a previous autobiographical sketch for DNA Repair (Linn, S. (2012) Life in the serendipitous lane: excitement and gratification in studying DNA repair. DNA Repair 11, 595–605), I wrote about my involvement in research on mechanisms of DNA repair. In this Reflections, I look back at how I became interested in free radical chemistry and biology and outline some of our bizarre (at the time) observations. Of course, these studies could never have succeeded without the exceptional aid of my mentors: my teachers; the undergraduate and graduate students, postdoctoral fellows, and senior lab visitors in my laboratory; and my faculty and staff colleagues here at Berkeley. I am so indebted to each and every one of these individuals for their efforts to overcome my ignorance and set me on the straight and narrow path to success in research. I regret that I cannot mention and thank each of these mentors individually. PMID:25713083

  14. Hydrophobic pocket targeting probes for enteroviruses

    NASA Astrophysics Data System (ADS)

    Martikainen, Mari; Salorinne, Kirsi; Lahtinen, Tanja; Malola, Sami; Permi, Perttu; Häkkinen, Hannu; Marjomäki, Varpu

    2015-10-01

    Visualization and tracking of viruses without compromising their functionality is crucial in order to understand virus targeting to cells and tissues, and to understand the subsequent subcellular steps leading to virus uncoating and replication. Enteroviruses are important human pathogens causing a vast number of acute infections, and are also suggested to contribute to the development of chronic diseases like type I diabetes. Here, we demonstrate a novel method to target site-specifically the hydrophobic pocket of enteroviruses. A probe, a derivative of Pleconaril, was developed and conjugated to various labels that enabled the visualization of enteroviruses under light and electron microscopes. The probe mildly stabilized the virus particle by increasing the melting temperature by 1-3 degrees, and caused a delay in the uncoating of the virus in the cellular endosomes, but could not however inhibit the receptor binding, cellular entry or infectivity of the virus. The hydrophobic pocket binding moiety of the probe was shown to bind to echovirus 1 particle by STD and tr-NOESY NMR methods. Furthermore, binding to echovirus 1 and Coxsackievirus A9, and to a lesser extent to Coxsackie virus B3 was verified by using a gold nanocluster labeled probe by TEM analysis. Molecular modelling suggested that the probe fits the hydrophobic pockets of EV1 and CVA9, but not of CVB3 as expected, correlating well with the variations in the infectivity and stability of the virus particles. EV1 conjugated to the fluorescent dye labeled probe was efficiently internalized into the cells. The virus-fluorescent probe conjugate accumulated in the cytoplasmic endosomes and caused infection starting from 6 hours onwards. Remarkably, before and during the time of replication, the fluorescent probe was seen to leak from the virus-positive endosomes and thus separate from the capsid proteins that were left in the endosomes. These results suggest that, like the physiological hydrophobic content

  15. A new procedure for the hydrophobization of cellulose fibre using laccase and a hydrophobic phenolic compound.

    PubMed

    Garcia-Ubasart, Jordi; Colom, Josep F; Vila, Carlos; Gómez Hernández, Nuria; Blanca Roncero, M; Vidal, Teresa

    2012-05-01

    A new biotechnological procedure using laccase in combination with a hydrophobic phenolic compound (lauryl gallate) for the hydrophobization of cellulose fibres and internal sizing of paper was developed. Cellulose fibres from hardwood kraft pulp were incubated with laccase (Lac), in combination with lauryl gallate (LG). The Lac-LG treatment resulted in the internal sizing of paper, and also in significantly reduced water penetration in the handsheets and wettability of the paper surface. Paper was found not to be effectively rendered hydrophobic by LG alone. SEM images of the fibre network revealed the presence of the sizing agent: a product of the reaction between laccase and lauryl gallate. Binding of lauryl gallate to cellulose fibres was suggested by the increase in kappa number of the pulp and further confirmed by IR spectroscopy. PMID:22440576

  16. Hydrophobic pocket targeting probes for enteroviruses

    NASA Astrophysics Data System (ADS)

    Martikainen, Mari; Salorinne, Kirsi; Lahtinen, Tanja; Malola, Sami; Permi, Perttu; Häkkinen, Hannu; Marjomäki, Varpu

    2015-10-01

    Visualization and tracking of viruses without compromising their functionality is crucial in order to understand virus targeting to cells and tissues, and to understand the subsequent subcellular steps leading to virus uncoating and replication. Enteroviruses are important human pathogens causing a vast number of acute infections, and are also suggested to contribute to the development of chronic diseases like type I diabetes. Here, we demonstrate a novel method to target site-specifically the hydrophobic pocket of enteroviruses. A probe, a derivative of Pleconaril, was developed and conjugated to various labels that enabled the visualization of enteroviruses under light and electron microscopes. The probe mildly stabilized the virus particle by increasing the melting temperature by 1-3 degrees, and caused a delay in the uncoating of the virus in the cellular endosomes, but could not however inhibit the receptor binding, cellular entry or infectivity of the virus. The hydrophobic pocket binding moiety of the probe was shown to bind to echovirus 1 particle by STD and tr-NOESY NMR methods. Furthermore, binding to echovirus 1 and Coxsackievirus A9, and to a lesser extent to Coxsackie virus B3 was verified by using a gold nanocluster labeled probe by TEM analysis. Molecular modelling suggested that the probe fits the hydrophobic pockets of EV1 and CVA9, but not of CVB3 as expected, correlating well with the variations in the infectivity and stability of the virus particles. EV1 conjugated to the fluorescent dye labeled probe was efficiently internalized into the cells. The virus-fluorescent probe conjugate accumulated in the cytoplasmic endosomes and caused infection starting from 6 hours onwards. Remarkably, before and during the time of replication, the fluorescent probe was seen to leak from the virus-positive endosomes and thus separate from the capsid proteins that were left in the endosomes. These results suggest that, like the physiological hydrophobic content

  17. Highly Hydrophobic Coatings from Waterborne Latexes.

    PubMed

    López, Ana B; de la Cal, José C; Asua, José M

    2016-08-01

    This work reports on the formation of highly hydrophobic coatings from waterborne latexes able to form films at ambient temperature. The contact angle of film forming copolymers of 2-ethylhexyl acrylate and perfluorodecyl acrylate (PFDA) was limited to 114° because flat surfaces were obtained. Attempts to increase the roughness of the film using blends of film-forming latexes with the latex of PFDA homopolymer (which is not film forming) were not successful under regular casting conditions because the PFDA particles accumulated at the film-substrate interface. Film formation engineering allowed modifying the morphology of the film obtaining a contact angle of 137°. PMID:27400332

  18. Atmospheric pressure plasma polymerization of 1,3-butadiene for hydrophobic finishing of textile substrates

    NASA Astrophysics Data System (ADS)

    Samanta, Kartick K.; Jassal, Manjeet; Agrawal, Ashwini K.

    2010-02-01

    Atmospheric pressure plasma processing of textile has both ecological and economical advantages over the wet-chemical processing. However, reaction in atmospheric pressure plasma has important challenges to be overcome before it can be successfully used for finishing applications in textile. These challenges are (i) generating stable glow plasma in presence liquid/gaseous monomer, and (ii) keeping the generated radicals active in the presence of contaminants such as oxygen and air. In this study, a stable glow plasma was generated at atmospheric pressure in the mixture of gaseous reactive monomer-1,3-butadiene and He and was made to react with cellulosic textile substrate. After 12 min of plasma treatment, the hydrophilic surface of the cellulosic substrate turned into highly hydrophobic surface. The hydrophobic finish was found to be durable to soap washing. After soap washing, a water drop of 37 μl took around 250 s to get absorbed in the treated sample compared to < 1 s in the untreated samples. The plasma modified samples showed water contact angle of around 134°. Both top and bottom sides of the fabric showed similar hydrophobic results in terms of water absorbency and contact angle. The results may be attributed to chemical reaction of butadiene with the cellulosic textile substrate. The surface characterization of the plasma modified samples under SEM and AFM revealed modification of the surface under <100 nm. The results showed that atmospheric pressure plasma can be successfully used for carrying out reaction of 1,3-butadiene with cellulosic textile substrates for producing hydrophobic surface finish.

  19. Thermoresponsive hyaluronic acid nanogels as hydrophobic drug carrier to macrophages.

    PubMed

    Fernandes Stefanello, Talitha; Szarpak-Jankowska, Anna; Appaix, Florence; Louage, Benoit; Hamard, Lauriane; De Geest, Bruno G; van der Sanden, Boudewijn; Nakamura, Celso Vataru; Auzély-Velty, Rachel

    2014-11-01

    Delivery systems for macrophages are particularly attractive since these phagocytic cells play a important role in immunological and inflammatory responses, also acting as host cells for microorganisms that are involved in deadly infectious diseases, such as leishmaniasis. Hyaluronic acid (HA) is specifically recognized by macrophages that are known to express HA receptors. Therefore, in this study, we focused on HA-based nanogels as drug carriers for these cells. The drug delivery was validated in an in vivo study on mice using intravital two-photon laser scanning microscopy. HA derivatives were modified with a biocompatible oligo(ethylene glycol)-based thermoresponsive polymer to form nanogels. These HA conjugates were readily prepared by varying the molar mass of initial HA and the degree of substitution via radical-mediated thiol-ene chemistry in aqueous solution. The derivatives were shown to self-assemble into spherical gel particles with diameters ranging from 150 to 214 nm above 37 °C. A poorly water-soluble two-photon dye was successfully loaded into the nanogels during this self-assembly process. In vitro cellular uptake tests using a RAW 264.7 murine macrophage cell line showed successful intracellular delivery of the hydrophobic dye. After intravenous injection in mice, the nanogels circulated freely in the blood but were rapidly phagocytized within 13 min by circulating macrophages and stored in the liver and spleen, as observed by two-photon microscopy. Benefit can be thus expected in using such a delivery system for the liver and spleen macrophage-associated diseases. PMID:25110287

  20. Development of the selective hydrophobic coagulation process

    SciTech Connect

    Yoon, R.H.; Luttrell, G.H.

    1992-01-01

    A novel technique for selectively coagulating and separating coal from dispersed mineral matter has been developed at Virginia Tech. The process, Selective Hydrophobic Coagulation (SHC), has been studied since 1986 under the sponsorship of the US Department of Energy. The SHC process differs from oil agglomeration, shear or polymer flocculation, and electrolytic coagulation processes in that it does not require reagents or additives to induce the formation of coagula. In most cases, simple pH control is all that is required to (i) induce the coagulation of coal particles and (ii) effectively disperse particles of mineral matter. If the coal is oxidized, a small dosage of reagents can be used to enhance the process. The technical work program was initiated on July 1, 1992. Force-distance curves were generated for DDOA Br-coated mica surfaces in water and used to calculate hydrophobicity constants and decay lengths for this system; and a new device for the measurement of water contact angles, similar to the Wilhelmy plate balance, has been built 225 kg samples of Pittsburgh No. 8 and Elkhom No. 3 seam coals were obtained; a static mixer test facility for the study of coagula growth was set up and was undergoing shakedown tests at the end of the quarter; a bench-scale lamella thickener was being constructed; and preliminary coagula/ mineral separation tests were being conducted in a bench-scale continuous drum filter.

  1. Development of the Selective Hydrophobic Coagulation process

    SciTech Connect

    Yoon, R.H.; Luttrell, G.H.

    1992-01-01

    A novel technique for selectively coagulating and separating coal from dispersed mineral matter has been developed at Virginia Tech. The process, Selective Hydrophobic Coagulation (SHC), has been studied since 1986 under the sponsorship of the US Department of Energy (Contracts AC22-86PC91221 and AC22-90PC90174). The SHC process differs from oil agglomeration, shear or polymer flocculation, and electrolytic coagulation processes in that it does not require reagents or additives to induce the formation of coagula. In most cases, simple pH control is all that is required to (1) induce the coagulation of coal particles and (2) effectively disperse particles of mineral matter. If the coal is oxidized, a small dosage of reagents can be used to enhance the process. During the quarter, the Anutech Mark IV surface force apparatus was used to generate surface force-distance data for the mica/dodecylamine hydrochloride system (Task 2.1.1). Work to characterize the hydrophobicity of this system and the mica/DDOA[sup [minus

  2. The Dewetting Transition and The Hydrophobic Effect.

    SciTech Connect

    Choudhury, Niharendu; Pettitt, Bernard M.

    2007-03-27

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. A molecular-level description of the behavior of water in hydrophobic spaces is presented in terms of the coupled effects of solute size and atomic solute-solvent interactions. For model solutes with surface areas near those of protein contacts, we identify three different regions of solute-water interaction to be associated with three distinctly different structural characteristics of water in the intersolute region: dry, oscillating, and wet. A first orderlike phase transition is confirmed from the wet to dry state bridged by a narrow region with liquid-vapor oscillations in the intersolute region as the strength of the solute-water attractive dispersion interaction decreases. We demonstrate that the recent idea that cavitation in the intersolute region of nanoscopic solutes is preceded by the formation of a vapor layer around an individual solute is not the general case. The appearance of density waves pulled up around and outside of a nanoscopic plate occurs at lower interaction strengths than are required to obtain a wet state between such plates. We further show that chemically reasonable estimates of the interaction strength lead to a microscopically wet state and a hydrophobic interaction characterized by traps and barriers to association and not by vacuum induced collapse.

  3. Peroxy radical partitioning during the AMMA radical intercomparison exercise

    NASA Astrophysics Data System (ADS)

    Andrés-Hernández, M. D.; Stone, D.; Brookes, D. M.; Commane, R.; Reeves, C. E.; Huntrieser, H.; Heard, D. E.; Monks, P. S.; Burrows, J. P.; Schlager, H.; Kartal, D.; Evans, M. J.; Floquet, C. F. A.; Ingham, T.; Methven, J.; Parker, A. E.

    2010-11-01

    Peroxy radicals were measured onboard two scientific aircrafts during the AMMA (African Monsoon Multidisciplinary Analysis) campaign in summer 2006. This paper reports results from the flight on 16 August 2006 during which measurements of HO2 by laser induced fluorescence spectroscopy at low pressure (LIF-FAGE) and total peroxy radicals (RO2* = HO2+ΣRO2, R = organic chain) by two similar instruments based on the peroxy radical chemical amplification (PeRCA) technique were subject of a blind intercomparison. The German DLR-Falcon and the British FAAM-BAe-146 flew wing tip to wing tip for about 30 min making concurrent measurements on 2 horizontal level runs at 697 and 485 hPa over the same geographical area in Burkina Faso. A full set of supporting measurements comprising photolysis frequencies, and relevant trace gases like CO, NO, NO2, NOy, O3 and a wider range of VOCs were collected simultaneously. Results are discussed on the basis of the characteristics and limitations of the different instruments used. Generally, no data bias are identified and the RO2* data available agree quite reasonably within the instrumental errors. The [RO2*]/[HO2] ratios, which vary between 1:1 and 3:1, as well as the peroxy radical variability, concur with variations in photolysis rates and in other potential radical precursors. Model results provide additional information about dominant radical formation and loss processes.

  4. Peroxy radical partitioning during the AMMA radical intercomparison exercise

    NASA Astrophysics Data System (ADS)

    Andrés-Hernández, M. D.; Stone, D.; Brookes, D. M.; Commane, R.; Reeves, C. E.; Huntrieser, H.; Heard, D. E.; Monks, P. S.; Burrows, J. P.; Schlager, H.; Kartal, D.; Evans, M. J.; Floquet, C. F. A.; Ingham, T.; Methven, J.; Parker, A. E.

    2010-04-01

    Peroxy radicals were measured onboard two scientific aircrafts during the AMMA (African Monsoon Multidisciplinary Analysis) campaign in summer 2006. This paper reports results from the flight on 16 August 2006 during which measurements of HO2 by laser induced fluorescence spectroscopy at low pressure (LIF-FAGE) and total peroxy radicals (RO2*=HO2+ΣRO2, R= organic chain) by two similar instruments based on the peroxy radical chemical amplification (PerCA) technique were subject of a blind intercomparison. The German DLR-Falcon and the British FAAM-BAe-146 flew wing tip to wing tip for about 30 min making concurrent measurements on 2 horizontal level runs at 697 and 485 hPa over the same geographical area in Burkina Faso. A full set of supporting measurements comprising photolysis frequencies, and relevant trace gases like CO, NO, NO2, NOy, O3 and a wider range of VOCs were collected simultaneously. Results are discussed on the basis of the characteristics and limitations of the different instruments used. Generally, no data bias are identified and the RO2* data available agree quite reasonably within the instrumental errors. The [RO2*]/[HO2] ratios, which vary between 1:1 and 3:1, as well as the peroxy radical variability, concur with variations in photolysis rates and in other potential radical precursors. Model results provide additional information about dominant radical formation and loss processes.

  5. Contacts Between Alcohols in Water Are Random Rather than Hydrophobic.

    PubMed

    Rankin, Blake M; Ben-Amotz, Dor; van der Post, Sietse T; Bakker, Huib J

    2015-02-19

    Given the importance of water-mediated hydrophobic interactions in a wide range of biological and synthetic self-assembly processes, it is remarkable that both the sign and the magnitude of the hydrophobic interactions between simple amphiphiles, such as alcohols, remain unresolved. To address this question, we have performed Raman hydration-shell vibrational spectroscopy and polarization-resolved femtosecond infrared experiments, as well as random mixing and molecular dynamics simulations. Our results indicate that there are no more hydrophobic contacts in aqueous solutions of alcohols ranging from methanol to tertiary butyl alcohol than in random mixtures of the same concentration. This implies that the interaction between small hydrophobic groups is weaker than thermal energy fluctuations. Thus, the corresponding water-mediated hydrophobic interaction must be repulsive, with a magnitude sufficient to negate the attractive direct van der Waals interaction between the hydrophobic groups. PMID:26262487

  6. Statistical Analyses of Hydrophobic Interactions: A Mini-Review.

    PubMed

    Pratt, Lawrence R; Chaudhari, Mangesh I; Rempe, Susan B

    2016-07-14

    This review focuses on the striking recent progress in solving for hydrophobic interactions between small inert molecules. We discuss several new understandings. First, the inverse temperature phenomenology of hydrophobic interactions, i.e., strengthening of hydrophobic bonds with increasing temperature, is decisively exhibited by hydrophobic interactions between atomic-scale hard sphere solutes in water. Second, inclusion of attractive interactions associated with atomic-size hydrophobic reference cases leads to substantial, nontrivial corrections to reference results for purely repulsive solutes. Hydrophobic bonds are weakened by adding solute dispersion forces to treatment of reference cases. The classic statistical mechanical theory for those corrections is not accurate in this application, but molecular quasi-chemical theory shows promise. Finally, because of the masking roles of excluded volume and attractive interactions, comparisons that do not discriminate the different possibilities face an interpretive danger. PMID:27258151

  7. School Finance-Radical Departure.

    ERIC Educational Resources Information Center

    Kimple, James

    1983-01-01

    It is proposed that New Jersey assume approximately 70 percent of the cost of its public schools. Several other proposals are presented, all a radical departure from current school funding practices. (BW)

  8. Free radical inactivation of pepsin

    NASA Astrophysics Data System (ADS)

    Josimović, Lj; Ruvarac, I.; Janković, I.; Jovanović, S. V.

    1994-06-01

    Alkylperoxy radicals containing one, two or three chlorine atoms, CO -2, O 2 - were reacted with pepsin in aqueous solutions. It was found that only Cl 3COO and CO -2 inactive pepsin, attacking preferentially the disulfide bridge. Transient spectra obtained upon completion of the Cl 3COO + pepsin reaction at pH 5 indicate that 20% of initially produced Cl 3COO radicals oxidizes tryptophan residues, and 40% disulfide bridges. The inactivation induced by the Cl 3COO radical increases at lower pH, and the maximal inactivation, Gin = 5.8, was observed at pH 1.5. The inactivation of pepsin by CO -2 radicals depends on the absorbed dose. The maximal inactivation, Gin = 4.5, was determined in the dose range from 38 to 53 Gy.

  9. Redox Properties of Free Radicals.

    ERIC Educational Resources Information Center

    Neta, P.

    1981-01-01

    Describes pulse radiolysis as a useful means in studing one-electron redox potentials. This method allows the production of radicals and the determination of their concentration and rates of reaction. (CS)

  10. Conductive hydrophobic hybrid textiles modified with carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Kowalczyk, D.; Brzeziński, S.; Makowski, T.; Fortuniak, W.

    2015-12-01

    The paper presents the results of modifying and testing modern hybrid polyester-cotton woven fabrics with deposited multi-wall carbon nanotubes and imparted hydrophobicity. The effect of the carbon nanotubes deposited on these fabrics on their conductive properties and hydrophobicity has been assessed. The electro-conductive and hydrophobic composite fabrics obtained in this way, being light, elastic and resistant to mechanical effects, make it possible to be widely used in various industrial fields.

  11. [Alcohol and free oxygen radicals].

    PubMed

    Mira, M L; Manso, C F

    1993-05-01

    Oxygen free radicals may be generated during ethanol metabolization by cytochrome P450, or due to the formation of xanthine oxidase by ethanol effect on xanthine dehydrogenase. After transformation into acetaldehyde, the metabolism of this compound by xanthine oxidase or by aldehyde oxidase also generates oxygen radicals. We present the hypothesis of a vicious cycle during ethanol metabolization by aldehyde oxidase, which would amplify the process and be responsible for an increased degree of lipid peroxidation. PMID:8393265

  12. Combined hydrophobicity and mechanical durability through surface nanoengineering

    DOE PAGESBeta

    Elliott, Paul R.; Stagon, Stephen P.; Huang, Hanchen; Furrer, David U.; Burlatsky, Sergei F.; Filburn, Thomas P.

    2015-04-08

    This paper reports combined hydrophobicity and mechanical durability through the nanoscale engineering of surfaces in the form of nanorod-polymer composites. Specifically, the hydrophobicity derives from nanoscale features of mechanically hard ZnO nanorods and the mechanical durability derives from the composite structure of a hard ZnO nanorod core and soft polymer shell. Experimental characterization correlates the morphology of the nanoengineered surfaces with the combined hydrophobicity and mechanical durability, and reveals the responsible mechanisms. Such surfaces may find use in applications, such as boat hulls, that benefit from hydrophobicity and require mechanical durability.

  13. Combined Hydrophobicity and Mechanical Durability through Surface Nanoengineering

    PubMed Central

    Elliott, Paul R.; Stagon, Stephen P.; Huang, Hanchen; Furrer, David U.; Burlatsky, Sergei F.; Filburn, Thomas P.

    2015-01-01

    This paper reports combined hydrophobicity and mechanical durability through the nanoscale engineering of surfaces in the form of nanorod-polymer composites. Specifically, the hydrophobicity derives from nanoscale features of mechanically hard ZnO nanorods and the mechanical durability derives from the composite structure of a hard ZnO nanorod core and soft polymer shell. Experimental characterization correlates the morphology of the nanoengineered surfaces with the combined hydrophobicity and mechanical durability, and reveals the responsible mechanisms. Such surfaces may find use in applications, such as boat hulls, that benefit from hydrophobicity and require mechanical durability. PMID:25851026

  14. Modulation of hydrophobic interactions by proximally immobilized ions.

    PubMed

    Ma, C Derek; Wang, Chenxuan; Acevedo-Vélez, Claribel; Gellman, Samuel H; Abbott, Nicholas L

    2015-01-15

    The structure of water near non-polar molecular fragments or surfaces mediates the hydrophobic interactions that underlie a broad range of interfacial, colloidal and biophysical phenomena. Substantial progress over the past decade has improved our understanding of hydrophobic interactions in simple model systems, but most biologically and technologically relevant structures contain non-polar domains in close proximity to polar and charged functional groups. Theories and simulations exploring such nanometre-scale chemical heterogeneity find it can have an important effect, but the influence of this heterogeneity on hydrophobic interactions has not been tested experimentally. Here we report chemical force microscopy measurements on alkyl-functionalized surfaces that reveal a dramatic change in the surfaces' hydrophobic interaction strengths on co-immobilization of amine or guanidine groups. Protonation of amine groups doubles the strength of hydrophobic interactions, and guanidinium groups eliminate measurable hydrophobic interactions in all pH ranges investigated. We see these divergent effects of proximally immobilized cations also in single-molecule measurements on conformationally stable β-peptides with non-polar subunits located one nanometre from either amine- or guanidine-bearing subunits. Our results demonstrate the importance of nanometre-scale chemical heterogeneity, with hydrophobicity not an intrinsic property of any given non-polar domain but strongly modulated by functional groups located as far away as one nanometre. The judicious placing of charged groups near hydrophobic domains thus provides a strategy for tuning hydrophobic driving forces to optimize molecular recognition or self-assembly processes. PMID:25592540

  15. Modulation of hydrophobic interactions by proximally immobilized ions

    NASA Astrophysics Data System (ADS)

    Ma, C. Derek; Wang, Chenxuan; Acevedo-Vélez, Claribel; Gellman, Samuel H.; Abbott, Nicholas L.

    2015-01-01

    The structure of water near non-polar molecular fragments or surfaces mediates the hydrophobic interactions that underlie a broad range of interfacial, colloidal and biophysical phenomena. Substantial progress over the past decade has improved our understanding of hydrophobic interactions in simple model systems, but most biologically and technologically relevant structures contain non-polar domains in close proximity to polar and charged functional groups. Theories and simulations exploring such nanometre-scale chemical heterogeneity find it can have an important effect, but the influence of this heterogeneity on hydrophobic interactions has not been tested experimentally. Here we report chemical force microscopy measurements on alkyl-functionalized surfaces that reveal a dramatic change in the surfaces' hydrophobic interaction strengths on co-immobilization of amine or guanidine groups. Protonation of amine groups doubles the strength of hydrophobic interactions, and guanidinium groups eliminate measurable hydrophobic interactions in all pH ranges investigated. We see these divergent effects of proximally immobilized cations also in single-molecule measurements on conformationally stable β-peptides with non-polar subunits located one nanometre from either amine- or guanidine-bearing subunits. Our results demonstrate the importance of nanometre-scale chemical heterogeneity, with hydrophobicity not an intrinsic property of any given non-polar domain but strongly modulated by functional groups located as far away as one nanometre. The judicious placing of charged groups near hydrophobic domains thus provides a strategy for tuning hydrophobic driving forces to optimize molecular recognition or self-assembly processes.

  16. Combined Hydrophobicity and Mechanical Durability through Surface Nanoengineering

    NASA Astrophysics Data System (ADS)

    Elliott, Paul R.; Stagon, Stephen P.; Huang, Hanchen; Furrer, David U.; Burlatsky, Sergei F.; Filburn, Thomas P.

    2015-04-01

    This paper reports combined hydrophobicity and mechanical durability through the nanoscale engineering of surfaces in the form of nanorod-polymer composites. Specifically, the hydrophobicity derives from nanoscale features of mechanically hard ZnO nanorods and the mechanical durability derives from the composite structure of a hard ZnO nanorod core and soft polymer shell. Experimental characterization correlates the morphology of the nanoengineered surfaces with the combined hydrophobicity and mechanical durability, and reveals the responsible mechanisms. Such surfaces may find use in applications, such as boat hulls, that benefit from hydrophobicity and require mechanical durability.

  17. Dynamics of Water Trapped between Hydrophobic Solutes.

    SciTech Connect

    Choudhury, Niharendu; Pettitt, Bernard M.

    2005-03-15

    We describe the model dynamical behavior of the solvent between two nanoscopic hydrophobic solutes. The dynamics of the vicinal water in various sized traps is found to be significantly different from bulk behavior. We consider the dynamics at normal temperature and pressure at three intersolute distances corresponding to the three solvent separated minima in the free energy profile between the solutes with attractions. These three states correspond to one, two, and three intervening layers of water molecules. Results are obtained from a molecular dynamics simulation at constant temperature and pressure (NPT) ensemble. Translational diffusion of water molecules trapped between the two solutes has been analyzed from the velocity correlation function as well as from the mean square displacement of the water molecules. The rotational behavior has been analyzed through the reorientational dynamics of the dipole moment vector of the water molecule by calculating both first and second rank dipole-dipole correlation functions. Both the translational and reorientational mobilities of water are found to be much slower at the smaller separation and increases as the separation between solutes becomes larger. The occupation time distribution functions calculated from the trajectories also show that the relaxation is much slower for the smallest intersolute separation as compared to other wider separations. The sublinear trend in mean square displacement and the stretched exponential decay of the relaxation of dipolar correlation and occupation distribution function indicate that the dynamical behavior of water in the confined region between two large hydrophobic solutes departs from usual Brownian behavior. This behavior is reminiscent of the behavior of water in the vicinity of protein surface clefts or trapped between two domains of a protein.

  18. Crystalline bipyridinium radical complexes and uses thereof

    DOEpatents

    Fahrenbach, Albert C.; Barnes, Jonathan C.; Li, Hao; Stoddart, J. Fraser; Basuray, Ashish Neil; Sampath, Srinivasan

    2015-09-01

    Described herein are methods of generating 4,4'-bipyridinium radical cations (BIPY.sup..cndot.+), and methods for utilizing the radical-radical interactions between two or more BIPY.sup..cndot.+ radical cations that ensue for the creation of novel materials for applications in nanotechnology. Synthetic methodologies, crystallographic engineering techniques, methods of physical characterization, and end uses are described.

  19. pH-Responsive Hydrogels with Dispersed Hydrophobic Nanoparticles for the Delivery of Hydrophobic Therapeutic Agents

    PubMed Central

    Schoener, Cody A.; Hutson, Heather N.; Peppas, Nicholas A.

    2012-01-01

    To investigate the delivery of hydrophobic therapeutic agents, a new class of polymer carriers was synthesized. These carriers are composed of two components: (i) a pH-responsive hydrogel composed of methacrylic acid grafted with poly(ethylene glycol) tethers, P(MAA-g-EG), and (ii) hydrophobic poly(methyl methacrylate) (PMMA) nanoparticles. Before the P(MAA-g-EG) hydrogel was crosslinked, PMMA nanoparticles were added to the solution and upon exposure to UV light they were photoencapsulated throughout the P(MAA-g-EG) hydrogel structure. The pH-responsive behavior of P(MAA-g-EG) is capable of triggered release of a loaded therapeutic agent, such as a low molecular weight drug or protein, when it passes from the stomach (low pH) to upper small intestine (neutral pH). The introduction of PMMA nanoparticles into the hydrogel structure affected the swelling behavior, therapeutic agent loading efficiency, and solute release profiles. In equilibrium swelling conditions the swelling ratio of nanoparticle-containing hydrogels decreased with increasing nanoparticle content. Loading efficiencies of the model therapeutic agent fluorescein ranged from 38 – 51 % and increased with increasing hydrophobic content. Release studies from neat P(MAA-g-EG) and the ensuing P(MAA-g-EG) hydrogels containing nanoparticles indicated that the transition from low pH (2.0) to neutral pH (7.0) triggered fluorescein release. Maximum fluorescein release depended on the structure and hydrophobicity of the carriers used in these studies. PMID:23087546

  20. Intermolecular Vibrations of Hydrophobic Amino Acids

    NASA Astrophysics Data System (ADS)

    Williams, Michael Roy Casselman

    Hydrophobic amino acids interact with their chemical environment through a combination of electrostatic, hydrogen bonding, dipole, induced dipole, and dispersion forces. These interactions all have their own characteristic energy scale and distance dependence. The low-frequency (0.1-5 THz, 5-150 cm-1) vibrational modes of amino acids in the solid state are a direct indicator of the interactions between the molecules, which include interactions between an amino acid functional group and its surroundings. This information is central to understanding the dynamics and morphology of proteins. The alpha-carbon is a chiral center for all of the hydrophobic amino acids, meaning that they exist in two forms, traditionally referred to as L- and D-enantiomers. This nomenclature indicates which direction the molecule rotates plane-polarized visible light (levorotory and dextrorotory). Chiral a-amino acids in proteins are exclusively the L-variety In the solid state, the crystal lattice of the pure L-enantiomer is the mirror image of the D-enantiomer crystal lattice. These solids are energetically identical. Enantiomers also have identical spectroscopic properties except when the measurement is polarization sensitive. A mixture of equal amounts D- and L-amino acid enantiomers can crystallize into a racemic (DL-) structure that is different from that of the pure enantiomers. Whether a solution of both enantiomers will crystallize into a racemic form or spontaneously resolve into a mixture of separate D- and L-crystals largely depends on the interactions between molecules available in the various possible configurations. This is an active area of research. Low-frequency vibrations with intermolecular character are very sensitive to changes in lattice geometry, and consequently the vibrational spectra of racemic crystals are usually quite distinct from the spectra of the crystals of the corresponding pure enantiomers in the far-infrared (far-IR). THz time-domain spectroscopy (THz

  1. Developing a general interaction potential for hydrophobic and hydrophilic interactions.

    PubMed

    Donaldson, Stephen H; Røyne, Anja; Kristiansen, Kai; Rapp, Michael V; Das, Saurabh; Gebbie, Matthew A; Lee, Dong Woog; Stock, Philipp; Valtiner, Markus; Israelachvili, Jacob

    2015-02-24

    We review direct force measurements on a broad class of hydrophobic and hydrophilic surfaces. These measurements have enabled the development of a general interaction potential per unit area, W(D) = -2γ(i)Hy exp(-D/D(H)) in terms of a nondimensional Hydra parameter, Hy, that applies to both hydrophobic and hydrophilic interactions between extended surfaces. This potential allows one to quantitatively account for additional attractions and repulsions not included in the well-known combination of electrostatic double layer and van der Waals theories, the so-called Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The interaction energy is exponentially decaying with decay length D(H) ≈ 0.3-2 nm for both hydrophobic and hydrophilic interactions, with the exact value of D(H) depending on the precise system and conditions. The pre-exponential factor depends on the interfacial tension, γ(i), of the interacting surfaces and Hy. For Hy > 0, the interaction potential describes interactions between partially hydrophobic surfaces, with the maximum hydrophobic interaction (i.e., two fully hydrophobic surfaces) corresponding to Hy = 1. Hydrophobic interactions between hydrophobic monolayer surfaces measured with the surface forces apparatus (SFA) are shown to be well described by the proposed interaction potential. The potential becomes repulsive for Hy < 0, corresponding to partially hydrophilic (hydrated) interfaces. Hydrated surfaces such as mica, silica, and lipid bilayers are discussed and reviewed in the context of the values of Hy appropriate for each system. PMID:25072835

  2. Hydroglyphics: Demonstration of Selective Wetting on Hydrophilic and Hydrophobic Surfaces

    ERIC Educational Resources Information Center

    Kim, Philseok; Alvarenga, Jack; Aizenberg, Joanna; Sleeper, Raymond S.

    2013-01-01

    A visual demonstration of the difference between hydrophilic and hydrophobic surfaces has been developed. It involves placing a shadow mask on an optically clear hydrophobic plastic dish, corona treating the surface with a modified Tesla coil, removing the shadow mask, and visualizing the otherwise invisible message or pattern by applying water,…

  3. Standard Electrode Potentials Involving Radicals in Aqueous Solution: Inorganic Radicals

    SciTech Connect

    Armstrong, David A.; Huie, Robert E.; Koppenol, Willem H.; Lymar, Sergei V.; Merenyi, Gabor; Neta, Pedatsur; Ruscic, Branko; Stanbury, David M.; Steenken, Steen; Wardman, Peter

    2015-12-01

    Recommendations are made for standard potentials involving select inorganic radicals in aqueous solution at 25 °C. These recommendations are based on a critical and thorough literature review and also by performing derivations from various literature reports. The recommended data are summarized in tables of standard potentials, Gibbs energies of formation, radical pKa’s, and hemicolligation equilibrium constants. In all cases, current best estimates of the uncertainties are provided. An extensive set of Data Sheets is appended that provide original literature references, summarize the experimental results, and describe the decisions and procedures leading to each of the recommendations

  4. Versatile Route to Colloidal Stability and Surface Functionalization of Hydrophobic Nanomaterials.

    PubMed

    Culver, Heidi R; Steichen, Stephanie D; Herrera-Alonso, Margarita; Peppas, Nicholas A

    2016-06-01

    We introduce a general method for the stabilization and surface functionalization of hydrophobic nanoparticles using an amphiphilic copolymer, poly(maleic anhydride-alt-1-octadecene)-poly(ethylene glycol) methacrylate (PMAO-PEGMA). Coating nanoparticles with PMAO-PEGMA results in colloidally stable nanoparticles decorated with reactive carboxylic acid and methacrylate functionalities, providing a versatile platform for chemical reactions. The versatility and ease of surface functionalization is demonstrated by varying both the core material and the chemistry used. Specifically, the carboxylic acid functionalities are used to conjugate wheat germ agglutinin to conducting polymer nanoparticles via carbodiimide-mediated coupling, and the methacrylate groups are used to link cysteamine to the surface of poly(ε-caprolactone) nanoparticles via thiol-ene click chemistry and to link temperature-responsive polymer shells to the surface of gold nanoparticles via free radical polymerization. PMID:27203863

  5. Mechanically Stabilized Tetrathiafulvalene Radical Dimers

    SciTech Connect

    Coskun, Ali; Spruell, Jason M.; Barin, Gokhan; Fahrenbach, Albert C.; Forgan, Ross S.; Colvin, Michael T.; Carmieli, Raanan; Benitez, Diego; Tkatchouk, Ekaterina; Friedman, Douglas C.; Sarjeant, Amy A.; Wasielewski, Michael R.; Goddard, William A.; Stoddart, J. Fraser

    2011-01-01

    Two donor-acceptor [3]catenanes—composed of a tetracationic molecular square, cyclobis(paraquat-4,4'-biphenylene), as the π-electron deficient ring and either two tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) containing macrocycles or two TTF-butadiyne-containing macrocycles as the π-electron rich components—have been investigated in order to study their ability to form TTF radical dimers. It has been proven that the mechanically interlocked nature of the [3]catenanes facilitates the formation of the TTF radical dimers under redox control, allowing an investigation to be performed on these intermolecular interactions in a so-called “molecular flask” under ambient conditions in considerable detail. In addition, it has also been shown that the stability of the TTF radical-cation dimers can be tuned by varying the secondary binding motifs in the [3]catenanes. By replacing the DNP station with a butadiyne group, the distribution of the TTF radical-cation dimer can be changed from 60% to 100%. These findings have been established by several techniques including cyclic voltammetry, spectroelectrochemistry and UV-vis-NIR and EPR spectroscopies, as well as with X-ray diffraction analysis which has provided a range of solid-state crystal structures. The experimental data are also supported by high-level DFT calculations. The results contribute significantly to our fundamental understanding of the interactions within the TTF radical dimers.

  6. The effect of heterogeneity and surface roughness on soil hydrophobicity

    NASA Astrophysics Data System (ADS)

    Hallin, I.; Bryant, R.; Doerr, S. H.; Douglas, P.

    2010-05-01

    Soil water repellency, or hydrophobicity, can develop under both natural and anthropogenic conditions. Forest fires, vegetation decomposition, microbial activity and oil spills can all promote hydrophobic behaviour in surrounding soils. Hydrophobicity can stabilize soil organic matter pools and decrease evapotranspiration, but there are many negative impacts of hydrophobicity as well: increased erosion of topsoil, an increasingly scarce resource; increased runoff, which can lead to flooding; and decreased infiltration, which directly affects plant health. The degree of hydrophobicity expressed by soil can vary greatly within a small area, depending partly on the type and severity of the disturbance as well as on temporal factors such as water content and microbial activity. To date, many laboratory investigations into soil hydrophobicity have focused on smooth particle surfaces. As a result, our understanding of how hydrophobicity develops on rough surfaces of macro, micro and nano-particulates is limited; we are unable to predict with certainty how these soil particles will behave on contact with water. Surface chemistry is the main consideration when predicting hydrophobic behaviour of smooth solids, but for particles with rough surfaces, hydrophobicity is believed to develop as a combination of surface chemistry and topography. Topography may reflect both the arrangement (aggregation) of soil particles and the distribution of materials adsorbed on particulate surfaces. Patch-wise or complete coverage of rough soil particles by hydrophobic material may result in solid/water contact angles ≥150° , at which point the soil may be classified as super-hydrophobic. Here we present a critical review of the research to date on the effects of heterogeneity and surface roughness on soil hydrophobicity in which we discuss recent advances, current trends, and future research areas. References: Callies, M., Y. Chen, F. Marty, A. Pépin and D. Quéré. 2005. Microfabricated

  7. Challenges and solutions for biofiltration of hydrophobic volatile organic compounds.

    PubMed

    Cheng, Yan; He, Huijun; Yang, Chunping; Zeng, Guangming; Li, Xiang; Chen, Hong; Yu, Guanlong

    2016-11-01

    Volatile organic compounds (VOCs) emitted to the environment highly probably result in ecological and health risks. Many biotechnologies for waste gases containing hydrophobic VOCs have been developed in recent years. However, these biological processes usually exhibit poor removal performances for hydrophobic VOCs due to the low bioavailability. This review presents an overview of enhanced removal of hydrophobic VOCs in biofilters. Mechanisms and problems relevant to the biological removal of hydrophobic VOCs are reviewed, and then solutions including the addition of surfactants, application of fungal biocatalysts, biofiltration with pretreatment, innovative bioreactors and utilization of hydrophilic compounds are discussed in detail. Future research needs are also proposed. This review provides new insights into hydrophobic VOC removal by biofiltration. PMID:27374790

  8. Radical-Mediated Enzymatic Polymerizations

    PubMed Central

    Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  9. Epistemological barriers to radical behaviorism

    PubMed Central

    O'Donohue, William T.; Callaghan, Glenn M.; Ruckstuhl, L. E.

    1998-01-01

    The historian and philosopher of science Gaston Bachelard proposed the concept of epistemological barriers to describe the intellectual challenges encountered by scientists in their work. In order to embrace novel ways of approaching a problem in science, scientists must overcome barriers or obstacles posed by their prior views. For example, Einsteinian physics presents scientists with claims that space is curved and that time and space are on the same continuum. We utilize Bachelard's concept of epistemological barriers to describe the differences between the intellectual journeys students pursuing advanced studies face when attempting to accept cognitive psychology or radical behaviorism. We contend that the folk psychological beliefs that students typically hold when entering these studies pose less challenge to cognitive psychology than to radical behaviorism. We also suggest that these barriers may also partly be involved in the problematic exegesis that has plagued radical behaviorism. In close, we offer some suggestions for dealing with these epistemological barriers. PMID:22478314

  10. Free radical decay in adamantane

    SciTech Connect

    Tegowski, A.T.; Pratt, D.W.

    1984-01-11

    Kinetic electron paramagnetic resonance (EPR) techniques have been used to characterize the decay behavior of the ''stable'' free radical 2-cyclohexanonyl in the plastic crystal phase f an adamantane matrix over the temperature range 257-313 K. Typical plots of the EPR signal intensity as a function of time are biexponential in nature, suggesting the existence of at least two channels for free radical decay. The activation parameters for both processes have been measured in both protonated and deuterated samples. A comparison of these results with those in other systems suggests that the host does, as expected, considerably reduce the pre-exponential factors for decay of the radical by bimolecular processes but has relatively little influence on the corresponding activation energies. 3 figures.

  11. Radical-Mediated Enzymatic Polymerizations.

    PubMed

    Zavada, Scott R; Battsengel, Tsatsral; Scott, Timothy F

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes--catalytic proteins--owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol-ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  12. Side Chain Hydrophobicity Modulates Therapeutic Activity and Membrane Selectivity of Antimicrobial Peptide Mastoparan-X

    PubMed Central

    Gjetting, Torben; Andresen, Thomas L.

    2014-01-01

    The discovery of new anti-infective compounds is stagnating and multi-resistant bacteria continue to emerge, threatening to end the “antibiotic era”. Antimicrobial peptides (AMPs) and lipo-peptides such as daptomycin offer themselves as a new potential class of antibiotics; however, further optimization is needed if AMPs are to find broad use as antibiotics. In the present work, eight analogues of mastoparan-X (MPX) were investigated, having side chain modifications in position 1, 8 and 14 to modulate peptide hydrophobicity. The self-association properties of the peptides were characterized, and the peptide-membrane interactions in model membranes were compared with the bactericidal and haemolytic properties. Alanine substitution at position 1 and 14 resulted in higher target selectivity (red blood cells versus bacteria), but also decreased bactericidal potency. For these analogues, the gain in target selectivity correlated to biophysical parameters showing an increased effective charge and reduction in the partitioning coefficient for membrane insertion. Introduction of an unnatural amino acid, with an octyl side chain by amino acid substitution, at positions 1, 8 and 14 resulted in increased bactericidal potency at the expense of radically reduced membrane target selectivity. Overall, optimized membrane selectivity or bactericidal potency was achieved by changes in side chain hydrophobicity of MPX. However, enhanced potency was achieved at the expense of selectivity and vice versa in all cases. PMID:24621994

  13. Intestine-Specific Delivery of Hydrophobic Bioactives from Oxidized Starch Microspheres with an Enhanced Stability.

    PubMed

    Wang, Shanshan; Chen, Yuying; Liang, Hao; Chen, Yiming; Shi, Mengxuan; Wu, Jiande; Liu, Xianwu; Li, Zuseng; Liu, Bin; Yuan, Qipeng; Li, Yuan

    2015-10-01

    An intestine-specific delivery system for hydrophobic bioactives with improved stability was developed. It consists of oxidized potato starch polymers, where the carboxyl groups were physically cross-linked via ferric ions. The model hydrophobic ingredients (β-carotene) were incorporated inside the starch microspheres via a double-emulsion method. Confocal laser scanning microscopy images showed that β-carotene were distributed homogeneously in the inner oil phase of the starch microspheres. The negative value of the ζ-potential of microspheres increased with increasing pH and decreasing ionic strength. In vitro release experiments showed that the microspheres were stable at acidic stomach conditions (pH < 2), whereas at neutral intestinal conditions (pH 7.0), they rupture to release the loaded β-carotene. The 1,1-diphenyl-2-picrylhydrazyl radical, 2,2-diphenyl-1-(2,4,6-trinitriphenyl), scavenging activity results suggested that microsphere-encapsulated β-carotene had an improved activity after thermal treatment at 80 °C. The storage stability of encapsulated β-carotene at room temperature was also enhanced. The starch microspheres showed potential as intestine-specific carriers with an enhanced stability. PMID:26414436

  14. Hydrophobic modification of wood via surface-initiated ARGET ATRP of MMA

    NASA Astrophysics Data System (ADS)

    Fu, Yanchun; Li, Gang; Yu, Haipeng; Liu, Yixing

    2012-01-01

    To convert the hydrophilic surface of wood into a hydrophobic surface, the present study investigated activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP) as a method of grafting methyl methacrylate (MMA) onto the wood surface. The wood treated with 2-bromoisobutyryl bromide and with the subsequently attached MMA via ARGET ATRP under different polymerization times (2 h, 4 h, 6 h, 8 h) were examined using scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. All the analyses confirmed that PMMA had been grafted onto the wood surface. Water contact angle measurement proved that the covering layer of PMMA on wood made the surface hydrophobic. Polymerization time had a positive influence on the contact angle value and higher contact angle can be produced with the prolongation of the polymerization time. When the reaction time was extended to 8 h, the contact angle of treated wood surface reached 130° in the beginning, and remained at 116° after 60 s. The ARGET ATRP method may raise an alteration on the wood surface modification.

  15. Donor free radical explosive composition

    DOEpatents

    Walker, Franklin E. [15 Way Points Rd., Danville, CA 94526; Wasley, Richard J. [4290 Colgate Way, Livermore, CA 94550

    1980-04-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a donor additive comprising an organic compound or mixture of organic compounds capable of releasing low molecular weight free radicals or ions under mechanical or electrical shock conditions and which is not an explosive, or an inorganic compound or mixture of inorganic compounds capable of releasing low molecular weight free radicals or ions under mechanical or electrical shock conditions and selected from ammonium or alkali metal persulfates.

  16. Hydrophobic peptide auxotrophy in Salmonella typhimurium.

    PubMed Central

    Brãnes, L V; Somers, J M; Kay, W W

    1981-01-01

    The growth of a pleiotropic membrane mutant of Salmonella typhimurium with modified lipopolysaccharide composition was found to be strictly dependent on the peptone component of complex media. Nutritional Shiftdown into minimal media allowed growth for three to four generations. Of 20 commercial peptones, only enzymatic digests supported growth to varying degrees. Neither trace cations, amino acids, vitamins, carbohydrates, lipids, glutathione, polyamines, carbodimides, nor synthetic peptides stimulated growth; however, cells still metabolized carbohydrates, and amino acid transport systems were shown to be functional. A tryptic digest of casein was fractionated into four electrophoretically different peptide fractions of 1,000 to 1,200 molecular weight which supported growth to varying degrees. The best of these was further fractionated to two highly hydrophopic peptides. N-terminal modifications eliminated biological activity. Fluorescein-conjugated goat antibody to rabbit immunoglobulin G was used as a probe to detect antipeptide antibody-peptide complexes on membrane preparations. Cells grown on peptone distributed the peptide into both inner and outer membranes. The peptide could be removed with chaotropic agents, and cells had to be pregrown in peptone-containing media to bind the hydrophobic peptide. The gene (hyp) responsible for peptide auxotrophy was mapped at 44 to 45 units by conjugation. Images PMID:7024254

  17. Targeting of the hydrophobic metabolome by pathogens.

    PubMed

    Helms, J Bernd; Kaloyanova, Dora V; Strating, Jeroen R P; van Hellemond, Jaap J; van der Schaar, Hilde M; Tielens, Aloysius G M; van Kuppeveld, Frank J M; Brouwers, Jos F

    2015-05-01

    The hydrophobic molecules of the metabolome - also named the lipidome - constitute a major part of the entire metabolome. Novel technologies show the existence of a staggering number of individual lipid species, the biological functions of which are, with the exception of only a few lipid species, unknown. Much can be learned from pathogens that have evolved to take advantage of the complexity of the lipidome to escape the immune system of the host organism and to allow their survival and replication. Different types of pathogens target different lipids as shown in interaction maps, allowing visualization of differences between different types of pathogens. Bacterial and viral pathogens target predominantly structural and signaling lipids to alter the cellular phenotype of the host cell. Fungal and parasitic pathogens have complex lipidomes themselves and target predominantly the release of polyunsaturated fatty acids from the host cell lipidome, resulting in the generation of eicosanoids by either the host cell or the pathogen. Thus, whereas viruses and bacteria induce predominantly alterations in lipid metabolites at the host cell level, eukaryotic pathogens focus on interference with lipid metabolites affecting systemic inflammatory reactions that are part of the immune system. A better understanding of the interplay between host-pathogen interactions will not only help elucidate the fundamental role of lipid species in cellular physiology, but will also aid in the generation of novel therapeutic drugs. PMID:25754025

  18. Vaults engineered for hydrophobic drug delivery.

    PubMed

    Buehler, Daniel C; Toso, Daniel B; Kickhoefer, Valerie A; Zhou, Z Hong; Rome, Leonard H

    2011-05-23

    The vault nanoparticle is one of the largest known ribonucleoprotein complexes in the sub-100 nm range. Highly conserved and almost ubiquitously expressed in eukaryotes, vaults form a large nanocapsule with a barrel-shaped morphology surrounding a large hollow interior. These properties make vaults an ideal candidate for development into a drug delivery vehicle. In this study, the first example of using vaults towards this goal is reported. Recombinant vaults are engineered to encapsulate the highly insoluble and toxic hydrophobic compound all-trans retinoic acid (ATRA) using a vault-binding lipoprotein complex that forms a lipid bilayer nanodisk. These recombinant vaults offer protection to the encapsulated ATRA from external elements. Furthermore, a cryo-electron tomography (cryo-ET) reconstruction shows the vault-binding lipoprotein complex sequestered within the vault lumen. Finally, these ATRA-loaded vaults show enhanced cytotoxicity against the hepatocellular carcinoma cell line HepG2. The ability to package therapeutic compounds into the vault is an important achievement toward their development into a viable and versatile platform for drug delivery. PMID:21506266

  19. Size selective hydrophobic adsorbent for organic molecules

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K. (Inventor); Hickey, Gregory S. (Inventor)

    1997-01-01

    The present invention relates to an adsorbent formed by the pyrolysis of a hydrophobic silica with a pore size greater than 5 .ANG., such as SILICALITE.TM., with a molecular sieving polymer precursor such as polyfurfuryl alcohol, polyacrylonitrile, polyvinylidene chloride, phenol-formaldehyde resin, polyvinylidene difluoride and mixtures thereof. Polyfurfuryl alcohol is the most preferred. The adsorbent produced by the pyrolysis has a silicon to carbon mole ratio of between about 10:1 and 1:3, and preferably about 2:1 to 1:2, most preferably 1:1. The pyrolysis is performed as a ramped temperature program between about 100.degree. and 800.degree. C., and preferably between about 100.degree. and 600.degree. C. The present invention also relates to a method for selectively adsorbing organic molecules having a molecular size (mean molecular diameter) of between about 3 and 6 .ANG. comprising contacting a vapor containing the small organic molecules to be adsorbed with the adsorbent composition of the present invention.

  20. Controlled release from thermo-sensitive PNVCL-co-MAA electrospun nanofibers: The effects of hydrophilicity/hydrophobicity of a drug.

    PubMed

    Liu, Lin; Bai, Shaoqing; Yang, Huiqin; Li, Shubai; Quan, Jing; Zhu, Limin; Nie, Huali

    2016-10-01

    The thermo-sensitive copolymer poly(N-vinylcaprolactam-co-methacrylic acid) (PNVCL-co-MAA) was synthesized by free radical polymerization and the resulting nanofibers were fabricated using an electrospinning process. The molecular weight of the copolymer was adjusted by varying the content of methacrylic acid (MAA) while keeping that of N-vinylcaprolactam (NVCL) constant. Hydrophilic captopril and hydrophobic ketoprofen were used as model drugs, and PNVCL-co-MAA nanofibers were used as the drug carrier to investigate the effects of drug on its release properties from nanofibers at different temperatures. The results showed that slow release over several hours was observed at 40°C (above the lower critical solution temperature (LCST) of PNVCL-co-MAA), while the drugs exhibited a burst release of several seconds at 20°C (below the LCST). Drug release slowed with increasing content of the hydrophobic monomer NVCL. The hydrophilic captopril was released at a higher rate than the hydrophobic ketoprofen. The drug release characteristics were dependent on the temperature, the portion of hydrophilic groups and hydrophobic groups in the copolymer and hydrophilicity/hydrophobicity of drug. Study on the mechanism of release showed that Korsmeyer-Peppas model as a major drug release mechanism. Given these results, the PNVCL-co-MAA copolymers are proposed to have useful applications in intellectual drug delivery systems. PMID:27287157

  1. Role of surfactant derived intermediates in the efficacy and mechanism for radiation chemical degradation of a hydrophobic azo dye, 1-phenylazo-2-naphthol.

    PubMed

    Das, Laboni; Chatterjee, Suchandra; Naik, Devidas B; Adhikari, Soumyakanti

    2015-11-15

    A combined methodology involving gamma and pulse radiolysis, product analysis and toxicity studies has been adopted to comprehend the degradation process of a model hydrophobic azo dye, 1-phenylazo-2-naphthol, emphasizing the role of the surfactant, which is an integral part of textile waste. Two new and important findings are underlined in this article. The first is the direct attestation of the hydrazyl radical-parent adduct, formed in the reaction of the dye with e(-)aq followed by protonation and subsequent addition to the unreacted dye molecule. This has been confirmed from concentration dependent studies. Secondly, we have clearly shown that in the reaction of hydroxyl radical with the dye in Triton X-100 media, the initially produced TX radicals cause reductive degradation of the dye. Identification and detailed analysis of HPLC and GCMS data reveals that similar products are formed in both the reactions of e(-)aq and OH radicals. Moreover, the cytotoxicity of 10(-4)moldm(-3) dye was found to be reduced significantly after irradiation. Thus, the present study not only depicts new pathways for the degradation of hydrophobic azo dye, but also demonstrates the role of a surfactant in the entire process. PMID:26001620

  2. Surface Hydrophobicity Causes SO2 Tolerance in Lichens

    PubMed Central

    Hauck, Markus; Jürgens, Sascha-René; Brinkmann, Martin; Herminghaus, Stephan

    2008-01-01

    Background and Aims The superhydrophobicity of the thallus surface in one of the most SO2-tolerant lichen species, Lecanora conizaeoides, suggests that surface hydrophobicity could be a general feature of lichen symbioses controlling their tolerance to SO2. The study described here tests this hypothesis. Methods Water droplets of the size of a raindrop were placed on the surface of air-dry thalli in 50 lichen species of known SO2 tolerance and contact angles were measured to quantify hydrophobicity. Key Results The wettability of lichen thalli ranges from strongly hydrophobic to strongly hydrophilic. SO2 tolerance of the studied lichen species increased with increasing hydrophobicity of the thallus surface. Extraction of extracellular lichen secondary metabolites with acetone reduced, but did not abolish the hydrophobicity of lichen thalli. Conclusions Surface hydrophobicity is the main factor controlling SO2 tolerance in lichens. It presumably originally evolved as an adaptation to wet habitats preventing the depression of net photosynthesis due to supersaturation of the thallus with water. Hydrophilicity of lichen thalli is an adaptation to dry or humid, but not directly rain-exposed habitats. The crucial role of surface hydrophobicity in SO2 also explains why many markedly SO2-tolerant species are additionally tolerant to other (chemically unrelated) toxic substances including heavy metals. PMID:18077467

  3. Characterization of water formation mechanisms on hydrophobic radome materials

    SciTech Connect

    Roberts, J.C.; Wienhold, P.D.; Nicholas, A.A.; Garner, P.N.

    1994-03-01

    The degree of hydrophobicity and contact angle of water on different radome coating materials was measured. The ability of these hydrophobic materials to bond to a radome substrate was also observed. The materials tested were; Raydell M-26-OS, Raydell M-15-OS, RA 7947, RA 7943, Teflon/Tedlar and Vellox-140. Each material was bonded to G-10 fiberglass panels and evaluated under conditions simulating dew formation, driving rain, freezing rain. Raydell M-26-OS had a relatively high contact angle, demonstrated excellent boding to a radome material, and had fair hydrophobic properties. RA 7947 and RA 7943 had relatively high contact angles, demonstrated poor and fair bonding, respectively, to a radome material, and exhibited good hydrophobic properties. The Teflon/Tedlar material had a low contact angle, demonstrated good bonding to a radome material, but showed fair to poor hydrophobic properties. The Vellox-140 and Raydell M-15-OS had relatively high to high contact angles, demonstrated excellent and possibly excellent bonding, respectively, to a radome material, and showed good to excellent, respectively, hydrophobic properties. These results were consistent whether the test temperature was 22{degrees}C (72{degrees}F) or -13{degrees}C (8{degrees}F) and whether the water was in the form of a mist or a concentrated stream. Long term tests and the effects of salt spray and dirt and the hydrophobic materials were not examined. 17 refs., 7 figs., 2 tabs.

  4. Students' Ideas and Radical Constructivism

    ERIC Educational Resources Information Center

    Sánchez Gómez, Pedro J.

    2016-01-01

    In this article, I study, from the point of view of the analytic philosophy of mind, the compatibility of students' ideas studies (SIS) with radical constructivism (RC). I demonstrate that RC is based on a psychology of "narrow mental states"; that is, the idea that the mental content of an individual can be fully characterised without…

  5. Robot-assisted radical cystectomy.

    PubMed

    Kurpad, Raj; Woods, Michael

    2015-12-01

    Robot-assisted radical cystectomy (RARC) has rapidly penetrated the field of urology since its inception in 2003. Several observational studies, retrospective reports, and three randomized controlled trials (RCT) have preliminarily demonstrated the safety and efficacy of (RARC). Additionally, results from the RAZOR RCT will be available in 2016-2017 to better substantiate the use of (RARC). PMID:26310514

  6. Free radicals, antioxidants, and nutrition.

    PubMed

    Fang, Yun-Zhong; Yang, Sheng; Wu, Guoyao

    2002-10-01

    Radiation hazards in outer space present an enormous challenge for the biological safety of astronauts. A deleterious effect of radiation is the production of reactive oxygen species, which result in damage to biomolecules (e.g., lipid, protein, amino acids, and DNA). Understanding free radical biology is necessary for designing an optimal nutritional countermeasure against space radiation-induced cytotoxicity. Free radicals (e.g., superoxide, nitric oxide, and hydroxyl radicals) and other reactive species (e.g., hydrogen peroxide, peroxynitrite, and hypochlorous acid) are produced in the body, primarily as a result of aerobic metabolism. Antioxidants (e.g., glutathione, arginine, citrulline, taurine, creatine, selenium, zinc, vitamin E, vitamin C, vitamin A, and tea polyphenols) and antioxidant enzymes (e.g., superoxide dismutase, catalase, glutathione reductase, and glutathione peroxidases) exert synergistic actions in scavenging free radicals. There has been growing evidence over the past three decades showing that malnutrition (e.g., dietary deficiencies of protein, selenium, and zinc) or excess of certain nutrients (e.g., iron and vitamin C) gives rise to the oxidation of biomolecules and cell injury. A large body of the literature supports the notion that dietary antioxidants are useful radioprotectors and play an important role in preventing many human diseases (e.g., cancer, atherosclerosis, stroke, rheumatoid arthritis, neurodegeneration, and diabetes). The knowledge of enzymatic and non-enzymatic oxidative defense mechanisms will serve as a guiding principle for establishing the most effective nutrition support to ensure the biological safety of manned space missions. PMID:12361782

  7. Radical Coupling Mechanisms in Lignification

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The mechansim by which lignification, the polymerization process by which lignins are formed, is via combinatorial radical coupling reactions. Understanding such reactions allows the range of structures in lignins to be understood, and the ability of lignins to accommodate various phenolic precursor...

  8. The Other Women: Radicalizing Feminism.

    ERIC Educational Resources Information Center

    Puigvert, Lidia; Darder, Antonia; Merrill, Barbara; de los Reyes, Eileen; Stromquist, Nelly

    A recent international symposium on radicalizing feminism explored ways of developing a dialogic feminism that emphasizes working in different settings under the common goal of including women who have been invisible in the dominant feminist literature by furthering theories and practices based on the principles of dialogic feminism. The seminar…

  9. Self-organization of hydrophobic soil and granular surfaces

    NASA Astrophysics Data System (ADS)

    McHale, Glen; Shirtcliffe, Neil J.; Newton, Michael I.; Pyatt, F. Brian; Doerr, Stefan H.

    2007-01-01

    Soil can become extremely water repellent following forest fires or oil spillages, thus preventing penetration of water and increasing runoff and soil erosion. Here the authors show that evaporation of a droplet from the surface of a hydrophobic granular material can be an active process, lifting, self-coating, and selectively concentrating small solid grains. Droplet evaporation leads to the formation of temporary liquid marbles and, as droplet volume reduces, particles of different wettabilities compete for water-air interfacial surface area. This can result in a sorting effect with self-organization of a mixed hydrophobic-hydrophilic aggregate into a hydrophobic shell surrounding a hydrophilic core.

  10. Hydrophobic Ambivalence: Teetering on the Edge of Randomness.

    PubMed

    Ben-Amotz, Dor

    2015-05-01

    Processes ranging from oil-water phase separation to the formation of solid clathrate hydrates send mixed messages regarding whether oil molecules hate or love to be surrounded by water. Recent experimental and theoretical results help decipher these mixed messages by illuminating the conditions under which the stability of a hydrophobic contact is expected to exceed thermal energy fluctuations - thus facilitating hydrophobic self-assembly and the emergence of structure from randomness. Important open questions remain regarding the dependence of hydrophobic interactions on molecular size and temperature, as well as the balance of direct and water-mediated interactions. PMID:26263336

  11. Electrokinetic instability near charge-selective hydrophobic surfaces

    NASA Astrophysics Data System (ADS)

    Shelistov, V. S.; Demekhin, E. A.; Ganchenko, G. S.

    2014-07-01

    The influence of the texture of a hydrophobic surface on the electro-osmotic slip of the second kind and the electrokinetic instability near charge selective surfaces (permselective membranes, electrodes, or systems of microchannels and nanochannels) is investigated theoretically using a simple model based on the Rubinstein-Zaltzman approach. A simple formula is derived to evaluate the decrease in the instability threshold due to hydrophobicity. The study is complemented by numerical investigations both of linear and nonlinear instabilities near a hydrophobic membrane surface. Theory predicts a significant enhancement of the ion flux to the surface and shows a good qualitative agreement with the available experimental data.

  12. Infectious Morbidity After Radical Vulvectomy

    PubMed Central

    Carson, Linda F.; Brooker, Doris C.; Carter, Jonathan R.; Twiggs, Leo B.

    1994-01-01

    Objective: This retrospective investigation describes the infectious morbidity of patients following radical vulvectomy with or without inguinal lymph node dissection. Methods: The charts of patients undergoing radical vulvectomy between January 1, 1986, and September 1, 1989, were reviewed for age, weight, cancer type, tumor stage, operative procedure(s), prophylactic antibiotic and its length of use, febrile morbidity, infection site, culture results, significant medical history, and length of use and number of drains or catheters used. Results: The study group was composed of 61 patients, 14 of whom underwent a radical vulvectomy and 47 who also had inguinal lymph node dissection performed. Twenty-nine patients (48%) had at least 1 postoperative infection. Five patients (8%) had 2 or more postoperative infections. The site and incidence of the infections were as follows: urinary tract 23%, wound 23%, lymphocyst 3%, lymphatics (lymphangitis) 5%, and bowel (pseudomembranous colitis) 3%. The most common pathogens isolated from both urine and wound sites were Pseudomonas aeruginosa, enterococcus, and Escherichia coli. A significant decrease in wound infection was demonstrated when separate incisions were made for inguinal lymph node dissection (P <0.05). The mean number of days to onset of postoperative infection for wound, urine, lymphatics, lymphocyst, and bowel were 11, 8, 57, 48, and 5, respectively. Conclusions: We conclude that the clinical appearance of post-radical vulvectomy infections is delayed when compared with other post-surgical wound infections. Second, utilizing separate inguinal surgical incisions may reduce infectious morbidity. Finally, tumor stage and type do not necessarily increase the infectious morbidity of radical vulvar surgery. PMID:18475379

  13. Evolving a polymerase for hydrophobic base analogues.

    PubMed

    Loakes, David; Gallego, José; Pinheiro, Vitor B; Kool, Eric T; Holliger, Philipp

    2009-10-21

    Hydrophobic base analogues (HBAs) have shown great promise for the expansion of the chemical and coding potential of nucleic acids but are generally poor polymerase substrates. While extensive synthetic efforts have yielded examples of HBAs with favorable substrate properties, their discovery has remained challenging. Here we describe a complementary strategy for improving HBA substrate properties by directed evolution of a dedicated polymerase using compartmentalized self-replication (CSR) with the archetypal HBA 5-nitroindole (d5NI) and its derivative 5-nitroindole-3-carboxamide (d5NIC) as selection substrates. Starting from a repertoire of chimeric polymerases generated by molecular breeding of DNA polymerase genes from the genus Thermus, we isolated a polymerase (5D4) with a generically enhanced ability to utilize HBAs. The selected polymerase. 5D4 was able to form and extend d5NI and d5NIC (d5NI(C)) self-pairs as well as d5NI(C) heteropairs with all four bases with efficiencies approaching, or exceeding, those of the cognate Watson-Crick pairs, despite significant distortions caused by the intercalation of the d5NI(C) heterocycles into the opposing strand base stack, as shown by nuclear magnetic resonance spectroscopy (NMR). Unlike Taq polymerase, 5D4 was also able to extend HBA pairs such as Pyrene: varphi (abasic site), d5NI: varphi, and isocarbostyril (ICS): 7-azaindole (7AI), allowed bypass of a chemically diverse spectrum of HBAs, and enabled PCR amplification with primers comprising multiple d5NI(C)-substitutions, while maintaining high levels of catalytic activity and fidelity. The selected polymerase 5D4 promises to expand the range of nucleobase analogues amenable to replication and should find numerous applications, including the synthesis and replication of nucleic acid polymers with expanded chemical and functional diversity. PMID:19778048

  14. Hydrophobic surfactant proteins strongly induce negative curvature.

    PubMed

    Chavarha, Mariya; Loney, Ryan W; Rananavare, Shankar B; Hall, Stephen B

    2015-07-01

    The hydrophobic surfactant proteins SP-B and SP-C greatly accelerate the adsorption of vesicles containing the surfactant lipids to form a film that lowers the surface tension of the air/water interface in the lungs. Pulmonary surfactant enters the interface by a process analogous to the fusion of two vesicles. As with fusion, several factors affect adsorption according to how they alter the curvature of lipid leaflets, suggesting that adsorption proceeds via a rate-limiting structure with negative curvature, in which the hydrophilic face of the phospholipid leaflets is concave. In the studies reported here, we tested whether the surfactant proteins might promote adsorption by inducing lipids to adopt a more negative curvature, closer to the configuration of the hypothetical intermediate. Our experiments used x-ray diffraction to determine how the proteins in their physiological ratio affect the radius of cylindrical monolayers in the negatively curved, inverse hexagonal phase. With binary mixtures of dioleoylphosphatidylethanolamine (DOPE) and dioleoylphosphatidylcholine (DOPC), the proteins produced a dose-related effect on curvature that depended on the phospholipid composition. With DOPE alone, the proteins produced no change. With an increasing mol fraction of DOPC, the response to the proteins increased, reaching a maximum 50% reduction in cylindrical radius at 5% (w/w) protein. This change represented a doubling of curvature at the outer cylindrical surface. The change in spontaneous curvature, defined at approximately the level of the glycerol group, would be greater. Analysis of the results in terms of a Langmuir model for binding to a surface suggests that the effect of the lipids is consistent with a change in the maximum binding capacity. Our findings show that surfactant proteins can promote negative curvature, and support the possibility that they facilitate adsorption by that mechanism. PMID:26153706

  15. Solubility Enhanced Oxidation of Hydrophobic Organic Contaminants

    NASA Astrophysics Data System (ADS)

    Boving, T. B.; Eberle, D. E.; Ball, R.

    2012-12-01

    In-situ chemical oxidation (ISCO) is a remediation technique considered to be effective at overcoming some of the limitations of conventional subsurface treatment processes for volatile and semi-volatile organic contaminants (VOC, SVOC). ISCO reactions occur predominately in the aqueous phase and as a result, contaminant availability is a major limiting factor, i.e. contaminants with higher aqueous solubility's are typically more accessible for oxidation than more hydrophobic, sorbed compounds. The purpose of this study was to determine the feasibility of a new integrated desorption-oxidation process for the remediation of contaminated waters and sediments. Specifically, this study examined the potential of using hydroxypropyl-β-cyclodextrin (HPCD), a modified cyclic sugar, and a blend of oxidants commercially known as OxyZone® (U.S. patent No. 7,667,087) for the remediation of polycyclic aromatic hydrocarbons (PAH). Laboratory scale batch experiments confirmed prior studies that HPCD increases the aqueous concentration of these contaminants, making a greater mass of contaminant available for subsequent oxidation. When exposed to the same amount of oxidant, the mass of PAH destroyed increased linearly with increasing HPCD concentration. Relative to PAH saturated solutions without HPCD, 11 times more PAH mass was destroyed when a PAH saturated 15 g/L HPCD solution was treated with the same mass of oxidant. Destruction of the aqueous phase contaminants followed first order exponential decay kinetics in both deionized water and HPCD solutions. However, the destruction of complexed PAH was slower than for uncomplexed PAH. The cause of this is likely due to the preferential destruction of the HPCD molecule by the oxidant, followed by the subsequent oxidation of the PAH. The destruction of the cyclodextrin was minimized by modifying the oxidant formulation. Overall, these findings establish the potential of utilizing HPCD and OxyZone® as an integrated desorption

  16. Ion-specific aggregation of hydrophobic particles.

    PubMed

    López-León, Teresa; Ortega-Vinuesa, Juan Luis; Bastos-González, Delfina

    2012-06-18

    This work shows that colloidal stability and aggregation kinetics of hydrophobic polystyrene (PS) nanospheres are extremely sensitive to the nature of the salt used to coagulate them. Three PS latices and four aggregating electrolytes, which all share the same cation (Na(+)) but have various anions located at different positions in the classical Hofmeister series depending on their kosmotropic or chaotropic character, are used. The present study focuses on analyzing different aggregating parameters, such as critical coagulation concentrations (CCC), cluster size distributions (CSD), initial kinetic constants K(11), and fractal dimensions of the aggregates d(f). While aggregation induced by SO(4)(2-) and Cl(-) behaved according to the predictions of the classical Derjaguin-Landau-Verwey-Overbeek theory, important discrepancies are found with NO(3)(-), which become dramatic when using SCN(-). These discrepancies among the anions were far more significant when they acted as counterions rather than as co-ions. While SO(4)(2-) and Cl(-) trigger fast diffusion-limited aggregation, SCN(-) gives rise to a stationary cluster size distribution in a few aggregation times when working with cationic PS particles. Clear differences are found among all analyzed parameters (CCC, CSD, K(11), and d(f)), and the experimental findings show that particles aggregate in potential wells whose depth is controlled by the chaotropic character of the anion. This paper presents new experimental evidence that may help to understand the microscopic origin of Hofmeister effects, as the observations are consistent with appealing theoretical models developed in the last few years. PMID:22556130

  17. Oxidation of ultrafast radical clock substrate probes by the soluble methane monooxygenase from Methylococcus capsulatus (Bath).

    PubMed

    Valentine, A M; LeTadic-Biadatti, M H; Toy, P H; Newcomb, M; Lippard, S J

    1999-04-16

    Radical clock substrate probes were used to assess the viability of a discrete substrate radical species in the mechanism of hydrocarbon oxidation by the soluble methane monooxygenase (sMMO) from Methylococcus capsulatus (Bath). New substituted cyclopropane probes were used with very fast ring-opening rate constants and other desirable attributes, such as the ability to discriminate between radical and cationic intermediates. Oxidation of these substrates by a reconstituted sMMO system resulted in no rearranged products, allowing an upper limit of 150 fs to be placed on the lifetime of a putative radical species. This limit strongly suggests that there is no such substrate radical intermediate. The two enantiomers of trans-1-methyl-2-phenyl-cyclopropane were prepared, and the regioselectivity of their oxidation to the corresponding cyclopropylmethanol and cyclopropylphenol products was determined. The results are consistent with selective orientation of the two enantiomeric substrates in the hydrophobic cavity at the active site of sMMO, specific models for which were examined by molecular modeling. PMID:10196150

  18. The inhibitory effects of γ-glutamylcysteine derivatives from fresh garlic on glycation radical formation.

    PubMed

    Shi, Fei; Bai, Bing; Ma, Shufeng; Ji, Shujuan; Liu, Ling

    2016-03-01

    The effects of three reactive peptides, γ-glutamylmethylcysteine (γ-GMC), γ-glutamylpropylcysteine (γ-GPC), and γ-glutamylbutylcysteine (γ-GBC) on the suppression of reactive radicals during the heating of l-lysine in the presence or absence of glucose was studied by electron spin resonance spectroscopy. γ-GMC and γ-GPC were extracted from fresh garlic, and γ-GBC was a synthetic peptide. The results showed that γ-GMC and γ-GPC effectively suppress formation of l-lysine radicals, but that γ-GBC exhibits low radical inhibition. The origin of the short peptides, and the length of their side chain, influenced their surface hydrophobicity and subsequent radical inhibition. In addition, the oxidation of l-lysine was inhibited by the peptides in a similar manner to their inhibition of the Maillard reaction (MR), and their radical inhibition was consistent with similar activity towards N(ε)-(carboxymethyl)lysine (CML). PMID:26471590

  19. Surface hydrophobization by electrostatic deposition of hydrophobically modified poly(acrylates) and their complexes with surfactants

    NASA Astrophysics Data System (ADS)

    Gîfu, Ioana Cătălina; Maxim, Monica Elisabeta; Iovescu, Alina; Simion, Elena Livia; Aricov, Ludmila; Anastasescu, Mihai; Munteanu, Cornel; Anghel, Dan-Florin

    2016-05-01

    The present study demonstrates the hydrophobic effect of poly(electrolyte) multilayer films when they are alkyl-grafted and complexed or not with surfactants. For this purpose, sodium hydrophobically modified poly(acrylates) (PACnNa, n = 10, 18) or their anionic complexes with alkyltrimethylammonium bromides (CxTAB, x = 10, 12, 14, 18), and the cationic poly(diallyldimethyldiammonium chloride) (PDDAMAC) are assembled by layer-by-layer deposition on a glass substrate. Contact angle (CA) measurements reveal that films constructed with PACnNa-CxTAB/PDADMAC are superior water repellants than those of PACnNa/PDADMAC. For example, the highest CA is obtained for the PAC18Na-C18TAB/PDADMAC. Moreover, it has been observed that the CA increases with the alkyl chain length of PACnNa and of surfactant. The film roughness and thickness have the same trend as wettability. Thinner and less coarse films are obtained by NaCl addition, as witnessed by SEM and AFM.

  20. Deuterium isotope effects on hydrophobic interactions: the importance of dispersion interactions in the hydrophobic phase.

    PubMed

    Turowski, Maciej; Yamakawa, Naoki; Meller, Jaroslaw; Kimata, Kazuhiro; Ikegami, Tohru; Hosoya, Ken; Tanaka, Nobuo; Thornton, Edward R

    2003-11-12

    Hydrogen/deuterium isotope effects on hydrophobic binding were examined by means of reversed-phase chromatographic separation of protiated and deuterated isotopologue pairs for a set of 10 nonpolar and low-polarity compounds with 10 stationary phases having alkyl and aryl groups bonded to the silica surface. It was found that protiated compounds bind to nonpolar moieties attached to silica more strongly than deuterated ones, demonstrating that the CH/CD bonds of the solutes are weakened or have less restricted motions when bound in the stationary phase compared with the aqueous solvent (mobile phase). The interactions responsible for binding have been further characterized by studies of the effects of changes in mobile phase composition, temperature dependence of binding, and QSRR (quantitative structure-chromatographic retention relationship) analysis, demonstrating the importance of enthalpic effects in binding and differentiation between the isotopologues. To explain our results showing the active role of the hydrophobic (stationary) phase we propose a plausible model that includes specific contributions from aromatic edge-to-face attractive interactions and attractive interactions of aliphatic groups with the pi clouds of aromatic groups present as the solute or in the stationary phase. PMID:14599224

  1. Hydrophobic cryogels for DNA adsorption: effect of embedding of monosize microbeads into cryogel network on their adsorptive performances.

    PubMed

    Emin Çorman, M; Bereli, Nilay; Özkara, Serpil; Uzun, Lokman; Denizli, Adil

    2013-11-01

    As alternative hydrophobic adsorbent for DNA adsorption, supermacroporous cryogel disks were synthesized via free radical polymerization. In this study, we have prepared two kinds of cryogel disks: (i) poly(2-hydroxyethyl methacrylate-N-methacryloyl-l-tryptophan) [p(HEMA-MATrp)] cryogel containing specific hydrophobic ligand MATrp; and (ii) monosize p(HEMA-MATrp) particles synthesized via suspension polymerization embedded into p(HEMA) cryogel structure to obtain p(HEMA-MATrp)/p(HEMA) composite cryogel disks. These cryogel disks containing hydrophobic functional group were characterized via swelling studies, Fourier transform infrared spectroscopy, elemental analysis, surface area measurements and scanning electron microscopy. DNA adsorption onto both p(HEMA-MATrp) cryogel and p(HEMA-MATrp)/p(HEMA) composite cryogels was investigated. Maximum adsorption of DNA on p(HEMA-MATrp) cryogel was found to be 15 mg/g polymer. Otherwise, p(HEMA-MATrp)/p(HEMA) composite cryogels significantly increased the DNA adsorption capacity to 38 mg/g polymer. Composite cryogels could be used repeatedly without significant loss on adsorption capacity after 10 repetitive adsorption-desorption cycles. PMID:23780689

  2. Fluoroalkyl and Alkyl Chains Have Similar Hydrophobicities in Binding to the “Hydrophobic Wall” of Carbonic Anhydrase

    SciTech Connect

    J Mecinovic; P Snyder; K Mirica; S Bai; E Mack; R Kwant; D Moustakas; A Heroux; G Whitesides

    2011-12-31

    The hydrophobic effect, the free-energetically favorable association of nonpolar solutes in water, makes a dominant contribution to binding of many systems of ligands and proteins. The objective of this study was to examine the hydrophobic effect in biomolecular recognition using two chemically different but structurally similar hydrophobic groups, aliphatic hydrocarbons and aliphatic fluorocarbons, and to determine whether the hydrophobicity of the two groups could be distinguished by thermodynamic and biostructural analysis. This paper uses isothermal titration calorimetry (ITC) to examine the thermodynamics of binding of benzenesulfonamides substituted in the para position with alkyl and fluoroalkyl chains (H{sub 2}NSO{sub 2}C{sub 6}H{sub 4}-CONHCH{sub 2}(CX{sub 2}){sub n}CX{sub 3}, n = 0-4, X = H, F) to human carbonic anhydrase II (HCA II). Both alkyl and fluoroalkyl substituents contribute favorably to the enthalpy and the entropy of binding; these contributions increase as the length of chain of the hydrophobic substituent increases. Crystallography of the protein-ligand complexes indicates that the benzenesulfonamide groups of all ligands examined bind with similar geometry, that the tail groups associate with the hydrophobic wall of HCA II (which is made up of the side chains of residues Phe131, Val135, Pro202, and Leu204), and that the structure of the protein is indistinguishable for all but one of the complexes (the longest member of the fluoroalkyl series). Analysis of the thermodynamics of binding as a function of structure is compatible with the hypothesis that hydrophobic binding of both alkyl and fluoroalkyl chains to hydrophobic surface of carbonic anhydrase is due primarily to the release of nonoptimally hydrogen-bonded water molecules that hydrate the binding cavity (including the hydrophobic wall) of HCA II and to the release of water molecules that surround the hydrophobic chain of the ligands. This study defines the balance of enthalpic and

  3. Hydrophobic mismatch sorts SNARE proteins into distinct membrane domains

    PubMed Central

    Milovanovic, Dragomir; Honigmann, Alf; Koike, Seiichi; Göttfert, Fabian; Pähler, Gesa; Junius, Meike; Müllar, Stefan; Diederichsen, Ulf; Janshoff, Andreas; Grubmüller, Helmut; Risselada, Herre J.; Eggeling, Christian; Hell, Stefan W.; van den Bogaart, Geert; Jahn, Reinhard

    2015-01-01

    The clustering of proteins and lipids in distinct microdomains is emerging as an important principle for the spatial patterning of biological membranes. Such domain formation can be the result of hydrophobic and ionic interactions with membrane lipids as well as of specific protein–protein interactions. Here using plasma membrane-resident SNARE proteins as model, we show that hydrophobic mismatch between the length of transmembrane domains (TMDs) and the thickness of the lipid membrane suffices to induce clustering of proteins. Even when the TMDs differ in length by only a single residue, hydrophobic mismatch can segregate structurally closely homologous membrane proteins in distinct membrane domains. Domain formation is further fine-tuned by interactions with polyanionic phosphoinositides and homo and heterotypic protein interactions. Our findings demonstrate that hydrophobic mismatch contributes to the structural organization of membranes. PMID:25635869

  4. Water's hydrogen bonds in the hydrophobic effect: a simple model.

    PubMed

    Xu, Huafeng; Dill, Ken A

    2005-12-15

    We propose a simple analytical model to account for water's hydrogen bonds in the hydrophobic effect. It is based on computing a mean-field partition function for a water molecule in the first solvation shell around a solute molecule. The model treats the orientational restrictions from hydrogen bonding, and utilizes quantities that can be obtained from bulk water simulations. We illustrate the principles in a 2-dimensional Mercedes-Benz-like model. Our model gives good predictions for the heat capacity of hydrophobic solvation, reproduces the solvation energies and entropies at different temperatures with only one fitting parameter, and accounts for the solute size dependence of the hydrophobic effect. Our model supports the view that water's hydrogen bonding propensity determines the temperature dependence of the hydrophobic effect. It explains the puzzling experimental observation that dissolving a nonpolar solute in hot water has positive entropy. PMID:16375338

  5. Hydrophobicity and hydrogen-bonded network in liquid water

    NASA Astrophysics Data System (ADS)

    Li, Je-Luen; Wingreen, Ned; Tang, Chao; Car, Roberto

    2004-03-01

    Hydrophobicity is the main driving force behind numerous important biological processes at molecular level, including protein folding and the formation of biological membranes. Yet few experimental probes can measure the local water structure around a hydrophobic solute, and our understanding of the detailed structure of hydrophobic hydration has to rely on molecular dynamics simulation. As a model system, several groups studied two methane molecules in liquid water and obtained the potential of mean force using Lennard-Jones potential and various water models. However, hydrophobic effect critically depends on the description of hydrogen-bonded network, and classical simulations may not be sufficient to descirbe the forming and breaking of hydrogen bonds. In this work, we apply ab initio molecular dynamics simulations to study this model system. Besides the potential of mean force between 2 methanes in water, the role of the local water structure will be highlighted.

  6. BIOSORPTION OF HYDROPHOBIC ORGANIC POLLUTANTS BY MIXED MICROBIAL POPULATIONS

    EPA Science Inventory

    In recognition of the need to estimate biosorption for natural microbial populations, the variability of partition coefficients for two hydrophobic pollutants to natural populations from a variety of aquatic systems was investigated. Biosorption partition coefficients for pyrene ...

  7. Hydrophobic composition based on mixed-molecular weight polyethylene

    NASA Astrophysics Data System (ADS)

    Gorlenko, Nikolay; Debelova, Natalya; Sarkisov, Yuriy; Volokitin, Gennadiy; Zavyalova, Elena; Lapova, Tatyana

    2016-01-01

    The paper presents investigations of compositions based on low and high molecular weight polyethylene so as to synthesize a hydrophobic composition for moisture protection of timber. X-ray phase analysis and measurements of the tear-off force of hydrophobic coating needed to apply to the timber surface and the limiting wetting angle are carried out to detect the hydrophobic, adhesive, electrophysical, and physicochemical properties of compositions. Kinetic dependencies are given for moisture absorption of timber specimens. It is shown that the preliminary formation of the texture by the surface patterning or its treatment with low-temperature plasma with the following protective coating results in the improvement of hydrophobic properties of the suggested compositions. These compositions can be used in the capacity of water repellents to protect building materials from moisture including restoration works.

  8. SEQUESTRATION OF HYDROPHOBIC ORGANIC CONTAMINANTS BY GEOSORBENTS. (R822626)

    EPA Science Inventory

    The chemical interactions of hydrophobic organic contaminants (HOCs) with soils and sediments (geosorbents) may result in strong binding and slow subsequent release rates that significantly affect remediation rates and endpoints. The underlying physical and chemical phenomena ...

  9. Macromolecular Brushes as Stabilizers of Hydrophobic Solute Nanoparticles.

    PubMed

    Luo, Hanying; Raciti, David; Wang, Chao; Herrera-Alonso, Margarita

    2016-06-01

    Macromolecular brushes bearing poly(ethylene glycol) and poly(d,l-lactide) side chains were used to stabilize hydrophobic solute nanoparticles formed by a rapid change in solvent quality. Unlike linear diblock copolymers with the same hydrophilic and hydrophobic block chemistries, the brush copolymer enabled the formation of ellipsoidal β-carotene nanoparticles, which in cosolvent mixtures developed into rod-like structures, resulting from a combination of Ostwald ripening and particle aggregation. The stabilizing ability of the copolymer was highly dependent on the mobility of the hydrophobic component, influenced by its molecular weight. As shown here, asymmetric amphiphilic macromolecular brushes of this type may be used as hydrophobic drug stabilizers and potentially assist the shape control of nonspherical aggregate morphologies. PMID:27035279

  10. Hydrophobic mismatch sorts SNARE proteins into distinct membrane domains

    NASA Astrophysics Data System (ADS)

    Milovanovic, Dragomir; Honigmann, Alf; Koike, Seiichi; Göttfert, Fabian; Pähler, Gesa; Junius, Meike; Müllar, Stefan; Diederichsen, Ulf; Janshoff, Andreas; Grubmüller, Helmut; Risselada, Herre J.; Eggeling, Christian; Hell, Stefan W.; van den Bogaart, Geert; Jahn, Reinhard

    2015-01-01

    The clustering of proteins and lipids in distinct microdomains is emerging as an important principle for the spatial patterning of biological membranes. Such domain formation can be the result of hydrophobic and ionic interactions with membrane lipids as well as of specific protein-protein interactions. Here using plasma membrane-resident SNARE proteins as model, we show that hydrophobic mismatch between the length of transmembrane domains (TMDs) and the thickness of the lipid membrane suffices to induce clustering of proteins. Even when the TMDs differ in length by only a single residue, hydrophobic mismatch can segregate structurally closely homologous membrane proteins in distinct membrane domains. Domain formation is further fine-tuned by interactions with polyanionic phosphoinositides and homo and heterotypic protein interactions. Our findings demonstrate that hydrophobic mismatch contributes to the structural organization of membranes.

  11. Hydrophobicity – Shake Flasks, Protein Folding and Drug Discovery

    PubMed Central

    Sarkar, Aurijit; Kellogg, Glen E.

    2009-01-01

    Hydrophobic interactions are some of the most important interactions in nature. They are the primary driving force in a number of phenomena. This is mostly an entropic effect and can account for a number of biophysical events such as protein-protein or protein-ligand binding that are of immense importance in drug design. The earliest studies on this phenomenon can be dated back to the end of the 19th century when Meyer and Overton independently correlated the hydrophobic nature of gases to their anesthetic potency. Since then, significant progress has been made in this realm of science. This review briefly traces the history of hydrophobicity research along with the theoretical estimation of partition coefficients. Finally, the application of hydrophobicity estimation methods in the field of drug design and protein folding is discussed. PMID:19929828

  12. Gastric mucosal barrier: hydrophobicity of stretched stomach lining.

    PubMed

    Hills, B A; Lichtenberger, L M

    1985-06-01

    Surface hydrophobicity of the luminal lining of the canine stomach has been studied as a very convenient means of following the adsorbed monolayer of surfactant believed to provide the gastric mucosal barrier. Hydrophobicity has been measured as the contact angle (theta) produced when a drop of saline is placed upon the surface. theta was found to decrease from 82 to 62 degrees upon 50% linear extension of samples of oxyntic mucosa from 10 dogs. When the phospholipid believed to cause the hydrophobicity was absorbed to glass slides, the contact angle was found to decrease with lower surface concentration. Thinning or "crazing" of the absorbed surfactant monolayer imparting the very hydrophobic nature of the luminal lining is discussed as a possible reason why ulcers tend to form at the crests of the folds, i.e., at points where the surface has been stretched and the monolayer disrupted. PMID:4003546

  13. Electron attachment to fluorocarbon radicals

    NASA Astrophysics Data System (ADS)

    Shuman, Nicholas

    2014-10-01

    Most plasma environments contain populations of short-lived species such as radicals, the chemistry of which can have significant effects on the overall chemistry of the system. However, few experimental measurements of the kinetics of electron attachment to radicals exist due to the inherent difficulties of working with transient species. Calculations from first principles have been attempted, but are arduous and, because electron attachment is so sensitive to the specifics of the potential surface, their accuracy has not been established. Electron attachment to small fluorocarbon radicals is particularly important, as the data are needed for predictive modeling of plasma etching of semiconductor materials, a key process in the industrial fabrication of microelectronics. We have recently developed a novel flowing afterglow technique to measure several types of otherwise difficult to study plasma processes, including thermal electron attachment to radicals. Variable Electron and Neutral Density Attachment Mass Spectrometry (VENDAMS) exploits dissociative electron attachment in a weakly ionized plasma as a radical source. Here, we apply VENDAMS to a series of halofluorocarbon precursors in order to measure the kinetics of thermal electron attachment to fluorocarbon radicals. Results are presented for CF2, CF3, C2F5,C2F3,1-C3F7, 2-C3F7, and C3F5 from 300 K to 900 K. Both the magnitude and the temperature dependences of rate coefficients as well as product branching between associative and dissociative attachment are highly system specific; however, thermal attachment to all species is inefficient, never exceeding 5% of the collision rate. The data are analyzed using a recently developed kinetic modeling approach, which uses extended Vogt-Wannier theory as a starting point, accounts for dynamic effects such as coupling between the electron and nuclear motions through empirically validated functional forms, and finally uses statistical theory to determine the fate of

  14. The stable tyrosyl radical in photosystem II: why D?

    PubMed

    Rutherford, A William; Boussac, Alain; Faller, Peter

    2004-04-12

    Two redox-active tyrosines are present in Photosysytem II, the water-oxidizing enzyme. While the tyrosine that is kinetically competent in electron transfer, TyrZ, may also have a role in the enzyme mechanism, the second tyrosine, TyrD, has a stable radical and is not directly involved in the redox chemistry associated with enzyme function. Nevertheless, reasonable mechanistic roles for TyrD have been postulated that satisfy desires to rationalise the presence of this cofactor, or, in English, we think we know what it does. First, the TyrD radical acts an oxidant of the Mn cluster in the lowest state of the redox accumulation cycle (i.e., S(0)), providing potential benefits in maintaining the cluster in the more stable higher valence states. This redox role may also be important during Mn assembly and indeed overreduced forms of the Mn cluster appear to be oxidised by TyrD(*). Second, the proton generated by the TyrD radical is thought to remain in its vicinity having an electrostatic influence on the location and potential of the chlorophyll cation, P(+). This effect may be important for the kinetics of TyrZ oxidation and may provide a significant thermodynamic boost to the enzyme. In addition, through its electrostatic influence, TyrD(*)(H(+)) may confine the highly oxidising cation P(+) to the chlorophyll nearest to TyrZ, thereby accelerating TyrZ oxidation and restricting the potentially damaging redox chemistry to one side of the reaction centre: the disposable D1 side. This second role, evidence for which is beginning to emerge, constitutes a new role for a redox-active tyrosine in biology: as a positive charge generator in a hydrophobic environment. In this short review, we focus on work relevant to these two roles. PMID:15100035

  15. Effects of Hydrophobic Surface Nanobubbles on the Flow in Nanochannels

    NASA Astrophysics Data System (ADS)

    Xie, Hui; Liu, Chao

    It has been demonstrated that there are nanobubbles on hydrophobic surface. Molecular dynamics simulation was adopted to investigate the impacts of the hydrophobic surface nanobubbles on fluid flow in nanochannel. A method for calculating the velocity of nanobubbles is presented. The results show that the bubbles on two plates enhance the velocity slip and disturb the flow. The behavior is attributed to the attractive force between nanobubbles.

  16. Flotation of marine microalgae: effect of algal hydrophobicity.

    PubMed

    Garg, Sourabh; Li, Yan; Wang, Liguang; Schenk, Peer M

    2012-10-01

    This study aims to understand the underlying reasons for the poor flotation response of marine microalgae. The flotation performance and hydrophobicity of a freshwater microalga (Chlorella sp. BR2) were compared to those of a marine microalga (Tetraselmis sp. M8) at different salinities in the presence of a cationic collector, tetradecyl trimethylammonium bromide. It was found that microalgal hydrophobicity played a more important role than salinity in determining the flotation performance. PMID:22858117

  17. Highly hydrophobic and oleophilic foam for selective absorption

    NASA Astrophysics Data System (ADS)

    Su, Changhong

    2009-12-01

    In this article, both highly hydrophobic and oleophilic foam were fabricated by coating inner surface of polyurethane (PU) foam with a super-hydrophobic film. The contact angle of the foam is large as 152.2° for water, and 0° for kerosene. The foam can absorb kerosene selectively from kerosene-water mixture and be regenerated easily. The foam may be used to reclaim oil from polluted natural water area resulted from shipwreck or leakage.

  18. Radical Puppets and the Language of Art

    ERIC Educational Resources Information Center

    Asher, Rikki

    2009-01-01

    Radical puppets are puppets with a social message. Radical puppets encourage creative ideas that lead toward understanding global and environmental aspects of society through the "art of the puppet," a phrase coined by American puppeteer Bill Baird (1965). There is a blending of performance and visual art in puppetry. Through radical puppetry,…

  19. Free-radical chemistry of sulfite.

    PubMed Central

    Neta, P; Huie, R E

    1985-01-01

    The free-radical chemistry of sulfite oxidation is reviewed. Chemical transformations of organic and biological molecules induced by sulfite oxidation are summarized. The kinetics of the free-radical oxidations of sulfite are discussed, as are the kinetics of the reactions of the sulfite-derived radicals SO3 and the peroxy derivative SO5 with organic compounds. PMID:3830699

  20. Mechanisms for Enhanced Hydrophobicity by Atomic-Scale Roughness.

    PubMed

    Katasho, Yumi; Liang, Yunfeng; Murata, Sumihiko; Fukunaka, Yasuhiro; Matsuoka, Toshifumi; Takahashi, Satoru

    2015-01-01

    It is well known that the close-packed CF3-terminated solid surface is among the most hydrophobic surfaces in nature. Molecular dynamic simulations show that this hydrophobicity can be further enhanced by the atomic-scale roughness. Consequently, the hydrophobic gap width is enlarged to about 0.6 nm for roughened CF3-terminated solid surfaces. In contrast, the hydrophobic gap width does not increase too much for a rough CH3-terminated solid surface. We show that the CF3-terminated surface exists in a microscopic Cassie-Baxter state, whereas the CH3-terminated surface exists as a microscopic Wenzel state. This finding elucidates the underlying mechanism for the different widths of the observed hydrophobic gap. The cage structure of the water molecules (with integrated hydrogen bonds) around CH3 terminal assemblies on the solid surface provides an explanation for the mechanism by which the CH3-terminated surface is less hydrophobic than the CF3-terminated surface. PMID:26337567

  1. Condensation Dynamics on Mimicked Metal Matrix Hydrophobic Nanoparticle-Composites

    NASA Astrophysics Data System (ADS)

    Damle, Viraj; Sun, Xiaoda; Rykaczewski, Konrad

    2014-11-01

    Use of hydrophobic surfaces promotes condensation in the dropwise mode, which is significantly more efficient than the common filmwise mode. However, limited longevity of hydrophobic surface modifiers has prevented their wide spread use in industry. Recently, metal matrix composites (MMCs) having microscale hydrophobic heterogeneities dispersed in hydrophilic metal matrix have been proposed as durable and self-healing alternative to hydrophobic surface coatings interacting with deposited water droplets. While dispersion of hydrophobic microparticles in MMC is likely to lead to surface flooding during condensation, the effect of dispersion of hydrophobic nanoparticles (HNPs) with size comparable to water nuclei critical radii and spacing is not obvious. To this end, we fabricated highly ordered arrays of Teflon nanospheres on silicon substrates that mimic the top surface of the MMCs with dispersed HNPs. We used light and electron microscopy to observe breath figures resulting from condensation on these surfaces at varied degrees of subcooling. Here, we discuss the relation between the droplet size distribution, Teflon nanosphere diameter and spacing, and condensation mode. KR acknowledges startup funding from ASU.

  2. Hydrophobic Association in Mixed Urea-TMAO Solutions.

    PubMed

    Ganguly, Pritam; van der Vegt, Nico F A; Shea, Joan-Emma

    2016-08-01

    The formation of a hydrophobic core is key to the folding and resulting function of most proteins in the cell. In several organisms, as well as in many in vitro experiments, protein folding is modulated by the presence of osmolytes, but the mechanism by which hydrophobic association occurs is not well understood. We present a study of the solvation thermodynamics of hydrophobic self-association in mixed-osmolyte urea-TMAO solutions, with neopentane as a model hydrophobic molecule. Using molecular dynamics simulations and the Kirkwood-Buff theory of solutions, we show that a sensitive balance between the TMAO-water and the TMAO-urea interactions governs the osmolyte-induced changes in hydrophobic association in mixed urea-TMAO solutions. This balance must be correctly incorporated in force-field parametrization because hydrophobic association can be either enhanced or prevented all together by slightly increasing or decreasing the osmolyte-water affinity and osmolyte-osmolyte self-affinity of TMAO molecules. PMID:27440555

  3. Soil Hydrophobicity in Andisol under Soil Surface Burning

    NASA Astrophysics Data System (ADS)

    Obuchi, Atsuko; Mizoguchi, Masaru; Nishimura, Taku; Imoto, Hiromi; Miyazaki, Tsuyoshi

    Soil is known to exhibit hydrophobic properties after a forest fire. Experiments conducted by DeBano et al., (1976) showed that the organic compounds in the soil become volatized under high-temperatures, move downward along the soil temperature gradient, and form a hydrophobic layer deep within the soil profile. However, less is known about effects of oxygen atmosphere on morphological changes of organic matter in soil. In this study, we sought to clarify the increase in soil hydrophobicity as well as the changes in carbon and nitrogen content in response to heating of the ground surface in the field and both column and muffle furnace heating in the laboratory. In the muffle furnace burning, soil samples heated under oxygen-deprived conditions exhibited similar carbon and nitrogen dynamics and increased hydrophobicity with temperatures those observed in the field and column experiments. Soil samples under oxygen-deprived condition showed hydrophobicity and some carbon content by heating with 300°C and higher, while almost no carbon remained after heating with 400°C under oxygen available condition. Soil C/N ratio increased by heating with higher temperature under oxygen-deprived condition. Results suggested limited supply of oxygen might have an effect to produce soil hydrophobicity under soil surface burning.

  4. Spontaneous formation of hydrophobic domains in isolated peptides.

    PubMed

    Gloaguen, Eric; Loquais, Yohan; Thomas, Jessica A; Pratt, David W; Mons, Michel

    2013-05-01

    Aromatic amino acids are known for their hydrophobicity and the active role they play in protein folding. Here, we investigate the intrinsic propensity of small peptides to form hydrophobic domains in the absence of solvent water molecules. The structures of three aromatic-rich isolated peptides, Ac-Phe-Phe-NH2 (FF), Ac-Trp-Tyr-NH2 (WY), and Ac-Phe-Phe-Phe-NH2 (FFF), all in the gas phase, have been studied by infrared-ultraviolet (IR/UV) double resonance laser spectroscopy, aided by dispersion-corrected density functional theory (DFT-D) calculations. Spontaneous formation of hydrophobic domains is systematically observed, whatever the secondary structure adopted by the backbone. Various types of aromatic-aromatic arrangements have been identified and associated to specific secondary structures, illustrating the interplay between the hydrophobic clusters and the backbone. Backbone NH amide groups surrounded by aromatic rings have also been evidenced and are found to contribute significantly to the stabilization of aromatic pairs. These results suggest that the formation of aromatic clusters involving contiguous residues might be a very efficient process leading to the formation of hydrophobic domains in the early stages of protein folding, well before a hydrophobic collapse into the tertiary structure. PMID:23551297

  5. Transmembrane Passage of Hydrophobic Compounds Through a Protein Channel Wall

    SciTech Connect

    Hearn, E.; Patel, D; Lepore, D; Indic, M; van den Berg, B

    2009-01-01

    Membrane proteins that transport hydrophobic compounds have important roles in multi-drug resistance and can cause a number of diseases, underscoring the importance of protein-mediated transport of hydrophobic compounds. Hydrophobic compounds readily partition into regular membrane lipid bilayers, and their transport through an aqueous protein channel is energetically unfavourable3. Alternative transport models involving acquisition from the lipid bilayer by lateral diffusion have been proposed for hydrophobic substrates. So far, all transport proteins for which a lateral diffusion mechanism has been proposed function as efflux pumps. Here we present the first example of a lateral diffusion mechanism for the uptake of hydrophobic substrates by the Escherichia coli outer membrane long-chain fatty acid transporter FadL. A FadL mutant in which a lateral opening in the barrel wall is constricted, but which is otherwise structurally identical to wild-type FadL, does not transport substrates. A crystal structure of FadL from Pseudomonas aeruginosa shows that the opening in the wall of the {beta}-barrel is conserved and delineates a long, hydrophobic tunnel that could mediate substrate passage from the extracellular environment, through the polar lipopolysaccharide layer and, by means of the lateral opening in the barrel wall, into the lipid bilayer from where the substrate can diffuse into the periplasm. Because FadL homologues are found in pathogenic and biodegrading bacteria, our results have implications for combating bacterial infections and bioremediating xenobiotics in the environment.

  6. Mechanisms for Enhanced Hydrophobicity by Atomic-Scale Roughness

    PubMed Central

    Katasho, Yumi; Liang, Yunfeng; Murata, Sumihiko; Fukunaka, Yasuhiro; Matsuoka, Toshifumi; Takahashi, Satoru

    2015-01-01

    It is well known that the close-packed CF3-terminated solid surface is among the most hydrophobic surfaces in nature. Molecular dynamic simulations show that this hydrophobicity can be further enhanced by the atomic-scale roughness. Consequently, the hydrophobic gap width is enlarged to about 0.6 nm for roughened CF3-terminated solid surfaces. In contrast, the hydrophobic gap width does not increase too much for a rough CH3-terminated solid surface. We show that the CF3-terminated surface exists in a microscopic Cassie–Baxter state, whereas the CH3-terminated surface exists as a microscopic Wenzel state. This finding elucidates the underlying mechanism for the different widths of the observed hydrophobic gap. The cage structure of the water molecules (with integrated hydrogen bonds) around CH3 terminal assemblies on the solid surface provides an explanation for the mechanism by which the CH3-terminated surface is less hydrophobic than the CF3-terminated surface. PMID:26337567

  7. Impact of Hydrophobic Chain Composition on Amphiphilic Macromolecule Antiatherogenic Bioactivity

    PubMed Central

    2015-01-01

    Amphiphilic macromolecules (AMs) composed of sugar backbones modified with branched aliphatic chains and a poly(ethylene glycol) (PEG) tail can inhibit macrophage uptake of oxidized low-density lipoproteins (oxLDL), a major event underlying atherosclerosis development. Previous studies indicate that AM hydrophobic domains influence this bioactivity through interacting with macrophage scavenger receptors, which can contain basic and/or hydrophobic residues within their binding pockets. In this study, we compare two classes of AMs to investigate their ability to promote athero-protective potency via hydrogen-bonding or hydrophobic interactions with scavenger receptors. A series of ether-AMs, containing methoxy-terminated aliphatic arms capable of hydrogen-bonding, was synthesized. Compared to analogous AMs containing no ether moieties (alkyl-AMs), ether-AMs showed improved cytotoxicity profiles. Increasing AM hydrophobicity via incorporation of longer and/or alkyl-terminated hydrophobic chains yielded macromolecules with enhanced oxLDL uptake inhibition. These findings indicate that hydrophobic interactions and the length of AM aliphatic arms more significantly influence AM bioactivity than hydrogen-bonding. PMID:25070717

  8. Peptide adsorption on the hydrophobic surface: A free energy perspective

    NASA Astrophysics Data System (ADS)

    Sheng, Yuebiao; Wang, Wei; Chen, P.

    2011-05-01

    Protein adsorption is a very attractive topic which relates to many novel applications in biomaterials, biotechnology and nanotechnology. Ionic complementary peptides are a group of novel nano-biomaterials with many biomedical applications. In this work, molecular dynamics simulations of the ionic-complementary peptide EAK16-II on a hydrophobic graphite surface were performed under neutral, acidic and basic solution conditions. Adsorption free energy contour maps were obtained by analyzing the dynamical trajectories. Hydrophobic interactions were found to govern the adsorption of the first peptide molecule, and both hydrophobic and electrostatic interactions contributed to the adsorption of the second peptide molecule. Especially under acidic and basic solution conditions, interplay existed among chain-chain hydrophobic, chain-surface hydrophobic and chain-chain electrostatic interactions during the adsorption of the second peptide molecule. Non-charged residues were found to lie on the graphite surface, while charged residue side-chains oriented towards the solution after the peptide deposited on the surface. These results provide a basis for understanding peptide adsorption on the hydrophobic surface under different solution conditions, which is useful for novel applications such as bioactive implant devices and drug delivery material design.

  9. Vector description of electric and hydrophobic interactions in protein homodimers.

    PubMed

    Mozo-Villarías, Angel; Cedano, Juan; Querol, Enrique

    2016-05-01

    This article describes the formation of homodimers from their constituting monomers, based on the rules set by a simple model of electric and hydrophobic interactions. These interactions are described in terms of the electric dipole moment (D) and hydrophobic moment vectors (H) of proteins. The distribution of angles formed by the two dipole moments of monomers constituting dimers were analysed, as well as the distribution of angles formed by the two hydrophobic moments. When these distributions were fitted to Gaussian curves, it was found that for biological dimers, the D vectors tend mostly to adopt a perpendicular arrangement with respect to each other, in which the constituting dipoles have the least interaction. A minor population tends towards an antiparallel arrangement implying maximum electric attraction. Also in biological dimers, the H vectors of most monomers tend to interact in such a way that the total hydrophobic moment of the dimer increases with respect to those of the monomers. This shows that hydrophobic moments have a tendency to align. In dimers originating in the crystallisation process, the distribution of angles formed by both hydrophobic and electric dipole moments appeared rather featureless, probably because of unspecific interactions in the crystallisation processes. The model does not describe direct interactions between H and D vectors although the distribution of angles formed by both vectors in dimers was analysed. It was found that in most cases these angles tended to be either small (both moments aligned parallel to each other) or large (antiparallel disposition). PMID:26658743

  10. [Erectile rehabilitation after radical prostatectomy].

    PubMed

    Droupy, S; Giuliano, F; Costa, P

    2009-12-01

    The concept of penile rehabilitation involves the procedures designed to improve oxygen delivery the penile erectile tissue to minimized tissue damage during the period of neural recovery following radical prostatectomy. Many basic research studies support the rationale and mechanism of the concept of penile rehabilitation, however they are few clinical studies in the literature that provide a clear medical evidence of its efficacy in patients. Waiting for new data, it is recommended to propose to the patients, following a radical prostatectomy, an active pharmacological penile rehabilitation. This rehabilitation involves counselling with the couple to have regular sexual activities, ideally 1 to 3 times a week. Penile erections could be induced by intracavernosal injections of PGE1 or improved by using PDE5 inhibitors on demand. The results of daily use of PDE5 inhibitor are conflicting and then it cannot be recommended systematically waiting for new data. The rehabilitation could be maintained for about 2 years as results improve with time. PMID:20123519

  11. Mutagenicity of Oxygen Free Radicals

    NASA Astrophysics Data System (ADS)

    Moody, Carmella S.; Hassan, Hosni M.

    1982-05-01

    Paraquat 1,1'-dimethyl-4,4'-bipyridinium dichloride) was used as an intracellular generator of oxygen free radicals and was found to be highly mutagenic for Salmonella typhimurium. It caused both base-pair substitution and frameshift mutations. Paraquat was much more toxic and mutagenic in a simple nutritionally restricted medium than in a rich complex medium. The mutagenicity of paraquat was dependent upon the presence of a supply of both electrons and oxygen. Cells containing high levels of superoxide dismutase (superoxide:superoxide oxidoreductase, EC 1.15.1.1) were more resistant to the toxicity and the mutagenicity of paraquat than were cells containing normal levels of this enzyme. The mutagenicity of paraquat thus appears to be due to its ability to exacerbate the intracellular production of superoxide radicals.

  12. Geoscientists and the Radical Middle

    NASA Astrophysics Data System (ADS)

    Tinker, S. W.

    2015-12-01

    Addressing the great challenges facing society requires industry, government, and academia to work together. I call this overlap space, where compromises are made and real solutions determined, the Radical Middle. Radical because it can appear at times as if the loudest and most publicly influential voices lie outside of the actual solution space, content to provoke but not problem-solve. One key area where geoscientists can play a lead role in the Radical Middle is in the overlap between energy, the environment, and the economy. Globally, fossil fuels still represent 85% of the aggregate energy mix. As existing conventional oil and natural-gas reservoir production continues to slowly decline, unconventional reservoirs, led today by shale and other more expensive resources, will represent a growing part of the oil and gas production mix. Many of these unconventional reservoirs require hydraulic fracturing. The positive economic impact of hydraulic fracturing and associated natural gas and oil production on the United States economy is well documented and undeniable. Yet there are environmental concerns about fracking, and some states and nations have imposed moratoria. This energy-environment-economy space is ideal for leadership from the geosciences. Another such overlap space is the potential for geoscience leadership in relations with China, whose economy and global presence continue to expand. Although China is building major hydropower and natural-gas power plants, as well as nuclear reactors, coal is still king—with the associated environmental impacts. Carbon sequestration—onshore in brine and to enhance oil recovery, as well as offshore—could prove viable. It is vital that educated and objective geoscientists from industry, government, and academia leave their corners and work together in the Radical Middle to educate the public and develop and deliver balanced, economically sensible energy and environmental strategies.

  13. Radical Smiles Rearrangement: An Update.

    PubMed

    Allart-Simon, Ingrid; Gérard, Stéphane; Sapi, Janos

    2016-01-01

    Over the decades the Smiles rearrangement and its variants have become essential synthetic tools in modern synthetic organic chemistry. In this mini-review we summarized some very recent results of the radical version of these rearrangements. The selected examples illustrate the synthetic power of this approach, especially if it is incorporated into a domino process, for the preparation of polyfunctionalized complex molecules. PMID:27399654

  14. Hydroxyl radical detection in vivo

    SciTech Connect

    Chevion, M.; Floyd, R.A.

    1986-05-01

    Hydroxyl radicals have been implicated as the actual species responsible for the deleterious effects of active oxygen in biology. However, in most cases, its presence has only been inferred by circumstantial evidence. Using electrochemical detection coupled to HPLC separation technique the authors can identify and quantitate (at sub-picomole level) the hydroxylated products of 3 aromatic compounds (phenol, salicylate, and 2-deoxy-guanosine) as a direct measure of hydroxyl radical formation. Firstly, the authors showed that mixing ascorbate with copper ions (in the absence of presence of a protein) yields catechols, dihydroxybenzoic acids and 8-OH-deoxy-guanosine (8-OHdG). This approach has been used to study the formation of OH in vivo. Human granulocytes stimulated with TPA showed that 8-OHdG was formed in the cellular DNA at high levels (one 8-OHdG/800 DNA bases). Unstimulated granulocytes contained 8-OHdG below detection level. Formation of 8-OHdG in the TPA-stimulated granulocytes DNA was decreased by the addition of SOD and catalase. Using salicylate as an in vivo scavenger of hydroxyl radicals the authors showed that the level of trapped-dihydroxybenzoic acids is increased approx.8 and approx.3 fold in the lungs and liver of paraquat-poisoned mice, respectively, as compared to normal animals. Similarly, the detected level of dihydroxybenzoic acids in the hearts of adriamycin-treated rats was increased over 100-fold as compared to the hearts of control animals.

  15. A radical way to burn

    SciTech Connect

    Ashley, S.

    1996-08-01

    By manipulating chamber geometries as well as engine cycle pressures and timing, engineers are exploiting a long-obscure technology known as activated radical combustion. Piston-driven internal combustion engines generally come in two varieties: compression-ignited diesels and spark-ignited gasoline power plants. There, is however, a third way to initiate burning of the fuel-air mixture. The technique--variously called radical ignition (RI), activated radical (AR) combustion, Toyota-Soken combustion, and active thermo-atmosphere combustion--is not exactly new, but only recently have engineers begun to exploit the process in practical power plants. These new units include a lightweight two-stroke racing-motorcycle engine, truck diesels with reduced soot output, and lean-burn spark-ignited car engines. This long-obscure combustion process is based on a range of specialized chemical kinetic and physical acoustic techniques developed over decades. Engineers manipulate fundamental combustion parameter such as chamber geometries, valving and porting configurations, and engine cycle pressures and timing to foster the formation of certain highly reactive chemical species that lower the fuel-air mixture`s flash point so that even modest compression make sit self-ignite. These chemical initiators are then retained into the next cycle to start combustion, allowing the engineer to run stably with no spark.

  16. Radical scavengers from heavy hydrocarbons

    SciTech Connect

    Kubo, Junichi

    1996-10-01

    The hydrogen-donating properties of some hydrocarbons form the basis for processes such as coal liquefaction and heavy oil upgrading. However, these hydrocarbons have seldom been used for other purposes, because their potential applications have not been well recognized. Research has indicated that these hydrogen-donating hydrocarbons can be used in important reactions as radical scavengers and have properties particular to those of pure hydrocarbons without functional groups containing heteroatoms. Over years of study researchers have found that pure hydrocarbons with radical-scavenging effects nearly as high as those in conventional hindered phenolic antioxidants can be produced from petroleum, and these hydrogen-donating hydrocarbons exhibit such effects even in oxidative atmospheres (i.e., they function as antioxidants). He has also shown that these mixtures have some properties particular to pure hydrocarbons without functional groups containing heteroatoms, and they`ve seen that a mechanism based on the steric effects appears when these hydrocarbons are used in heavy oil hydroprocessing. Hydrogen-donating hydrocarbons should be a viable resource in many applications. In this article, he presents radical-scavenging abilities, characteristics as pure hydrocarbons, and applications on the basis of the studies.

  17. Free-radical-mediated DNA binding.

    PubMed Central

    O'Brien, P J

    1985-01-01

    Free-radical metabolites can be generated metabolically by a one-electron reductase-catalyzed reaction or a "peroxidase" catalyzed oxidation or by photoactivation of a wide variety of aromatic xenobiotics. Radicals may also be generated during lipid peroxidation. Some radicals can react with DNA or bind covalently or noncovalently as a dismutation product or as a dimer, trimer or polymeric product. Modification to the DNA can result in single-strand breaks, loss of template activity, and crosslinking. The binding can prevent enzymic digestion. In some cases, the radicals react with oxygen, resulting before conversion to DNA reactive oxygen species. Most radicals probably do not interact with DNA. PMID:3007090

  18. Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

    NASA Technical Reports Server (NTRS)

    Kumar, Nitin; Couzis, Alex; Maldarelli, Charles; Singh, Bhim S. (Technical Monitor)

    2000-01-01

    Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid/surfaces. At a hydrophobic surface, the air/hydrophobic solid tension is low, and the solid/aqueous tension is high. A large contact angle forms as the aqueous/air tension acts together with the solid/air tension to balance the large solid/aqueous tension. The aqueous phase, instead of spreading, is held in a meniscus by the large angle. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants (i.e. amphiphiles with a hydrophobic chain of methylene groups attached to a large polar group to give aqueous solubility) do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm or polyethylene. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3)) and an extended ethoxylate (-(OCH2CH2)n-) polar group in the form of a chain with seven or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (lermed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread and can be used in microgravity. We propose that the trisiloxane surfactants superspread when the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross sectional area of the disk is larger than that of the extended ethoxylate chain, the

  19. A New Hydrophobic Catalyst for Tritium Separation from Nuclear Effluents

    SciTech Connect

    Popescu, I.; Ionita, Gh.; Stefanescu, I.; Kitamoto, A.

    2005-07-15

    The hydrophobic catalysts were originally conceived in Canada for the deuterium enrichment and tritium separation by hydrogen-liquid water isotopic exchange in nuclear field. Unlike the conventional hydrophilic catalysts, which becomes inefficient to direct contact with liquid water, the hydrophobic catalysts kept a high catalytic activity and stability, even under the direct contact with liquid water or in presence of humid gas. Based on the long experience of the authors, in the preparation, testing and evaluation of the performances of hydrophobic catalysts, and based on the reviewed references, this paper presents up-to-date R and D activities on the preparation methods and applications of the hydrophobic catalysts, in tritium separation. The objectives of the paper are: (1) to provide a database for selection of the most appropriate catalyst and catalytic packing for above mentioned processes, (2) to asses and to find a new procedure for preparation of a new improved hydrophobic catalyst. From reviewed references we consider that platinum remains the most active and efficient catalytic metal and the TEFLON is the best wetproofing agent. A new improved hydrophobic Pt-catalyst has been proposed and is now underway. The main steps and experimental conditions of preparation are largely discussed. A new wet-proofing agent and a new binding agents (titanium oxide, cerium oxide, zirconium oxide) with catalytic role are proposed and tested. The physico-structural parameters of new improved catalyst have been determined and are discussed in details. The new proposal is a promising idea to improve the performances of conventional hydrophobic Pt-catalysts.

  20. Compatibility assessment of methods used for soil hydrophobicity determination

    NASA Astrophysics Data System (ADS)

    Papierowska, Ewa; Szatyłowicz, Jan; Kalisz, Barbara; Łachacz, Andrzej; Matysiak, Wojciech; Debaene, Guillaume

    2016-04-01

    Soil hydrophobicity is a global problem. Effect of hydrophobicity on the soil environment is very important, because it can cause irreversible changes in ecosystems, leading to their complete degradation. The choice of method used to determine soil hydrophobicity is not simple because there is no obvious criteria for their selection. The results obtained by various methods may not be coherent and may indicate different degrees of hydrophobicity within the same soil sample. The objective of the study was to assess the compatibility between methods used to determine the hydrophobicity of selected organic and mineral-organic soils. Two groups of soil materials were examined: hydrogenic (87 soil samples) and autogenic soils (19 soil samples) collected from 41 soil profiles located in north-eastern Poland. Air-dry soil samples were used. Hydrophobicity was determined using two different methods i.e. on the basis of wetting contact angle measurements between water and solid phase of soils and with water drop penetration time tests. The value of the wetting contact angle was measured using the sessile drop method with optical goniometer CAM 100 (KSV Instruments). The wetting contact angles were determined at room temperature (20° C) within 10 min after sample preparation using standard procedure. In addition, water drop penetration time was measured. In order to compare the methods used for the assessment of soil hydrophobicity, the agreement between observers model was applied. In this model five categories of soil hydrophobicity were proposed according to the class used in the soil hydrofobicity classification based on water drop penetration time test. Based on this classification the values of the weighted kappa coefficients were calculated using SAS 9.4 (SAS Institute, 2013, Cary NC) for evaluating relationships between between the different investigated methods. The results of agreement were presented in forms of agreement charts. Research results indicated good

  1. Spectrofluorimetric assessment of the surface hydrophobicity of proteins.

    PubMed Central

    Cardamone, M; Puri, N K

    1992-01-01

    The equilibrium binding of the apolar fluorescent dye 1-anilinonaphthalene-8-sulphonate (ANS) to bacteriorhodopsin, BSA, chicken egg lysozyme, ovalbumin, porcine somatotrophin (PST) and bovine pancreatic ribonuclease (RNAase) was quantitatively evaluated using Scatchard- and Klotz-plot analyses. On the basis of the average association constant for ANS binding sites (Ka), the proteins could be ranked in order of surface hydrophobicity as: Bacteriorhodopsin greater than BSA greater than ovalbumin greater than PST greater than lysozyme greater than RNAase. The number of protein-ANS binding sites was determined as 54, 10, 3, 1, 2 and 1 respectively. The ANS-based assessment of the surface hydrophobicity of these proteins was generally in agreement with the average hydrophobicity based on amino acid sequence [Bigelow (1967) J. Theor. Biol. 16, 187-211], except for results with PST and ovalbumin. The proteins were also analysed by reversed-phase h.p.l.c. using C1 and C8 columns. There was no significant correlation between ANS and reversed-phase-h.p.l.c. assessment of hydrophobicity, with the results obtained by h.p.l.c. being dependent upon the column used. ANS-based measurement of surface hydrophobicity appears to be the most appropriate means for assessing proteins such as to reflect their overall three-dimensional structure in solution. PMID:1546973

  2. Interaction of surfactants with hydrophobic surfaces in nanopores.

    PubMed

    Brumaru, Claudiu; Geng, Maxwell L

    2010-12-21

    Surfactant-induced wetting of hydrophobic nanopores is investigated. SDS micelles interact with the C18 layer on the nanopore walls with their hydrophobic tails, creating a charged wall lining with their head groups and inducing a breakthrough of the aqueous solution to wet the pores. The surface coverage of the surfactant molecules is evaluated electrophoretically. A surprising discovery is that pore wetting is achieved with 0.73 μmol/m(2) coverage of SDS surfactant, corresponding to only 18% of a monolayer on the walls of the nanopores. Clearly, the surfactant molecules cannot organize as a compact uninterrupted monolayer. Instead, formation of hemimicelles is thermodynamically favored. Modeling shows that, to be consistent with the experimental observations, the aggregation number of hemimicelles is lower than 25 and the size of hemimicelle is limited to a maximum radius of 11.7 Å. The hydrophobic tails of SDS thus penetrate into and intercalate with the C18 layer. The insight gained in the C18-surfactant interactions is essential in the surfactant-induced solubilization of hydrophobic nanoporous particles. The results have bearing on the understanding of the nature of hydrophobic interactions. PMID:21043464

  3. How protein chemists learned about the hydrophobic factor.

    PubMed

    Tanford, C

    1997-06-01

    It is generally accepted today that the hydrophobic force is the dominant energetic factor that leads to the folding of polypeptide chains into compact globular entities. This principle was first explicitly introduced to protein chemists in 1938 by Irving Langmuir, past master in the application of hydrophobicity to other problems, and was enthusiastically endorsed by J.D. Bernal. But both proposal and endorsement came in the course of a debate about a quite different structural principle, the so-called "cyclol hypothesis" proposed by D. Wrinch, which soon proved to be theoretically and experimentally unsupportable. Being a more tangible idea, directly expressed in structural terms, the cyclol hypothesis received more attention than the hydrophobic principle and the latter never actually entered the mainstream of protein science until 1959, when it was thrust into the limelight in a lucid review by W. Kauzmann. A theoretical paper by H.S. Frank and M. Evans, not itself related to protein folding, probably played a major role in the acceptance of the hydrophobicity concept by protein chemists because it provided a crude but tangible picture of the origin of hydrophobicity per se in terms of water structure. PMID:9194199

  4. How protein chemists learned about the hydrophobic factor.

    PubMed Central

    Tanford, C.

    1997-01-01

    It is generally accepted today that the hydrophobic force is the dominant energetic factor that leads to the folding of polypeptide chains into compact globular entities. This principle was first explicitly introduced to protein chemists in 1938 by Irving Langmuir, past master in the application of hydrophobicity to other problems, and was enthusiastically endorsed by J.D. Bernal. But both proposal and endorsement came in the course of a debate about a quite different structural principle, the so-called "cyclol hypothesis" proposed by D. Wrinch, which soon proved to be theoretically and experimentally unsupportable. Being a more tangible idea, directly expressed in structural terms, the cyclol hypothesis received more attention than the hydrophobic principle and the latter never actually entered the mainstream of protein science until 1959, when it was thrust into the limelight in a lucid review by W. Kauzmann. A theoretical paper by H.S. Frank and M. Evans, not itself related to protein folding, probably played a major role in the acceptance of the hydrophobicity concept by protein chemists because it provided a crude but tangible picture of the origin of hydrophobicity per se in terms of water structure. PMID:9194199

  5. Free radicals and activated oxygen.

    PubMed

    Famaey, J P

    1982-01-01

    Superoxide anion (0(-2)), hydrogen peroxide (H2O2) and hydroxyl radical (OH.) are products of the biological reduction of 0(2). They are very reactive and poorly tolerated within living systems and enzymes that catalytically scavenge these products have been evolved as defense mechanisms. These include superoxide dismutases (SOD), catalase and peroxidases. Large amounts of O-2 are produced by different enzymatic and non enzymatic biological processes. Large amounts of activated oxygens are produced by phagocytosing cells such as macrophages and polymorphonuclear cells. This production is associated with the bactericidal actions of these cells but it also largely contributes to exacerbate and sustain the inflammation where these cells congregate. The arachidonic acid pathway triggered by the inflammatory stimuli is also a source for these oxidizing radicals. The production of activated oxygens has been associated with the normal aging process but also with various toxic reactions (e.g. the toxicity of the herbicide paraquat, of the ionizing radiations, of certain antibiotics such as streptonigrin, etc. . . .). O-2 induces the depolymerization of hyaluronic acid which lends viscosity and lubricating properties to synovial fluids. SOD possess antiinflammatory properties and a bovine SOD, orgotein, has now been largely investigated by intramuscular and intraarticular injections in the treatment of rheumatic diseases. Various antiinflammatory compounds (e.g. the salicylates) are able either to inhibit the production of these oxygen radicals or to scavenge them which seems of importance for their antiinflammatory properties. Singlet oxygen, another activated oxygen, might also play a role in the inflammatory process. PMID:6295769

  6. Hydrophobic matrix-free graphene-oxide composites with isotropic and nematic states

    NASA Astrophysics Data System (ADS)

    Wåhlander, Martin; Nilsson, Fritjof; Carlmark, Anna; Gedde, Ulf W.; Edmondson, Steve; Malmström, Eva

    2016-08-01

    We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been immobilised on anionic GO and subsequently grafted with hydrophobic polymer grafts. Dense grafts of PBA, PBMA and PMMA with a wide range of average graft lengths (MW: 1-440 kDa) were polymerised by surface-initiated controlled radical precipitation polymerisation from the statistical MI. The surface modification is designed similarly to bimodal graft systems, where the cationic MI generates nanoparticle repulsion, similar to dense short grafts, while the long grafts offer miscibility in non-polar environments and cohesion. The state-of-the-art dispersions of grafted GO were in the isotropic state. Transparent and translucent matrix-free GO-composites could be melt-processed directly using only grafted GO. After processing, birefringence due to nematic alignment of grafted GO was observed as a single giant Maltese cross, 3.4 cm across. Permeability models for composites containing aligned 2D-fillers were developed, which were compared with the experimental oxygen permeability data and found to be consistent with isotropic or nematic states. The storage modulus of the matrix-free GO-composites increased with GO content (50% increase at 0.67 wt%), while the significant increases in the thermal stability (up to 130 °C) and the glass transition temperature (up to 17 °C) were dependent on graft length. The tuneable matrix-free GO-composites with rapid thermo-responsive shape-memory effects are promising candidates for a vast range of applications, especially selective membranes and sensors.We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been

  7. Aromatic-radical oxidation chemistry

    SciTech Connect

    Glassman, I.; Brezinsky, K.

    1993-12-01

    The research effort has focussed on discovering an explanation for the anomalously high CO{sub 2} concentrations observed early in the reaction sequence of the oxidation of cyclopentadiene. To explain this observation, a number of plausible mechanisms have been developed which now await experimental verification. One experimental technique for verifying mechanisms is to probe the reacting system by perturbing the radical concentrations. Two forms of chemical perturbation of the oxidation of cyclopentadiene were begun during this past year--the addition of NO{sub 2} and CO to the reacting mixture.

  8. Laser spectroscopy of hydrocarbon radicals

    SciTech Connect

    Chen, P.

    1993-12-01

    The author reports the application of supersonic jet flash pyrolysis to the specific preparation of a range of organic radicals, biradicals, and carbenes in a skimmed molecular beam. Each species was produced cleanly and specifically, with little or no secondary reactions by the thermal dissociation of appropriately designed and synthesized organic precursors. Photoelectron spectra of the three isomeric C{sub 3}H{sub 2} carbenes, ortho-benzyne, and the {alpha},3-dehydrotoluene biradical, were used to establish adiabatic ionization potentials for use in thermochemical determinations.

  9. Iron and iron derived radicals

    SciTech Connect

    Borg, D.C.; Schaich, K.M.

    1987-04-01

    We have discussed some reactions of iron and iron-derived oxygen radicals that may be important in the production or treatment of tissue injury. Our conclusions challenge, to some extent, the usual lines of thought in this field of research. Insofar as they are born out by subsequent developments, the lessons they teach are two: Think fastexclamation Think smallexclamation In other words, think of the many fast reactions that can rapidly alter the production and fate of highly reactive intermediates, and when considering the impact of competitive reactions on such species, think how they affect the microenvironment (on the molecular scale) ''seen'' by each reactive molecule. 21 refs., 3 figs., 1 tab.

  10. Fluorescent graphene oxide via polymer grafting: an efficient nanocarrier for both hydrophilic and hydrophobic drugs.

    PubMed

    Kundu, Aniruddha; Nandi, Sudipta; Das, Pradip; Nandi, Arun K

    2015-02-18

    Functionalized graphene-based drug delivery vehicles have conquered a significant position because functionalization improves its biocompatibility and stability in cell medium, leaving sufficient graphitic basal plane for drug loading through π-π stacking. In this study, poly(N-isopropylacrylamide) (PNIPAM) is covalently grafted from the surface of graphene oxide (GO) via a facile, eco-friendly and an easy procedure of free radical polymerization (FRP) using ammonium persulfate initiator. Various spectroscopic and microscopic studies confirm the successful grafting of PNIPAM from GO surface. PNIPAM-grafted GO (GPNM) exhibits enhanced thermal stability, improved dispersibility both in aqueous and cell medium, and better biocompatibility and cell viability compared to GO. Interestingly, GPNM displays an exciting fluorescence property in aqueous medium, which is a hike of intensity at 36 °C due to the lower critical solution temperature (LCST) of PNIPAM chains (32 °C). Moreover both hydrophilic (doxorubicin (DOX)) and hydrophobic (indomethacin (IMC)) drugs loaded on the surface of GPNM hybrid exhibits its efficacy as an efficient carrier for both types of drugs. Cellular uptakes of free DOX and DOX-loaded GPNM (GPNM-DOX) are evidenced both from optical and fluorescence imaging of live cells, and the efficiency of drug is significantly improved in the loaded system. The release of DOX from GPNM-DOX was achieved at pH 4, relevant to the environment of cancer cells. The pH-triggered release of hydrophobic drug was also studied using UV-vis spectroscopy via alginate encapsulation, showing a great enhancement at pH = 7.4. The IMC is also found to be released by human serum albumin using dialysis technique. The GPNM nanomaterial shows the property of simultaneous loading of DOX and IMC as well as pH-triggered simultaneous release of both of the drugs. PMID:25612470

  11. Hydrophobic matrix-free graphene-oxide composites with isotropic and nematic states.

    PubMed

    Wåhlander, Martin; Nilsson, Fritjof; Carlmark, Anna; Gedde, Ulf W; Edmondson, Steve; Malmström, Eva

    2016-08-21

    We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been immobilised on anionic GO and subsequently grafted with hydrophobic polymer grafts. Dense grafts of PBA, PBMA and PMMA with a wide range of average graft lengths (MW: 1-440 kDa) were polymerised by surface-initiated controlled radical precipitation polymerisation from the statistical MI. The surface modification is designed similarly to bimodal graft systems, where the cationic MI generates nanoparticle repulsion, similar to dense short grafts, while the long grafts offer miscibility in non-polar environments and cohesion. The state-of-the-art dispersions of grafted GO were in the isotropic state. Transparent and translucent matrix-free GO-composites could be melt-processed directly using only grafted GO. After processing, birefringence due to nematic alignment of grafted GO was observed as a single giant Maltese cross, 3.4 cm across. Permeability models for composites containing aligned 2D-fillers were developed, which were compared with the experimental oxygen permeability data and found to be consistent with isotropic or nematic states. The storage modulus of the matrix-free GO-composites increased with GO content (50% increase at 0.67 wt%), while the significant increases in the thermal stability (up to 130 °C) and the glass transition temperature (up to 17 °C) were dependent on graft length. The tuneable matrix-free GO-composites with rapid thermo-responsive shape-memory effects are promising candidates for a vast range of applications, especially selective membranes and sensors. PMID:27230294

  12. Preservation of York Minster historic limestone by hydrophobic surface coatings.

    PubMed

    Walker, Rachel A; Wilson, Karen; Lee, Adam F; Woodford, Julia; Grassian, Vicki H; Baltrusaitis, Jonas; Rubasinghege, Gayan; Cibin, Giannantonio; Dent, Andrew

    2012-01-01

    Magnesian limestone is a key construction component of many historic buildings that is under constant attack from environmental pollutants notably by oxides of sulfur via acid rain, particulate matter sulfate and gaseous SO(2) emissions. Hydrophobic surface coatings offer a potential route to protect existing stonework in cultural heritage sites, however, many available coatings act by blocking the stone microstructure, preventing it from 'breathing' and promoting mould growth and salt efflorescence. Here we report on a conformal surface modification method using self-assembled monolayers of naturally sourced free fatty acids combined with sub-monolayer fluorinated alkyl silanes to generate hydrophobic (HP) and super hydrophobic (SHP) coatings on calcite. We demonstrate the efficacy of these HP and SHP surface coatings for increasing limestone resistance to sulfation, and thus retarding gypsum formation under SO(2)/H(2)O and model acid rain environments. SHP treatment of 19th century stone from York Minster suppresses sulfuric acid permeation. PMID:23198088

  13. Preservation of York Minster historic limestone by hydrophobic surface coatings

    NASA Astrophysics Data System (ADS)

    Walker, Rachel A.; Wilson, Karen; Lee, Adam F.; Woodford, Julia; Grassian, Vicki H.; Baltrusaitis, Jonas; Rubasinghege, Gayan; Cibin, Giannantonio; Dent, Andrew

    2012-11-01

    Magnesian limestone is a key construction component of many historic buildings that is under constant attack from environmental pollutants notably by oxides of sulfur via acid rain, particulate matter sulfate and gaseous SO2 emissions. Hydrophobic surface coatings offer a potential route to protect existing stonework in cultural heritage sites, however, many available coatings act by blocking the stone microstructure, preventing it from `breathing' and promoting mould growth and salt efflorescence. Here we report on a conformal surface modification method using self-assembled monolayers of naturally sourced free fatty acids combined with sub-monolayer fluorinated alkyl silanes to generate hydrophobic (HP) and super hydrophobic (SHP) coatings on calcite. We demonstrate the efficacy of these HP and SHP surface coatings for increasing limestone resistance to sulfation, and thus retarding gypsum formation under SO2/H2O and model acid rain environments. SHP treatment of 19th century stone from York Minster suppresses sulfuric acid permeation.

  14. Preservation of York Minster historic limestone by hydrophobic surface coatings

    PubMed Central

    Walker, Rachel A.; Wilson, Karen; Lee, Adam F.; Woodford, Julia; Grassian, Vicki H.; Baltrusaitis, Jonas; Rubasinghege, Gayan; Cibin, Giannantonio; Dent, Andrew

    2012-01-01

    Magnesian limestone is a key construction component of many historic buildings that is under constant attack from environmental pollutants notably by oxides of sulfur via acid rain, particulate matter sulfate and gaseous SO2 emissions. Hydrophobic surface coatings offer a potential route to protect existing stonework in cultural heritage sites, however, many available coatings act by blocking the stone microstructure, preventing it from ‘breathing' and promoting mould growth and salt efflorescence. Here we report on a conformal surface modification method using self-assembled monolayers of naturally sourced free fatty acids combined with sub-monolayer fluorinated alkyl silanes to generate hydrophobic (HP) and super hydrophobic (SHP) coatings on calcite. We demonstrate the efficacy of these HP and SHP surface coatings for increasing limestone resistance to sulfation, and thus retarding gypsum formation under SO2/H2O and model acid rain environments. SHP treatment of 19th century stone from York Minster suppresses sulfuric acid permeation. PMID:23198088

  15. A script to highlight hydrophobicity and charge on protein surfaces

    PubMed Central

    Hagemans, Dominique; van Belzen, Ianthe A. E. M.; Morán Luengo, Tania; Rüdiger, Stefan G. D.

    2015-01-01

    The composition of protein surfaces determines both affinity and specificity of protein-protein interactions. Matching of hydrophobic contacts and charged groups on both sites of the interface are crucial to ensure specificity. Here, we propose a highlighting scheme, YRB, which highlights both hydrophobicity and charge in protein structures. YRB highlighting visualizes hydrophobicity by highlighting all carbon atoms that are not bound to nitrogen and oxygen atoms. The charged oxygens of glutamate and aspartate are highlighted red and the charged nitrogens of arginine and lysine are highlighted blue. For a set of representative examples, we demonstrate that YRB highlighting intuitively visualizes segments on protein surfaces that contribute to specificity in protein-protein interfaces, including Hsp90/co-chaperone complexes, the SNARE complex and a transmembrane domain. We provide YRB highlighting in form of a script that runs using the software PyMOL. PMID:26528483

  16. Ice friction: The effects of surface roughness, structure, and hydrophobicity

    NASA Astrophysics Data System (ADS)

    Kietzig, Anne-Marie; Hatzikiriakos, Savvas G.; Englezos, Peter

    2009-07-01

    The effect of surface roughness, structure, and hydrophobicity on ice friction is studied systematically over a wide range of temperature and sliding speeds using several metallic interfaces. Hydrophobicity in combination with controlled roughness at the nanoscale is achieved by femtosecond laser irradiation to mimic the lotus effect on the slider's surface. The controlled roughness significantly increases the coefficient of friction at low sliding speeds and temperatures well below the ice melting point. However, at temperatures close to the melting point and relatively higher speeds, roughness and hydrophobicity significantly decrease ice friction. This decrease in friction is mainly due to the suppression of capillary bridges in spite of the presence of surface asperities that facilitate their formation. Finally, grooves oriented in the sliding direction also significantly decrease friction in the low velocity range compared to scratches and grooves randomly distributed over a surface.

  17. The hydrophobic effect and its role in cold denaturation.

    PubMed

    Dias, Cristiano L; Ala-Nissila, Tapio; Wong-ekkabut, Jirasak; Vattulainen, Ilpo; Grant, Martin; Karttunen, Mikko

    2010-02-01

    The hydrophobic effect is considered the main driving force for protein folding and plays an important role in the stability of those biomolecules. Cold denaturation, where the native state of the protein loses its stability upon cooling, is also attributed to this effect. It is therefore not surprising that a lot of effort has been spent in understanding this phenomenon. Despite these efforts, many unresolved fundamental aspects remain. In this paper we review and summarize the thermodynamics of proteins, the hydrophobic effect and cold denaturation. We start by accounting for these phenomena macroscopically then move to their atomic-level description. We hope this review will help the reader gain insights into the role played by the hydrophobic effect in cold denaturation. PMID:19616532

  18. Is water structure around hydrophobic groups clathrate-like?

    PubMed Central

    Head-Gordon, T

    1995-01-01

    The term "clathrate structure" is quantified for solvation of nonpolar groups by enumerating hydrogen-bonded ring sizes both in the solvation shell and through the shell-bulk interface and comparing it to a bulk control using the ST4 water model. For clathrate-like structure to be evident, the distributions along the hydrophobic surface are expected to be dominated by pentagons, with significant depletion of hexagons and larger polygons. While the distribution in this region is indeed distinguished by a large number of pentagons, there are significant contributions from hexagons and larger rings as well. Calculated polygon distributions through the shell-bulk interface indicate that when water structure is highly cooperative along the hydrophobic surface, hydrogen-bonded pathways leading back into bulk are then reduced. These results are qualitatively consistent with the observation that hydrophobicity is proportional to the nonpolar solute surface area. Images Fig. 1 Fig. 2 Fig. 3 Fig. 4 Fig. 5 Fig. 6 PMID:11607575

  19. Ice friction: The effects of surface roughness, structure, and hydrophobicity

    SciTech Connect

    Kietzig, Anne-Marie; Hatzikiriakos, Savvas G.; Englezos, Peter

    2009-07-15

    The effect of surface roughness, structure, and hydrophobicity on ice friction is studied systematically over a wide range of temperature and sliding speeds using several metallic interfaces. Hydrophobicity in combination with controlled roughness at the nanoscale is achieved by femtosecond laser irradiation to mimic the lotus effect on the slider's surface. The controlled roughness significantly increases the coefficient of friction at low sliding speeds and temperatures well below the ice melting point. However, at temperatures close to the melting point and relatively higher speeds, roughness and hydrophobicity significantly decrease ice friction. This decrease in friction is mainly due to the suppression of capillary bridges in spite of the presence of surface asperities that facilitate their formation. Finally, grooves oriented in the sliding direction also significantly decrease friction in the low velocity range compared to scratches and grooves randomly distributed over a surface.

  20. Enzymatic treatments of pulp using laccase and hydrophobic compounds.

    PubMed

    Garcia-Ubasart, Jordi; Esteban, Alberto; Vila, Carlos; Roncero, M Blanca; Colom, Josep F; Vidal, Teresa

    2011-02-01

    The aim of this work was to develop an innovative method for the internal sizing of paper by use of laccase and hydrophobic compounds. Nine different products containing hydrophobic moieties were tested in combination with laccase derived from Trametes villosa on Eucalyptus globulus kraft pulp in order to assess their internal sizing capability. The strongest internal sizing effect was obtained with lauryl gallate (LG). Heat treatment of the handsheets was found to increase the resistance to water absorption of internally sized samples significantly. Tests were conducted under variable operating conditions, including enzyme and reactant doses and treatment time. In addition to altering the water absorption rate, internal sizing with the laccase-LG treatments was found to affect the mechanical and optical properties of the handsheets. As shown in this work, treatments based on laccase and a hydrophobic compound (particularly lauryl gallate), can provide a new, effective biotechnological method for the internal sizing of paper. PMID:21050744

  1. Graphene oxide as a radical initiator: Free radical and controlled radical polymerization of sodium 4-vinylbenzenesulfonate with graphene oxide

    DOE PAGESBeta

    Voylov, Dmitry N.; Saito, Tomonori; Lokitz, Bradley S.; Uhrig, David; Wang, Yangyang; Agapov, Alexander L.; Holt, Adam P.; Bocharova, Vera; Kisliuk, Alexander; Sokolov, Alexei P.

    2016-01-19

    The free radical and controlled radical polymerization of sodium 4-vinylbenzenesulfonate using graphene oxide as a radical initiator was studied. This work demonstrates that graphene oxide can initiate radical polymerization in an aqueous solution without any additional initiator. Poly(sodium 4-vinylbenzenesulfonate) obtained via reversible addition fragmentation chain transfer polymerization had a controlled molecular weight with a very narrow polydispersity ranging between 1.01 and 1.03. Furthermore, the reduction process of graphene oxide as well as the resulting composite material properties were analyzed in detail.

  2. Aging Oxidation Reactions on Atmospheric Black Carbon by OH Radicals. A Theoretical Modeling Study.

    PubMed

    Rojas, Laura; Peraza, Alexander; Ruette, Fernando

    2015-12-31

    Aging processes of black carbon (BC) particles require knowledge of their chemical reactivities, which have impact on cloud condensation nuclei (CCN) activities, radiant properties and health problems related to air pollutions. In the present work, interactions between several OH radicals with BC (modeled with a coronene molecule) were calculated by using DFT and PM6 codes as described by Mysak et al. Water interaction with BC was also included. Results show that OH radical adsorption is preferred on border sites, independent of the theoretical method employed. Potential energy curves using DFT(TPSS-D3) approach for OH chemisorption showed small-energy barriers, as reported in previous work with PM6. A dipole moment has been created, and the hydrophobic coronene surface is transformed to hydrophilic after the first OH chemisorption. Several stages were found in the BC aging by OH radicals, thus (a) Hydroxylation of coronene by several OH radical would lead to H abstractions directly from the substrate. (b) Abstraction of H from adsorbed OH (at the border sites) drives a C-C bond breaking and the formation of carboxyl groups. (c) Hydrogen abstraction from carboxyl group produces decarboxylation (CO2 plus water) as experimentally obtained. Potential energy curves of one of the reactive path were calculated with the PM6 method. The formation of products was confirmed using DFT. Coronene interaction with O2 was also considered to have a realistic atmospheric environment. PMID:26605439

  3. Radical formation and radiation damage in adamantane

    SciTech Connect

    Lloyd, R.V.; DiGregorio, S.; DiMauro, L.; Wood, D.E.

    1980-10-30

    Unequivocal samples of the 1-adamantyl (1-Ad) and 2-Ad radicals have been prepared in a matrix of adamantane (Ad) by the simultaneous deposition of atomic sodium, 1- or 2-bromoadamantane, and adamantance at 77 K. The EPR spectrum of the 1-Ad radical contrary to previous reports has a clearly resolved hyperfine structure that can be analyzed in terms of the solution parameters of Krusic et al., and the spectrum of the 2-Ad radical is identical with that previously reported by Ferrell et al. It is also shown that conditions of purification and irradiation can greatly affect the spectra obtained upon X irradiation of Ad itself. Depending upon conditions, alicyclic radicals that are primary products of ring-opening reactions or benzylic-type radicals that are probably secondary reaction products can also be obtained in addition to 1-Ad and 2-Ad radicals.

  4. [Free radicals in immunology and infectious diseases].

    PubMed

    Racek, J; Holecek, V; Sedlácek, D; Panzner, P

    2001-04-01

    Free radicals contribute significantly in modification of immune processes and inflammatory reactions. They are produced by activated phagocytes which use them for killing microorganisms. Free radicals facilitate production of cytokines, which are important as modifiers of inflammatory reactions. Formation of free radicals is influenced by antioxidants which can thus modify the intensity of inflammatory reaction and immune response. The authors describe in detail the contribution of free radicals in etiology and pathogenesis of autoimmune diseases including rheumatoid arthritis, multiple sclerosis or amyotrophic lateral sclerosis. The role of free radicals and modifying influence of antioxidants in viral, bacterial, parasitic and mycotic diseases is described in the second part of the review. Finally, influence of free radicals and antioxidants on immunity changes in patients with malignant tumours, during aging and physical exercise is discussed. PMID:11329733

  5. Intercalation of small hydrophobic molecules in lipid bilayers containing cholesterol

    SciTech Connect

    Worcester, D.L.; Hamacher, K.; Kaiser, H.; Kulasekere, R.; Torbet, J.

    1994-12-31

    Partitioning of small hydrophobic molecules into lipid bilayers containing cholesterol has been studied using the 2XC diffractometer at the University of Missouri Research Reactor. Locations of the compounds were determined by Fourier difference methods with data from both deuterated and undeuterated compounds introduced into the bilayers from the vapor phase. Data fitting procedures were developed for determining how well the compounds were localized. The compounds were found to be localized in a narrow region at the center of the hydrophobic layer, between the two halves of the bilayer. The structures are therefore intercalated structures with the long axis of the molecules in the plane of the bilayer.

  6. Intercalation of small hydrophobic molecules in lipid bilayers containing cholesterol.

    PubMed

    Worcester, D L; Hamacher, K; Kaiser, H; Kulasekere, R; Torbet, J

    1996-01-01

    Partitioning of small hydrophobic molecules into lipid bilayers containing cholesterol has been studied using the 2XC diffractometer at the University of Missouri Research Reactor. Locations of the compounds were determined by Fourier difference methods with data from both deuterated and undeuterated compounds introduced into the bilayers from the vapor phase. Data fitting procedures were developed for determining how well the compounds were localized. The compounds were found to be localized in a narrow region at the center of the hydrophobic layer, between the two halves of the bilayer. The structures are therefore intercalated structures with the long axis of the molecules in the plane of the bilayer. PMID:9031514

  7. Oxygen release from nanobubbles adsorbed on hydrophobic particles

    NASA Astrophysics Data System (ADS)

    Zhao, Wanchen; Hu, Xiutao; Duan, Juan; Liu, Ting; Liu, Minghuan; Dong, Yaming

    2014-07-01

    On the hydrophobic particles, the carrying capacity of nano/microbubbles and the quantity of oxygen released in the hypoxic environment are still unknown while the bubbles blow out. This is very important to the biological and medical systems. Here, an experiment was designed and the change of the dissolved oxygen in a solution was monitored. The results indicated that the concentrations of dissolved oxygen in hypoxic environment changed dramatically, especially when the ultrasound vibration was applied. Furthermore, the amount of oxygen release also implied the quantity dependence of nano/microbubbles on the sizes and the hydrophobicity of the particles.

  8. Sticking polydisperse hydrophobic magnetite nanoparticles to lipid membranes.

    PubMed

    Paulus, Michael; Degen, Patrick; Brenner, Thorsten; Tiemeyer, Sebastian; Struth, Bernd; Tolan, Metin; Rehage, Heinz

    2010-10-19

    The formation of a layer of hydrophobic magnetite (Fe(3)O(4)) nanoparticles stabilized by lauric acid is analyzed by in situ X-ray reflectivity measurements. The data analysis shows that the nanoparticles partially disperse their hydrophobic coating. Consequently, a Langmuir layer was formed by lauric acid molecules that can be compressed into an untilted condensed phase. A majority of the nanoparticles are attached to the Langmuir film integrating lauric acid residue on their surface into the Langmuir film. Hence, the particles at the liquid-gas interface can be identified as so-called Janus beads, which are amphiphilic solids having two sides with different functionality. PMID:20873726

  9. Formulation and evaluation of a hydrophobic composite plastic.

    PubMed

    Craig, R G; Wang, T K

    1980-09-01

    A hydrophobic co-polymer, heptafluorobutylmethacrylate co-para vinyl phenol, was compounded with ethylene glycol dimethacrylate and silanated quartz to produce a hydrophobic composite. The experimental composite had satisfactory working properties and had mechanical properties comparable to commercial composite but a higher modulus of resilience. The wear resistance was equal to or greater than the commercial composite depending on whether a two-body abrasion test or a track width versus normal load test was used for the evaluation. The thermal coefficient of expansion and water sorption values were somewhat higher than those of commercial composites. PMID:6936517

  10. Simple Interface Engineering of Graphene Transistors with Hydrophobizing Stamps.

    PubMed

    Chae, Soo Sang; Choi, Won Jin; Yang, Cheol-Soo; Lee, Tae Il; Lee, Jeong-O

    2016-06-15

    We demonstrate a simple surface engineering method for fabricating graphene transistors by using hydrophobizing stamps. By simply contact-printing hydrophobizing stamp that is made with polydimethylsiloxane (PDMS) on a standard silicon substrate for a certain contact-time, it was possible to control the contact angle of the substrate and electrical characteristics of the graphene transistors supported on the substrate. Moreover, graphene transistors supported on the engineered silicon substrate showed improved performances, including an increase in carrier mobility and loss of hysteresis. As a proof-of-concept experiment, a simple logic gate operation was demonstrated by connecting a pristine graphene device with an interface-engineered device. PMID:27238560

  11. Robust hydrophobic Fe-based amorphous coating by thermal spraying

    NASA Astrophysics Data System (ADS)

    Zhang, C.; Wu, Y.; Liu, L.

    2012-09-01

    Metallic surface is intrinsically hydrophilic due to its high surface energy. In this work, we present a different picture that highly hydrophobic metallic coatings could be directly fabricated by thermal spraying of Fe-based amorphous powders through the surface roughness control. These hydrophobic coatings are amorphous, exhibiting super-high hardness and excellent corrosion resistance. With low surface energy modification, the coatings become superhydrophobic and exhibit clearly self-cleaning effect. The present work opens a window for the applications of the amorphous coatings.

  12. Electron spin resonance spectra of nitroxyl radicals

    NASA Astrophysics Data System (ADS)

    Botek, Edith; Zarycz, Natalia; Champagne, Benoît; Sciannaméa, Valérie; Detrembleur, Christophe

    2012-12-01

    Hyperfine coupling constants (HFCCs) of nitroxyl radicals were calculated using density functional theory (DFT) to address the structure of nitroxide intermediates in controlled radical polymerization. In a preliminary step, the reliability of different theoretical methods has been substantiated by comparing calculated HFCCs to experimental data for a set of acyclic and cyclic alkylnitroxyl radicals. In a second step this tested approach was applied to support experimental evidence of several nitroxide-mediated polymerization (NMP) reactions.

  13. Quantitative determination of atmospheric hydroperoxyl radical

    DOEpatents

    Springston, Stephen R.; Lloyd, Judith; Zheng, Jun

    2007-10-23

    A method for the quantitative determination of atmospheric hydroperoxyl radical comprising: (a) contacting a liquid phase atmospheric sample with a chemiluminescent compound which luminesces on contact with hydroperoxyl radical; (b) determining luminescence intensity from the liquid phase atmospheric sample; and (c) comparing said luminescence intensity from the liquid phase atmospheric sample to a standard luminescence intensity for hydroperoxyl radical. An apparatus for automating the method is also included.

  14. Free-radical chemistry of sulfite

    SciTech Connect

    Neta, P.; Huie, R.E.

    1985-12-01

    The free-radical chemistry of sulfite oxidation is reviewed. Chemical transformations of organic and biological molecules induced by sulfite oxidation are summarized. The kinetics of the free-radical oxidations of sulfite are discussed, as are the kinetics of the reactions of the sulfite-derived radicals SO/sub 3/ and the peroxy derivative SO/sub 5/ with organic compounds. 98 references.

  15. Energetics of mechanical destruction of middle radicals

    NASA Astrophysics Data System (ADS)

    Kvachadze, N. G.; Tomashevskii, E. E.; Zhizhenkov, V. V.

    2015-11-01

    The breaking strain of a model fragment of a middle radical in a rigid polymer matrix has been calculated. The force and energy characteristics of the destruction of the radical and the formation of double bonds have been estimated. The dissociation energy and the strength of Cβ-Cγ bonds for trans- and gaucheconformers of radicals have been determined. It has been established that the probability of breaking of the β bonds essentially depends of the conformation structure of the macroradicals.

  16. Spin trapping of radicals in tritiated methanol

    NASA Astrophysics Data System (ADS)

    Halpern, A.

    1984-01-01

    The radicals in [methyl- 3H]-methanol have been detected by spin trapping with PBN. Two radicals observed in deaerated samples at 273 K are methoxy and hydroxymethyl radicals. The relative contribution of these two radicals changes with the storage time, finally only the PBNCH 2OH adduct being observed. This behaviour is hypothetically explained as resulting from the secondary reactions with a product formed in methanol by internal β-radiolysis or otherwise, whose steadily increasing concentration accelerates the decay of the PBNCH 3O adduct.

  17. Physiological aspects of free-radical reactions.

    PubMed Central

    Yamazaki, I; Tamura, M; Nakajima, R; Nakamura, M

    1985-01-01

    Enzymes which catalyze the formation of free radicals in vitro will catalyze similar reactions in vivo. We believe that the formation of some kinds of free radicals has definite physiological meanings in metabolism. In this sense, the enzymes forming such free radicals are concluded to be in evolutionally advanced states. Elaborated structure and function of enzymes such as horseradish peroxidase and microsomal flavoproteins support the idea. Deleterious and side reactions caused by free radicals are assumed to be minimized in vivo by localizing the reactions, but this assumption should be verified by future studies. PMID:3007098

  18. Dynamics of Radical-Mediated Enzyme Catalyses

    NASA Astrophysics Data System (ADS)

    Warncke, Kurt

    1997-11-01

    An emergent class of enzymes harnesses the extreme reactivity of electron-deficient free radical species to perform some of the most difficult reactions in biology. The regio- and stereo-selectivity achieved by these enzymes defies long-held ideas that radical reactions are non-specific. The common primary step in these catalyses is metal- or metallocenter-assisted generation of an electron-deficient organic "initiator radical". The initiator radical abstracts a hydrogen atom from the substrate, opening a new reaction channel for rearrangement to the product. Our aim is to elucidate the detailed molecular mechanisms of the radical pair separation and radical rearrangement steps. Radical pair separation and substrate radical rearrangement are tracked by using time-resolved (10-7 to 10-3 s) techniques of pulsed-electron paramagnetic resonance spectroscopy (FT-EPR, ESEEM). Synchronous time-evolution of the reactions is attained by triggering with a visible laser pulse. Transient non-Boltzmann population of the states of the spin-coupled systems, and resultant electron spin polarization, facilitates study at or near room temperature under conditions where the enzymes are operative. The systems examined include ethanolamine deaminase, a vitamin B12 coenzyme-dependent enzyme, ribonucleotide reductase and photosynthetic reaction centers. The electronic and nuclear structural and kinetic information obtained from the pulsed-EPR studies is used to address how the initiator radicals are stabilized against deleterious recombination with the metal, and to distinguish the participation of concerted versus sequential rearrangement pathways.

  19. Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

    NASA Technical Reports Server (NTRS)

    Kumar, Nitin; Couzis, Alex; Maldareili, Charles; Singh, Bhim (Technical Monitor)

    2001-01-01

    Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid surfaces. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants; (i.e., amphiphiles with a hydrophobic moiety consisting of an extended chain of (aliphatic) methylene -CH2- groups attached to a large polar group to give aqueous solubility) are capable of reducing the contact angles on surfaces which are not very hydrophobic, but do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm, polyethylene or self assembled monolayers. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3) and an extended ethoxylate (-(OCH2CH2)a-) polar group in the form of a chain with four or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (termed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread. We propose that the trisiloxane surfactants superspread because their structure allows them to strongly lower the high hydrophobic solid/aqueous tension when they adsorb to the solid surface. When the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross-sectional area of the disk is larger than that of the extended ethoxylate chain, the disks can form a space-filling mat on the surface which

  20. DNA Binding Hydroxyl Radical Probes

    PubMed Central

    Tang, Vicky J; Konigsfeld, Katie M; Aguilera, Joe A; Milligan, Jamie R

    2011-01-01

    The hydroxyl radical is the primary mediator of DNA damage by the indirect effect of ionizing radiation. It is a powerful oxidizing agent produced by the radiolysis of water and is responsible for a significant fraction of the DNA damage associated with ionizing radiation. There is therefore an interest in the development of sensitive assays for its detection. The hydroxylation of aromatic groups to produce fluorescent products has been used for this purpose. We have examined four different chromophores which produce fluorescent products when hydroxylated. Of these, the coumarin system suffers from the fewest disadvantages. We have therefore examined its behavior when linked to a cationic peptide ligand designed to bind strongly to DNA. PMID:22125376

  1. Students' Ideas and Radical Constructivism

    NASA Astrophysics Data System (ADS)

    Sánchez Gómez, Pedro J.

    2016-04-01

    In this article, I study, from the point of view of the analytic philosophy of mind, the compatibility of students' ideas studies (SIS) with radical constructivism (RC). I demonstrate that RC is based on a psychology of narrow mental states; that is, the idea that the mental content of an individual can be fully characterised without any reference external to her or him. I show that this fact imposes some severe restrictions to SIS to be incorporated into RC. In particular, I argue that only qualitative studies can comply with the requirement of narrowness. Nevertheless, I propose that quantitative works can be employed as sources of types in order to study token actual students. I use this type-token dichotomy to put forward an outline of a theory of the relation between school contents and mental contents. In this view, token mental contents regarding a given topic can be defined, and probed, only by resorting to typical school contents.

  2. Students' Ideas and Radical Constructivism

    NASA Astrophysics Data System (ADS)

    Sánchez Gómez, Pedro J.

    2016-08-01

    In this article, I study, from the point of view of the analytic philosophy of mind, the compatibility of students' ideas studies (SIS) with radical constructivism (RC). I demonstrate that RC is based on a psychology of narrow mental states; that is, the idea that the mental content of an individual can be fully characterised without any reference external to her or him. I show that this fact imposes some severe restrictions to SIS to be incorporated into RC. In particular, I argue that only qualitative studies can comply with the requirement of narrowness. Nevertheless, I propose that quantitative works can be employed as sources of types in order to study token actual students. I use this type-token dichotomy to put forward an outline of a theory of the relation between school contents and mental contents. In this view, token mental contents regarding a given topic can be defined, and probed, only by resorting to typical school contents.

  3. Radical surgery in septic abortion.

    PubMed

    Chatterjee, P; Ghosh, M; Ghosh, S

    1979-08-01

    At R.G. Kar Medical College Hospital, Calcutta, 10 cases of septic abortion from 1975-1977 were studied. Hysterectomies were preformed on 4 cases due to emergency situations including traumatised uterine fundus and perforated cervix, and on 6 cases after conservative treatment. Upon performing laparotomy in 9 cases, a uterine rent was detected; in 1 case there was a perforation in the posterior wall of the cervix, and in 5 cases mechanical obstructions due to internal adhesions to the uterine rent were found. 4 patients died primarily because of the patients seeking help too late. It is suggested that under high risk circumstances, laparotomy is advantageous to conservative medical management since bowel injuries and mechanical obstructions can only be detected by laparotomy. Radical surgery, however, should be undertaken before the patients general condition deteriorates to the point that the patient cannot tolerate surgical intervention. PMID:12336028

  4. Free radicals and ocular disease.

    PubMed

    Anderson, R E; Kretzer, F L; Rapp, L M

    1994-01-01

    Ames, Shigenaga, and Hagen recently published a thorough review of the relationship between oxidants, antioxidants, and degenerative diseases of ageing. They point out that only 9% of Americans daily consume the two fruits and three vegetables recommended by the National Cancer Institute and the National Research Council/National Academy of Science. In addition to antioxidants, these foodstuffs contain many essential micronutrients. To date, specific recommendations for antioxidant supplementation have not been made by any governmental agency or professional association. A number of clinical, basic, and epidemiological studies have implicated free radical induced lipid peroxidation in various ocular disorders. It would seem prudent that those persons at greatest risk for these disorders take some precautions, which could include sunglasses that filter ultraviolet light; hats that shield the eyes from direct sunlight; and the ingestion of fruits, vegetables, and antioxidants. PMID:7771292

  5. Biomimetic solution against dewetting in a highly hydrophobic nanopore.

    PubMed

    Picaud, Fabien; Paris, Guillaume; Gharbi, Tijani; Balme, Sébastien; Lepoitevin, Mathilde; Tangaraj, Vidhyadevi; Bechelany, Mikhael; Janot, Jean Marc; Balanzat, Emmanuel; Henn, François

    2016-06-14

    A water molecule is the foundation of life and is the primary compound in every living system. While many of its properties are understood in a bulk solvent, its behavior in a small hydrophobic nanopore still raises fundamental questions. For instance, a wetting/dewetting transition in a hydrophobic solid-state or a polymer nanopore occurs stochastically and can only be prevented by external physical stimuli. Controlling these transitions would be a primary requirement to improve many applications. Some biological channels, such as gramicidin A (gA) proteins, show a high rate of water and ion diffusion in their central subnanochannel while their external surface is highly hydrophobic. The diameter of this channel is significantly smaller than the inner size of the lowest artificial nanopore in which water drying occurs (i.e. 1.4 nm). In this paper, we propose an innovative idea to generate nanopore wetting as a result of which the application of an external field is no longer required. In a nanopore, the drying or wetting of the inner walls occurs randomly (in experiments and in simulations). However, we have shown how the confinement of gA, in a dried hydrophobic nanopore, rapidly generates a stable wetting of the latter. We believe that this simple idea, based on biomimetism, could represent a real breakthrough that could help to improve and develop new nanoscale applications. PMID:27157717

  6. DEVELOPMENT OF A HYDROPHOBIC SUBSTANCE TO MITIGATE PAVEMENT ICE ADHESION

    EPA Science Inventory

    The specific problem to which this report is addressed is the development of a hydrophobic substance to mitigate the adhesion of ice to pavement as an alternative to deicing chemicals. The factors involved in evaluating this concept are the following: Economics; safety; environme...

  7. Highly efficient hydrophobic titania ceramic membranes for water desalination.

    PubMed

    Kujawa, Joanna; Cerneaux, Sophie; Koter, Stanisław; Kujawski, Wojciech

    2014-08-27

    Hydrophobic titania ceramic membranes (300 kD) were prepared by grafting of C6F13C2H4Si(OC2H5)3 and C12F25C2H4Si(OC2H5)3 molecules and thus applied in membrane distillation (MD) process of NaCl solutions. Grafting efficiency and hydrophobicity were evaluated by contact angle measurement, atomic force microscopy, scanning electron microscopy, nitrogen adsorption/desorption, and liquid entry pressure measurement of water. Desalination of NaCl solutions was performed using the modified hydrophobic membranes in air gap MD (AGMD) and direct contact MD (DCMD) processes in various operating conditions. High values of NaCl retention coefficient (>99%) were reached. The permeate fluxes were in the range 231-3692 g·h(-1)·m(-2), depending on applied experimental conditions. AGMD mode appeared to be more efficient showing higher fluxes and selectivity in desalination. Overall mass transfer coefficients (K) for membranes tested in AGMD were constant over the investigated temperature range. However, K values in DCMD increased at elevated temperature. The hydrophobic layer was also stable after 4 years of exposure to open air. PMID:25084346

  8. Pair correlations that link the hydrophobic and Hofmeister effects.

    PubMed

    Besford, Quinn Alexander; Liu, Maoyuan; Gray-Weale, Angus

    2016-06-01

    The Hofmeister effect describes how different ions make solutes more or less hydrophobic. The effect is thought to occur due to structural changes in the solvent induced by the ion's presence, particularly in water. In this study, the structural changes in water due to the presence of ions are investigated by molecular dynamics simulations of various monatomic ions in the SPC/E water model. Structural analyses reveal specific orientations of solvating waters around each of the ions studied. Using a new method, these orientations are quantified by a set of pair correlation functions that describe dipole-ion correlations in structure. These correlations are shown to contribute to the potential of mean force between waters and the ion of interest, and therefore to the free energy of the system. The magnitude of this free energy is found to result in a Hofmeister series for the various ions studied, therefore demonstrating a Hofmeister effect with respect to water's structure that is quantified by pair correlation functions. Most crucially, the pair correlations that lead to this Hofmeister effect also contribute to the hydrophobic effect (the entropy of hydrophobic solvation) [Liu et al., J. Chem. Phys., 2015, 142, 114117], and those which dominate the hydrophobic effect are modulated by an ion's presence, therefore demonstrating a mechanistic link between the two effects. PMID:27222936

  9. The Hydrophobic Effect in Solute Partitioning and Interfacial Tension

    PubMed Central

    Jackson, Meyer B.

    2016-01-01

    Studies of the partitioning of hydrophobic solutes between water and nonpolar solvents provide estimates for the energy cost of creating hydrophobic-water contacts. This energy is a factor of three lower than the work of adhesion derived from interfacial tension measurements. This discrepancy noted by Tanford in 1979 is widely viewed as a serious challenge to our understanding of hydrophobic interactions. However, the interfacial energy of a water-alkane interface depends on chain length. A simple analysis of published data shows that the loss of rotational freedom of an alkane chain at an interface accounts quantitatively for the length-dependent contribution to interfacial tension, leaving a length-independent contribution very close to the free energy of transfer per unit of solvent accessible surface area. This analysis thus clarifies the discrepancy between the thermodynamic and interfacial tension measurements of hydrophobic interaction energy. Alkanes do not loose rotational freedom when transferred between two different liquid phases but they do at an interface. This reconciles the difference between microscopic and macroscopic measurements. Like the partitioning free energy, the work of adhesion also has a large entropy and small enthalpy at 20 oC. PMID:26813712

  10. Lipid-Rhodopsin Hydrophobic Mismatch Alters Rhodopsin Helical Content

    SciTech Connect

    Soubias,O.; Niu, S.; Mitchell, D.; Gawrisch, K.

    2008-01-01

    The ability of photoactivated rhodopsin to achieve the enzymatically active metarhodopsin II conformation is exquisitely sensitive to bilayer hydrophobic thickness. The sensitivity of rhodopsin to the lipid matrix has been explained by the hydrophobic matching theory, which predicts that lipid bilayers adjust elastically to the hydrophobic length of transmembrane helices. Here, we examined if bilayer thickness adjusts to the length of the protein or if the protein alters its conformation to adapt to the bilayer. Purified bovine rhodopsin was reconstituted into a series of mono-unsaturated phosphatidylcholines with 14-20 carbons per hydrocarbon chain. Changes of hydrocarbon chain length were measured by 2H NMR, and protein helical content was quantified by synchrotron radiation circular dichroism and conventional circular dichroism. Experiments were conducted on dark-adapted rhodopsin, the photo-intermediates metarhodopsin I/II/III, and opsin. Changes of bilayer thickness upon rhodopsin incorporation and photoactivation were mostly absent. In contrast, the helical content of rhodopsin increased with membrane hydrophobic thickness. Helical content did not change measurably upon photoactivation. The increases of bilayer thickness and helicity of rhodopsin are accompanied by higher metarhodopsin II/metarhodopsin I ratios, faster rates of metarhodopsin II formation, an increase of tryptophan fluorescence, and higher temperatures of rhodopsin denaturation. The data suggest a surprising adaptability of this G protein-coupled membrane receptor to properties of the lipid matrix.

  11. Water repellency in hydrophobic nanocapsules--molecular view on dewetting.

    PubMed

    Müller, Achim; Garai, Somenath; Schäffer, Christian; Merca, Alice; Bögge, Hartmut; Al-Karawi, Ahmed Jasim M; Prasad, Thazhe Kootteri

    2014-05-26

    The hydrophobic effect plays a major role in a variety of important phenomena in chemistry, materials science and biology, for instance in protein folding and protein-ligand interactions. Studies--performed within cavities of the unique metal oxide based porous capsules of the type {(pentagon)12(linker)30}≡{(W)W5}12{Mo2(ligand)}30 with different acetate/water ligand ratios--have provided unprecedented results revealing segregation/repellency of the encapsulated "water" from the internal hydrophobic ligand walls of the capsules, while the disordered water molecules, interacting strongly with each other via hydrogen bonding, form in all investigated cases the same type of spherical shell. The present results can be (formally) compared--but only regarding the repellency effect--with the amazing "action" of the (super)hydrophobic Lotus (Nelumbo) leaves, which are self-cleaning based on water repellency resulting in the formation of water droplets picking up dirt. The present results were obtained by constructing deliberately suitable hydrophobic interiors within the mentioned capsules. PMID:24782303

  12. The Hydrophobic Effect in Solute Partitioning and Interfacial Tension.

    PubMed

    Jackson, Meyer B

    2016-01-01

    Studies of the partitioning of hydrophobic solutes between water and nonpolar solvents provide estimates for the energy cost of creating hydrophobic-water contacts. This energy is a factor of three lower than the work of adhesion derived from interfacial tension measurements. This discrepancy noted by Tanford in 1979 is widely viewed as a serious challenge to our understanding of hydrophobic interactions. However, the interfacial energy of a water-alkane interface depends on chain length. A simple analysis of published data shows that the loss of rotational freedom of an alkane chain at an interface accounts quantitatively for the length-dependent contribution to interfacial tension, leaving a length-independent contribution very close to the free energy of transfer per unit of solvent accessible surface area. This analysis thus clarifies the discrepancy between the thermodynamic and interfacial tension measurements of hydrophobic interaction energy. Alkanes do not loose rotational freedom when transferred between two different liquid phases but they do at an interface. This reconciles the difference between microscopic and macroscopic measurements. Like the partitioning free energy, the work of adhesion also has a large entropy and small enthalpy at 20 (o)C. PMID:26813712

  13. The Hydrophobic Effect in Solute Partitioning and Interfacial Tension

    NASA Astrophysics Data System (ADS)

    Jackson, Meyer B.

    2016-01-01

    Studies of the partitioning of hydrophobic solutes between water and nonpolar solvents provide estimates for the energy cost of creating hydrophobic-water contacts. This energy is a factor of three lower than the work of adhesion derived from interfacial tension measurements. This discrepancy noted by Tanford in 1979 is widely viewed as a serious challenge to our understanding of hydrophobic interactions. However, the interfacial energy of a water-alkane interface depends on chain length. A simple analysis of published data shows that the loss of rotational freedom of an alkane chain at an interface accounts quantitatively for the length-dependent contribution to interfacial tension, leaving a length-independent contribution very close to the free energy of transfer per unit of solvent accessible surface area. This analysis thus clarifies the discrepancy between the thermodynamic and interfacial tension measurements of hydrophobic interaction energy. Alkanes do not loose rotational freedom when transferred between two different liquid phases but they do at an interface. This reconciles the difference between microscopic and macroscopic measurements. Like the partitioning free energy, the work of adhesion also has a large entropy and small enthalpy at 20 oC.

  14. Impact of a hydrophobic granular stream in water

    NASA Astrophysics Data System (ADS)

    Utter, Brian; Mandeles, Harry; Parkhouse, Jacob

    We experimentally investigate the flow of a stream of hydrophobic granular particles impacting a water surface from above. The granular sample is composed of a mixture of hydrophobic and hydrophilic grains and the concentration, stream diameter, and drop height are independently controlled. While granular flows are common in nature and industry, effects of surface chemistry on flow behavior have received relatively little attention. The present experiment complements rheological measurements performed in parallel and aims to elucidate prior experiments on hydrophobic samples in a rotating drum. The present experimental geometry allows us to compare the behavior of granular streams to prior work on impacts of solids and fluid streams. Sequential images of the granular stream in water are taken and analyzed. We present data on the size, length, and shape of the aggregate streams with variations in concentration, entering stream diameter, and drop height. We find that increased hydrophobic grain concentration leads to increased aggregation due to an effectively cohesive interaction mediated by entrained air. At lower concentrations, the stream exhibits a lateral instability. Finally, we will make connections to rheology and rotating drum results. This work was supported by NSF CBET award 1067598.

  15. Water uptake in biochars: The roles of porosity and hydrophobicity

    EPA Science Inventory

    We assessed the effects of porosity and hydrophobicity on water uptake by biochars. Biochars were produced from two feedstocks (hazelnut shells and Douglas fir chips) at three production temperatures (370 °C, 500 °C, and 620 °C). To distinguish the effects of porosity from the ...

  16. Hydrophobic bile acids, genomic instability, Darwinian selection, and colon carcinogenesis

    PubMed Central

    Payne, Claire M; Bernstein, Carol; Dvorak, Katerina; Bernstein, Harris

    2008-01-01

    Sporadic colon cancer is caused predominantly by dietary factors. We have selected bile acids as a focus of this review since high levels of hydrophobic bile acids accompany a Western-style diet, and play a key role in colon carcinogenesis. We describe how bile acid-induced stresses cause cell death in susceptible cells, contribute to genomic instability in surviving cells, impose Darwinian selection on survivors and enhance initiation and progression to colon cancer. The most likely major mechanisms by which hydrophobic bile acids induce stresses on cells (DNA damage, endoplasmic reticulum stress, mitochondrial damage) are described. Persistent exposure of colon epithelial cells to hydrophobic bile acids can result in the activation of pro-survival stress-response pathways, and the modulation of numerous genes/proteins associated with chromosome maintenance and mitosis. The multiple mechanisms by which hydrophobic bile acids contribute to genomic instability are discussed, and include oxidative DNA damage, p53 and other mutations, micronuclei formation and aneuploidy. Since bile acids and oxidative stress decrease DNA repair proteins, an increase in DNA damage and increased genomic instability through this mechanism is also described. This review provides a mechanistic explanation for the important link between a Western-style diet and associated increased levels of colon cancer. PMID:21677822

  17. Molecular simulation study of cooperativity in hydrophobic association.

    PubMed Central

    Czaplewski, C.; Rodziewicz-Motowidło, S.; Liwo, A.; Ripoll, D. R.; Wawak, R. J.; Scheraga, H. A.

    2000-01-01

    To investigate the cooperativity of hydrophobic interactions, the potential of mean force of two- and three-molecule methane clusters in water was determined by molecular dynamics simulations using two methods: umbrella-sampling with the weighted histogram analysis method and thermodynamic integration. Two water models, TIP3P and TIP4P, were used, while each methane molecule was modeled as a united atom. It was found that the three-body potential of mean force is not additive, i.e., it cannot be calculated as a sum of two-body contributions, but requires an additional three-body cooperative term. The cooperative term, which amounts to only about 10% of the total hydrophobic association free energy, was found to increase the strength of hydrophobic association; this finding differs from the results of earlier Monte Carlo studies with the free energy perturbation method of Rank and Baker (1997). As in the work of Rank and Baker, the solvent contribution to the potential of mean force was found to be well approximated by the molecular surface of two methane molecules. Moreover, we also found that the cooperative term is well represented by the difference between the molecular surface of the three-methane cluster and those of all three pairs of methane molecules. In addition, it was found that, while there is a cooperative contribution to the hydrophobic association free energy albeit a small one, the errors associated with the use of pairwise potentials are comparable to or larger than this contribution. PMID:10892816

  18. Surface functionalized hydrophobic porous particles toward water treatment application.

    PubMed

    Abbaspourrad, Alireza; Carroll, Nick J; Kim, Shin-Hyun; Weitz, David A

    2013-06-18

    A microfluidic-based approach for the fabrication of organic contaminants absorbing core-shell particles is demonstrated. The hydrophobic porous core absorbs oil while the hydrophilic surface enables the particles to be well-dispersed in aqueous solutions. These particles can uptake oil from aqueous solution saturated with oil or via direct contact with oil blobs as depicted in the figure. PMID:23649837

  19. Profile of the Interface between a Hydrophobic Surface and Water

    NASA Astrophysics Data System (ADS)

    Perez-Salas, Ursula; Stalgren, Johan; Majkrzak, Charles; Heinrich, Frank; Toney, Michael; Vanderah, David

    2008-03-01

    Aqueous interfaces are ubiquitous and play a fundamental role in biology, chemistry, and geology. The structure of water near interfaces is of the utmost importance, including chemical reactivity and macromolecular function. Theoretical work by Chandler et al. on polar-apolar interfaces predicts that a water depletion layer exists between a hydrophobic surface and bulk water for hydrophobes larger than ˜20nm2 (a ˜4A in radius apolar molecule). Until now, what the interface really looks like remains in dispute since recent experiments give conflicting results: from complete wetting (no water depletion layer) to a water depletion layer. Those experiments that have found a water depletion layer report 40-70% water in the depletion zone: 40 -70% and a width of ˜3A. However, an alternative interpretation to the profiles exists where no depletion layer is required. By studying hydrophobic SAM surfaces against several water mixtures we obtained the hydrophobic/water profile by phase sensitive neutron reflectivity. With this model independent technique we observe a 2 times wider and drier depletion water layer: 6A thick and 0-25% water. Given the level of disagreement, I will review the topic of immiscible interfaces and show how phase sensitive reflectometry is unique in obtaining nm resolution profiles without fitting bias.

  20. Orientational Dynamics of Water at an Extended Hydrophobic Interface.

    PubMed

    Xiao, Shunhao; Figge, Florian; Stirnemann, Guillaume; Laage, Damien; McGuire, John A

    2016-05-01

    We report on the orientational dynamics of water at an extended hydrophobic interface with an octadecylsilane self-assembled monolayer on fused silica. The interfacial dangling OH stretch mode is excited with a resonant pump, and its evolution followed in time by a surface-specific, vibrationally resonant, infrared-visible sum-frequency probe. High sensitivity pump-probe anisotropy measurements and isotopic dilution clearly reveal that the decay of the dangling OH stretch excitation is almost entirely due to a jump to a hydrogen-bonded configuration that occurs in 1.61 ± 0.10 ps. This is more than twice as fast as the jump time from one hydrogen-bonded configuration to another in bulk H2O but about 50% slower than the reported out-of-plane reorientation at the air/water interface. In contrast, the intrinsic population lifetime of the dangling OH stretch in the absence of such jumps is found to be >10 ps. Molecular dynamics simulations of air/water and hexane/water interfaces reproduce the fast jump dynamics of interfacial dangling OH with calculated jump times of 1.4 and 1.7 ps for the air and hydrophobic interfaces, respectively. The simulations highlight that while the air/water and hydrophobic/water surfaces exhibit great structural similarities, a small stabilization of the OH groups by the hydrophobic interface produces the pronounced difference in the dynamics of dangling bonds. PMID:27045950

  1. Molecular orientation of tropoelastin is determined by surface hydrophobicity.

    PubMed

    Le Brun, Anton P; Chow, John; Bax, Daniel V; Nelson, Andrew; Weiss, Anthony S; James, Michael

    2012-02-13

    Tropoelastin is the precursor of the extracellular protein elastin and is utilized in tissue engineering and implant technology by adapting the interface presented by surface-bound tropoelastin. The preferred orientation of the surface bound protein is relevant to biointerface interactions, as the C-terminus of tropoelastin is known to be a binding target for cells. Using recombinant human tropoelastin we monitored the binding of tropoelastin on hydrophilic silica and on silica made hydrophobic by depositing a self-assembled monolayer of octadecyl trichlorosilane. The layered organization of deposited tropoelastin was probed using neutron and X-ray reflectometry under aqueous and dried conditions. In a wet environment, tropoelastin retained a solution-like structure when adsorbed on silica but adopted a brush-like structure when on hydrophobized silica. The orientation of the surface-bound tropoelastin was investigated using cell binding assays and it was found that the C-terminus of tropoelastin faced the bulk solvent when bound to the hydrophobic surface, but a mixture of orientations was adopted when tropoelastin was bound to the hydrophilic surface. Drying the tropoelastin-coated surfaces irreversibly altered these protein structures for both hydrophilic and hydrophobic surfaces. PMID:22176209

  2. Biochemical characterization of the small hydrophobic protein of avian metapneumovirus

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Avian metapneumovirus (aMPV) is a paramyxovirus that has three membrane-associate proteins: glycoprotein (G), fusion (F), and small hydrophobic (SH) proteins. Among them, the SH protein is a small type II integral membrane protein that is incorporated into virions and is only present in certain para...

  3. Peroxy radical measurements with NCAR's chemical amplifier

    NASA Technical Reports Server (NTRS)

    Cantrell, Christopher; Shetter, Richard; Calvert, Jack G.

    1994-01-01

    The present NCAR instrument for HO2/RO2 measurements has been described previously. It is based on the reactions involving HO2, RO2, and HO radicals with CO and NO. Since (HO2) + (RO2) + (HO) is much greater than (HO) for most atmospheres, it is useful as a peroxy radical detector. Operation of the instrument depends on the creation of a chemical chain reaction which is initiated as HO2 and RO2 radicals in ambient air encounter added NO gas; this forms an NO2 molecule and an HO or RO radical: HO2(RO2) + NO yields HO(RO) + NO2. RO radicals react relatively efficiently with O2 to form an HO2 radical, and subsequently an HO-radical, by reaction with NO. CO gas added to the reaction chamber during part of the operating cycle, recycles the HO to HO2; HO + CO (+O2) yields HO2 + CO2. The reaction sequence may form several hundred NO2 molecules per HO2 (RO2) originally present, before chain termination occurs. The added CO is replaced by N2 addition periodically so that the chain reaction is suppressed, and a 'blank' signal resulting from NO2, O3 and possibly other NO2-forming species (non-chain processes) in ambient air is recorded. The difference between the signal with and without CO is proportional to the peroxy radical concentration. The NO2 produced is monitored using a sensitive luminol chemiluminescence detector system. In the NCAR instrument the length of the amplification chain is determined using a stable source of HO2 radicals (H2O2 thermal decomposition); the ratio of the signal seen with CO present to that with N2 present gives the sensitivity of the instrument to HO2 (molecules of NO2 formed/peroxy radical). The instrument is automated to carry out in hourly repeated cycles: (1) chain length determination; (2) NO2 calibration; and (3) linearity check on the response of signals. One minute averages of signals are normally recorded. The sensitivity of the instrument to detect peroxy radicals is in the pptv range. The present instrument has operated

  4. Instantaneous Directional Growth of Block Copolymer Nanowires During Heterogeneous Radical Polymerization (HRP).

    PubMed

    Lu, Chunliang; Urban, Marek W

    2016-04-13

    Polymeric nanowires that consist of ultrahigh molecular weight block copolymers were instantaneously prepared via one-step surfactant-free heterogeneous radical polymerization (HRP). Under heterogeneous reaction and initiator-starvation conditions, the sequential copolymerization of hydrophilic and hydrophobic monomers facilitates the formation of amphiphilic ultrahigh molecular weight block copolymers, which instantaneously assemble to polymeric nanowires. As polymerization progresses, initially formed nanoparticles exhibit the directional growth due to localized repulsive forces of hydrophilic blocks and confinement of the hydrophobic blocks that adopt favorable high aspect ratio nanowire morphologies. Using one-step synthetic approach that requires only four ingredients (water as a solvent, two polymerizable monomers (one hydrophilic and one hydrophobic), and water-soluble initiator), block copolymer nanowires ∼70 nm in diameter and hundreds of microns in length are instantaneously grown. For example, when 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) and styrene (St) were copolymerized, high aspect ratio nanowires consist of ultrahigh (>10(6) g/mol) molecular weight pDMAEMA-b-St block copolymers and the presence of temperature responsive pDMAEMA blocks facilitates nanowire diameter changes as a function of temperature. These morphologies may serve as structural components of the higher order biological constructs at micro and larger length scales, ranging from single strand nanowires to engineered biomolecular networks capable of responding to diverse and transient environmental signals, and capable of dimensional changes triggered by external stimuli. PMID:27002238

  5. Hydrophobic Agglomeration of Mineral Fines in Aqueous Suspensions and its Application in Flotation: a Review

    NASA Astrophysics Data System (ADS)

    Yang, Bingqiao; Song, Shaoxian

    2014-05-01

    Hydrophobic agglomeration is originated from the hydrophobic attraction between particles, which is essentially different from electrolyte coagulation and polymer flocculation. It is applied to mineral processing in floc-flotation process to improve the recovery of mineral fines. In this paper, the applications of this phenomenon in mineral fines were summarized, including the origin of hydrophobic agglomeration, the main factors affect hydrophobic agglomeration (particle hydrophobicity, shear rate and duration, nonpolar oil and tank geometry), as well as hydrophobic agglomeration based separation processes (carrier flotation and floc-flotation).

  6. Consistent Treatment of Hydrophobicity in Protein Lattice Models Accounts for Cold Denaturation

    NASA Astrophysics Data System (ADS)

    van Dijk, Erik; Varilly, Patrick; Knowles, Tuomas P. J.; Frenkel, Daan; Abeln, Sanne

    2016-02-01

    The hydrophobic effect stabilizes the native structure of proteins by minimizing the unfavorable interactions between hydrophobic residues and water through the formation of a hydrophobic core. Here, we include the entropic and enthalpic contributions of the hydrophobic effect explicitly in an implicit solvent model. This allows us to capture two important effects: a length-scale dependence and a temperature dependence for the solvation of a hydrophobic particle. This consistent treatment of the hydrophobic effect explains cold denaturation and heat capacity measurements of solvated proteins.

  7. Consistent Treatment of Hydrophobicity in Protein Lattice Models Accounts for Cold Denaturation.

    PubMed

    van Dijk, Erik; Varilly, Patrick; Knowles, Tuomas P J; Frenkel, Daan; Abeln, Sanne

    2016-02-19

    The hydrophobic effect stabilizes the native structure of proteins by minimizing the unfavorable interactions between hydrophobic residues and water through the formation of a hydrophobic core. Here, we include the entropic and enthalpic contributions of the hydrophobic effect explicitly in an implicit solvent model. This allows us to capture two important effects: a length-scale dependence and a temperature dependence for the solvation of a hydrophobic particle. This consistent treatment of the hydrophobic effect explains cold denaturation and heat capacity measurements of solvated proteins. PMID:26943560

  8. Alex Bloom, Pioneer of Radical State Education

    ERIC Educational Resources Information Center

    Fielding, Michael

    2005-01-01

    Alex Bloom is one of the greatest figures of radical state education in England. His approach to "personalised learning" and the development of a negotiated curriculum was immeasurably more profound and more inspiring than anything to emerge thus far from the current DfES. His approach to student voice was much more radical than anything presently…

  9. Radical Behaviorism and Buddhism: Complementarities and Conflicts

    ERIC Educational Resources Information Center

    Diller, James W.; Lattal, Kennon A.

    2008-01-01

    Comparisons have been made between Buddhism and the philosophy of science in general, but there have been only a few attempts to draw comparisons directly with the philosophy of radical behaviorism. The present review therefore considers heretofore unconsidered points of comparison between Buddhism and radical behaviorism in terms of their…

  10. Rearrangement of sulfonamidyl radicals with hydrogen migration

    SciTech Connect

    Troyanskii, E.I.; Lazareva, M.I.; Nikishin, G.I.

    1987-01-20

    One-step outlying oxidative chlorination of alkanesulfonamides by the action of the Na/sub 2/S/sub 2/O/sub 8/-CuCl/sub 2/ system via intermediate sulfonamidyl radicals gives 3- and 4-chloroalkanesulfonamides. Rearrangements of sulfonamidyl radicals with H atom migration from the sulfonyl segment predominates over rearrangement with H atom migration from the amide segment.

  11. What Is Radical in School Geography Today?

    ERIC Educational Resources Information Center

    Morgan, John

    2011-01-01

    This article addresses the question of what "radical school geography" might look like in the present historical moment. It traces the history of a distinctive "radical" tradition in school geography, most prominently associated with the work of John Huckle, who argued for the importance of understanding the content and pedagogy of school…

  12. Oxygen radical production by avian leukocytes.

    PubMed

    Conlon, P; Smith, D; Gowlett, T

    1991-04-01

    Oxygen radical production by heterophils of red-tailed hawks and chickens, and by neutrophils of calves, was evaluated in a chemiluminescence microassay. Leukocytes were isolated by centrifugation of blood in capillary tubes and then challenged with opsonized zymosan in the presence of luminol. Avian heterophils produced significantly fewer oxygen radicals than did bovine neutrophils. PMID:1884301

  13. Free Radical Mechanisms in Autoxidation Processes.

    ERIC Educational Resources Information Center

    Simic, Michael G.

    1981-01-01

    Discusses the use of steady-state radiation chemistry and pulse radiolysis for the generation of initial free radicals and formation of peroxy radicals in the autoxidation process. Provides information regarding the autoxidation process. Defines autoxidation reactions and antioxidant action. (CS)

  14. Radical Voices; A Film Course Study Guide.

    ERIC Educational Resources Information Center

    Kernan, Margot

    The leftist radical ideas current in the 1960s and 1970s are expressed in the films discussed in this cinema study guide. The radical film takes extreme and avant-garde approaches to the somewhat publicly taboo topics of sex, social issues, and religion. Among the films discussed, I AM CURIOUS (YELLOW) and SOMETHING DIFFERENT show women in their…

  15. Radical Constructivism: Between Realism and Solipsism.

    ERIC Educational Resources Information Center

    Martinez-Delgado, Alberto

    2002-01-01

    Criticizes radical constructivism of the Glasersfeld type, pointing out some contradictions between the declared radical principles and their theoretical and practical development. Suggests the possibility of an ideological substratum in the construction and hegemonic success of subjective constructivism, and briefly advances an alternative…

  16. Ideals Adrift: An Educational Approach to Radicalization

    ERIC Educational Resources Information Center

    van San, Marion; Sieckelinck, Stijn; de Winter, Micha

    2013-01-01

    These days, the radicalization of young people is above all viewed as a security risk. Almost all research into this phenomenon has been carried out from a legal, criminological or socio-psychological perspective with a focus on detecting and containing the risks posed by radicalization. In the light of the political developments since September…

  17. Electrophilicity and nucleophilicity index for radicals.

    PubMed

    De Vleeschouwer, Freija; Van Speybroeck, Veronique; Waroquier, Michel; Geerlings, Paul; De Proft, Frank

    2007-07-01

    Radicals can be regarded as electrophilic/nucleophilic, depending on their tendency to attack sites of relatively higher/lower electron density. In this paper, an electrophilicity scale, global as well as local, and a nucleophilicity scale for 35 radicals is reported. The global electrophilicity scale correlates well with the nucleophilicity scale, suggesting that these concepts are inversely related. PMID:17559221

  18. A combination of evolutionary trace method, molecular surface accessibility and hydrophobicity analysis to design a high hydrophobicity laccase.

    PubMed

    Mohamad, Saharuddin Bin; Ong, Ai Ling; Khairuddin, Raja Farhana; Ripen, Adiratna Mat

    2010-01-01

    Laccases are industrially attractive enzymes and their applications have expanded to the field of bioremediation. The challenge of today's biotechnology in enzymatic studies is to design enzymes that not only have a higher activity but are also more stable and could fit well with the condition requirements. Laccases are known to oxidize non-natural substrates like polycyclic aromatic hydrocarbons (PAHs). We suppose by increasing the hydrophobicity of laccase, it would increase the chance of the enzyme to meet the hydrophobic substrates in a contamination site, therefore increasing the bioremediation efficacy of PAHs from environment. In this attempt, the applications of evolutionary trace (ET), molecular surface accessibility and hydrophobicity analysis on laccase sequences and laccase's crystal structure (1KYA) are described for optimal design of an enzyme with higher hydrophobicity. Our analysis revealed that Q23A, Q45I, N141A, Q237V, N262L, N301V, N331A, Q360L and Q482A could be promising exchanges to be tested in mutagenesis experiments. PMID:22430288

  19. Hydrophobic modification of polymethyl methacrylate as intraocular lenses material to improve the cytocompatibility.

    PubMed

    Wang, Bailiang; Lin, Quankui; Shen, Chenghui; Tang, Junmei; Han, Yuemei; Chen, Hao

    2014-10-01

    The development of posterior capsule opacification (PCO) after intraocular lenses (IOL) implantation for dealing with cataract is mainly due to the severe loss of the human lens epithelial cells (HLECs) during surgery contact. A novel poly (hedral oligomeric silsesquioxane-co-methyl methacrylate) copolymer (allyl POSS-PMMA) was synthesized by free radical polymerization method to promote the adhesion of HLECs. FT-IR and (1)H NMR measurements indicated the existence of POSS cage in the product, which demonstrated the successful synthesis of allyl POSS-PMMA copolymer. Effect of allyl POSS in the hybrids on crystal structure, surface wettability and morphology, optical transmission, thermodynamic properties and cytocompatibility was investigated in detail. X-ray diffraction peaks at 2θ∼11° and 12° indicated that POSS molecules had aggregated and crystallized. Thermogravimetric analysis-differential scanning calorimeter and optical transmission measurements confirmed that the allyl POSS-PMMA copolymer had high glass transition temperatures (more than 100°C) and good transparency. The hydrophilicity and morphology of PMMA and copolymers surfaces were characterized by static water contact angle and atomic force microscopy. The results revealed that the surface of the allyl POSS-PMMA copolymer displayed higher hydrophobicity and higher roughness than that of pure PMMA. The surface biocompatibility was evaluated by morphology and activity measurement with HLECs in vitro. The results verified that the surface of allyl POSS-PMMA copolymer films had more HLECs adhesion and better spreading morphology than that of PMMA film. PMID:24972346

  20. Photophysical and electron-transfer properties of pseudoisocyanine in the hydrophobic microdomain of an aqueous polyelectrolyte

    SciTech Connect

    Jones, G. II; Oh, C. )

    1994-03-03

    The binding of pseudoisocyanine (PIC[sup +]) to the polyelectrolyte poly(methacrylic acid) (PMAA) has profound effects on the photophysical and photochemical properties of this prototypical cyanine dye. The hydrophobic dye was bound in the microdomain of the compact conformation of the polymer in its (uncharged, [open quotes]hypercoiled[close quotes]) acid form at pH < 4.0 in water. Under these conditions, the fluorescence quantum yield for PIC[sup +] was increased 600-fold and its lifetime is extended to 2.7 ns. The dye triplet state observed by flash photolysis provided a very long-lived phototransient ([lambda][sub max] = 640 nm, 50-100-[mu]s decay time). Electron-transfer quenching was investigated using the oxidant tetranitromethane (TNM) which provided the semioxidized dye radical intermediate (440-nm transient) on cobinding within PMAA hypercoils. The dye was also bound to a covalently modified form of PMAA in which polymer chains were end-labeled with 9-methylanthracene moieties. Electron transfer between anthracene chromophores and PIC[sup +] within the polymer domain was observed. 71 refs., 14 figs., 2 tabs.

  1. Partitioning MOF-5 into Confined and Hydrophobic Compartments for Carbon Capture under Humid Conditions.

    PubMed

    Ding, Nan; Li, Haiwei; Feng, Xiao; Wang, Qianyou; Wang, Shan; Ma, Li; Zhou, Junwen; Wang, Bo

    2016-08-17

    Metal-organic frameworks (MOFs), by virtue of their remarkable uptake capability, selectivity, and ease of regeneration, hold great promise for carbon capture from fossil fuel combustion. However, their stability toward moisture together with the competitive adsorption of water against CO2 drastically dampens their capacity and selectivity under real humid flue gas conditions. In this work, an effective strategy was developed to tackle the above obstacles by partitioning the channels of MOFs into confined, hydrophobic compartments by in situ polymerization of aromatic acetylenes. Specifically, polynaphthylene was formed via a radical reaction inside the channels of MOF-5 and served as partitions without altering the underlying structure of the framework. Compared with pristine MOF-5, the resultant material (PN@MOF-5) exhibits a doubled CO2 capacity (78 vs 38 cm(3)/g at 273 K and 1 bar), 23 times higher CO2/N2 selectivity (212 vs 9), and significantly improved moisture stability. The dynamic CO2 adsorption capacity can be largely maintained (>90%) under humid conditions during cycles. This strategy can be applied to other MOF materials and may shed light on the design of new MOF-polymer materials with tunable pore sizes and environments to promote their practical applications. PMID:27477091

  2. Roaming radical pathways for the decomposition of alkanes.

    SciTech Connect

    Harding, L. B.; Klippenstein, S. J.

    2010-01-01

    CASPT2 calculations predict the existence of roaming radical pathways for the decomposition of propane, n-butane, isobutane and neopentane. The roaming radical paths lead to the formation of an alkane and an alkene instead of the expected radical products. The predicted barriers for the roaming radical paths lie {approx}1 kcal/mol below the corresponding radical asymptotes.

  3. Simple and fast PO-CL method for the evaluation of antioxidant capacity of hydrophilic and hydrophobic antioxidants

    NASA Astrophysics Data System (ADS)

    Zargoosh, Kiomars; Ghayeb, Yousef; Azmoon, Behnaz; Qandalee, Mohammad

    2013-08-01

    A simple and fast procedure is described for evaluating the antioxidant activity of hydrophilic and hydrophobic compounds by using the peroxyoxalate-chemiluminescence (PO-CL) reaction of Bis(2,4,6-trichlorophenyl) oxalate (TCPO) with hydrogen peroxide in the presence of di(tert-butyl)2-(tert-butylamino)-5-[(E)-2-phenyl-1-ethenyl]3,4-furandicarboxylate as a highly fluorescent fluorophore. The IC50 values of the well-known antioxidants were calculated and the results were expressed as gallic equivalent antioxidant capacity (GEAC). It was found that the proposed method is free of physical quenching and oxidant interference, for this reason, proposed method is able to determine the accurate scavenging activity of the antioxidants to the free radicals. Finally, the proposed method was applied to the evaluation of antioxidant activity of complex real samples such as soybean oil and sunflower oil (as hydrophobic samples) and honey (as hydrophilic sample). To the best of our knowledge, this is the first time that total antioxidant activity can be determined directly in soybean oil, sunflower oil and honey (not in their extracts) using PO-CL reactions.

  4. Flocculation, hydrophobic agglomeration and filtration of ultrafine coal

    NASA Astrophysics Data System (ADS)

    Yu, Zhimin

    In coal preparation plant circuits, fine coal particles are aggregated either by oil agglomeration or by flocculation. In a new hydrophobic agglomeration process, recently developed hydrophobic latices are utilized. While the selectivity of such aggregation processes determines the beneficiation results, the degree of aggregation has a strong effect on fine coal filtration. The aim of this research was to study the fundamentals and analyze the common grounds for these processes, including the potential effect of the coal surface properties. The selective flocculation tests, in which three types of coal, which differed widely in surface wettability, and three additives (hydrophobic latices, a semi-hydrophobic flocculant and a typical hydrophilic polyelectrolyte) were utilized, showed that coal wettability plays a very important role in selective flocculation. The abstraction of a hydrophobic latex on coal and silica revealed that the latex had a much higher affinity towards hydrophobic coal than to hydrophilic mineral matter. As a result, the UBC-1 hydrophobic latex flocculated only hydrophobic coal particles while the polyelectrolyte (PAM) flocculated all the tested coal samples and minerals, showing no selectivity in the fine coal beneficiation. The oil agglomeration was tested using kerosene emulsified with various surfactants (e.g. cationic, anionic and non-ionic). Surfactants enhance not only oil emulsification, hence reducing oil consumption (down to 0.25--0.5%), but also entirely change the electrokinetic properties of the droplets and affect the interaction energy between oil droplets and coal particles. Consequently, the results found in the course of the experimental work strongly indicate that even oxidized coals can be agglomerated if cationic surfactants are used to emulsify the oil. Oil agglomeration of the Ford-4 ultrafine coal showed that even at extremely low oil consumption (0.25 to 0.5%), a clean coal product with an ash content around 5% at over

  5. Halogenated silanes, radicals, and cations

    NASA Astrophysics Data System (ADS)

    Wang, Liming; He, Yi-Liang

    2008-09-01

    Quantum chemistry study has been carried out on the structure and energetics of halogenated silanes, radicals, and cations (SiHxXy0,+1, X = F, Cl, Br; x + y = 1-4). The geometries are optimized at B3LYP/6-31+G(2df,p) level. The adiabatic ionization energiess (IEas), relative energetics of cations, proton affinities (PAs) of silanes, and the enthalpies of formation are predicted using G3(CC) model chemistry. Non-classical ion complex structures are found for hydrogenated cations and transition states connecting classical and non-classical structures are also located. The most stable cations for silylene and silyl radicals have their classical divalent and trivalent structures, and those for silanes have non-classical structures except for SiH3Br+ and SiH2Br2+. The non-classical structures for halosilane cations imply difficulty in experimentally measurement of the adiabatic ionization energies using photoionization or photoelectron studies. For SiH3X, SiH2X2, and SiHX3, the G3(CC) adiabatic IEas to classical ionic structures closest to their neutrals agree better with the photoelectron spectroscopic measurements. The transition states between classical and non-classical structures also hamper the photoionization determination of the appearance energies for silylene cations from silanes. The G3(CC) results for SiHx0,+1 agree excellently with the photoionization mass spectrometric study, and the results for fluorinated and chlorinated species also agree with the previous theoretical predictions at correlation levels from BAC-MP4 to CCSD(T)/CBS. The predicted enthalpy differences between SiH2Cl+, SiHCl2+, and SiCl3+ are also in accordance with previous kinetics study. The G3(CC) results show large discrepancies to the collision-induced charge transfer and/or dissociation reactions involving SiFx+ and SiClx+ ions, for which the G3(CC) enthalpies of formation are also significantly differed from the previous theoretical predictions, especially on SiFx+ (x = 2-4). The G3

  6. Pilot study of radical hysterectomy versus radical trachelectomy on sexual distress.

    PubMed

    Brotto, Lori A; Smith, Kelly B; Breckon, Erin; Plante, Marie

    2013-01-01

    Radical trachelectomy, which leaves the uterus intact, has emerged as a desirable surgical option for eligible women with early-stage cervical cancer who wish to preserve fertility. The available data suggest excellent obstetrical outcomes with radical trachelectomy, and no differences in sexual responding between radical trachelectomy and radical hysterectomy. There is a need to examine the effect of radical hysterectomy on sexual distress given that it is distinct from sexual function. Participants were 34 women diagnosed with early-stage cervical cancer. The authors report 1-month postsurgery data for 29 women (radical hysterectomy group: n = 17, M age = 41.8 years; radical trachelectomy group: n = 12, M age = 31.8 years), and 6-month follow-up data on 26 women. Whereas both groups experienced an increase in sex-related distress immediately after surgery, distress continued to increase 6 months after surgery for the radical hysterectomy group but decreased in the radical trachelectomy group. There were no between-group differences in mood, anxiety, or general measures of health. The decrease in sex-related distress in the radical trachelectomy but not in the radical hysterectomy group suggests that the preservation of fertility may have attenuated sex-related distress. Care providers should counsel women exploring surgical options for cervical cancer about potential sex distress-related sequelae. PMID:23656625

  7. Purification and in vitro antioxidative effects of giant squid muscle peptides on free radical-mediated oxidative systems.

    PubMed

    Rajapakse, Niranjan; Mendis, Eresha; Byun, Hee-Guk; Kim, Se-Kwon

    2005-09-01

    Low molecular weight peptides obtained from ultrafiltration (UF) of giant squid (Dosidicus gigas) muscle protein were studied for their antioxidative effects in different in vitro oxidative systems. The most potent two peptides, Asn-Ala-Asp-Phe-Gly-Leu-Asn-Gly-Leu-Glu-Gly-Leu-Ala (1307 Da) and Asn-Gly-Leu-Glu-Gly-Leu-Lys (747 Da), exhibited their antioxidant potential to act as chain-breaking antioxidants by inhibiting radical-mediated peroxidation of linoleic acid, and their activities were closer to highly active synthetic antioxidant, butylated hydroxytoluene. Addition of these peptides could enhance the viability of cytotoxic embryonic lung fibroblasts significantly (P<.05) at a low concentration of 50 microg/ml, and it was presumed due to the suppression of radical-induced oxidation of membrane lipids. Electron spin trapping studies revealed that the peptides were potent scavengers of free radicals in the order of carbon-centered (IC(50) 396.04 and 304.67 microM), hydroxyl (IC(50) 497.32 and 428.54 microM) and superoxide radicals (IC(50) 669.34 and 573.83 microM). Even though the exact molecular mechanism for scavenging of free radicals was unclear, unusually high hydrophobic amino acid composition (more than 75%) of giant squid muscle peptides was presumed to be involved in the observed activities. PMID:16115545

  8. Radiolytic generation of radical cations in xenon matrices. Tetramethylcyclopropane radical cation and its transformations

    SciTech Connect

    Qin, X.Z.; Trifunac, A.D. )

    1990-04-05

    Radiolytic generation of radical cations in xenon matrices containing electron scavengers is illustrated by studying the 1,1,2,2-tetramethylcyclopropane radical cation. Dilute and concentrated solutions of tetramethylcyclopropane in xenon without electron scavengers and neat tetramethylcyclopropane yielded neutral radicals upon {gamma}-irradiation. Speculation on the mechanisms of radical formation is presented. The radical species observed in the {gamma}-irradiation of neat tetramethylcyclopropane appears to be identical with the paramagnetic species observed in CF{sub 2}ClCFCl{sub 2} above 120 K, suggesting that a neutral radical rather than the ring-opened distonic radical cation is observed in the CF{sub 2}ClCFCl{sub 2} matrix.

  9. Activity of catalytic silver nanoparticles modulated by capping agent hydrophobicity.

    PubMed

    Janani, Seralathan; Stevenson, Priscilla; Veerappan, Anbazhagan

    2014-05-01

    In this paper, a facile in situ method is reported for the preparation of catalytic silver nanoparticles (AgNPs) using N-acyl tyramine (NATA) with variable hydrophobic acyl length. Scanning electron microscopic analysis shows that NATA exists initially as larger aggregates in alkaline aqueous solution. The addition of AgNO3 dissociates these larger aggregate and subsequently promotes the formation of self-assembled NATA and AgNPs. Characterization of AgNPs using UV-vis spectroscopy, scanning electron microscope and transmission electron microscope revealed that the hydrophobic acyl chain length of NATA does not influence the particle size, shape and morphology. All NATA-AgNPs yielded relatively identical values in full width at half-maximum (FWHM) analysis, indicating that the AgNPs prepared with NATA are relatively polydispersed at all tested acyl chain lengths. These nanoparticles are able to efficiently catalyze the reduction of 4-nitro phenol to 4-amino phenol, 2-nitro aniline to 1,2-diamino benzene, 2,4,6-trinitro phenol to 2,4,6-triamino phenol by NaBH4 in an aqueous environment. The reduction reaction rate is determined to be pseudo-first order and the apparent rate constant is linearly dependent on the hydrophobic acyl chain length of the NATA. All reaction kinetics presented an induction period, which is dependent on the N-acyl chain length, indicating that the hydrophobic effects play a critical role in bringing the substrate to the metal nanoparticle surface to induce the catalytic reaction. In this study, however, the five catalytic systems have similar size and polydispersity, differing only in terms of capping agent hydrophobicity, and shows different catalytic activity with respect to the alkyl chain length of the capping agent. As discussed, the ability to modulate the metal nanoparticles catalytic property, by modifying the capping agent hydrophobicity represents a promising future for developing an efficient nanocatalyst without altering the size

  10. Order and correlation contributions to the entropy of hydrophobic solvation

    NASA Astrophysics Data System (ADS)

    Liu, Maoyuan; Besford, Quinn Alexander; Mulvaney, Thomas; Gray-Weale, Angus

    2015-03-01

    The entropy of hydrophobic solvation has been explained as the result of ordered solvation structures, of hydrogen bonds, of the small size of the water molecule, of dispersion forces, and of solvent density fluctuations. We report a new approach to the calculation of the entropy of hydrophobic solvation, along with tests of and comparisons to several other methods. The methods are assessed in the light of the available thermodynamic and spectroscopic information on the effects of temperature on hydrophobic solvation. Five model hydrophobes in SPC/E water give benchmark solvation entropies via Widom's test-particle insertion method, and other methods and models are tested against these particle-insertion results. Entropies associated with distributions of tetrahedral order, of electric field, and of solvent dipole orientations are examined. We find these contributions are small compared to the benchmark particle-insertion entropy. Competitive with or better than other theories in accuracy, but with no free parameters, is the new estimate of the entropy contributed by correlations between dipole moments. Dipole correlations account for most of the hydrophobic solvation entropy for all models studied and capture the distinctive temperature dependence seen in thermodynamic and spectroscopic experiments. Entropies based on pair and many-body correlations in number density approach the correct magnitudes but fail to describe temperature and size dependences, respectively. Hydrogen-bond definitions and free energies that best reproduce entropies from simulations are reported, but it is difficult to choose one hydrogen bond model that fits a variety of experiments. The use of information theory, scaled-particle theory, and related methods is discussed briefly. Our results provide a test of the Frank-Evans hypothesis that the negative solvation entropy is due to structured water near the solute, complement the spectroscopic detection of that solvation structure by

  11. Order and correlation contributions to the entropy of hydrophobic solvation

    SciTech Connect

    Liu, Maoyuan; Besford, Quinn Alexander; Mulvaney, Thomas; Gray-Weale, Angus

    2015-03-21

    The entropy of hydrophobic solvation has been explained as the result of ordered solvation structures, of hydrogen bonds, of the small size of the water molecule, of dispersion forces, and of solvent density fluctuations. We report a new approach to the calculation of the entropy of hydrophobic solvation, along with tests of and comparisons to several other methods. The methods are assessed in the light of the available thermodynamic and spectroscopic information on the effects of temperature on hydrophobic solvation. Five model hydrophobes in SPC/E water give benchmark solvation entropies via Widom’s test-particle insertion method, and other methods and models are tested against these particle-insertion results. Entropies associated with distributions of tetrahedral order, of electric field, and of solvent dipole orientations are examined. We find these contributions are small compared to the benchmark particle-insertion entropy. Competitive with or better than other theories in accuracy, but with no free parameters, is the new estimate of the entropy contributed by correlations between dipole moments. Dipole correlations account for most of the hydrophobic solvation entropy for all models studied and capture the distinctive temperature dependence seen in thermodynamic and spectroscopic experiments. Entropies based on pair and many-body correlations in number density approach the correct magnitudes but fail to describe temperature and size dependences, respectively. Hydrogen-bond definitions and free energies that best reproduce entropies from simulations are reported, but it is difficult to choose one hydrogen bond model that fits a variety of experiments. The use of information theory, scaled-particle theory, and related methods is discussed briefly. Our results provide a test of the Frank-Evans hypothesis that the negative solvation entropy is due to structured water near the solute, complement the spectroscopic detection of that solvation structure by

  12. Order and correlation contributions to the entropy of hydrophobic solvation.

    PubMed

    Liu, Maoyuan; Besford, Quinn Alexander; Mulvaney, Thomas; Gray-Weale, Angus

    2015-03-21

    The entropy of hydrophobic solvation has been explained as the result of ordered solvation structures, of hydrogen bonds, of the small size of the water molecule, of dispersion forces, and of solvent density fluctuations. We report a new approach to the calculation of the entropy of hydrophobic solvation, along with tests of and comparisons to several other methods. The methods are assessed in the light of the available thermodynamic and spectroscopic information on the effects of temperature on hydrophobic solvation. Five model hydrophobes in SPC/E water give benchmark solvation entropies via Widom's test-particle insertion method, and other methods and models are tested against these particle-insertion results. Entropies associated with distributions of tetrahedral order, of electric field, and of solvent dipole orientations are examined. We find these contributions are small compared to the benchmark particle-insertion entropy. Competitive with or better than other theories in accuracy, but with no free parameters, is the new estimate of the entropy contributed by correlations between dipole moments. Dipole correlations account for most of the hydrophobic solvation entropy for all models studied and capture the distinctive temperature dependence seen in thermodynamic and spectroscopic experiments. Entropies based on pair and many-body correlations in number density approach the correct magnitudes but fail to describe temperature and size dependences, respectively. Hydrogen-bond definitions and free energies that best reproduce entropies from simulations are reported, but it is difficult to choose one hydrogen bond model that fits a variety of experiments. The use of information theory, scaled-particle theory, and related methods is discussed briefly. Our results provide a test of the Frank-Evans hypothesis that the negative solvation entropy is due to structured water near the solute, complement the spectroscopic detection of that solvation structure by

  13. Characteristics of Radical Reactions, Spin Rules, and a Suggestion for the Consistent Use of a Dot on Radical Species

    ERIC Educational Resources Information Center

    Wojnarovits, Laszlo

    2011-01-01

    In many chemical reactions, reactive radicals have been shown to be transient intermediates. The free radical character of a chemical species is often, but not always, indicated by adding a superscript dot to the chemical formula. A consistent use of this radical symbol on all species that have radical character is suggested. Free radicals have a…

  14. Kinetics of Propargyl Radical Dissociation.

    PubMed

    Klippenstein, Stephen J; Miller, James A; Jasper, Ahren W

    2015-07-16

    Due to the prominent role of the propargyl radical for hydrocarbon growth within combustion environments, it is important to understand the kinetics of its formation and loss. The ab initio transition state theory-based master equation method is used to obtain theoretical kinetic predictions for the temperature and pressure dependence of the thermal decomposition of propargyl, which may be its primary loss channel under some conditions. The potential energy surface for the decomposition of propargyl is first mapped at a high level of theory with a combination of coupled cluster and multireference perturbation calculations. Variational transition state theory is then used to predict the microcanonical rate coefficients, which are subsequently implemented within the multiple-well multiple-channel master equation. A variety of energy transfer parameters are considered, and the sensitivity of the thermal rate predictions to these parameters is explored. The predictions for the thermal decomposition rate coefficient are found to be in good agreement with the limited experimental data. Modified Arrhenius representations of the rate constants are reported for utility in combustion modeling. PMID:25871530

  15. Fabrication of Hydrophobic Nanostructured Surfaces for Microfluidic Control.

    PubMed

    Morikawa, Kyojiro; Tsukahara, Takehiko

    2016-01-01

    In the field of micro- and nanofluidics, various kinds of novel devices have been developed. For such devices, not only fluidic control but also surface control of micro/nano channels is essential. Recently, fluidic control by hydrophobic nanostructured surfaces have attracted much attention. However, conventional fabrication methods of nanostructures require complicated steps, and integration of the nanostructures into micro/nano channels makes fabrication procedures even more difficult and complicated. In the present study, a simple and easy fabrication method of nanostructures integrated into microchannels was developed. Various sizes of nanostructures were successfully fabricated by changing the plasma etching time and etching with a basic solution. Furthermore, it proved possible to construct highly hydrophobic nanostructured surfaces that could effectively control the fluid in microchannels at designed pressures. We believe that the fabrication method developed here and the results obtained are valuable contributions towards further applications in the field of micro- and nanofluidics. PMID:26753710

  16. Hydrophobicity in DLC films prepared by electrodeposition technique

    NASA Astrophysics Data System (ADS)

    Paul, R.; Dalui, S.; Das, S. N.; Bhar, R.; Pal, A. K.

    2008-12-01

    Diamond-like carbon (DLC) films were deposited by electrodeposition technique onto SnO 2-coated glass substrates by using a mixture of acetic acid and water as electrolyte at a fixed applied voltage 2.14 V. The films showed two distinct broad Raman characteristic peaks located at ˜1365 cm -1 (D-line) and 1575 cm -1 (G-line). Band gaps of the films varied between 1.98 and 2.35 eV. Hydrophobicity in these films was studied by measuring the contact angles of water droplets and it was found that the films were extremely hydrophobic. The results were interpreted in terms of hybridization of carbon in these DLC films.

  17. Laser-treated hydrophobic paper: an inexpensive microfluidic platform.

    PubMed

    Chitnis, Girish; Ding, Zhenwen; Chang, Chun-Li; Savran, Cagri A; Ziaie, Babak

    2011-03-21

    We report a method for fabricating inexpensive microfluidic platforms on paper using laser treatment. Any paper with a hydrophobic surface coating (e.g., parchment paper, wax paper, palette paper) can be used for this purpose. We were able to selectively modify the surface structure and property (hydrophobic to hydrophilic) of several such papers using a CO(2) laser. We created patterns down to a minimum feature size of 62±1 µm. The modified surface exhibited a highly porous structure which helped to trap/localize chemical and biological aqueous reagents for analysis. The treated surfaces were stable over time and were used to self-assemble arrays of aqueous droplets. Furthermore, we selectively deposited silica microparticles on patterned areas to allow lateral diffusion from one end of a channel to the other. Finally, we demonstrated the applicability of this platform to perform chemical reactions using luminol-based hemoglobin detection. PMID:21264372

  18. Diglycerol-based polyesters: melt polymerization with hydrophobic anhydrides.

    PubMed

    Dakshinamoorthy, Deivasagayam; Weinstock, Allison K; Damodaran, Krishnan; Iwig, David F; Mathers, Robert T

    2014-10-01

    The melt polymerization of diglycerol with bicyclic anhydride monomers derived from a naturally occurring monoterpene provides an avenue for polyesters with a high degree of sustainability. The hydrophobic anhydrides are synthesized at ambient temperature via a solvent-free Diels-Alder reaction of α-phellandrene with maleic anhydride. Subsequent melt polymerizations with tetra-functional diglycerol are effective under a range of [diglycerol]/[anhydride] ratios. The hydrophobicity of α-phellandrene directly impacts the swelling behavior of the resulting polyesters. The low E factors (<2), large amount of bio-based content (>75%), ambient temperature monomer synthesis, and polymer degradability represent key factors in the design of these sustainable polyesters. PMID:25138308

  19. Composite chitosan hydrogels for extended release of hydrophobic drugs.

    PubMed

    Delmar, Keren; Bianco-Peled, Havazelet

    2016-01-20

    A composite chitosan hydrogel durable in physiological conditions intended for sustained release of hydrophobic drugs was investigated. The design is based on chitosan crosslinked with genipin with embedded biocompatible non-ionic microemulsion (ME). A prolonged release period of 48 h in water, and of 24h in phosphate buffer saline (PBS) of pH 7.4 was demonstrated for Nile red and curcumin. The differences in release patterns in water and PBS were attributed to distinct dissimilarities in the swelling behaviors; in water, the hydrogels swell enormously, while in PBS they expel water and shrink. The release mechanism dominating this system is complex due to intermolecular bonding between the oil droplets and the polymeric network, as confirmed by Fourier transform infrared spectroscopy (FTIR) experiments. This is the first time that oil in water microemulsions were introduced into a chitosan hydrogels for the creation of a hydrophobic drug delivery system. PMID:26572389

  20. Laser Treatment of Sintered Silicon Carbide Surface for Enhanced Hydrophobicity

    NASA Astrophysics Data System (ADS)

    Yilbas, Bekir Sami; Bhushan, Bharat

    2014-01-01

    In this study, laser treatment of sintered SiC surfaces is carried out to enhance the surface hydrophobicity. Morphological and metallurgical changes of the treated surfaces are evaluated using optical and scanning electron microscopy, energy dispersive spectroscopy, and x-ray diffraction (XRD). Microhardness and fracture toughness are measured using indentation tests. The residual stresses present are determined using the XRD technique. The wetting characteristics of the treated surfaces are assessed through contact angle measurements. It is found that the laser-treated surfaces consist of fine grooves and pillars and that the resulting surface roughness enhances the surface hydrophobicity. The fracture toughness of the treated surface is reduced possibly because of the microhardness increase at the surface. The residual stress formed in the surface region is on the order of 1.8 GPa, and it is compressive.

  1. Stable low-loss optical nanofibres embedded in hydrophobic aerogel.

    PubMed

    Xiao, Limin; Grogan, M D W; Wadsworth, W J; England, R; Birks, T A

    2011-01-17

    Nanofibres, optical fibres narrower than the wavelength of light, degrade in hours on exposure to air. We show that encapsulation in hydrophobic silica aerogel (refractive index 1.05) provides protection and stability (over 2 months) without sacrificing low attenuation, strong confinement and accessible evanescent field. The measured attenuation was <0.03 dB/mm, over 10 × lower than reported with other encapsulants. This enables many nanofibre applications based on their extreme small size and strong external evanescent field, such as optical sensors, nonlinear optics, nanofibre circuits and high-Q resonators. The aerogel is more than a waterproof box, it is a completely-compatible gas-permeable material in intimate contact with the nanofibre and hydrophobic on both the macroscopic and molecular scales. Its benefits are illustrated by experiments on gas sensing (exploiting the aerogel's porosity) and supercontinuum generation (exploiting its ultra-low index). PMID:21263617

  2. Ordered silicon nanorod arrays with controllable geometry and robust hydrophobicity

    NASA Astrophysics Data System (ADS)

    Zi-Wen, Wang; Jia-Qi, Cai; Yi-Zhi, Wu; Hui-Jie, Wang; Xiao-Liang, Xu

    2015-01-01

    Highly ordered silicon nanorod (SiNR) arrays with controllable geometry are fabricated via nanosphere lithography and metal-assisted chemical etching. It is demonstrated that the key to achieving a high-quality metal mask is to construct a non-close-packed template that can be removed with negligible damage to the mask. Hydrophobicity of SiNR arrays of different geometries is also studied. It is shown that the nanorod structures are effectively quasi-hydrophobic with a contact angle as high as 142°, which would be useful in self-cleaning nanorod-based device applications. Project supported by the National Natural Science Foundation of China (Grant No. 51272246) and the Scientific and Technological Research Foundation of Anhui Province, China (Grant No. 12010202035).

  3. Gas adsorption and accumulation on hydrophobic surfaces: Molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Luo, Qing-Qun; Yang, Jie-Ming

    2015-09-01

    Molecular dynamics simulations show that the gas dissolved in water can be adsorbed at a hydrophobic interface and accumulates thereon. Initially, a water depletion layer appears on the hydrophobic interface. Gas molecules then enter the depletion layer and form a high-density gas-enriched layer. Finally, the gas-enriched layer accumulates to form a nanobubble. The radian of the nanobubble increases with time until equilibrium is reached. The equilibrium state arises through a Brenner-Lohse dynamic equilibrium mechanism, whereby the diffusive outflux is compensated by an influx near the contact line. Additionally, supersaturated gas also accumulates unsteadily in bulk water, since it can diffuse back into the water and is gradually adsorbed by a solid substrate. Project supported by the National Natural Science Foundation of China (Grant No. 21376161).

  4. Morphology of Air Nanobubbles Trapped atHydrophobic Nanopatterned Surfaces

    SciTech Connect

    Checco, A.; Hofmann, T.; DiMasi, E.; Black, C.T.; Ocko, B.M.

    2010-04-01

    The details of air nanobubble trapping at the interface between water and a nanostructured hydrophobic silicon surface are investigated using X-ray scattering and contact angle measurements. Large-area silicon surfaces containing hexagonally packed, 20 nm wide hydrophobic cavities provide ideal model surfaces for studying the morphology of air nanobubbles trapped inside cavities and its dependence on the cavity depth. Transmission small-angle X-ray scattering measurements show stable trapping of air inside the cavities with a partial water penetration of 5-10 nm into the pores, independent of their large depth variation. This behavior is explained by consideration of capillary effects and the cavity geometry. For parabolic cavities, the liquid can reach a thermodynamically stable configuration - a nearly planar nanobubble meniscus - by partially penetrating into the pores. This microscopic information correlates very well with the macroscopic surface wetting behavior.

  5. Repulsive effects of hydrophobic diamond thin films on biomolecule detection

    NASA Astrophysics Data System (ADS)

    Ruslinda, A. Rahim; Ishiyama, Y.; Penmatsa, V.; Ibori, S.; Kawarada, H.

    2015-02-01

    The repulsive effect of hydrophobic diamond thin film on biomolecule detection, such as single-nucleotide polymorphisms and human immunodeficiency virus type 1 trans-activator of transcription peptide protein detection, was investigated using a mixture of a fluorine-, amine-, and hydrogen-terminated diamond surfaces. These chemical modifications lead to the formation of a surface that effectively resists the nonspecific adsorption of proteins and other biomolecules. The effect of fluorine plasma treatment on elemental composition was also investigated via X-ray photoelectron spectroscopy (XPS). XPS results revealed a fluorocarbon layer on the diamond thin films. The contact angle measurement results indicated that the fluorine-treated diamond thin films were highly hydrophobic with a surface energy value of ∼25 mN/m.

  6. Review: Milk Proteins as Nanocarrier Systems for Hydrophobic Nutraceuticals.

    PubMed

    Kimpel, Florian; Schmitt, Joachim J

    2015-11-01

    Milk proteins and milk protein aggregates are among the most important nanovehicles in food technology. Milk proteins have various functional properties that facilitate their ability to carry hydrophobic nutraceutical substances. The main functional transport properties that were examined in the reviewed studies are binding of molecules or ions, surface activity, aggregation, gelation, and interaction with other polymers. Hydrophobic binding has been investigated using caseins and isolated β-casein as well as whey proteins. Surface activity of caseins has been used to create emulsion-based carrier systems. Furthermore, caseins are able to self-assemble into micelles, which can incorporate molecules. Gelation and interaction with other polymers can be used to encapsulate molecules into protein networks. The release of transported substances mainly depends on pH and swelling behavior of the proteins. The targeted use of nanocarrier systems requires specific knowledge about the binding mechanisms between the proteins and the carried substances in a certain food matrix. PMID:26467442

  7. Macromolecular transport of hydrophobic contaminants in aqueous environments

    SciTech Connect

    Enfield, C.G.; Bengtsson, G.

    1988-01-01

    The mobility of a model macromolecule, blue dextran, was compared under laboratory conditions to the mobility of tritiated water through a sandy soil. The blue dextran eluted from the soil prior to the tritiated water. The phenomenon was compared to exclusion chromatography where molecules are separated by size with the largest eluting first and each molecule flowing through a different portion of the total porosity. When the soil was amended with a mixture of kaolinite and bentonite clay, the porosity occupied by the macromolecule was decreased. The implications to hydrophobic chemical transport based on the presence and mobility of a macromolecule were evaluated from a theoretical basis. Macromolecules should increase the relative mobility of slightly mobile compounds more than they increase the relative mobility of highly mobile compounds. Very hydrophobic compounds should show greater mobility under natural conditions than predicted, ignoring the presence of dissolved organic carbon.

  8. Nanoscale encapsulation: the structure of cations in hydrophobic microporous aluminosilicates

    SciTech Connect

    Wasserman, S.R.; Yuchs, S.E.; Giaquinta, D.; Soderholm, L.; Song, Kang

    1996-10-01

    Hydrophobic microporous aluminosilicates, created by organic surface modification of inherently hydrophilic materials such as zeolites and clays, are currently being investigated as storage media for hazardous cations. Use of organic monolayers to modify the surface of an aluminosilicate after introducing an ion into the zeolite/clay reduces the interaction of water with the material. Resulting systems are about 20 times more resistant to leaching of stored ion. XAS spectra from the encapsulated ion demonstrate that byproducts from the organic modifier can complex with the stored cation. This complexation can result in a decreased affinity of the cation for the aluminosilicate matrix. Changing the organic modifier eliminates this problem. XAS spectra also indicate that the reactivity and speciation of the encapsulated ion may change upon application of the hydrophobic layer.

  9. Controlling film topography to form highly hydrophobic waterborne coatings.

    PubMed

    López, Ana B; de la Cal, José C; Asua, José M

    2016-08-17

    Coatings have a tremendous impact on economy as they reduce corrosion that has an estimated cost of 3% of the world's GDP. Hydrophobic coatings are particularly efficient for this purpose and the challenge is to produce cost effective and environmentally friendly, highly hydrophobic, cohesive and non-porous coatings applicable to large and irregular surfaces. This work shows that this goal can be achieved by forming wrinkles on the surface of waterborne coatings through fine-tuning of the film forming conditions. The proof of concept was demonstrated by using waterborne dispersions of copolymers of 1H,1H,2H,2H-perfluorodecyl acrylate and 2-ethylhexyl acrylate, and using the temperature and hardness of the copolymer as control variables during film formation. This allowed the formation of transparent films with a wrinkled surface that had a contact angle of 133°, which represents an increase of 20° with respect to the film cast under standard conditions. PMID:27476531

  10. Studies on synthesis esterified zirconium glyphosates and their hydrophobic properties

    NASA Astrophysics Data System (ADS)

    Zhang, Yaqing; Li, Minglei; Ji, Xuemei; Xu, Qinghong

    2010-03-01

    A series of new organic-modified zirconium glyphosate compounds were synthesized based on the reactions between esterified glyphosates and ZrOCl 2. FT-IR spectra, solid-state 31P MAS NMR and elementary analysis proved the formation of these new compounds. Powder X-ray diffraction (PXRD) patterns and transmission electron microscope (TEM) images proved these compounds had lamellar structures. Scanning electronic microscope (SEM) images showed that solvents used in synthesis had great influence on the morphologies of products. Water contact angle measurements showed that the hydrophobic property of the products was a function of the number of carbon in esterified glyphosates, increased from 0° of zirconium glyphosate to 133° of dodecyl zirconium glyphosate. The present study offered a new route to synthesize organic-modified α-Zr(HPO 4) 2·H 2O (α-ZrP) materials with various morphology and controllable hydrophobic property.

  11. Radical scavenging activities of niacin-related compounds.

    PubMed

    Ogata, Shin; Takeuchi, Masayo; Teradaira, Shin; Yamamoto, Naokuni; Iwata, Keiko; Okumura, Katsuzumi; Taguchi, Hiroshi

    2002-03-01

    We investigated whether niacin-related compounds had radical-scavenging activity by electron spin resonance methods. Many compounds, but not trigonelline, had radical-scavenging activity against hydroxyl radicals. However, for the nitric oxide radical and 1,1-diphenyl-2-picrylhydrazyl radical, only nicotinic acid hydrazide and isonicotinic acid hydrazide had scavenging activities. These results suggest that the moiety of hydrazide might have an important role in scavenging abilities of various radicals. PMID:12005062

  12. Fabrication of super-hydrophobic duo-structures

    NASA Astrophysics Data System (ADS)

    Zhang, X. Y.; Zhang, F.; Jiang, Y. J.; Wang, Y. Y.; Shi, Z. W.; Peng, C. S.

    2015-04-01

    Recently, super-hydrophobicity has attracted increasing attention due to its huge potential in the practical applications. In this paper, we have presented a duo-structure of the combination of micro-dot-matrix and nano-candle-soot. Polydimethylsiloxane (PDMS) was used as a combination layer between the dot-matrix and the soot particles. Firstly, a period of 9-μm dot-matrix was easily fabricated on the K9 glass using the most simple and mature photolithography process. Secondly, the dot-matrix surface was coated by a thin film of PDMS (elastomer: hardener=10:1) which was diluted by methylbenzene at the volume ratio of 1:8. Thirdly, we held the PDMS modified surface over a candle flame to deposit a soot layer and followed by a gentle water-risen to remove the non-adhered particles. At last, the samples were baked at 85°C for 2 hours and then the duo-structure surface with both micro-size dot-matrix and nano-size soot particles was obtained. The SEM indicated this novel surface morphology was quite like a lotus leaf of the well-know micro-nano-binary structures. As a result, the contact angle meter demonstrated such surface exhibited a perfect super-hydrophobicity with water contact angle of 153° and sliding angle of 3°. Besides, just listed as above, the fabrication process for our structure was quite more easy, smart and low-cost compared with the other production technique for super-hydrophobic surfaces such as the phase separation method, electrochemical deposition and chemical vapor deposition etc. Hence, this super-hydrophobic duo-structure reported in this letter was a great promising candidate for a wide and rapid commercialization in the future.

  13. De novo design of the hydrophobic cores of proteins.

    PubMed Central

    Desjarlais, J. R.; Handel, T. M.

    1995-01-01

    We have developed and experimentally tested a novel computational approach for the de novo design of hydrophobic cores. A pair of computer programs has been written, the first of which creates a "custom" rotamer library for potential hydrophobic residues, based on the backbone structure of the protein of interest. The second program uses a genetic algorithm to globally optimize for a low energy core sequence and structure, using the custom rotamer library as input. Success of the programs in predicting the sequences of native proteins indicates that they should be effective tools for protein design. Using these programs, we have designed and engineered several variants of the phage 434 cro protein, containing five, seven, or eight sequence changes in the hydrophobic core. As controls, we have produced a variant consisting of a randomly generated core with six sequence changes but equal volume relative to the native core and a variant with a "minimalist" core containing predominantly leucine residues. Two of the designs, including one with eight core sequence changes, have thermal stabilities comparable to the native protein, whereas the third design and the minimalist protein are significantly destabilized. The randomly designed control is completely unfolded under equivalent conditions. These results suggest that rational de novo design of hydrophobic cores is feasible, and stress the importance of specific packing interactions for the stability of proteins. A surprising aspect of the results is that all of the variants display highly cooperative thermal denaturation curves and reasonably dispersed NMR spectra. This suggests that the non-core residues of a protein play a significant role in determining the uniqueness of the folded structure. PMID:8535237

  14. Hydrophobic and Electrostatic Cell Surface Properties of Thermophilic Dairy Streptococci

    PubMed Central

    van der Mei, H. C.; de Vries, J.; Busscher, H. J.

    1993-01-01

    Microbial adhesion to hydrocarbons (MATH) and microelectrophoresis were done in 10 mM potassium phosphate solutions to characterize the surfaces of thermophilic dairy streptococci, isolated from pasteurizers. Regardless of whether they were grown (in M17 broth) with lactose, sucrose, or glucose added, strains were relatively hydrophilic (showing low initial removal rates by hexadecane) and slightly negatively charged. A tendency exists for cells grown with sucrose added to be more hydrophilic than cells grown with glucose or lactose added. Also, the lowest isoelectric points, i.e., the pH values for which the zeta potentials are zero, were measured for strains with glucose added to the growth medium. The isoelectric points for the strains were all rather high, between pH 3 and 5, indicative of protein-rich surfaces, although X-ray photoelectron spectroscopy did not measure excessively large amounts of nitrogen on the cell surfaces. Both MATH and microelectrophoresis were done as a function of pH. Maxima in hydrophobicity were observed at certain pH values. Usually these pH values were in the range of the isoelectric points of the cells. Thus it appears that MATH measures an interplay of hydrophobicity and electrostatic interactions. MATH measures solely hydrophobicity only when electrostatic interactions are absent, i.e., close to the isoelectric points of the cells. Considering that these thermophilic streptococci are all rather hydrophilic, a possible pathway to prevent fouling in the pasteurization process might be to render the heat exchanger plates of the pasteurizer more hydrophobic. PMID:16349127

  15. Formation of ice nanotube with hydrophobic guests inside carbon nanotube.

    PubMed

    Tanaka, Hideki; Koga, Kenichiro

    2005-09-01

    A composite ice nanotube inside a carbon nanotube has been explored by molecular-dynamics and grand canonical Monte Carlo simulations. It is made from an octagonal ice nanotube whose hollow space contains hydrophobic guest molecules such as neon, argon, and methane. It is shown that the attractive interaction of the guest molecules stabilizes the ice nanotube. The guest occupancy of the hollow space is calculated by the same method as applied to clathrate hydrates. PMID:16164361

  16. Thermodynamics of hydrogen bond and hydrophobic interactions in cyclodextrin complexes.

    PubMed Central

    Ross, P D; Rekharsky, M V

    1996-01-01

    Values of K, delta G(o), delta H(o), delta S(o) and delta C(po) for the binding reaction of small organic ligands forming 1:1 complexes with either alpha- or beta-cyclodextrin were obtained by titration calorimetry from 15 degrees C to 45 degrees C. A hydrogen bond or hydrophobic interaction was introduced by adding a single functional group to the ligand. The thermodynamics of binding with and without the added group are compared to estimate the contribution of the hydrogen bond or hydrophobic interaction. A change in the environment of a functional group is required to influence the binding thermodynamics, but molecular size-dependent solute-solvent interactions have no effect. For phenolic O-H-O hydrogen bond formation, delta H(o) varies from -2 to -1.4 kcal mol(-1) from 15 degrees C to 45 degrees C, and delta C(p) is increased by 18 cal K(-1) mol(-1). The hydrophobic interaction has an opposite effect: in alpha-cyclodextrin, delta C(po) = -13.3 cal K(-1) mol(-1) per ligand -CH(2)-, identical to values found for the transfer of a -CH(2)-group from water to a nonpolar environment. At room temperature, the hydrogen bond and the -CH(2)-interaction each contribute about -600 cal mol(-1) to the stability (delta G(o)) of the complex. With increased temperature, the hydrogen bond stability decreases (i.e., hydrogen bonds "melt"), but the stability of the hydrophobic interaction remains essentially constant. PMID:8889190

  17. The position of hydrophobic residues tunes peptide self-assembly.

    PubMed

    Bortolini, Christian; Liu, Lei; Gronewold, Thomas M A; Wang, Chen; Besenbacher, Flemming; Dong, Mingdong

    2014-08-21

    The final structure and properties of synthetic peptides mainly depend on their sequence composition and experimental conditions. This work demonstrates that a variation in the positions of hydrophobic residues within a peptide sequence can tune the self-assembly. Techniques employed are atomic force microscopy, transmission electron microscopy and an innovative method based on surface acoustic waves. In addition, a systematic investigation on pH dependence was carried out by utilizing constant experimental parameters. PMID:24995505

  18. Competition of charge- versus radical-directed fragmentation of gas-phase protonated cysteine sulfinyl radicals.

    PubMed

    Love, Chasity B; Tan, Lei; Francisco, Joseph S; Xia, Yu

    2013-04-24

    The fragmentation behavior of various cysteine sulfinyl ions (intact, N-acetylated, and O-methylated), new members of the gas-phase amino acid radical ion family, was investigated by low-energy collision-induced dissociation (CID). The dominant fragmentation channel for the protonated cysteine sulfinyl radicals ((SO•)Cys) was the radical-directed Cα-Cβ homolytic cleavage, resulting in the formation of glycyl radical ions and loss of CH2SO. This channel, however, was not observed for protonated N-acetylated cysteine sulfinyl radicals (Ac-(SO•)Cys); instead, charge-directed H2O loss followed immediately by SH loss prevailed. Counterintuitively, the H2O loss did not derive from the carboxyl group but involved the sulfinyl oxygen, a proton, and a Cβ hydrogen atom. Theoretical calculations suggested that N-acetylation significantly increases the barrier (~14 kcal mol(-1)) for the radical-directed fragmentation channel because of its reduced capability to stabilize the thus-formed glycyl radical ions via the captodative effect. N-Acetylation also assists in moving the proton to the sulfinyl site, which reduces the barrier for H2O loss. Our studies demonstrate that for cysteine sulfinyl radical ions, the stability of the product ions (glycyl radical ions) and the location of the charge (proton) can significantly modulate the competition between radical- and charge-directed fragmentation. PMID:23527556

  19. Expanding Radical SAM Chemistry by Using Radical Addition Reactions and SAM Analogues.

    PubMed

    Ji, Xinjian; Li, Yongzhen; Xie, Liqi; Lu, Haojie; Ding, Wei; Zhang, Qi

    2016-09-19

    Radical S-adenosyl-l-methionine (SAM) enzymes utilize a [4Fe-4S] cluster to bind SAM and reductively cleave its carbon-sulfur bond to produce a highly reactive 5'-deoxyadenosyl (dAdo) radical. In almost all cases, the dAdo radical abstracts a hydrogen atom from the substrates or from enzymes, thereby initiating a highly diverse array of reactions. Herein, we report a change of the dAdo radical-based chemistry from hydrogen abstraction to radical addition in the reaction of the radical SAM enzyme NosL. This change was achieved by using a substrate analogue containing an olefin moiety. We also showed that two SAM analogues containing different nucleoside functionalities initiate the radical-based reactions with high efficiencies. The radical adduct with the olefin produced in the reaction was found to undergo two divergent reactions, and the mechanistic insights into this process were investigated in detail. Our study demonstrates a promising strategy in expanding radical SAM chemistry, providing an effective way to access nucleoside-containing compounds by using radical SAM-dependent reactions. PMID:27573794

  20. Granulation of increasingly hydrophobic formulations using a twin screw granulator.

    PubMed

    Yu, Shen; Reynolds, Gavin K; Huang, Zhenyu; de Matas, Marcel; Salman, Agba D

    2014-11-20

    The application of twin screw granulation in the pharmaceutical industry has generated increasing interest due to its suitability for continuous processing. However, an understanding of the impact of formulation properties such as hydrophobicity on intermediate and finished product quality has not yet been established. Hence, the current work investigated the granulation behaviour of three formulations containing increasing amounts of hydrophobic components using a Consigma™-1 twin screw granulator. Process conditions including powder feed rate, liquid to solid ratio, granulation liquid composition and screw configuration were also evaluated. The size of the wet granules was measured in order to enable exploration of granulation behaviour in isolation without confounding effects from downstream processes such as drying. The experimental observations indicated that the granulation process was not sensitive to the powder feed rate. The hydrophobicity led to heterogeneous liquid distribution and hence a relatively large proportion of un-wetted particles. Increasing numbers of kneading elements led to high shear and prolonged residence time, which acted to enhance the distribution of liquid and feeding materials. The bimodal size distributions considered to be characteristic of twin screw granulation were primarily ascribed to the breakage of relatively large granules by the kneading elements. PMID:25124058

  1. Exploring the dewetting transition in the hydrophobic collapse of melittin

    NASA Astrophysics Data System (ADS)

    Varilly, Patrick; Patel, Amish J.; Chandler, David

    2011-03-01

    We present our recent results on understanding the hydrophobic collapse of melittin dimers. Melittin dimers have large, complementary hydrophobic patches, and the dimer collapse mechanism involves a dewetting transition [Liu, Huang, Zhou and Berne, Nature 437, 159--162 (2005)]. As a result, melittin has become a model system for studying dewetting transitions in proteins. We apply our recently- developed tools for probing density fluctuations in water [Patel, Varilly and Chandler, JPCB 114, 1632--1637 (2010)] to understand this dewetting transition in terms of free energy surfaces, their bistability and their barrier heights. We show how the hydrophobic character of melittin's tetramerization surface results in an enhanced probability of density depletion next to that surface. When two dimers come together, the density depletion is further enhanced, so that even at large separations, there is a metastable dry phase in the region between the dimers. As the dimers come together, the dry phase is stabilized and eventually the wet phase is destabilized, leading to the collapse of the dimers. We explore how mutations that have been observed to suppress the dewetting transition affect the corresponding free energy surfaces and discuss our ongoing efforts to fully map out the reaction coordinate of melittin collapse.

  2. Induced hydrophobic recovery of oxygen plasma-treated surfaces

    PubMed Central

    Guckenberger, David J.; Berthier, Erwin; Young, Edmond W. K.; Beebe, David J.

    2014-01-01

    Plasma treatment is a widely used method in microfabrication laboratories and the plasticware industry to functionalize surfaces for device bonding and preparation for mammalian cell culture. However, spatial control of plasma treatment is challenging because it typically requires a tedious masking step that is prone to alignment errors. Currently, there are no available methods to actively revert a surface from a treated hydrophilic state to its original hydrophobic state. Here, we describe a method that relies on physical contact treatment (PCT) to actively induce hydrophobic recovery of plasma-treated surfaces. PCT involves applying brushing and peeling processes with common wipers and tapes to reverse the wettability of hydrophilized surfaces while simultaneously preserving hydrophilicity of non-contacted surfaces. We demonstrate that PCT is a user-friendly method that allows 2D and 3D surface patterning of hydrophobic regions, and the protection of hydrophilic surfaces from unwanted PCT-induced recovery. This method will be useful in academic and industrial settings where plasma treatment is frequently used. PMID:22592853

  3. Droplet evaporation on heated hydrophobic and superhydrophobic surfaces.

    PubMed

    Dash, Susmita; Garimella, Suresh V

    2014-04-01

    The evaporation characteristics of sessile water droplets on smooth hydrophobic and structured superhydrophobic heated surfaces are experimentally investigated. Droplets placed on the hierarchical superhydrophobic surface subtend a very high contact angle (∼160°) and demonstrate low roll-off angle (∼1°), while the hydrophobic substrate supports corresponding values of 120° and ∼10°. The substrates are heated to different constant temperatures in the range of 40-60 °C, which causes the droplet to evaporate much faster than in the case of natural evaporation without heating. The geometric parameters of the droplet, such as contact angle, contact radius, and volume evolution over time, are experimentally tracked. The droplets are observed to evaporate primarily in a constant-contact-angle mode where the contact line slides along the surface. The measurements are compared with predictions from a model based on diffusion of vapor into the ambient that assumes isothermal conditions. This vapor-diffusion-only model captures the qualitative evaporation characteristics on both test substrates, but reasonable quantitative agreement is achieved only for the hydrophobic surface. The superhydrophobic surface demonstrates significant deviation between the measured evaporation rate and that obtained using the vapor-diffusion-only model, with the difference being amplified as the substrate temperature is increased. A simple model considering thermal diffusion through the droplet is used to highlight the important role of evaporative cooling at the droplet interface in determining the droplet evaporation characteristics on superhydrophobic surfaces. PMID:24827255

  4. Water's structure around hydrophobic solutes and the iceberg model.

    PubMed

    Galamba, N

    2013-02-21

    The structure of water in the hydration shells of small hydrophobic solutes was investigated through molecular dynamics. The results show that a subset of water molecules in the first hydration shell of a nonpolar solute have a significantly enhanced tetrahedrality and a slightly larger number of hydrogen bonds, relative to the molecules in water at room temperature, consistent with the experimentally observed negative excess entropy and increased heat capacity of hydrophobic solutions at room temperature. This ordering results from the rearrangement of a small number of water molecules near the nonpolar solutes that occupy one to two vertices of the enhanced water tetrahedra. Although this structuring is not nearly like that often associated with a literal interpretation of the term "iceberg" in the Frank and Evans iceberg model, it does support a moderate interpretation of this model. Thus, the tetrahedral orientational order of this ensemble of water molecules is comparable to that of liquid water at ~10 °C, although not accompanied by the small contraction of the O-O distance observed in cold water. Further, we show that the structural changes of water in the vicinity of small nonpolar solutes cannot be inferred from the water radial distribution functions, explaining why this increased ordering is not observed through neutron diffraction experiments. The present results restore a molecular view where the slower translational and reorientational dynamics of water near hydrophobic groups has a structural equivalent resembling water at low temperatures. PMID:23360515

  5. Surprising high hydrophobicity of polymer networks from hydrophilic components.

    PubMed

    Attanasio, Agnese; Bayer, Ilker S; Ruffilli, Roberta; Ayadi, Farouk; Athanassiou, Athanassia

    2013-06-26

    We report a simple and inexpensive method of fabricating highly hydrophobic novel materials based on interpenetrating networks of polyamide and poly(ethyl cyanoacrylate) hydrophilic components. The process is a single-step solution casting from a common solvent, formic acid, of polyamide and ethyl cyanoacrylate monomers. After casting and subsequent solvent evaporation, the in situ polymerization of ethyl cyanoacrylate monomer forms polyamide-poly(ethyl cyanoacrylate) interpenetrating network films. The interpenetrating networks demonstrate remarkable waterproof properties allowing wettability control by modulating the concentration of the components. In contrast, pure polyamide and poly(ethyl cyanoacrylate) films obtained from formic acid solutions are highly hygroscopic and hydrophilic, respectively. The polymerization of ethyl cyanoacrylate in the presence of polyamide promotes molecular interactions between the components, which reduce the available hydrophilic moieties and render the final material hydrophobic. The wettability, morphology, and thermo-physical properties of the polymeric coatings were characterized. The materials developed in this work take advantage of the properties of both polymers in a single blend and above all, due to their hydrophobic nature and minimal water uptake, can extend the application range of the individual polymers where water repellency is required. PMID:23713478

  6. Functional bacterial amyloid increases Pseudomonas biofilm hydrophobicity and stiffness

    PubMed Central

    Zeng, Guanghong; Vad, Brian S.; Dueholm, Morten S.; Christiansen, Gunna; Nilsson, Martin; Tolker-Nielsen, Tim; Nielsen, Per H.; Meyer, Rikke L.; Otzen, Daniel E.

    2015-01-01

    The success of Pseudomonas species as opportunistic pathogens derives in great part from their ability to form stable biofilms that offer protection against chemical and mechanical attack. The extracellular matrix of biofilms contains numerous biomolecules, and it has recently been discovered that in Pseudomonas one of the components includes β-sheet rich amyloid fibrils (functional amyloid) produced by the fap operon. However, the role of the functional amyloid within the biofilm has not yet been investigated in detail. Here we investigate how the fap-based amyloid produced by Pseudomonas affects biofilm hydrophobicity and mechanical properties. Using atomic force microscopy imaging and force spectroscopy, we show that the amyloid renders individual cells more resistant to drying and alters their interactions with hydrophobic probes. Importantly, amyloid makes Pseudomonas more hydrophobic and increases biofilm stiffness 20-fold. Deletion of any one of the individual members of in the fap operon (except the putative chaperone FapA) abolishes this ability to increase biofilm stiffness and correlates with the loss of amyloid. We conclude that amyloid makes major contributions to biofilm mechanical robustness. PMID:26500638

  7. Enhancement of hydrophobic chromophore fluorescence by adsorption to nanospheres

    NASA Astrophysics Data System (ADS)

    Blair, Elizabeth; Carr, Aaron; Krishnan, Rajagopal; Nordlund, Thomas M.

    2003-11-01

    Optical properties of hydrophobic molecules are usually studied in solvents of low dielectric constant. However, biologically or medically important molecules often exist in a mixed hydrophobic/ aqueous environment, e.g., in emulsions or membranes. In order to study optical processes occurring in oily sunscreen agents, octyl salicylate and octyl methoxycinnamate, in a model aqueous/hydrophobic environment, we dispersed the agents in suspensions of polystyrene nanospheres, ranging in diameter from 30 to 1500 nm. The spheres had sulfate functional groups and a low negative charge on the surface. Adsorption of salicylate resulted in a fluorescence intensity enhancement of 6 +/- 0.5 compared to a solution in methanol. The enhancement was independent of sphere diameter. Cinnamate had a much lower enhancement, about 1.5. The enhancement correlates with fluorescence yield vs. dielectric constant in organic solvents: the adsorbed chromophore acts as if it were surrounded by a material of dielectric constant less than 2, in spite of the presence of neighboring water molecules.

  8. Direct Assembly of Hydrophobic Nanoparticles to Multifunctional Structures

    SciTech Connect

    Lu, Zhenda; Yin, Yadong; Chi, Miaofang

    2011-01-01

    We present a general process that allows convenient production of multifunctional composite particles by direct self-assembly of hydrophobic nanoparticles on host nanostructures containing high-density surface thiol groups. Hydrophobic nanoparticles of various compositions and combinations can be directly assembled onto the host surface through the strong coordination interactions between metal cations and thiol groups. The resulting structures can be further conveniently overcoated with a layer of normal silica to stabilize the assemblies and render them highly dispersible in water for biomedical applications. As the entire fabrication process does not involve complicated surface modification procedures, the hydrophobic ligands on the nanoparticles are not disturbed significantly so that they retain their original properties such as highly efficient luminescence. Many complex composite nanostructures with tailored functions can be efficiently produced by using this versatile approach. For example, multifunctional nonspherical nanostructures can be efficiently produced by using mercapto-silica coated nano-objects of arbitrary shapes as hosts for immobilizing functional nanoparticles. Multilayer structures can also be achieved by repeating the mercapto-silica coating and nanoparticle immobilization processes. Such assembly approach will provide the research community a highly versatile, configurable, scalable, and reproducible process for the preparation of various multifunctional structures.

  9. Water transport through functionalized nanotubes with tunable hydrophobicity

    SciTech Connect

    Moskowitz, Ian; Snyder, Mark A.; Mittal, Jeetain

    2014-11-14

    Molecular dynamics simulations are used to study the occupancy and flow of water through nanotubes comprised of hydrophobic and hydrophilic atoms, which are arranged on a honeycomb lattice to mimic functionalized carbon nanotubes (CNTs). We consider single-file motion of TIP3P water through narrow channels of (6,6) CNTs with varying fractions (f) of hydrophilic atoms. Various arrangements of hydrophilic atoms are used to create heterogeneous nanotubes with separate hydrophobic/hydrophilic domains along the tube as well as random mixtures of the two types of atoms. The water occupancy inside the nanotube channel is found to vary nonlinearly as a function of f, and a small fraction of hydrophilic atoms (f ≈ 0.4) are sufficient to induce spontaneous and continuous filling of the nanotube. Interestingly, the average number of water molecules inside the channel and water flux through the nanotube are less sensitive to the specific arrangement of hydrophilic atoms than to the fraction, f. Two different regimes are observed for the water flux dependence on f – an approximately linear increase in flux as a function of f for f < 0.4, and almost no change in flux for higher f values, similar to the change in water occupancy. We are able to define an effective interaction strength between nanotube atoms and water's oxygen, based on a linear combination of interaction strengths between hydrophobic and hydrophilic nanotube atoms and water, that can quantitatively capture the observed behavior.

  10. On the Mechanism of Hydrophobic Association of Nanoscopic Solutes

    SciTech Connect

    Choudhury, Niharendu; Pettitt, Bernard M.

    2005-04-07

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The hydration behavior of two planar nanoscopic hydrophobic solutes in liquid water at normal temperature and pressure is investigated by calculating the potential of mean force between them at constant pressure as a function of the solute-solvent interaction potential. The importance of the effect of weak attractive interactions between the solute atoms and the solvent on the hydration behavior is clearly demonstrated. We focus on the underlying mechanism behind the contrasting results obtained in various recent experimental and computational studies on water near hydrophobic solutes. The length scale where crossover from a solvent separated state to the contact pair state occurs is shown to depend on the solute sizes as well as on details of the solute-solvent interaction. We find the mechanism for attractive mean forces between the plates is very different depending on the nature of the solute-solvent interaction which has implications for the mechanism of the hydrophobic effect for biomolecules.

  11. Marginally hydrophobic transmembrane α-helices shaping membrane protein folding

    PubMed Central

    De Marothy, Minttu T; Elofsson, Arne

    2015-01-01

    Cells have developed an incredible machinery to facilitate the insertion of membrane proteins into the membrane. While we have a fairly good understanding of the mechanism and determinants of membrane integration, more data is needed to understand the insertion of membrane proteins with more complex insertion and folding pathways. This review will focus on marginally hydrophobic transmembrane helices and their influence on membrane protein folding. These weakly hydrophobic transmembrane segments are by themselves not recognized by the translocon and therefore rely on local sequence context for membrane integration. How can such segments reside within the membrane? We will discuss this in the light of features found in the protein itself as well as the environment it resides in. Several characteristics in proteins have been described to influence the insertion of marginally hydrophobic helices. Additionally, the influence of biological membranes is significant. To begin with, the actual cost for having polar groups within the membrane may not be as high as expected; the presence of proteins in the membrane as well as characteristics of some amino acids may enable a transmembrane helix to harbor a charged residue. The lipid environment has also been shown to directly influence the topology as well as membrane boundaries of transmembrane helices—implying a dynamic relationship between membrane proteins and their environment. PMID:25970811

  12. Phenylalanine functionalized zwitterionic monolith for hydrophobic interaction electrochromatography.

    PubMed

    Wang, Jiabin; Jia, Wenchao; Lin, Xucong; Wu, Xiaoping; Xie, Zenghong

    2013-12-01

    A novel phenylalanine (Phe) functionalized zwitterionic monolith for hydrophobic electrochromatography was prepared by a two-step procedure involving the synthesis of glycidyl methacrylate based polymer monolith and subsequent on-column chemical modification with Phe via ring-opening reaction of epoxides. Benefitting from the hydrophobicity of both methacrylate-based matrix and aromatic group of Phe, this monolith could exhibit good hydrophobic interaction for the separation. Typical RP chromatographic behavior was observed toward various solutes. The well-controlled cathodic or anodic EOF of the prepared column could be facilely switched by altering the pH values of running buffers. The separation mechanism of this Phe functionalized zwitterionic monolith is discussed in detail. Two mixed-mode mechanisms of RP/cation exchange and RP/anion exchange could be further realized on the same monolith in different pH condition of the mobile phase. Versatile separation capabilities of neutral, basic, and acidic analytes have been successfully achieved in this zwitterionic monolith by CEC method. PMID:24242631

  13. Probing the hydrophobic effect of noncovalent complexes by mass spectrometry.

    PubMed

    Bich, Claudia; Baer, Samuel; Jecklin, Matthias C; Zenobi, Renato

    2010-02-01

    The study of noncovalent interactions by mass spectrometry has become an active field of research in recent years. The role of the different noncovalent intermolecular forces is not yet fully understood since they tend to be modulated upon transfer into the gas phase. The hydrophobic effect, which plays a major role in protein folding, adhesion of lipid bilayers, etc., is absent in the gas phase. Here, noncovalent complexes with different types of interaction forces were investigated by mass spectrometry and compared with the complex present in solution. Creatine kinase (CK), glutathione S-transferase (GST), ribonuclease S (RNase S), and leucine zipper (LZ), which have dissociation constants in the nM range, were studied by native nanoelectrospray mass spectrometry (nanoESI-MS) and matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) combined with chemical cross-linking (XL). Complexes interacting with hydrogen bonds survived the transfer into gas phase intact and were observed by nanoESI-MS. Complexes that are bound largely by the hydrophobic effect in solution were not detected or only at very low intensity. Complexes with mixed polar and hydrophobic interactions were detected by nanoESI-MS, most likely due to the contribution from polar interactions. All noncovalent complexes could easily be studied by XL MALDI-MS, which demonstrates that the noncovalently bound complexes are conserved, and a real "snap-shot" of the situation in solution can be obtained. PMID:19931466

  14. Hydrophobic Core Flexibility Modulates Enzyme Activity in HIV-1 Protease

    SciTech Connect

    Mittal, Seema; Cai, Yufeng; Nalam, Madhavi N.L.; Bolon, Daniel N.A.; Schiffer, Celia A.

    2012-09-11

    Human immunodeficiency virus Type-1 (HIV-1) protease is crucial for viral maturation and infectivity. Studies of protease dynamics suggest that the rearrangement of the hydrophobic core is essential for enzyme activity. Many mutations in the hydrophobic core are also associated with drug resistance and may modulate the core flexibility. To test the role of flexibility in protease activity, pairs of cysteines were introduced at the interfaces of flexible regions remote from the active site. Disulfide bond formation was confirmed by crystal structures and by alkylation of free cysteines and mass spectrometry. Oxidized and reduced crystal structures of these variants show the overall structure of the protease is retained. However, cross-linking the cysteines led to drastic loss in enzyme activity, which was regained upon reducing the disulfide cross-links. Molecular dynamics simulations showed that altered dynamics propagated throughout the enzyme from the engineered disulfide. Thus, altered flexibility within the hydrophobic core can modulate HIV-1 protease activity, supporting the hypothesis that drug resistant mutations distal from the active site can alter the balance between substrate turnover and inhibitor binding by modulating enzyme activity.

  15. Cononsolvency behavior of hydrophobes in water + methanol mixtures.

    PubMed

    Mochizuki, Kenji; Koga, Kenichiro

    2016-06-28

    The molecular origin of cononsolvency behavior is explored using molecular dynamics simulations. Cononsolvency behavior in aggregations of methane molecules and conformational changes of those clusters dissolved in water + methanol mixtures are confirmed by re-entrant changes in the solvent-mediated interactions with increasing methanol concentration. The results indicate that the cononsolvency behavior arises from the solute-solute hydrophobic interactions rather than other interactions such as solute-solvent hydrophilic interactions. Furthermore, we show that even the van der Waals interaction is not necessary to induce the cononsolvency behavior by investigating the dimerization process of repulsive cavities. The non-monotonic change of the solvent-mediated interaction results from the difference in the concentration dependencies of excess chemical potentials between an isolated methane and methane clusters. The concentration dependencies of the excess chemical potentials are decomposed into contributions from various intermolecular effective interactions through the framework of the Kirkwood-Buff theory, and then we show that the change of the relative magnitude between hydrophobe-methanol and hydrophobe-water effective interactions with increasing methanol concentration is responsible for the cononsolvency behavior. PMID:27251342

  16. The mechanism study of efficient degradation of hydrophobic nonylphenol in solution by a chemical-free technology of sonophotolysis.

    PubMed

    Xu, L J; Chu, W; Lee, Po-Heng; Wang, Jian

    2016-05-01

    Nonylphenol is a hydrophobic endocrine disrupting compound, which can inhibit the growth of sewage bacteria in biological processes. This study investigated the degradation of 4-n-nonylphenol (NP) in water by a chemical-free technology of sonophotolysis with emphasis on the impacts of several important parameters, including light intensity, solution pH, two commonly seen inorganic ions (i.e. NO3(-) and HCO3(-)), and principally on the examination of degradation mechanisms. It was found that, solution pH could significantly influence both NP degradation efficiency and the synergistic effect of sonophotolytic process, where higher synergistic effect was obtained at more acidic condition. In addition, the presence of NO3(-) accelerated NP degradation by both acting as a photosensitizer and providing NO2 radicals, while HCO3(-) had little effect on NP degradation. Identification of intermediates of NP degradation indicated that NP sonophotolysis was mainly initiated by the formation of hydroxy-NP, and a new intermediate di-hydroxy-NP was identified for the first time ever in this study. Through thermodynamic analysis, results indicated that both ortho- and meta-hydroxy-NP species can coexist in the solution but the ortho-4-NBZQ (4-nonyl-benzoquinone) is dominant. In addition, the mechanism of ortho-hydroxy-NP formation was suggested by the addition of HO and H radicals. PMID:26855185

  17. Unexpected in-situ Free Radical Generation and Catalysis to Ag/Polymer Nanocomposite

    NASA Astrophysics Data System (ADS)

    Pang, Yifan; Wei, Ruixue; Wang, Jintao; Wei, Liuhe; Li, Chunhui

    2015-07-01

    In this study, we discover unexpectedly that simple reaction of AgNO3 with oleic acid (OA) without solvent and surfactant could generate alkyl free radical which can catalyze double-bond polymerization of OA to form 1D polymeric oleic acid (POA) chain. In certain conditions, these POA chains circumvolute tightly each other to form microspheres and micro-plates in which monodisperse 4-5 nm Ag nanoparticles (NPs) were absorbed. It has been revealed that alkyl free radical generated during the redox reaction of carboxyl group of OA with Ag+ at relative low temperature. Then, the alkyl free radical catalyzed the double-bond polymerization of OA when the reaction temperature was further increased. Different from commonly-seen hydrophobic nanoparticles prepared in oleic acid-based microemulsion system, the nanocomposites cannot dispersed in n-hexane and could dispersed in ethanol and THF. The unusual dispersion behavior has been explained in terms of their structure and polarity of POA chain. The method combines the nucleation of Ag nanoparticles and the polymerization of monomer in a facile one-pot reaction, which provides a novel way for metal-polymer microsphere nanocomposite with low-cost, easy-operation and high-yield.

  18. Unexpected in-situ Free Radical Generation and Catalysis to Ag/Polymer Nanocomposite

    PubMed Central

    Pang, Yifan; Wei, Ruixue; Wang, Jintao; Wei, Liuhe; Li, Chunhui

    2015-01-01

    In this study, we discover unexpectedly that simple reaction of AgNO3 with oleic acid (OA) without solvent and surfactant could generate alkyl free radical which can catalyze double-bond polymerization of OA to form 1D polymeric oleic acid (POA) chain. In certain conditions, these POA chains circumvolute tightly each other to form microspheres and micro-plates in which monodisperse 4-5 nm Ag nanoparticles (NPs) were absorbed. It has been revealed that alkyl free radical generated during the redox reaction of carboxyl group of OA with Ag+ at relative low temperature. Then, the alkyl free radical catalyzed the double-bond polymerization of OA when the reaction temperature was further increased. Different from commonly-seen hydrophobic nanoparticles prepared in oleic acid-based microemulsion system, the nanocomposites cannot dispersed in n-hexane and could dispersed in ethanol and THF. The unusual dispersion behavior has been explained in terms of their structure and polarity of POA chain. The method combines the nucleation of Ag nanoparticles and the polymerization of monomer in a facile one-pot reaction, which provides a novel way for metal-polymer microsphere nanocomposite with low-cost, easy-operation and high-yield. PMID:26160118

  19. Free-radical-mediated protein inactivation and recovery during protein photoencapsulation.

    PubMed

    Lin, Chien-Chi; Sawicki, Suzanne M; Metters, Andrew T

    2008-01-01

    Photoencapsulation of protein therapeutics is very attractive for preparing biomolecule-loaded hydrogels for a variety of biomedical applications. However, detrimental effects of highly active radical species generated during photoencapsulation must be carefully evaluated to maintain efficient hydrogel cross-linking while preserving the structure and bioactivity of encapsulated biomolecules. Here, we examine the free-radical-mediated inactivation and incomplete release of proteins from photocurable hydrogels utilizing lysozyme as a conservative model system. Various protein photoencapsulation conditions were tested to determine the factors affecting lysozyme structural integrity and bioactivity. It was found that a portion of the lysozyme becomes conjugated to polymer chains at high photoinitiator concentrations and long polymerization times. We also found that the more hydrophilic photoinitiator Irgacure-2959 (I-2959, 2-hydroxy-1-[4-(hydroxyethoxy)phenyl]-2-methyl-1-propanone) causes more damage to lysozyme compared to the hydrophobic photoinitiator Irgacure-651 (I-651, 2,2-dimethoxy-2-phenylacetophenone), even though I-2959 has been previously shown to be more cytocompatible. Furthermore, while nonacrylated PEG provides only limited protection from the denaturing free radicals that are present during hydrogel curing, acrylated PEG macromers effectively preserve lysozyme structural integrity and bioactivity in the presence of either photoinitiator. Overall, these findings indicate how photopolymerization conditions (e.g., photoinitiator type and concentration, UV exposure time, etc.) must be optimized to obtain a functional hydrogel device that can preserve protein bioactivity and provide maximal protein release. PMID:18088094

  20. 13C Nuclear Magnetic Resonance and Electron Paramagnetic Spectroscopic Comparison of Hydrophobic Acid, Transphilic Acid, and Reverse Osmosis May 2012 Isolates of Organic Matter from the Suwannee River

    PubMed Central

    Nwosu, Ugwumsinachi G.; Cook, Robert L.

    2015-01-01

    Abstract Dissolved organic matter (DOM) is found in most natural waters at concentrations low enough to make DOM isolation methodologies critical to full analytical characterization and preservation. During the last few decades, two major protocols have been developed for the extraction of DOM isolates from natural waters. These methods utilize XAD resins and reverse osmosis (RO). In this work, the hydrophobic acid (May 2012 HPOA) and transphilic acid (May 2012 TPIA) isolates from XAD-8 and XAD-4 resins, respectively, were compared with the RO (May 2012 RO) natural organic matter isolate of the Suwannee River water using 13C nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopies. 13C NMR analysis showed that the May 2012 RO isolate could be viewed as a hybrid of the more hydrophobic May 2012 HPOA isolate and more hydrophilic May 2012 TPIA isolate. The May 2012 HPOA isolate is shown to be higher in alkyl and aromatic moieties, while the May 2012 TPIA isolate is higher in O-alkyl moieties. EPR analysis revealed that the May 2012 TPIA and, in particular, May 2012 HPOA isolates had higher radical concentrations than the May 2012 RO isolate. It is postulated that some of the radical concentrations came from the use of base during the isolation procedures, especially in the XAD method. PMID:25565761

  1. On the Definition of Hydrophobicity, Conditions for Porosity and the Attachment of Hydrophobic Particles to the Surface of Water

    NASA Astrophysics Data System (ADS)

    McHale, Glen; Shirtcliffe, Neil J.; Newton, Michael I.; Hamlett, Christopher

    2010-05-01

    Teflon® is usually regarded as the classic example of what is meant by a hydrophobic surface. However, it has recently been argued on the basis of experimental data that hydrophobic solids can have a significant attraction to the surface of water and, in that sense, could be regarded as relatively hydrophilic. The meaning of the terms "hydrophobic" and "hydrophilic" differ between subject fields, but in surface science they are related to concepts of wetting. Understanding why a solid surface commonly described as "hydrophobic" (i.e. water-fearing) can behave in a "hydrophilic" (i.e. water-liking) manner is important in understanding the conditions under which water will penetrate a granular material, such as a sandy soil, or will collect and transport away the grains of the material thus eroding the surface. In this work, we clarify what is meant by hydrophobic and hydrophilic and show why these terms often do not simply indicate surface chemistry, but can include assumptions about the relative orientation of surfaces, and surface rigidity and topography. We will show why a contact angle below 90 degrees, commonly referred to as hydrophilic, does not necessarily result in water penetration into a fixed bed of solid grains. We will also describe a key experiment showing that when smooth solid films of Teflon® are contacted by a droplet of water, the solid quasi-instantaneously wraps around the droplet. This effect can be understood as a direct consequence of the attempt of the solid-water-air interfaces to minimize surface free energy, but with the usual restriction of a rigid solid substrate relaxed; this wrapping is energetically favored for all solids which have a Young's law contact angle less than 180 degrees. In this sense, we argue, all solids can be regarded as absolutely hydrophilic (to some extent) and that a contact angle of 90 degrees does not provide a simple classification of the transition from hydrophilic to hydrophobic tendencies unless roughness

  2. Tunable Surface Hydrophobicity and Fluid Transport through Nanoporous Membranes

    NASA Astrophysics Data System (ADS)

    Ostrowski, Joseph H. J.

    There are more than three billion people across the globe that struggle to obtain clean drinkable water. One of the most promising avenues for generating potable water is through reverse osmosis and nanofiltration. Both solutions require a semipermeable membrane that prohibits passage of unwanted solute particles but allows passage of the solvent. Atomically thin two-dimensional membranes based on porous graphene show great promise as semipermeable materials, but modeling fluid flow on length scales between the microscopic (nanometer and smaller) and macroscopic (micron and larger) regimes presents formidable challenges. This thesis explores both equilibrium and nonequilibrium aspects of this problem and develops new methodology for simulating systems away from thermal equilibrium. First, we hypothesize that there is a wetting penalty for water as it tries to breach a sheet of graphene that should be naturally hydrophobic. By using equilibrium molecular dynamics simulations, we show that the hydrophobicity depends sensitively on the degree of electrical doping, offering an opportunity to tune the hydrophobic effect of graphene using small amounts of doping. The wetting contact angle, a measure of hydrophobicity, changes dramatically with the voltage applied to single layer graphene. We find that the sensitivity of the hydrophobic effect to voltage depends not on hydrogen bonding motifs at the interface between graphene and water, but instead on a phenomenon known as electrowetting. The theory of electrowetting predicts that the difference in surface tensions that defines the contact angle is quartic in the voltage, rather than quadratic, as it would be in bilayer graphene or in a two-dimensional metal. To explore the nonequilibrium aspects of fluid passage through atomically thin membranes, we developed a molecular dynamics methodology for simulating fluid flow at constant flux based on Gauss's principle of least constraint. This method develops microscopic

  3. A Mechanochemical Switch to Control Radical Intermediates

    PubMed Central

    2015-01-01

    B12-dependent enzymes employ radical species with exceptional prowess to catalyze some of the most chemically challenging, thermodynamically unfavorable reactions. However, dealing with highly reactive intermediates is an extremely demanding task, requiring sophisticated control strategies to prevent unwanted side reactions. Using hybrid quantum mechanical/molecular mechanical simulations, we follow the full catalytic cycle of an AdoB12-dependent enzyme and present the details of a mechanism that utilizes a highly effective mechanochemical switch. When the switch is “off”, the 5′-deoxyadenosyl radical moiety is stabilized by releasing the internal strain of an enzyme-imposed conformation. Turning the switch “on,” the enzyme environment becomes the driving force to impose a distinct conformation of the 5′-deoxyadenosyl radical to avoid deleterious radical transfer. This mechanochemical switch illustrates the elaborate way in which enzymes attain selectivity of extremely chemically challenging reactions. PMID:24846280

  4. A mechanochemical switch to control radical intermediates.

    PubMed

    Brunk, Elizabeth; Kellett, Whitney F; Richards, Nigel G J; Rothlisberger, Ursula

    2014-06-17

    B₁₂-dependent enzymes employ radical species with exceptional prowess to catalyze some of the most chemically challenging, thermodynamically unfavorable reactions. However, dealing with highly reactive intermediates is an extremely demanding task, requiring sophisticated control strategies to prevent unwanted side reactions. Using hybrid quantum mechanical/molecular mechanical simulations, we follow the full catalytic cycle of an AdoB₁₂-dependent enzyme and present the details of a mechanism that utilizes a highly effective mechanochemical switch. When the switch is "off", the 5'-deoxyadenosyl radical moiety is stabilized by releasing the internal strain of an enzyme-imposed conformation. Turning the switch "on," the enzyme environment becomes the driving force to impose a distinct conformation of the 5'-deoxyadenosyl radical to avoid deleterious radical transfer. This mechanochemical switch illustrates the elaborate way in which enzymes attain selectivity of extremely chemically challenging reactions. PMID:24846280

  5. The Electronic Spectrum of the Fulvenallenyl Radical.

    PubMed

    Chakraborty, Arghya; Fulara, Jan; Maier, John P

    2016-01-01

    The fulvenallenyl radical was produced in 6 K neon matrices after mass-selective deposition of C7H5(-) and C7H5(+) generated from organic precursors in a hot cathode ion source. Absorption bands commencing at λ=401.3 nm were detected as a result of photodetachment of electrons from the deposited C7H5(-) and also by neutralization of C7H5(+) in the matrix. The absorption system is assigned to the 1 (2)B1 ←X (2)B1 transition of the fulvenallenyl radical on the basis of electronic excitation energies calculated with the MS-CASPT2 method. The vibrational excitation bands detected in the spectrum concur with the structure of the fulvenallenyl radical. Employing DFT calculations, it is found that the fulvenallenyl anion and its radical are the global minima on the potential energy surface among plausible structures of C7H5. PMID:26593635

  6. Fast beam studies of free radical photodissociation

    SciTech Connect

    Neumark, D.M.

    1993-12-01

    The authors have developed a novel technique for studying the photodissociation spectroscopy and dynamics of free radicals. In these experiments, radicals are generated by laser photodetachment of a fast (6-8 keV) mass-selected negative ion beam. The resulting radicals are photodissociated with a second laser, and the photofragments are collected and detected with high efficiency using a microchannel plate detector. The overall process is: ABC{sup -} {yields} ABC + e{sup -} {yields} A + BC, AB + C. Two types of fragment detection schemes are used. To map out the photodissociation cross-section of the radical, the photodissociation laser is scanned and the total photofragment yield is measured as a function of wavelength. In other experiments, the photodissociation frequency is fixed and the photofragment masses, kinetic energy release, and scattering angle is determined for each photodissociation event.

  7. [Robotic laparoscopic radical prostatectomy: update 2008].

    PubMed

    John, H

    2008-03-01

    Radical prostatectomy aims for optimal tumor control, minimal morbidity, and best functional outcomes of urinary continence and erection. With the introduction of the robotic daVinci surgical system an impressive shift from open radical to robotic laparoscopic prostatectomy (RLP) has occurred especially in the USA. Unfortunately, initial and instrumental costs and maintenance fees of the system are still very high. Compared with the open retropubic approach, RLP has a similar short-term outcome in oncological control, potency, and urinary continence but potentially distinctly favorable benefits in blood loss, transfusion rates, and minor complications. However, RLP is still in its infancy compared to open radical prostatectomy. Inter-institutional trials with the same validated questionnaires are necessary for the future to evaluate oncological and functional results conclusively. The individual surgeon's experience with his routinely preferred technique remains the crucial key for a successful oncological and functional outcome in radical prostatectomy, whatever technology is used. PMID:18231769

  8. HETEROGENOUS PHOTOREACTION OF FORMALDEHYDE WITH HYDROXYL RADICALS

    EPA Science Inventory

    Atmospheric heterogeneous photoreactions occur between formaldehyde and hydroxyl radicals to produce formic acid. hese photoreactions not only occur in clouds, but also in other tropospheric hydrometeors such as precipitation and dew droplets. xperiments were performed by irradia...

  9. [Pulmonary toxicity of free radicals of oxygen].

    PubMed

    Housset, B; Junod, A

    1983-01-01

    Free oxygen radicals result from aerobic cellular metabolism; their toxicity is prevented by immediate degradation due to an endless variety of biochemical systems. The nature of these radicals, their cellular production as well as the defence mechanism which oppose their toxic effects are successively and briefly analysed. The potential role of these radicals in the genesis of different lung diseases is still poorly understood. However, certain toxic agents (oxygen, gas pollutants, ionising radiation, toxic products) can act as a whole or at least in part by their intermediaries. The experimental arguments in favour of this hypothesis are reviewed in passing. If the relative importance of the toxic mechanism is still imprecise, free radicals are certainly implicated in pulmonary disease and constitute a new aspect of respiratory patho-physiology. PMID:6189156

  10. Innovation Type, Radicalness, and the Adoption Process.

    ERIC Educational Resources Information Center

    Damanpour, Fariborz

    1988-01-01

    Reviews studies on the impact of organizational factors on the adoption of innovations along three dimensions (innovation type, innovation radicalness, and stages of adoption), finding considerable agreement. Proposes a research agenda for future studies. (SR)

  11. RADICALLY CONTESTED ASSERTIONS IN ECOSYSTEM MANAGEMENT

    EPA Science Inventory

    Ecosystem management is a magnet for controversy, in part because some of its formulations rest on questionable assertions that are radically contested. These assertions are important to understanding much of the conflict surrounding ecosystem management and, therrefore, deserve...

  12. Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

    NASA Technical Reports Server (NTRS)

    Kumar, Nitin; Couzis, Alex; Maldareili, Charles; Singh, Bhim (Technical Monitor)

    2001-01-01

    Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid surfaces. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants; (i.e., amphiphiles with a hydrophobic moiety consisting of an extended chain of (aliphatic) methylene -CH2- groups attached to a large polar group to give aqueous solubility) are capable of reducing the contact angles on surfaces which are not very hydrophobic, but do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm, polyethylene or self assembled monolayers. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3) and an extended ethoxylate (-(OCH2CH2)a-) polar group in the form of a chain with four or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (termed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread. We propose that the trisiloxane surfactants superspread because their structure allows them to strongly lower the high hydrophobic solid/aqueous tension when they adsorb to the solid surface. When the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross-sectional area of the disk is larger than that of the extended ethoxylate chain, the disks can form a space-filling mat on the surface which

  13. Catalytic Radical Domino Reactions in Organic Synthesis

    PubMed Central

    Sebren, Leanne J.; Devery, James J.; Stephenson, Corey R.J.

    2014-01-01

    Catalytic radical-based domino reactions represent important advances in synthetic organic chemistry. Their development benefits synthesis by providing atom- and step-economical methods to complex molecules. Intricate combinations of radical, cationic, anionic, oxidative/reductive, and transition metal mechanistic steps result in cyclizations, additions, fragmentations, ring-expansions, and rearrangements. This Perspective summarizes recent developments in the field of catalytic domino processes. PMID:24587964

  14. Regioselective Radical Arylation of 3-Hydroxypyridines.

    PubMed

    Fürst, Michael C D; Bock, Leonard R; Heinrich, Markus R

    2016-07-01

    The titanium(III)-mediated radical arylation of 3-hydroxypyridines was found to proceed with high regioselectivity for the 2-position. Using aryldiazonium chlorides, which were prepared from the corresponding anilines, as aryl radical sources, a range of 3-hydroxy-2-phenylpyridines were obtained in moderate to good yields under simple reaction conditions. Reactions of ortho-carboxylic ester substituted phenyldiazonium salts directly provided tricyclic benzopyranopyridinones. PMID:27258367

  15. The stabilization energies of polyenyl radicals

    NASA Astrophysics Data System (ADS)

    Luo, Yu-Ran; Holmes, John L.

    1994-10-01

    The resonance stabilization energies, Es, of polyenyl radicals can be estimated by the equation Es( N)=-13.2+[3.95-15.8(2) -2/ n] kcal mol -1, where N is the number of C, C-π bonds in the polyenyl radicals. This correlation has been extended for predicting the weakest HC, CC and COH bond dissociation energies in vitamin A and similar compounds.

  16. Fast rotational motion of water molecules increases ordering of hydrophobes in solutions and may cause hydrophobic chains to collapse

    NASA Astrophysics Data System (ADS)

    Mohorič, Tomaž; Bren, Urban; Vlachy, Vojko

    2015-12-01

    Using the molecular dynamics simulations with separate thermostats for translational and rotational degrees of freedom, we investigate the effects of water's rotational motion on the interaction among Lennard-Jones solutes. The situation with rotational temperature higher than the translational one (TR > TT) is mimicking the effects of microwaves on model solutions. Molecular dynamics simulations suggest that solutions of Lennard-Jones solutes become increasingly more structured with the rise in TR, while keeping the TT constant. This is evidenced by an increase of the first and the second peak of the solute-solute radial distribution function. In addition, the first peak moves toward slightly larger distances; the effect seems to be caused by the destabilization of water molecules in the first hydration shell around hydrophobic solutes. More evidence of strong effects of the rotationally excited water is provided by the simulations of short hydrophobic polymers, which upon an increase in TR assume more compact conformations. In these simulations, we see the re-distribution of water molecules, which escape from hydrophobic "pockets" to better solvate the solvent exposed monomers.

  17. Fast rotational motion of water molecules increases ordering of hydrophobes in solutions and may cause hydrophobic chains to collapse.

    PubMed

    Mohorič, Tomaž; Bren, Urban; Vlachy, Vojko

    2015-12-28

    Using the molecular dynamics simulations with separate thermostats for translational and rotational degrees of freedom, we investigate the effects of water's rotational motion on the interaction among Lennard-Jones solutes. The situation with rotational temperature higher than the translational one (TR > TT) is mimicking the effects of microwaves on model solutions. Molecular dynamics simulations suggest that solutions of Lennard-Jones solutes become increasingly more structured with the rise in TR, while keeping the TT constant. This is evidenced by an increase of the first and the second peak of the solute-solute radial distribution function. In addition, the first peak moves toward slightly larger distances; the effect seems to be caused by the destabilization of water molecules in the first hydration shell around hydrophobic solutes. More evidence of strong effects of the rotationally excited water is provided by the simulations of short hydrophobic polymers, which upon an increase in TR assume more compact conformations. In these simulations, we see the re-distribution of water molecules, which escape from hydrophobic "pockets" to better solvate the solvent exposed monomers. PMID:26723695

  18. Incorporation of hydrophobized mineral particles in activated sludge flocs: a way to assess ballasting efficiency.

    PubMed

    Defontaine, G; Thormann, J; Lartiges, B S; El Samrani, A G; Barrs, O

    2005-01-01

    The role of mineral surface hydrophobicity in attachment to activated sludge flocs was investigated. Fluorite and quartz particles of similar granulometry were hydrophobized by adsorbing sodium oleate and dodecylamine chloride, respectively. Mineral hydrophobicity was assessed by flotation expriments. The attachment of particles to microbial flocs was determined by optical microscopy. The results indicate that hydrophobized particles are always better incorporated within activated sludge flocs than non-coated particles. A comparison with Aquatal particles used as sludge ballast reveals that hydrophobized minerals are associated with microbial flocs to the same extent. PMID:16459790

  19. Inactivation of Bacillus atrophaeus by OH radicals

    NASA Astrophysics Data System (ADS)

    Ono, Ryo; Yonetamari, Kenta; Tokumitsu, Yusuke; Yonemori, Seiya; Yasuda, Hachiro; Mizuno, Akira

    2016-08-01

    The inactivation of Bacillus atrophaeus by OH radicals is measured. This study aims to evaluate the bactericidal effects of OH radicals produced by atmospheric-pressure nonthermal plasma widely used for plasma medicine; however, in this study, OH radicals are produced by vacuum ultraviolet (VUV) photolysis of water vapor instead of plasma to allow the production of OH radicals with almost no other reactive species. A 172 nm VUV light from a Xe2 excimer lamp irradiates a He–H2O mixture flowing in a quartz tube to photodissociate H2O to produce OH, H, O, HO2, H2O2, and O3. The produced reactive oxygen species (ROS) flow out of the quartz tube nozzle to the bacteria on an agar plate and cause inactivation. The inactivation by OH radicals among the six ROS is observed by properly setting the experimental conditions with the help of simulations calculating the ROS densities. A 30 s treatment with approximately 0.1 ppm OH radicals causes visible inactivation.

  20. Hydroxyl radical oxidation of feruloylated arabinoxylan.

    PubMed

    Bagdi, Attila; Tömösközi, Sándor; Nyström, Laura

    2016-11-01

    Feruloylated arabinoxylan (AX) has a unique capacity to form covalent gels in the presence of certain oxidizing agents. The present study demonstrates that hydroxyl radical oxidation does not provoke ferulic acid dimerization and thus oxidative gelation. We studied the hydroxyl radical mediated oxidation of an alkali-extracted AX preparation (purity: 92g/100g dry matter) that showed gel-forming capability upon peroxidase/hydrogen peroxide treatment. Hydroxyl radicals were produced with ascorbate-driven Fenton reaction and the radical formation was monitored with electron paramagnetic resonance, using a POBN/EtOH spin trapping system. Oxidation was carried out at different catalytic concentrations of iron (50 and 100μM) and at different temperatures (20°C, 50°C, and 80°C). It was demonstrated that hydroxyl radical oxidation does not provoke gel formation, but viscosity decrease in AX solution, which suggests polymer degradation. Furthermore, it was demonstrated that hydroxyl radical formation in AX solution can be initiated merely by increasing temperature. PMID:27516272

  1. Radicalization and Radical Catalysis of Biomass Sugars: Insights from First-principles Studies

    NASA Astrophysics Data System (ADS)

    Yang, Gang; Zhu, Chang; Zou, Xianli; Zhou, Lijun

    2016-07-01

    Ab initio and density functional calculations are conducted to investigate the radicalization processes and radical catalysis of biomass sugars. Structural alterations due to radicalization generally focus on the radicalized sites, and radicalization affects H-bonds in D-fructofuranose more than in D-glucopyranose, potentially with outcome of new H-bonds. Performances of different functionals and basis sets are evaluated for all radicalization processes, and enthalpy changes and Gibbs free energies for these processes are presented with high accuracy, which can be referenced for subsequent experimental and theoretical studies. It shows that radicalization can be utilized for direct transformation of biomass sugars, and for each sugar, C rather than O sites are always preferred for radicalization, thus suggesting the possibility to activate C-H bonds of biomass sugars. Radical catalysis is further combined with Brønsted acids, and it clearly states that functionalization fundamentally regulates the catalytic effects of biomass sugars. In presence of explicit water molecules, functionalization significantly affects the activation barriers and reaction energies of protonation rather than dehydration steps. Tertiary butyl and phenyl groups with large steric hindrances or hydroxyl and amino groups resulting in high stabilities for protonation products drive the protonation steps to occur facilely at ambient conditions.

  2. Selective Radical-Radical Cross-Couplings: Design of a Formal β-Mannich Reaction.

    PubMed

    Jeffrey, Jenna L; Petronijević, Filip R; MacMillan, David W C

    2015-07-01

    A direct β-coupling of cyclic ketones with imines has been accomplished via the synergistic combination of photoredox catalysis and organocatalysis. Transient β-enaminyl radicals derived from ketones via enamine and oxidative photoredox catalysis readily combine with persistent α-amino radicals in a highly selective hetero radical-radical coupling. This novel pathway to γ-aminoketones is predicated upon the use of DABCO as both a base and an electron transfer agent. This protocol also formally allows for the direct synthesis of β-Mannich products via a chemoselective three-component coupling of aryl aldehydes, amines, and ketones. PMID:26075347

  3. Radicalization and Radical Catalysis of Biomass Sugars: Insights from First-principles Studies.

    PubMed

    Yang, Gang; Zhu, Chang; Zou, Xianli; Zhou, Lijun

    2016-01-01

    Ab initio and density functional calculations are conducted to investigate the radicalization processes and radical catalysis of biomass sugars. Structural alterations due to radicalization generally focus on the radicalized sites, and radicalization affects H-bonds in D-fructofuranose more than in D-glucopyranose, potentially with outcome of new H-bonds. Performances of different functionals and basis sets are evaluated for all radicalization processes, and enthalpy changes and Gibbs free energies for these processes are presented with high accuracy, which can be referenced for subsequent experimental and theoretical studies. It shows that radicalization can be utilized for direct transformation of biomass sugars, and for each sugar, C rather than O sites are always preferred for radicalization, thus suggesting the possibility to activate C-H bonds of biomass sugars. Radical catalysis is further combined with Brønsted acids, and it clearly states that functionalization fundamentally regulates the catalytic effects of biomass sugars. In presence of explicit water molecules, functionalization significantly affects the activation barriers and reaction energies of protonation rather than dehydration steps. Tertiary butyl and phenyl groups with large steric hindrances or hydroxyl and amino groups resulting in high stabilities for protonation products drive the protonation steps to occur facilely at ambient conditions. PMID:27405843

  4. Radicalization and Radical Catalysis of Biomass Sugars: Insights from First-principles Studies

    PubMed Central

    Yang, Gang; Zhu, Chang; Zou, Xianli; Zhou, Lijun

    2016-01-01

    Ab initio and density functional calculations are conducted to investigate the radicalization processes and radical catalysis of biomass sugars. Structural alterations due to radicalization generally focus on the radicalized sites, and radicalization affects H-bonds in D-fructofuranose more than in D-glucopyranose, potentially with outcome of new H-bonds. Performances of different functionals and basis sets are evaluated for all radicalization processes, and enthalpy changes and Gibbs free energies for these processes are presented with high accuracy, which can be referenced for subsequent experimental and theoretical studies. It shows that radicalization can be utilized for direct transformation of biomass sugars, and for each sugar, C rather than O sites are always preferred for radicalization, thus suggesting the possibility to activate C-H bonds of biomass sugars. Radical catalysis is further combined with Brønsted acids, and it clearly states that functionalization fundamentally regulates the catalytic effects of biomass sugars. In presence of explicit water molecules, functionalization significantly affects the activation barriers and reaction energies of protonation rather than dehydration steps. Tertiary butyl and phenyl groups with large steric hindrances or hydroxyl and amino groups resulting in high stabilities for protonation products drive the protonation steps to occur facilely at ambient conditions. PMID:27405843

  5. Studies on polyurethane adhesives and surface modification of hydrophobic substrates

    NASA Astrophysics Data System (ADS)

    Krishnamoorthy, Jayaraman

    studies involved making functionalized, thickness-controlled, wettability-controlled multilayers on hydrophobic substrates and the adsorption of carboxylic acid-terminated poly(styrene-b-isoprene) on alumina/silica substrates. Poly(vinyl alcohol) has been shown to adsorb onto hydrophobic surfaces irreversibly due to hydrophobic interactions. This thin semicrystalline coating is chemically modified using acid chlorides, butyl isocyanate and butanal to form thicker and hydrophobic coatings. The products of the modification reactions allow adsorption of a subsequent layer of poly(vinyl alcohol) that could subsequently be hydrophobized. This 2-step (adsorption/chemical modification) allows layer-by-layer deposition to prepare coatings with thickness, chemical structure and wettability control on any hydrophobic surface. Research on adsorption characteristics of carboxylic acid-terminated poly(styrene-b-isoprene) involved syntheses of block copolymers with the functional group present at specific ends. Comparative adsorption studies for carboxylic acid-terminated and hydrogen-terminated block copolymers was carried out on alumina and silica substrates.

  6. Practicing Radical Pedagogy: Balancing Ideals with Institutional Constraints.

    ERIC Educational Resources Information Center

    Sweet, Stephen

    1998-01-01

    Describes radical pedagogy and observes that an overview of "Teaching Sociology" suggests that few teachers fully practice it. Argues that while professors are free to teach radical theory, radical pedagogy is hindered by institutional constraints. Concludes that radical teachers may benefit from remaining more within the confines imposed by their…

  7. Plasma surface modification and hydrophobic barrier coating of paper

    NASA Astrophysics Data System (ADS)

    Sahin, Halil Turgut

    2001-07-01

    Development of new technologies for production of alternative paper properties with minimal environmental hazards was the goal of this project. In this study, the utilization of various chemicals under radio frequency (RF) plasma environments was investigated for creation of hydrophobic barrier properties and deposition of electrically conductive conjugated thin layers on the surface of paper. Four basic approaches have been utilized to impart hydrophobic barriers to the paper without affecting bulk properties; argon plasma treatment after Teflon-like chemical; 1,1,1,2 tetrafluoroethane (TFE) predeposition, carbon tetrafluoride (CF4) plasma treatment after TFE pre-deposition, carbon tetrafluoride plasma treatment alone and octamethylcyclotetrasiloxane (OMCTSO) plasma treatment of paper under an RF-glow discharge. The chosen chemicals were found to enhance the properties of the paper substrates and surface analysis aided explanation of the mechanism of hydrophobic barrier improvements on paper. An attempt was also made to prepare oriented thin films of pi-conjugated polymers on paper surfaces with a pulsed plasma technique for incorporation of electrically conductive layers. Progressive changes in composition, with varying plasma duty cycles during the plasma polymerization, were observed with thiophene. The results of this study provide additional support for the unusually good control of film chemistry available via the pulsed plasma technique. Electrical conductivity measurements indicated that fragmented thiophene films were obtained under mild plasma conditions, but the discontinuous thiophene film was found to be oriented. The electrical behavior of the thiophene derived deposited layer was dramatically improved with chemical doping. Correlation of the changes of paper surface properties with changes in plasma parameters are partially explained by based on surface chemistry, although other structural features of the paper morphology were also affected to some

  8. Hydrophobic and moisture-stable metal–organic frameworks

    SciTech Connect

    Fernandez, Carlos A.; Nune, Satish K.; Annapureddy, Harsha V.; Dang, Liem X.; McGrail, B. Peter; Zheng, Feng; Polikarpov, Evgueni; King, David L.; Freeman, Charles J.; Brooks, Kriston P.

    2015-08-15

    Metal-organic frameworks (MOFs) have proved to be very attractive for applications including gas storage, separation, sensing and catalysis. In particular, CO2 separation from flue gas in post-combustion processes is one of the main focuses of research among the scientific community. One of the major issues that are preventing the successful commercialization of these novel materials (e.g., MgDOBDC and NiDOBDC) is their high affinity towards water that not only compromises gas sorption capacity but also the chemical stability. In this paper, we demonstrate a novel post-synthesis modification approach to modify MOFs towards increasing hydrophobic behavior and chemical stability against moisture without compromising CO2 sorption capacity. Our approach consists of incorporating hydrophobic moieties on the external surface of the MOFs via physical adsorption. The rationale behind this concept is to increase the surface hydrophobicity in the porous materials without the need of introducing bulky functionalities inside the pore which compromises the sorption capacity toward other gases. This allows MOF interaction/sorption of CO2 molecules comparable to unmodified MOFs. We herein report preliminary results on three routinely studied MOF materials [MIL-101(Cr), MgDOBDC and NiDOBDC] demonstrating that the polymer-modified MOFs retain CO2 sorption capacity while reducing the water adsorption up to three times, respect to the un-modified materials, via an equilibrium effect. Furthermore, the water stability of the polymer-functionalized MOFs is significantly higher than the water stability of the bare material. Molecular dynamic simulations demonstrated that this equilibrium effect implies a fundamental and permanent change in the water sorption capacity of MOFs. This approach can also be employed to render moisture stability and selectivity to MOFs that find applications in gas separations, catalysis and sensing where water plays a critical role in compromising MOF

  9. Polydiacetylene Liposomal Aequorin Bioluminescent Device for Detection of Hydrophobic Compounds.

    PubMed

    Yamamoto, Ryoko; Takegami, Shigehiko; Konishi, Atsuko; Horikawa, Hikari; Yonezawa, Sayumi; Kitade, Tatsuya

    2016-06-01

    In this study, a polydiacetylene liposomal aequorin bioluminescent device (PLABD) that functioned through control of the membrane transport of Ca(2+) ions was developed for detecting hydrophobic compounds. In the PLABD, aequorin was encapsulated in an internal water phase and a calcium ionophore (CI) was contained in a hydrophobic region. Membrane transport of Ca(2+) ions across the CI was suppressed by polymerization between diacetylene molecules. On addition of an analyte, the membrane transport of Ca(2+) ions across the CI increased, and Ca(2+) ions from the external water phase could diffuse into the internal water phase via the CI, which resulted in bioluminescence of the aequorin. Lidocaine, procaine, and procainamide were used as model compounds to test the validity of the detection mechanism of the PLABD. When each analyte was added to a suspension of the PLABD, bioluminescence from the aequorin in the PLABD was observed, and the level of this bioluminescence increased with increasing analyte concentration. There was a linear relationship between the logarithm of the analyte concentration and the bioluminescence for all analytes as follows: R = 0.89 from 10 nmol L(-1) to 10 mmol L(-1) for lidocaine, R = 0.66 from 10 nmol L(-1) to 100 μmol L(-1) for procaine, and R = 0.74 from 100 nmol L(-1) to 100 μmol L(-1) for procainamide. Compared to the traditional colorimetric method using polydiacetylene liposome, the PLABD was superior for both the sensitivity and dynamic range. Thus, PLABD is a valid, simple, and sensitive signal generator for detection of hydrophobic compounds that interact with PLABD membranes. PMID:27146598

  10. Hydrophobic and moisture-stable metal-organic frameworks.

    PubMed

    Fernandez, Carlos A; Nune, Satish K; Annapureddy, Harsha V; Dang, Liem X; McGrail, B Peter; Zheng, Feng; Polikarpov, Evgueni; King, David L; Freeman, Charles; Brooks, Kriston P

    2015-08-14

    Metal-organic frameworks (MOFs) have proved to be very attractive for applications including gas storage, separation, sensing and catalysis. In particular, CO(2) separation from flue gas in post-combustion processes is one of the main focuses of research among the scientific community. One of the major issues that are preventing the successful commercialization of these novel materials is their high affinity towards water that not only compromises gas sorption capacity but also the chemical stability. In this paper, we demonstrate a novel post-synthesis modification approach to modify MOFs towards increasing hydrophobic behaviour and chemical stability against moisture without compromising CO(2) sorption capacity. Our approach consists of incorporating hydrophobic moieties on the external surface of the MOFs via physical adsorption. The rationale behind this concept is to increase the surface hydrophobicity in the porous materials without the need of introducing bulky functionalities inside the pore which compromises the sorption capacity toward other gases. We herein report preliminary results on routinely studied MOF materials [MIL-101(Cr) and NiDOBDC] demonstrating that the polymer-modified MOFs retain CO(2) sorption capacity while reducing the water adsorption up to three times, with respect to the un-modified materials, via an equilibrium effect. Furthermore, the water stability of the polymer-functionalized MOFs is significantly higher than the water stability of the bare material. Molecular dynamic simulations demonstrated that this equilibrium effect implies a fundamental and permanent change in the water sorption capacity of MOFs. This approach can also be employed to render moisture stability and selectivity to MOFs that find applications in gas separations, catalysis and sensing where water plays a critical role in compromising MOF performance and recyclability. PMID:25970023

  11. Modelling Soil Water Characteristic Curves for the Investigation of Hydrophobicity

    NASA Astrophysics Data System (ADS)

    Hallin, Ingrid; Matthews, Peter; Laudone, Maurizio; Van Keulen, Geertje; Doerr, Stefan; Francis, Lewis; Dudley, Ed; Gazze, Andrea; Quinn, Gerry; Whalley, Richard; Ashton, Rhys

    2016-04-01

    Soil hydrophobicity presents a major challenge for the future, as it reduces both plant-available water and irrigation efficiency, and can increase flooding hazards and erosion. A collaborative research project has been set up in the UK to study hydrophobicity over a wide range of length scales. At core scale, we are investigating the wetting behaviour of water repellent soils in order to model percolation through hydrophobic pore spaces. To that end, water retention measurements were carried out on both wettable and forcibly-wetted water-repellent soils collected from three locations in England and Wales. The data were then fitted with both the commonly used Van Genuchten model and an alternative model from PoreXpert, a software program that analyses and models porous materials. The Van Genuchten model fits a curve to the data using parameters related to air entry suction, irreducible water content and pore size distribution. By contrast, PoreXpert uses a Boltzmann-annealed simplex to find a best-fit curve based on parameters directly related to the void structure of the soil: the size of the voids, the shape of the void size distribution, and how the voids are connected to each other. Both Van Genuchten and PoreXpert fit the experimental data well, but where Van Genuchten forces an S-shaped curve that can mask small variations, PoreXpert gives a closer fit of no pre-defined shape that captures subtle differences between data points. This allows us to calculate differences in the effective pore and throat size distributions, and provides a mechanistic framework from which to model additional hydrologic behaviour in water repellent soil. Simulations of capillary induced wetting based on these mechanistic postulates are then compared to wicking experiments at the core scale, which can then be upscaled and applied to other soils.

  12. Primordial Oil Slick and the Formation of Hydrophobic Tetrapyrrole Macrocycles

    PubMed Central

    Soares, Ana R. M.; Taniguchi, Masahiko; Chandrashaker, Vanampally

    2012-01-01

    Abstract The functional end products of the extant biosynthesis of tetrapyrrole macrocycles in photosynthetic organisms are hydrophobic: chlorophylls and bacteriochlorophylls. A model for the possible prebiogenesis of hydrophobic analogues of nature's photosynthetic pigments was investigated by reaction of acyclic reactants in five media: aqueous solution (pH 7, 60°C, 24 h); aqueous solution containing 0.1 M decanoic acid (which forms a turbid suspension of vesicles); or aqueous solution accompanied by dodecane, mesitylene, or a five-component organic mixture (each of which forms a phase-separated organic layer). The organic mixture was composed of equimolar quantities of decanoic acid, dodecane, mesitylene, naphthalene, and pentyl acetate. The reaction of 1,5-dimethoxy-3-methylpentan-2,4-dione and 1-aminobutan-2-one to give etioporphyrinogens was enhanced in the presence of decanoic acid, affording (following chemical oxidation) etioporphyrins (tetraethyltetramethylporphyrins) in yields of 1.4–10.8% across the concentration range of 3.75–120 mM. The yield of etioporphyrins was greater in the presence of the five-component organic mixture (6.6% at 120 mM) versus that with dodecane or mesitylene (2.1% or 2.9%, respectively). The reaction in aqueous solution with no added oil-slick constituents resulted in phase separation—where the organic reactants themselves form an upper organic layer—and the yield of etioporphyrins was 0.5–2.6%. Analogous reactions leading to uroporphyrins (hydrophilic, eight carboxylic acids) or coproporphyrins (four carboxylic acids) were unaffected by the presence of decanoic acid or dodecane, and all yields were at most ∼2% or ∼8%, respectively. Taken together, the results indicate a facile means for the formation of highly hydrophobic constituents of potential value for prebiotic photosynthesis. Key Words: Origin of life—Prebiotic—Oil slick—Porphyrinogen—Porphyrin—Pyrrole—Partition. Astrobiology 12, 1055

  13. Contact electrochemical replication of hydrophilic-hydrophobic monolayer patterns.

    PubMed

    Zeira, Assaf; Chowdhury, Devasish; Maoz, Rivka; Sagiv, Jacob

    2008-12-23

    Contact electrochemical replication (CER) is a novel pattern replication methodology advanced in this laboratory that offers the unprecedented capability of direct one-step reproduction of monolayer surface patterns consisting of hydrophilic domains surrounded by a hydrophobic monolayer background (hydrophilic @ hydrophobic monolayer patterns), regardless of how the initial "master" pattern was created. CER is based on the direct electrochemical transfer of information, through aqueous electrolyte bridges acting as an information transfer medium, between two organosilane monolayers self-assembled on smooth silicon wafer surfaces. Upon the application of an appropriate voltage bias between a patterned monolayer/silicon specimen playing the role of "stamp" and a monolayer/silicon specimen playing the role of "target", the hydrophilic features of the stamp are copied onto the hydrophobic surface of the target. It is shown that this electrochemical printing process may be implemented under a variety of experimental configurations conducive to the formation of nanometric electrolyte bridges between stamp and target; however, using plain liquid water for this purpose is, in general, not satisfactory because of the high surface tension, volatility, and incompressibility of water. High-fidelity replication of monolayer patterns with variable size of hydrophilic features was achieved by replacing water with a sponge-like hydrogel that is nonvolatile, compressible, and binds specifically to the hydrophilic features of such patterns. Since any copy resulting from the CER process can equally perform as stamp in a subsequent CER step, this methodology offers the rather unique option of multiple parallel reproduction of an initially fabricated master pattern. PMID:19206292

  14. How hydrophobically modified chitosans are stabilized by biocompatible lipid aggregates.

    PubMed

    Ruocco, Nino; Frielinghaus, Heide; Vitiello, Giuseppe; D'Errico, Gerardino; Leal, Leslie G; Richter, Dieter; Ortona, Ornella; Paduano, Luigi

    2015-08-15

    Nanostructured hydrogels composed by biocompatible molecules are formulated and characterized. They are based on a polymer network formed by hydrophobically modified chitosans (HMCHIT or CnCHIT) in which vesicles of monoolein (MO) and oleic acid or sodium oleate (NaO), depending on pH, are embedded. The best conditions for gel formation, in terms of pH, length of the hydrophobic moieties of chitosan, and weight proportion among the three components were estimated by visual inspection of a large number of samples. Among all possible combinations, the system C12CHIT-MO-NaO in the weight proportion (1:1:1) is optimal for the formation of a well-structured gel-like system, which is also confirmed by rheological experiments. Electron paramagnetic resonance (EPR) measurements unambiguously show the presence of lipid bilayers in this mixture, indicating that MO-NaO vesicles are stabilized by C12CHIT even at acid pH. A wide small angle neutron scattering investigation performed on several ternary systems of general formula CnCHIT-MO-NaO shows that the length of the hydrophobic tail Cn is a crucial parameter in stabilizing the polymer network in which lipid vesicles are embedded. Structural parameters for the vesicles are determined by using a multilamellar model that admits the possibility of displacement of the center of each shell. The number of shells tends to be reduced by increasing the polymer content. The thickness and the distance between consecutive lamellae are not influenced by either the polymer or MO-NaO concentration. The hydrogel presented in this work, being fully biocompatible and nanostructured, is well-suited for possible application in drug delivery. PMID:25935287

  15. Polymer hydrophilicity and hydrophobicity induced by femtosecond laser direct irradiation

    NASA Astrophysics Data System (ADS)

    Wang, Z. K.; Zheng, H. Y.; Lim, C. P.; Lam, Y. C.

    2009-09-01

    Controlled modification of surface wettability of polymethyl methacrylate (PMMA) was achieved by irradiation of PMMA surface with femtosecond laser pulses at various laser fluences and focus distances. Fluences from 0.40 to 2.1 J/cm2 produced a hydrophobic surface and 2.1 to 52.7 J/cm2 (maximum investigated) produced a hydrophilic surface. Fluences less than 0.31 J/cm2 had no effect on the wettability of the raw PMMA. This change in wettability was caused dominantly by laser induced chemical structure modification and not by a change in surface roughness.

  16. From hydrophobic to superhydrophobic and superhydrophilic siloxanes by thermal treatment.

    PubMed

    Karapanagiotis, Ioannis; Manoudis, Panagiotis N; Zurba, Andreea; Lampakis, Dimitrios

    2014-11-11

    The cross-influence effects of treatment temperature and time on the wettability of a siloxane elastomer is investigated in detail, through static and tilt contact angle measurements. The material is heated at 400, 500, 600, 650, 700, and 800 °C for various periods, ranging from 1 to 300 s. The siloxane surface is subjected to multiple wettability transitions with treatment time: from intrinsic hydrophobicity to superhydrophobicity (and water repellency) and then through intermediate stages (hydrophobicity and hydrophilicity) to superhydrophilicity. For the time scale used herein (1-300 s), this scenario is recorded for treatment at 650, 700, and 800 °C. For treatment at lower temperatures (400, 500, and 600 °C) only the first transition, from intrinsic hydrophobicity to superhydrophobicity, is recorded. Scanning electron microscopy, micro-Fourier transform infrared (micro-FTIR), and micro-Raman spectroscopies are employed to correlate the aforementioned wettability transitions with structural and chemical changes of the siloxane surface, developed during thermal treatment. It is shown that the first transition from intrinsic hydrophobicity to superhydrophobicity is accompanied by a severe surface-structure evolution that increases surface roughness. Once superhydrophobicity is achieved, the surface structure reaches a saturation point and it is not subjected to any other change with further thermal treatment. FTIR spectroscopy shows that the intensity of the O-H/C-H peaks increases/decreases with treatment time, and Raman measurements show that the C-Si-C vibrations gradually disappear with treatment time. The evaporation of a droplet resting on a superhydrophobic, water-repellent siloxane surface, which was produced after appropriate thermal treatment, is monitored. It is shown that droplet evaporation initially follows the constant contact area mode. At later evaporation stages, a transition to the constant contact angle mode is recorded. Finally, it is

  17. Does the rhizosphere hydrophobicity limit root water uptake?

    NASA Astrophysics Data System (ADS)

    Zare, Mohsen; Ahmed, Mutez; Kroener, Eva; Carminati, Andrea

    2015-04-01

    The ability of plants to extract water from the soil is influenced by the hydraulic conductivity of roots and their rhizosphere. Recent experiments showed that the rhizosphere turned hydrophobic after drying and it remained dry after rewetting [1]. Our objective was to investigate whether rhizosphere hydrophobicity is a limit to root water uptake after drying. To quantify the effect of rhizosphere hydrophobicity on root water uptake, we used neutron radiography to trace the transport of deuterated water (D2O) in the roots of lupines experiencing a severe, local soil drying. The plants were grown in aluminum containers (30×30×1 cm) filled with sandy soil. The soil was partitioned into nine compartments using three horizontal and three vertical layers of coarse sand (thickness of 1cm) as capillary barrier. When the plants were 28 days old, we let one of the upper lateral compartments dry to a water content of 2-4%, while keeping the other compartments to a water content of 20%. Then we injected 10 ml of D2O in the dry compartment and 10 ml in the symmetric location. The radiographs showed that root water uptake in the soil region that was let dry and then irrigated was 4-8 times smaller than in the wet soil region[2]. In a parallel experiment, we used neutron radiography to monitor the rehydration of lupine roots that were irrigated after a severe drying experiment. Based on root swelling and additional data on the xylem pressure, we calculated the hydraulic conductivity of the root-rhizosphere continuum. We found that the hydraulic conductivity of the root-rhizosphere continuum was initially 5.75×10-14 m s-1and it increased to 4.26×10-12 m s-1after four hours. Both experiments show that rhizosphere hydrophobicity after drying is associated with a reduction in root water uptake and a big decrease in hydraulic conductivity of the soil-root system. [1] Carminati et al (2010) Plant and Soil. Vol. 332: 163-176. [2] Zarebanadkouki and Carmianti (2013) Journal of Plant

  18. High contact angle hysteresis of superhydrophobic surfaces: Hydrophobic defects

    NASA Astrophysics Data System (ADS)

    Chang, Feng-Ming; Hong, Siang-Jie; Sheng, Yu-Jane; Tsao, Heng-Kwong

    2009-08-01

    A typical superhydrophobic surface is essentially nonadhesive and exhibits very low water contact angle (CA) hysteresis, so-called Lotus effect. However, leaves of some plants such as scallion and garlic with an advancing angle exceeding 150° show very serious CA hysteresis. Although surface roughness and epicuticular wax can explain the very high advancing CA, our analysis indicates that the unusual hydrophobic defect, diallyl disulfide, is the key element responsible for contact line pinning on allium leaves. After smearing diallyl disulfide on an extended polytetrafluoroethylene (PTFE) film, which is originally absent of CA hysteresis, the surface remains superhydrophobic but becomes highly adhesive.

  19. Cholesterol and fat lowering with hydrophobic polysaccharide derivatives.

    PubMed

    Čopíková, Jana; Taubner, Tomáš; Tůma, Jan; Synytsya, Andriy; Dušková, Dagmar; Marounek, Milan

    2015-02-13

    Hydrophobic derivatives of highly methylated citrus pectin, chitosan and cellulose were prepared and tested as potential cholesterol lowering agents. Elemental analysis and spectroscopic methods confirmed high substitution degree for all of them. Substitution with long alkyl/acyl groups led to significant changes in physical and thermal properties of modified polysaccharides. Sorption of cholate and cholesterol by these polysaccharide-based sorbents was estimated in comparison with the synthetic drug cholestyramine. It was found that modified polysaccharides have high affinity to cholesterol. By contrast, cholestyramine was effective only in cholate sorption. PMID:25458291

  20. Improved Angiostatic Activity of Dasatinib by Modulation with Hydrophobic Chains

    PubMed Central

    2015-01-01

    Dasatinib is an orally active nonselective tyrosine kinase inhibitor used to treat certain types of adult leukemia. By inhibiting PDGFR-β and SFKs in both tumor cells and tumor-associated endothelial cells, dasatinib inhibits tumor growth and angiogenesis. Herein, dasatinib derivatives modified with hydrophobic chains were prepared and evaluated for their in vitro antiproliferative selectivity and their in vivo antiangiogenic activity. For one of the derivatives, modified with a long perfluorinated chain, a significant enhancement in antiangiogenic activity was observed. Combined, these results suggest a possible generic route to modulate the angiostatic activity of drugs. PMID:25815152

  1. Nonisothermal water transport through hydrophobic membranes in a stirred cell

    SciTech Connect

    Vazquez-Gonzalez, M.I.; Martinez, L.

    1994-10-01

    This paper studies the transport of pure water through microporous hydrophobic membranes in a stirred cell when bathed by two phases at different temperatures. The dependence of the phenomena on the stirring rate and on the average temperature has been investigated. The influence of these operating conditions on the mass transfer rate is discussed while keeping in mind the theories of mass and heat transfer within the membrane and adjoining liquids. The concept of temperature polarization is introduced in the transport equations, and it is shown to be important in the interpretation of our experimental results.

  2. Durable hydrophobic sol-gel finishing for textiles

    NASA Astrophysics Data System (ADS)

    Vihodceva, S.; Kukle, S.; Bitenieks, J.

    2015-03-01

    The surface of cotton textile was modified to create a water-repellent finishing by depositing a modifying coatings using the sol-gel technique. Treated textiles evaluated using scanning electron microscopy, X-Ray powder diffraction (XRD). The wettability of treated fabrics was characterized by water contact angle and drop test. The results showed that the cotton textile treated with 7.5 wt.% zinc acetate dihydrate sol showed excellent hydrophobic properties, water contact angle could reach 145°C without decreasing after 50 hydrothermal treatment cycles.

  3. Antioxidant Activity of Caffeic Acid against Iron-Induced Free Radical Generation--A Chemical Approach.

    PubMed

    Genaro-Mattos, Thiago C; Maurício, Ângelo Q; Rettori, Daniel; Alonso, Antonio; Hermes-Lima, Marcelo

    2015-01-01

    Caffeic acid (CA) is a phenolic compound widely found in coffee beans with known beneficial effects in vivo. Many studies showed that CA has anti-inflammatory, anti-mutagenic, antibacterial and anti-carcinogenic properties, which could be linked to its antioxidant activity. Taking in consideration the reported in vitro antioxidant mechanism of other polyphenols, our working hypothesis was that the CA antioxidant activity could be related to its metal-chelating property. With that in mind, we sought to investigate the chemical antioxidant mechanism of CA against in vitro iron-induced oxidative damage under different assay conditions. CA was able to prevent hydroxyl radical formation promoted by the classical Fenton reaction, as determined by 2-deoxyribose (2-DR) oxidative degradation and DMPO hydroxylation. In addition to its ability to prevent hydroxyl radical formation, CA had a great inhibition of membrane lipid peroxidation. In the lipid peroxidation assays CA acted as both metal-chelator and as hydrogen donor, preventing the deleterious action promoted by lipid-derived peroxyl and alkoxyl radicals. Our results indicate that the observed antioxidant effects were mostly due to the formation of iron-CA complexes, which are able to prevent 2-DR oxidation and DMPO hydroxylation. Noteworthy, the formation of iron-CA complexes and prevention of oxidative damage was directly related to the pH of the medium, showing better antioxidant activity at higher pH values. Moreover, in the presence of lipid membranes the antioxidant potency of CA was much higher, indicating its enhanced effectiveness in a hydrophobic environment. Overall, our results show that CA acts as an antioxidant through an iron chelating mechanism, preventing the formation of free hydroxyl radicals and, therefore, inhibiting Fenton-induced oxidative damage. The chemical properties of CA described here--in association with its reported signaling effects--could be an explanation to its beneficial effects

  4. Antioxidant Activity of Caffeic Acid against Iron-Induced Free Radical Generation—A Chemical Approach

    PubMed Central

    Genaro-Mattos, Thiago C.; Maurício, Ângelo Q.; Rettori, Daniel; Alonso, Antonio; Hermes-Lima, Marcelo

    2015-01-01

    Caffeic acid (CA) is a phenolic compound widely found in coffee beans with known beneficial effects in vivo. Many studies showed that CA has anti-inflammatory, anti-mutagenic, antibacterial and anti-carcinogenic properties, which could be linked to its antioxidant activity. Taking in consideration the reported in vitro antioxidant mechanism of other polyphenols, our working hypothesis was that the CA antioxidant activity could be related to its metal-chelating property. With that in mind, we sought to investigate the chemical antioxidant mechanism of CA against in vitro iron-induced oxidative damage under different assay conditions. CA was able to prevent hydroxyl radical formation promoted by the classical Fenton reaction, as determined by 2-deoxyribose (2-DR) oxidative degradation and DMPO hydroxylation. In addition to its ability to prevent hydroxyl radical formation, CA had a great inhibition of membrane lipid peroxidation. In the lipid peroxidation assays CA acted as both metal-chelator and as hydrogen donor, preventing the deleterious action promoted by lipid-derived peroxyl and alkoxyl radicals. Our results indicate that the observed antioxidant effects were mostly due to the formation of iron-CA complexes, which are able to prevent 2-DR oxidation and DMPO hydroxylation. Noteworthy, the formation of iron-CA complexes and prevention of oxidative damage was directly related to the pH of the medium, showing better antioxidant activity at higher pH values. Moreover, in the presence of lipid membranes the antioxidant potency of CA was much higher, indicating its enhanced effectiveness in a hydrophobic environment. Overall, our results show that CA acts as an antioxidant through an iron chelating mechanism, preventing the formation of free hydroxyl radicals and, therefore, inhibiting Fenton-induced oxidative damage. The chemical properties of CA described here—in association with its reported signaling effects—could be an explanation to its beneficial effects

  5. Synthesis and biological evaluation of piperic acid amides as free radical scavengers and α-glucosidase inhibitors.

    PubMed

    Takao, Koichi; Miyashiro, Takaki; Sugita, Yoshiaki

    2015-01-01

    A series of piperic acid amides (4-24, 29, 30) were synthesized and their 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging and α-glucosidase inhibitory activities were evaluated. Among the synthesized compounds, the amides 11, 13 and 15, which contain o-methoxyphenol, catechol or 5-hydroxyindole moieties, showed potent DPPH free radical scavenging activity (11: EC50 140 µM; 13: EC50 28 µM; 15: EC50 20 µM). The amides 10, 18 and 23 showed higher inhibitory activity of α-glucosidase (10: IC50 21 µM; 18: IC50 21 µM; 23: IC50 12 µM). These data suggest that the hydrophobicity of the conjugated amines is an important determinant of α-glucosidase inhibitory activity. In addition, the amides 13 and 15 showed both potent DPPH free radical scavenging activity and α-glucosidase inhibitory activity (13: IC50 46 µM; 15: IC50 46 µM). This is the first report identifying the DPPH free radical scavenging and α-glucosidase inhibitory activities of piperic acid amides and suggests that these amides may serve as lead compounds for the development of novel α-glucosidase inhibitors with antioxidant activity. PMID:25948326

  6. Substrate radical intermediates in soluble methane monooxygenase

    SciTech Connect

    Liu Aimin; Jin Yi; Zhang Jingyan; Brazeau, Brian J.; Lipscomb, John D. . E-mail: lipsc001@umn.edu

    2005-12-09

    EPR spin-trapping experiments were carried out using the three-component soluble methane monooxygenase (MMO). Spin-traps 5,5-dimethyl-1-pyrroline N-oxide (DMPO), {alpha}-4-pyridyl-1-oxide N-tert-butylnitrone (POBN), and nitrosobenzene (NOB) were used to investigate the possible formation of substrate radical intermediates during catalysis. In contrast to a previous report, the NADH-coupled oxidations of various substrates did not produce any trapped radical species when DMPO or POBN was present. However, radicals were detected by these traps when only the MMO reductase component and NADH were present. DMPO and POBN were found to be weak inhibitors of the MMO reaction. In contrast, NOB is a strong inhibitor for the MMO-catalyzed nitrobenzene oxidation reaction. When NOB was used as a spin-trap in the complete MMO system with or without substrate, EPR signals from an NOB radical were detected. We propose that a molecule of NOB acts simultaneously as a substrate and a spin-trap for MMO, yielding the long-lived radical and supporting a stepwise mechanism for MMO.

  7. Electrochemistry and spectroelectrochemistry of nitroxyl free radicals

    SciTech Connect

    Fish, J.R.; Swarts, S.G.; Sevilla, M.D.; Malinski, T.

    1988-06-30

    This work reports electrochemical and spectroelectrochemical studies of the two nitroxyl radicals 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-yloxy (3-carbamoyl-PROXYL). Oxidation and reduction reactions have been observed in aqueous media over the pH range 2-12 in the potential range -0.8 to +0.8 V by differential pulse voltammetry, cyclic voltammetry, and thin-layer UV-visible spectroelectrochemistry, and the reaction products have been characterized by IR, NMR, and ESR spectrometry. At pH values less than 10, characteristic electrochemical behavior is observed to be analogous for both radicals, and the products from electron transfer compare quite favorably with those found by pulse radiolysis of aqueous solutions of nitroxyl radicals. At pH 2-9, a stable cation from a reversible oxidation and hydroxylamine following an irreversible reduction, as well as hydroxylated cation at pH higher than 9, are the same as those obtained in pulse radiolysis experiments. Spectroscopic evidence indicates that behavior following reduction at high pH differs for the two radicals. At pH 12, reduced TEMPO may undergo structural changes leading to the formation of a new radical consisting of a seven-membered ring.

  8. Radical-pair based avian magnetoreception

    NASA Astrophysics Data System (ADS)

    Procopio, Maria; Ritz, Thorsten

    2014-03-01

    Behavioural experiments suggest that migratory birds possess a magnetic compass sensor able to detect the direction of the geomagnetic. One hypothesis for the basis of this remarkable sensory ability is that the coherent quantum spin dynamics of photoinduced radical pair reactions transduces directional magnetic information from the geomagnetic field into changes of reaction yields, possibly involving the photoreceptor cryptochrome in the birds retina. The suggested radical-pair based avian magnetoreception has attracted attention in the field of quantum biology as an example of a biological sensor which might exploit quantum coherences for its biological function. Investigations on such a spin-based sensor have focussed on uncovering the design features for the design of a biomimetic magnetic field sensor. We study the effects of slow fluctuations in the nuclear spin environment on the directional signal. We quantitatively evaluate the robustness of signals under fluctuations on a timescale longer than the lifetime of a radical pair, utilizing two models of radical pairs. Our results suggest design principles for building a radical-pair based compass sensor that is both robust and highly directional sensitive.

  9. Modeling Radicalization Phenomena in Heterogeneous Populations.

    PubMed

    Galam, Serge; Javarone, Marco Alberto

    2016-01-01

    The phenomenon of radicalization is investigated within a mixed population composed of core and sensitive subpopulations. The latest includes first to third generation immigrants. Respective ways of life may be partially incompatible. In case of a conflict core agents behave as inflexible about the issue. In contrast, sensitive agents can decide either to live peacefully adjusting their way of life to the core one, or to oppose it with eventually joining violent activities. The interplay dynamics between peaceful and opponent sensitive agents is driven by pairwise interactions. These interactions occur both within the sensitive population and by mixing with core agents. The update process is monitored using a Lotka-Volterra-like Ordinary Differential Equation. Given an initial tiny minority of opponents that coexist with both inflexible and peaceful agents, we investigate implications on the emergence of radicalization. Opponents try to turn peaceful agents to opponents driving radicalization. However, inflexible core agents may step in to bring back opponents to a peaceful choice thus weakening the phenomenon. The required minimum individual core involvement to actually curb radicalization is calculated. It is found to be a function of both the majority or minority status of the sensitive subpopulation with respect to the core subpopulation and the degree of activeness of opponents. The results highlight the instrumental role core agents can have to hinder radicalization within the sensitive subpopulation. Some hints are outlined to favor novel public policies towards social integration. PMID:27166677

  10. Modeling Radicalization Phenomena in Heterogeneous Populations

    PubMed Central

    2016-01-01

    The phenomenon of radicalization is investigated within a mixed population composed of core and sensitive subpopulations. The latest includes first to third generation immigrants. Respective ways of life may be partially incompatible. In case of a conflict core agents behave as inflexible about the issue. In contrast, sensitive agents can decide either to live peacefully adjusting their way of life to the core one, or to oppose it with eventually joining violent activities. The interplay dynamics between peaceful and opponent sensitive agents is driven by pairwise interactions. These interactions occur both within the sensitive population and by mixing with core agents. The update process is monitored using a Lotka-Volterra-like Ordinary Differential Equation. Given an initial tiny minority of opponents that coexist with both inflexible and peaceful agents, we investigate implications on the emergence of radicalization. Opponents try to turn peaceful agents to opponents driving radicalization. However, inflexible core agents may step in to bring back opponents to a peaceful choice thus weakening the phenomenon. The required minimum individual core involvement to actually curb radicalization is calculated. It is found to be a function of both the majority or minority status of the sensitive subpopulation with respect to the core subpopulation and the degree of activeness of opponents. The results highlight the instrumental role core agents can have to hinder radicalization within the sensitive subpopulation. Some hints are outlined to favor novel public policies towards social integration. PMID:27166677

  11. Tuning the Reactivity of Radical through a Triplet Diradical Cu(II) Intermediate in Radical Oxidative Cross-Coupling

    PubMed Central

    Zhou, Liangliang; Yi, Hong; Zhu, Lei; Qi, Xiaotian; Jiang, Hanpeng; Liu, Chao; Feng, Yuqi; Lan, Yu; Lei, Aiwen

    2015-01-01

    Highly selective radical/radical cross-coupling is paid more attention in bond formations. However, due to their intrinsic active properties, radical species are apt to achieve homo-coupling instead of cross-coupling, which makes the selective cross-coupling as a great challenge and almost untouched. Herein a notable strategy to accomplish direct radical/radical oxidative cross-coupling has been demonstrated, that is metal tuning a transient radical to a persistent radical intermediate followed by coupling with another transient radical. Here, a transient nitrogen-centered radical is tuned to a persistent radical complex by copper catalyst, followed by coupling with a transient allylic carbon-centered radical. Firstly, nitrogen-centered radical generated from N-methoxybenzamide stabilized by copper catalyst was successfully observed by EPR. Then DFT calculations revealed that a triplet diradical Cu(II) complex formed from the chelation N-methoxybenzamide nitrogen-centered radical to Cu(II) is a persistent radical species. Moreover, conceivable nitrogen-centered radical Cu(II) complex was observed by high-resolution electrospray ionization mass spectrometry (ESI-MS). Ultimately, various allylic amides derivatives were obtained in good yields by adopting this strategy, which might inspire a novel and promising landscape in radical chemistry. PMID:26525888

  12. Tuning the Reactivity of Radical through a Triplet Diradical Cu(II) Intermediate in Radical Oxidative Cross-Coupling

    NASA Astrophysics Data System (ADS)

    Zhou, Liangliang; Yi, Hong; Zhu, Lei; Qi, Xiaotian; Jiang, Hanpeng; Liu, Chao; Feng, Yuqi; Lan, Yu; Lei, Aiwen

    2015-11-01

    Highly selective radical/radical cross-coupling is paid more attention in bond formations. However, due to their intrinsic active properties, radical species are apt to achieve homo-coupling instead of cross-coupling, which makes the selective cross-coupling as a great challenge and almost untouched. Herein a notable strategy to accomplish direct radical/radical oxidative cross-coupling has been demonstrated, that is metal tuning a transient radical to a persistent radical intermediate followed by coupling with another transient radical. Here, a transient nitrogen-centered radical is tuned to a persistent radical complex by copper catalyst, followed by coupling with a transient allylic carbon-centered radical. Firstly, nitrogen-centered radical generated from N-methoxybenzamide stabilized by copper catalyst was successfully observed by EPR. Then DFT calculations revealed that a triplet diradical Cu(II) complex formed from the chelation N-methoxybenzamide nitrogen-centered radical to Cu(II) is a persistent radical species. Moreover, conceivable nitrogen-centered radical Cu(II) complex was observed by high-resolution electrospray ionization mass spectrometry (ESI-MS). Ultimately, various allylic amides derivatives were obtained in good yields by adopting this strategy, which might inspire a novel and promising landscape in radical chemistry.

  13. Tuning the Reactivity of Radical through a Triplet Diradical Cu(II) Intermediate in Radical Oxidative Cross-Coupling.

    PubMed

    Zhou, Liangliang; Yi, Hong; Zhu, Lei; Qi, Xiaotian; Jiang, Hanpeng; Liu, Chao; Feng, Yuqi; Lan, Yu; Lei, Aiwen

    2015-01-01

    Highly selective radical/radical cross-coupling is paid more attention in bond formations. However, due to their intrinsic active properties, radical species are apt to achieve homo-coupling instead of cross-coupling, which makes the selective cross-coupling as a great challenge and almost untouched. Herein a notable strategy to accomplish direct radical/radical oxidative cross-coupling has been demonstrated, that is metal tuning a transient radical to a persistent radical intermediate followed by coupling with another transient radical. Here, a transient nitrogen-centered radical is tuned to a persistent radical complex by copper catalyst, followed by coupling with a transient allylic carbon-centered radical. Firstly, nitrogen-centered radical generated from N-methoxybenzamide stabilized by copper catalyst was successfully observed by EPR. Then DFT calculations revealed that a triplet diradical Cu(II) complex formed from the chelation N-methoxybenzamide nitrogen-centered radical to Cu(II) is a persistent radical species. Moreover, conceivable nitrogen-centered radical Cu(II) complex was observed by high-resolution electrospray ionization mass spectrometry (ESI-MS). Ultimately, various allylic amides derivatives were obtained in good yields by adopting this strategy, which might inspire a novel and promising landscape in radical chemistry. PMID:26525888

  14. Effect of Substrate and Cell Surface Hydrophobicity on Phosphate Utilization in Bacteria

    PubMed Central

    Lemke, M. J.; Churchill, P. F.; Wetzel, R. G.

    1995-01-01

    We measured the rates of utilization of hydrophobic and hydrophilic phosphate compounds in gram-negative bacteria with different surface hydrophobicities, isolated from wetland habitats. Three hydrophobic and two hydrophilic bacterial species were selected for study by measuring cell adherence to hydrocarbons. The bacteria were grown under phosphorus-limited conditions with P(infi), hydrophilic (beta)-glycerophosphate, or hydrophobic phosphatidic acid as the phosphate source. Hydrophilic bacteria grew most rapidly on P(infi), followed by (beta)-glycerophosphate. Phosphatidic acid did not support growth or did so at a much later time (40 h) than did the other phosphate treatments. Although all hydrophobic species grew well on these substrates, the rate of growth of two Acinetobacter baumannii isolates on phosphatidic acid exceeded the rate of growth on phosphate or (beta)-glycerophosphate. A membrane phospholipid and lipopolysaccharide were used as a source of phosphorus by hydrophobic species, whereas hydrophilic species could not use the membrane phospholipids and used lipopolysaccharide to a lesser extent. Besides hydrophobic interaction between cells and substrate, phosphatase activity, which was cell bound in hydrophilic species but 30 to 50% unbound in hydrophobic species, affected cell growth. Dialyzed culture supernatant containing phosphatase from hydrophobic species increased the phosphate availability to hydrophilic species. Additionally, cellular extracts from a hydrophilic species, when added to hydrophilic cells, permitted growth on hydrophobic phosphate sources. Naturally occurring amphiphilic humic acids affected the utilization of P(infi) and (beta)-glycerophosphate in bacteria with hydrophilic surfaces but did not affect hydrophobic bacteria. Our results indicate that hydrophobic phosphate sources can be used by bacteria isolated from aquatic environments as the sole phosphorus source for growth. This utilization, in part, appears to be related to

  15. Effects of surface hydrophobicity on the conformational changes of polypeptides of different length

    NASA Astrophysics Data System (ADS)

    Mu, Yan

    2011-09-01

    We studied the effects of surface hydrophobicity on the conformational changes of different length polypeptides by calculating the free energy difference between peptide structures using the bias-potential Monte Carlo technique and the probability ratio method. It was found that the hydrophobic surface plays an important role in the stability of secondary structures of the polypeptides with hydrophobic side chains. For short GAAAAG peptides, the hydrophobic surface destabilizes the α helix but stabilizes the β hairpin in the entire temperature region considered in our study. Interestingly, when the surface hydrophobic strength ɛhpsf≥ɛhp, the most stable structure in the low temperature region changes from α helix to β hairpin, and the corresponding phase transition temperature increases slightly. For longer GAAAAAAAAAAG peptides, the effects of the relatively weak hydrophobic surface (ɛhpsf < ɛhp) on α-helical structures may be neglected, while the relatively strongly hydrophobic surface (ɛhpsf≥ɛhp) leads to the obvious partial helicity loss. In contrast, the stability of β structures can be enhanced significantly by the hydrophobic surface, especially by the strongly hydrophobic surface, at low and intermediate temperatures. At high temperatures, in addition to thermal fluctuations, the strongly hydrophobic surface (ɛhpsf>ɛhp) may further disturb the formation of both α-helical and β structures. Moreover, the phase transition temperature between α-helical structures and random coils significantly decreases due to the helicity loss when ɛhpsf>ɛhp. Our findings provide a basic and quantitative picture for understanding the effects of a hydrophobic surface on the conformational changes of the polypeptides with hydrophobic side chains. From an application viewpoint, the present study is helpful in developing alternative strategies of producing high-quality biological fibrillar materials and functional nanoscale devices by the self-assembly of

  16. Isolation of Hypervalent Group-16 Radicals and Their Application in Organic-Radical Batteries.

    PubMed

    Imada, Yasuyuki; Nakano, Hideyuki; Furukawa, Ko; Kishi, Ryohei; Nakano, Masayoshi; Maruyama, Hitoshi; Nakamoto, Masaaki; Sekiguchi, Akira; Ogawa, Masahiro; Ohta, Toshiaki; Yamamoto, Yohsuke

    2016-01-20

    Using a newly prepared tridentate ligand, we isolated hypervalent sulfur and selenium radicals for the first time and characterized their structures. X-ray crystallography, electron spin resonance spectroscopy, and density functional theory calculations revealed a three-coordinate hypervalent structure. Utilizing the reversible redox reactions between hypervalent radicals and the corresponding anions bearing Li(+), we developed organic radical batteries with these compounds as cathode-active materials. Furthermore, an all-radical battery, with these compounds as the cathode and a silyl radical as the anode, was developed that exhibited a practical discharge potential of ∼ 1.8 V and stable cycle performance, demonstrating the potential of these materials for use in metal-free batteries that can replace conventional Li-ion batteries where Li is used in the metal form. PMID:26721786

  17. Hydroxyl Radical Generation from Environmentally Persistent Free Radicals (EPFRs) in PM2.5

    PubMed Central

    Gehling, William; Khachatryan, Lavrent; Dellinger, Barry

    2015-01-01

    Hydroxyl radicals were generated from an aqueous suspension of ambient PM2.5 and detected utilizing 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trap coupled with electron paramagnetic resonance (EPR) spectroscopy. Results from this study suggested the importance of environmentally persistent free radicals (EPFRs) in PM2.5 to generate significant levels of ·OH without the addition of H2O2. Particles for which the EPFRs were allowed to decay over time induced less hydroxyl radical. Additionally, higher particle concentrations produced more hydroxyl radical. Some samples did not alter hydroxyl radical generation when the solution was purged by air. This is ascribed to internal, rather than external surface associated EPFRs. PMID:24004313

  18. Surface modification of nanoporous 1,2-polybutadiene by atom transfer radical polymerization or click chemistry.

    PubMed

    Guo, Fengxiao; Jankova, Katja; Schulte, Lars; Vigild, Martin E; Ndoni, Sokol

    2010-02-01

    Surface-initiated atom transfer radical polymerization (ATRP) and click chemistry were used to obtain functional nanoporous polymers based on nanoporous 1,2-polybutadiene (PB) with gyroid morphology. The ATRP monolith initiator was prepared by immobilizing bromoester initiators onto the pore walls through two different methodologies: (1) three-step chemical conversion of double bonds of PB into bromoisobutyrate, and (2) photochemical functionalization of PB with bromoisobutyrate groups. Azide functional groups were attached onto the pore walls before click reaction with alkynated MPEG. Following ATRP-grafting of hydrophilic polyacrylates and click of MPEG, the originally hydrophobic samples transformed into hydrophilic nanoporous materials. The successful modification was confirmed by infrared spectroscopy, contact angle measurements and measurements of spontaneous water uptake, while the morphology was investigated by small-angle X-ray scattering and transmission electron microscopy. PMID:20099923

  19. Encapsulation and suspension of hydrophobic liquids via electro-hydrodynamics.

    PubMed

    Díaz Gómez, Juan E; Marín, Alvaro G; Marquez, Manuel; Barrero, Antonio; Loscertales, Ignacio G

    2006-09-01

    There are situations in which bioactive products of interest in biotechnology turn out to be hydrophobic. To reach high uniform levels of such products in water-based host fluids, such as those existing in many biological environments, one strategy consists on dividing the bioactive product into tiny micrometer (or sub-micrometer) pieces, since these are much more amenable of being uniformly dispersed and stabilized in the host fluid. On the other hand, if the bioactive product must act at specific locations, these micrometer pieces need to be hold in place, an objective that may be achieved by encapsulating them in mats of fibers. Here we demonstrate how these tasks may be accomplished by resorting to the generation and control of electrified coaxial jets of a hydrophilic liquid surrounding the hydrophobic liquid carrying the bioactive substance. When the process is carried out inside a dielectric liquid, double oil/water/oil and simple oil/water emulsions may be formed. On the other hand, when the process runs in air and a biopolymer is added to the hydrophilic liquid, then non woven mats of beaded nanofibers, encapsulating the bioactive product in the beads, are generated. PMID:16941444

  20. Characterization of hydrophobic nanoporous particle liquids for energy absorption

    NASA Astrophysics Data System (ADS)

    Hsu, Yi; Liu, Yingtao

    2016-04-01

    Recently, the development of hydrophobic nanoporous technologies has drawn increased attention, especially for the applications of energy absorption and impact protection. Although significant amount of research has been conducted to synthesis and characterize materials to protect structures from impact damage, the tradition methods focused on converting kinetic energy to other forms, such as heat and cell buckling. Due to their high energy absorption efficiency, hydrophobic nanoporous particle liquids (NPLs) are one of the most attractive impact mitigation materials. During impact, such particles directly trap liquid molecules inside the non-wetting surface of nanopores in the particles. The captured impact energy is simply stored temporarily and isolated from the original energy transmission path. In this paper we will investigate the energy absorption efficiency of combinations of silica nanoporous particles and with multiple liquids. Inorganic particles, such as nanoporous silica, are characterized using scanning electron microscopy. Small molecule promoters, such as methanol and ethanol, are introduced to the prepared NPLs. Their effects on the energy absorption efficiency are studied in this paper. NPLs are prepared by dispersing the studied materials in deionized water. Energy absorption efficiency of these liquids are experimentally characterized using an Instron mechanical testing frame and in-house develop stainless steel hydraulic cylinder system.

  1. How hydrophobic drying forces impact the kinetics of molecular recognition.

    PubMed

    Mondal, Jagannath; Morrone, Joseph A; Berne, B J

    2013-08-13

    A model of protein-ligand binding kinetics, in which slow solvent dynamics results from hydrophobic drying transitions, is investigated. Molecular dynamics simulations show that solvent in the receptor pocket can fluctuate between wet and dry states with lifetimes in each state that are long enough for the extraction of a separable potential of mean force and wet-to-dry transitions. We present a diffusive surface hopping model that is represented by a 2D Markovian master equation. One dimension is the standard reaction coordinate, the ligand-pocket separation, and the other is the solvent state in the region between ligand and binding pocket which specifies whether it is wet or dry. In our model, the ligand diffuses on a dynamic free-energy surface which undergoes kinetic transitions between the wet and dry states. The model yields good agreement with results from explicit solvent molecular dynamics simulation and an improved description of the kinetics of hydrophobic assembly. Furthermore, it is consistent with a "non-Markovian Brownian theory" for the ligand-pocket separation coordinate alone. PMID:23901110

  2. Dynamics of hydrophobic organic contaminants in the Baltic proper pelagial

    SciTech Connect

    Axelman, J.; Broman, D.; Naef, C.; Pettersen, H.

    1995-12-31

    Hydrophobic organic contaminants occur in different forms in natural water. Apart from being truly dissolved in water they partition into dissolved organic carbon (DOC) and particles of different sizes including pelagic bacteria, phytoplankton and zooplankton. The distribution between the different forms is dependent on carbon turnover rates in and transport between the different compartments and on the physical and chemical properties of the compound in focus. The water phase, the DOC-phase and two particle size fractions, 0.2--2pm and 2--20 pm representing the base of the pelagic food web, were analyzed for their content of PCBs and PAHs during summer and winter conditions in the open sea in the Baltic proper. New methods for separating truly dissolved from DOC-bound compounds have been developed using a high capacity perfusion adsorbent and large scale gas sparging. The small particle size fraction was sampled using high volume tangential flow filtration. The possibility to separate between these four different compartments has given a more detailed picture of the short term dynamics of hydrophobic organic compounds in the important base of the pelagial food web.

  3. EWOD driven cleaning of bioparticles on hydrophobic and superhydrophobic surfaces.

    PubMed

    Jönsson-Niedziółka, M; Lapierre, F; Coffinier, Y; Parry, S J; Zoueshtiagh, F; Foat, T; Thomy, V; Boukherroub, R

    2011-02-01

    Environmental air monitoring is of great interest due to the large number of people concerned and exposed to different possible risks. From the most common particles in our environment (e.g. by-products of combustion or pollens) to more specific and dangerous agents (e.g. pathogenic micro-organisms), there are a large range of particles that need to be controlled. In this article we propose an original study on the collection of electrostatically deposited particles using electrowetting droplet displacement. A variety of particles were studied, from synthetic particles (e.g. Polystyrene Latex (PSL) microsphere) to different classes of biological particle (proteins, bacterial spores and a viral simulant). Furthermore, we have compared ElectroWetting-On-Dielectric (EWOD) collecting efficiency using either a hydrophobic or a superhydrophobic counter electrode. We observe different cleaning efficiencies, depending on the hydrophobicity of the substrate (varying from 45% to 99%). Superhydrophobic surfaces show the best cleaning efficiency with water droplets for all investigated particles (MS2 bacteriophage, BG (Bacillus atrophaeus) spores, OA (ovalbumin) proteins, and PSL). PMID:21103534

  4. Quantitative structure-hydrophobicity relationships of molecular fragments and beyond.

    PubMed

    Zou, Jian-Wei; Huang, Meilan; Huang, Jian-Xiang; Hu, Gui-Xiang; Jiang, Yong-Jun

    2016-03-01

    Quantitative structure-property relationship (QSPR) models were firstly established for the hydrophobic substituent constant (πX) using the theoretical descriptors derived solely from electrostatic potentials (EPSs) at the substituent atoms. The descriptors introduced are found to be related to hydrogen-bond basicity, hydrogen-bond acidity, cavity, or dipolarity/polarizability terms in linear solvation energy relationship, which endows the models good interpretability. The predictive capabilities of the models constructed were also verified by rigorous Monte Carlo cross-validation. Then, eight groups of meta- or para-disubstituted benzenes and one group of substituted pyridines were investigated. QSPR models for individual systems were achieved with the ESP-derived descriptors. Additionally, two QSPR models were also established for Rekker's fragment constants (foct), which is a secondary-treatment quantity and reflects average contribution of the fragment to logP. It has been demonstrated that the descriptors derived from ESPs at the fragments, can be well used to quantitatively express the relationship between fragment structures and their hydrophobic properties, regardless of the attached parent structure or the valence state. Finally, the relations of Hammett σ constant and ESP quantities were explored. It implies that σ and π, which are essential in classic QSAR and represent different type of contributions to biological activities, are also complementary in interaction site. PMID:26826800

  5. Bioinspired multifunctional vanadium dioxide: improved thermochromism and hydrophobicity.

    PubMed

    Qian, Xukun; Wang, Ning; Li, Yunfeng; Zhang, Junhu; Xu, Zhichuan; Long, Yi

    2014-09-01

    Vanadium dioxide (VO2) films with moth-eye nanostructures have been fabricated to enhance the thermochromic properties with different periodicity (d) to achieve antireflection (AR). It is revealed that the films with smaller d (210 and 440 nm) could increase both the luminous transmission (Tlum) and infrared transmission (TIR) at 25 and 90 °C, as the d is smaller than the given wavelength and the gradient refractive index produces antireflection. The average Tlum and TIR of VO2 increase with decreasing d. Compared with the planar film, the AR sample with periodicity of 210 nm and thickness of 140 nm can offer approximately 10% enhancement of Tlum and 24.5% increase in solar modulation (ΔTsol). With the addition of hydrophobic overcoat on the patterned VO2, ∼120° contact angle could be achieved. The present approach can tailor the optical transmittance in different wavelengths at high and low temperature together with self-cleaning, opening new avenues for producing hydrophobic VO2 with enhanced thermochromic properties for smart window applications. PMID:25164486

  6. Orientational dynamics of water at an extended hydrophobic interface

    NASA Astrophysics Data System (ADS)

    Figge, Florian; Xiao, Shunhao; McGuire, John A.; Stirnemann, Guillaume; Laage, Damien

    Aqueous interfaces are central to many physical processes, but the dynamics of interfacial water molecules have been little studied. We have measured the orientational dynamics of water at its interface with a self-assembled monolayer of octadecylsilane on fused silica. A surface-sensitive sum-frequency probe generated by mixing a visible and a vibrationally resonant infrared (IR) pulse is used to monitor the dangling (non-hydrogen-bonded) OH stretch vibration after excitation with a resonant IR pump pulse. By measuring pure and isotopically diluted water with orthogonal pump polarizations, we find that relaxation of the dangling OH stretch excitation is dominated by the out-of-plane jump from a dangling to a hydrogen-bonded configuration and the subsequent redistribution of energy from the surface hydrogen-bonded OH stretch excitation. The out-of-plane jump time is 1.5(1)ps, 30% slower than that reported for the air-water interface and twice as short as the jump time between hydrogen bonded configurations in the bulk. Molecular dynamics simulations indicate that the slower dynamics at the hydrophobic interface compared to the water-air interface are due to the hydrogen bonds at the hydrophobic interface being stronger than those at the water-air interface. The authors acknowledge support from the National Science Foundation (Grant No. CHE- 1151590).

  7. Hydrophobic Silica Nanoparticles Induce Gel Phases in Phospholipid Monolayers.

    PubMed

    Orsi, Davide; Rimoldi, Tiziano; Guzmán, Eduardo; Liggieri, Libero; Ravera, Francesca; Ruta, Beatrice; Cristofolini, Luigi

    2016-05-17

    Silica nanoparticles (SiNP) can be incorporated in phospholipid layers to form hybrid organic-inorganic bidimensional mesostructures. Controlling the dynamics in these mesostructures paves the way to high-performance drug-delivery systems. Depending on the different hydrophobicity/hydrophilicity of SiNP, recent X-ray reflectivity experiments have demonstrated opposite structural effects. While these are reasonably well understood, less is known about the effects on the dynamics, which in turn determine molecular diffusivity and the possibility of drug release. In this work we characterize the dynamics of a mixed Langmuir layer made of phospholipid and hydrophobic SiNP. We combine X-ray photon correlation spectroscopy and epifluorescence discrete Fourier microscopy to cover more than 2 decades of Q-range (0.3-80 μm(-1)). We obtain evidence for the onset of an arrested state characterized by intermittent stress-relaxation rearrangement events, corresponding to a gel dominated by attractive interactions. We compare this with our previous results from phospholipid/hydrophilic SiNP films, which show an arrested glassy phase of repulsive disks. PMID:27133453

  8. Injectable micellar supramolecular hydrogel for delivery of hydrophobic anticancer drugs.

    PubMed

    Fu, CuiXiang; Lin, XiaoXiao; Wang, Jun; Zheng, XiaoQun; Li, XingYi; Lin, ZhengFeng; Lin, GuangYong

    2016-04-01

    In this paper, an injectable micellar supramolecular hydrogel composed of α-cyclodextrin (α-CD) and monomethoxy poly(ethylene glycol)-b-poly(ε-caplactone) (MPEG5000-PCL5000) micelles was developed by a simple method for hydrophobic anticancer drug delivery. By mixing α-CD aqueous solution and MPEG5000-PCL5000 micelles, an injectable micellar supramolecular hydrogel could be formed under mild condition due to the inclusion complexation between α-CD and MPEG segment of MPEG5000-PCL5000 micelles. The resultant supramolecular hydrogel was thereafter characterized by X-ray diffraction (XRD) and Scanning electron microscopy (SEM). The effect of α-CD amount on the gelation time, mechanical strength and thixotropic property was studied by a rheometer. Payload of hydrophobic paclitaxel (PTX) to supramolecular hydrogel was achieved by encapsulation of PTX into MPEG5000-PCL5000 micelles prior mixing with α-CD aqueous solution. In vitro release study showed that the release behavior of PTX from hydrogel could be modulated by change the α-CD amount in hydrogel. Furthermore, such supramolecular hydrogel could enhance the biological activity of encapsulated PTX compared to free PTX, as indicated by in vitro cytotoxicity assay. All these results indicated that the developed micellar supramolecular hydrogel might be a promising injectable drug delivery system for anticancer therapy. PMID:26886821

  9. Sliding drops across alternating hydrophobic and hydrophilic stripes

    NASA Astrophysics Data System (ADS)

    Sbragaglia, M.; Biferale, L.; Amati, G.; Varagnolo, S.; Ferraro, D.; Mistura, G.; Pierno, M.

    2014-01-01

    We perform a joint numerical and experimental study to systematically characterize the motion of 30 μl drops of pure water and of ethanol in water solutions, sliding over a periodic array of alternating hydrophobic and hydrophilic stripes with a large wettability contrast and a typical width of hundreds of microns. The fraction of the hydrophobic areas has been varied from about 20% to 80%. The effects of the heterogeneous patterning can be described by a renormalized value of the critical Bond number, i.e., the critical dimensionless force needed to depin the drop before it starts to move. Close to the critical Bond number we observe a jerky motion characterized by an evident stick-slip dynamics. As a result, dissipation is strongly localized in time, and the mean velocity of the drops can easily decrease by an order of magnitude compared to the sliding on the homogeneous surface. Lattice Boltzmann numerical simulations are crucial for disclosing to what extent the sliding dynamics can be deduced from the computed balance of capillary, viscous, and body forces by varying the Bond number, the surface composition, and the liquid viscosity. Beyond the critical Bond number, we characterize both experimentally and numerically the dissipation inside the droplet by studying the relation between the average velocity and the applied volume forces.

  10. Sliding drops across alternating hydrophobic and hydrophilic stripes.

    PubMed

    Sbragaglia, M; Biferale, L; Amati, G; Varagnolo, S; Ferraro, D; Mistura, G; Pierno, M

    2014-01-01

    We perform a joint numerical and experimental study to systematically characterize the motion of 30 μl drops of pure water and of ethanol in water solutions, sliding over a periodic array of alternating hydrophobic and hydrophilic stripes with a large wettability contrast and a typical width of hundreds of microns. The fraction of the hydrophobic areas has been varied from about 20% to 80%. The effects of the heterogeneous patterning can be described by a renormalized value of the critical Bond number, i.e., the critical dimensionless force needed to depin the drop before it starts to move. Close to the critical Bond number we observe a jerky motion characterized by an evident stick-slip dynamics. As a result, dissipation is strongly localized in time, and the mean velocity of the drops can easily decrease by an order of magnitude compared to the sliding on the homogeneous surface. Lattice Boltzmann numerical simulations are crucial for disclosing to what extent the sliding dynamics can be deduced from the computed balance of capillary, viscous, and body forces by varying the Bond number, the surface composition, and the liquid viscosity. Beyond the critical Bond number, we characterize both experimentally and numerically the dissipation inside the droplet by studying the relation between the average velocity and the applied volume forces. PMID:24580236

  11. Hydrophobicity and thermodynamic response for aqueous solutions of amphiphiles

    NASA Astrophysics Data System (ADS)

    Zemánková, Katerina; Troncoso, Jacobo; Cerdeiriña, Claudio A.; Romaní, Luis; Anisimov, Mikhail A.

    2016-06-01

    The anomalous behavior of aqueous solutions of amphiphiles in the water-rich region is analyzed via a phenomenological approach that utilizes the isobaric heat capacity Cp as an experimental probe. We report extensive data for solutions of 14 amphiphiles as a function of temperature at atmospheric pressure. Beyond that, Cp data but also isobaric thermal expansivities and isothermal compressibilities for three solutions of tert-butanol as a function of both temperature and pressure are presented. Results rule out the possibility that the observed phenomenology is associated with the anomalous thermodynamics of pure water. Indeed, our Cp data, quantitatively consistent with recent spectroscopic analyses, suggest that water-mediated interactions between the nonpolar parts of amphiphiles are at the origin of anomalies, with the effects of such "hydrophobic aggregation" being observed at mole fractions as small as 0.01. Physicochemical details like the size, the electronic charge distribution and the geometry of amphiphile molecules as well as third-order derivatives of the Gibbs energy and the associated Koga lines support the above claims while they further contribute to characterizing the role of hydrophobicity in these phenomena. Progress with a view to gain a deeper, more concrete understanding remains.

  12. Laccase catalyzed covalent coupling of fluorophenols increases lignocellulose surface hydrophobicity.

    PubMed

    Kudanga, Tukayi; Prasetyo, Endry Nugroho; Widsten, Petri; Kandelbauer, Andreas; Jury, Sandra; Heathcote, Carol; Sipilä, Jussi; Weber, Hansjoerg; Nyanhongo, Gibson S; Guebitz, Georg M

    2010-04-01

    This work presents for the first time the mechanistic evidence of a laccase-catalyzed method of covalently grafting hydrophobicity enhancing fluorophenols onto Fagus sylvatica veneers. Coupling of fluorophenols onto complex lignin model compounds guaiacylglycerol beta-guaiacyl ether and syringylglycerol beta-guaiacyl ether was demonstrated by LC-MS and NMR. Laccase-mediated coupling increased binding of 4-[4-(trifluoromethyl)phenoxy]phenol (4,4-F3MPP) and 4-(trifluoromethoxy)phenol (4-F3MP) to veneers by 77.1% and 39.2%, respectively. XPS studies showed that laccase-catalyzed grafting of fluorophenols resulted in a fluorine content of 6.39% for 4,4-F3MPP, 3.01% for 4-F3MP and 0.26% for 4-fluoro-2-methylphenol (4,2-FMP). Grafting of the fluorophenols 4,2-FMP, 4-F3MP and 4,4-F3MPP led to a 9.6%, 28.6% and 65.5% increase in hydrophobicity, respectively, when compared to treatments with the respective fluorophenols in the absence of laccase, in good agreement with XPS data. PMID:20044252

  13. Effect of morphology of hydrophobic surfaces on cavitation kinetics

    SciTech Connect

    LUZAR,ALENKA; LEUNG,KEVIN

    2000-04-24

    Cavitation has been suggested to be a possible source of long range interactions between mesoscopic hydrophobic surfaces. While evaporation is predicted by thermodynamics, little is known about its kinetics. Glauber dynamics Monte Carlo simulations of a lattice gas close to liquid-gas coexistence and confined between partially drying surfaces are used to model the effect of water confinement on the dynamics of surface-induced phase transition. Specifically, they examine how kinetics of induced evaporation change as the texture of hydrophobic surfaces is varied. Evaporation rates are considerably slowed with relatively small amount of hydrophilic coverage. However, the distribution of hydrophilic patches is found to be crucial, with the homogeneous one being much more effective in slowing the formation of vapor tubes which triggers the evaporation process. They estimate the free energy barrier of vapor tube formation via transition state theory, using a constrained forward-backward umbrella sampling technique applied to the metastable, confined liquid. Furthermore, to relate simulation rates to experimental ones, they perform simulations using the mass-conserving Kawasaki algorithm. They predict evaporation time scales that range from hundreds of picoseconds in the case of mesoscopic surfaces {approximately} 10{sup 4} nm{sup 2} to tens of nanoseconds for smaller surfaces {approximately} 40 nm{sup 2}, when the two surfaces are {approximately} 10 solvent layers apart. The present study demonstrates that cavitation is kinetically viable in real systems and should be considered in studies of processes at confined geometry.

  14. Atomistic Hydrodynamics and the Dynamical Hydrophobic Effect in Porous Graphene.

    PubMed

    Strong, Steven E; Eaves, Joel D

    2016-05-19

    Mirroring their role in electrical and optical physics, two-dimensional crystals are emerging as novel platforms for fluid separations and water desalination, which are hydrodynamic processes that occur in nanoscale environments. For numerical simulation to play a predictive and descriptive role, one must have theoretically sound methods that span orders of magnitude in physical scales, from the atomistic motions of particles inside the channels to the large-scale hydrodynamic gradients that drive transport. Here, we use constraint dynamics to derive a nonequilibrium molecular dynamics method for simulating steady-state mass flow of a fluid moving through the nanoscopic spaces of a porous solid. After validating our method on a model system, we use it to study the hydrophobic effect of water moving through pores of electrically doped single-layer graphene. The trend in permeability that we calculate does not follow the hydrophobicity of the membrane but is instead governed by a crossover between two competing molecular transport mechanisms. PMID:27139634

  15. Differences in hydration structure near hydrophobic and hydrophilic amino acids.

    PubMed Central

    Head-Gordon, T; Sorenson, J M; Pertsemlidis, A; Glaeser, R M

    1997-01-01

    We use molecular dynamics to simulate recent neutron scattering experiments on aqueous solutions of N-acetyl-leucine-amide and N-acetyl-glutamine-amide, and break down the total scattering function into contributions from solute-solute, solute-water, water-water, and intramolecular correlations. We show that the shift of the main diffraction peak to smaller angle that is observed for leucine, but not for glutamine, is attributable primarily to alterations in water-water correlations relative to bulk. The perturbation of the water hydrogen-bonded network extends roughly two solvation layers from the hydrophobic side chain surface, and is characterized by a distribution of hydrogen bonded ring sizes that are more planar and are dominated by pentagons in particular than those near the hydrophilic side chain. The different structural organization of water near the hydrophobic solute that gives rise to the inward shift in the main neutron diffraction peak under ambient conditions may also provide insight into the same directional shift for pure liquid water as it is cooled and supercooled. Images FIGURE 4 FIGURE 5 FIGURE 6 PMID:9336206

  16. Bioaccumulation of hydrophobic chemicals in an agricultural food chain

    SciTech Connect

    McLachlan, M.S.

    1995-12-31

    The concentrations of PCDD/Fs, PCBs and hexachlorobenzene were measured in an air-plant/soil-cow-human food chain in southern Germany. The data were interpreted using the fugacity modeling concept. The fugacities in air, soil and plants were found to be similar for many of the compounds, suggesting near equilibrium partitioning, while the fugacities increased somewhat from feed to cows` milk, indicating that moderate biomagnification takes place in the cow. However, a decrease in fugacity of several orders of magnitude from air to plants to cows` milk was observed for more involatile, hydrophobic compounds. This phenomenon, termed biodilution, could be attributed to two processes. Firstly, the air/plant partitioning of involatile compounds does not approach equilibrium due to the kinetically limiting air side resistance. Secondly, very hydrophobic compounds are more poorly absorbed in the digestive tract of the cow. Metabolism in cows also resulted in biodilution of certain congeners. The fugacities in human milk were 20 to 50 times higher than in cows` milk, indicating strong biomagnification.

  17. Drag Reduction for Flow Past a Perfectly Hydrophobic Surface

    NASA Astrophysics Data System (ADS)

    McHale, Glen; Newton, Michael I.; Flynn, Morris R.; Gruncell, Brian R. K.; Sandham, Neil D.; Busse, Angela

    2014-11-01

    We consider drag reduction for flow past a perfectly hydrophobic sphere (i.e. a vanishing Cassie solid surface fraction or with a Leidenfrost layer). At small Re number an exact analytical model for drag can be constructed for a sphere encapsulated in a layer of a gas (a ``plastron''). This predicts an optimum thickness for the gas layer for maximum drag reduction due to a competition between increased lubrication of the flow and increased cross-section for drag by the compound object (the solid plus its surface-retained layer of gas). Using numerical simulations for a perfectly hydrophobic solid sphere in water we show that the maximum drag reduction increases from 19% to 50% as the Re number increases to 100; this is due to suppression of flow separation and a narrower wake. Introducing roughness into the simulations to model a superhydrophobic surface with a finite Cassie fraction results in less drag reduction because the vortex regime is no longer fully suppressed. Finally, we describe an analytical model of flow resistance through tubes or channels using similar boundary conditions to the flow past a gas-encapsulated sphere. We acknowledge funding from the UK EPSRC (EP/G058318/1, EP/G069581/1 and EP/L026899/1) and the Canadian NSERC.

  18. Synthesis of new fluoromethacrylates and their hydrophobic properties

    SciTech Connect

    Soulen, R.L.; Huang, A.X.; Maher, C.J.

    1993-12-31

    This report continues the search for the ideal fluoromethacrylate or fluoroacrylate which is compatible in copolymerization with methyl methacrylate and also provide maximum hydrophobicity to the polymer without significant loss of mechanical or optical properties. In this study the authors have prepared the methacrylate of the following fluoroalcohols: 2,2,2-trifluoroethyl, 1,1,1,3,3,3-hexafluoro-2-propyl, perfluoro tertiary butyl, heptafluoro-2-propyl, and 1,1,2 tris (trifluoromethyl)-2,3,3,3-tetrafluoropropyl alcohol. Copolymers of methyl methacrylate were prepared with 5, 10, 20, and 30 weight percent of fluoromonomer in the polymerization mixture. Sample disks of the copolymers and similarly prepared samples of pure methyl methacrylate were immersed in 120{degrees}F water and the weight increase due to water absorption determined over a 3000-5000 hour period. Test samples from an F-4 aircraft canopy were included for comparison. In all cases, the fluoromonomer addition provided a significant decrease in the bulk water absorbed in the copolymer. Comparison of fluoromonomer structure and ability to promote hydrophobic properties will be shown.

  19. Stable ferrofluids of magnetite nanoparticles in hydrophobic ionic liquids.

    PubMed

    Mestrom, Luuk; Lenders, Jos J M; de Groot, Rick; Hooghoudt, Tonnis; Sommerdijk, Nico A J M; Artigas, Marcel Vilaplana

    2015-07-17

    Ferrofluids (FFs) of metal oxide nanoparticles in ionic liquids (ILs) are a potentially useful class of magnetic materials for many applications because of their properties related to temperature/pressure stability, hydrophobicity, viscosity and recyclability. In this work, the screening of several designer surfactants for their stabilizing capabilities has resulted in the synthesis of stable FFs of superparamagnetic 7 ± 2 nm magnetite (Fe3O4) nanoparticles in the hydrophobic IL 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(R)MIM][NTf2]). The designed and synthesized 1-butyl-3-(10-carboxydecyl)-1H-imidazol-3-ium bromide (ILC10-COOH) surfactant that combines the same imidazole moiety as the IL with a long alkyl chain ensured compatibility with the IL and increased the steric repulsion between the magnetite nanoparticles sufficiently such that stable dispersions of up to 50 wt% magnetite were obtained according to stability tests in the presence of a magnetic field (0.5-1 Tesla). Cryo-transmission electron microscopy (cryo-TEM) of the IL-based FFs allowed direct visualization of the surfactant-stabilized nanoparticles in the ILs and the native, hardly aggregated state of their dispersion. PMID:26118409

  20. Stable ferrofluids of magnetite nanoparticles in hydrophobic ionic liquids

    NASA Astrophysics Data System (ADS)

    Mestrom, Luuk; Lenders, Jos J. M.; de Groot, Rick; Hooghoudt, Tonnis; Sommerdijk, Nico A. J. M.; Vilaplana Artigas, Marcel

    2015-07-01

    Ferrofluids (FFs) of metal oxide nanoparticles in ionic liquids (ILs) are a potentially useful class of magnetic materials for many applications because of their properties related to temperature/pressure stability, hydrophobicity, viscosity and recyclability. In this work, the screening of several designer surfactants for their stabilizing capabilities has resulted in the synthesis of stable FFs of superparamagnetic 7 ± 2 nm magnetite (Fe3O4) nanoparticles in the hydrophobic IL 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([CRMIM][NTf2]). The designed and synthesized 1-butyl-3-(10-carboxydecyl)-1H-imidazol-3-ium bromide (ILC10-COOH) surfactant that combines the same imidazole moiety as the IL with a long alkyl chain ensured compatibility with the IL and increased the steric repulsion between the magnetite nanoparticles sufficiently such that stable dispersions of up to 50 wt% magnetite were obtained according to stability tests in the presence of a magnetic field (0.5-1 Tesla). Cryo-transmission electron microscopy (cryo-TEM) of the IL-based FFs allowed direct visualization of the surfactant-stabilized nanoparticles in the ILs and the native, hardly aggregated state of their dispersion.

  1. Supramolecular Hydrophobic Aggregates in Hydrogels Partially Inhibit Ice Formation.

    PubMed

    Wiener, Clinton G; Tyagi, Madhusudan; Liu, Yun; Weiss, R A; Vogt, Bryan D

    2016-06-23

    Prevention of ice crystallization is a challenging problem with implications in diverse applications, as well as examining the fundamental low temperature physics of water. Here, we demonstrate a simple route, inspired by water confinement in antifreeze proteins, to inhibit crystallization and provide high water mobility of highly supercooled water using supramolecular hydrogels of copolymers of dimethylacrylamide (DMA) and 2-(N-ethylperfluorooctane sulfonamido)ethyl acrylate (FOSA). These hydrogels can suppress or inhibit freezing of their water, depending on the copolymer composition. Dynamic and static neutron scattering indicate that hydrogels using the copolymer with 22 mol % FOSA partially inhibit ice formation. This behavior is attributed to confinement (<2 nm) of water between the hydrophobic FOSA nanodomains that prevents 45% of the water within the hydrogel from freezing even at 205 K. Very fast dynamics of the amorphous water are observed at 220 K with an effective local diffusivity decreased by only a factor of 2 from that observed at 295 K within the hydrogel using the copolymer with 22 mol % FOSA. The spacing between the hydrophobic nanodomains, tuned through the copolymer composition, appears to modulate the water that can crystallize. These fully hydrated hydrogels (at equilibrium with liquid water at 295 K) can enable a significant fraction of highly supercooled water to be stable down to at least 205 K. PMID:27228304

  2. Cyclodextrin-polyhydrazine degradable gels for hydrophobic drug delivery.

    PubMed

    Jalalvandi, Esmat; Cabral, Jaydee; Hanton, Lyall R; Moratti, Stephen C

    2016-12-01

    An injectable and biocompatible hydrogel system was designed for hydrophobic drug delivery. This hydrogel consisted of degradable polymers with cyclodextrin (CD) moieties. CD groups were used to increase the solubility of a hydrophobic molecule (nicardipine) in an aqueous solution through the formation of the inclusion complex. Two sets of gels were prepared by mixing oxidized dextran (DA) and CD functionalized polyhydrazine (PH) at physiological conditions and different level of crosslinking via hydrazone bonds. Cytotoxicity studies on the gels and their components confirmed the biocompatibility of these materials. Gel-30 with higher crosslinking density showed a two week degradation period whereas this period was 10days for gel-10, with lower crosslinking density, to complete degradation. The results from swelling tests and rheological measurements were also found to be dependent on crosslinking density of the hydrogels. Release profile of the hydrogel displayed a sustained release of nicardipin up to 6days for gel-30 and a 4day release with initial burst release for gel-10. PMID:27612699

  3. Hydrophobic flocculation flotation for beneficiating fine coal and minerals

    SciTech Connect

    Song, S.; Valdivieso, A.L.

    1998-06-01

    It is shown that hydrophobic flocculation flotation (HFF) is an effective process to treat finely ground ores and slimes so as to concentrate coal and mineral values at a fine size range. The process is based on first dispersing the fine particles suspension, followed by flocculation of fine mineral values or coal in the form of hydrophobic surfaces either induced by specifically adsorbed surfactants or from nature at the conditioning of the slurry with the shear field of sufficient magnitude. The flocculation is intensified by the addition of a small amount of nonpolar oil. finely ground coals, ilmenite slimes, and gold finely disseminated in a slag have been treated by this process. Results are presented indicating that cleaned coal with low ash and sulfur remaining and high Btu recovery can be obtained, and the refractory ores of ilmenite slimes and fine gold-bearing slag can be reasonably concentrated, leading to better beneficiation results than other separation techniques. In addition, the main operating parameters affecting the HFF process are discussed.

  4. Vapor transport through short hydrophobic nanopores for desalination

    NASA Astrophysics Data System (ADS)

    Lee, Jongho; O'Hern, Sean; Laoui, Tahar; Rahman, Faizur; Karnik, Rohit

    2011-11-01

    We propose a concept for desalination of water by reverse osmosis (RO) using a vapor-trapping membrane composed of short hydrophobic nanopores and separates the salt water (feed) and the fresh water (permeate) on each side. The feed water is vaporized by applied pressure and the water vapor condenses on the permeate side accompanied by recovery of latent heat. A probabilistic model based on rarified gas conditions predicted 3-5 times larger mass flux by the proposed membrane than conventional RO membranes at temperatures in the range of 30-50C. To realize the short hydrophobic nanopores, gold was deposited at the entrance of alumina pores followed by SAM formation. The fraction of leaking pores was confirmed to be less than 0.2% using a calcium ion indicator (Fluo-4). Finally, a microfluidic flow cell was fabricated for characterizing the transport properties of the membranes. The authors would like to thank the King Fahd University of Petroleum and Minerals in Dhahran, Saudi Arabia, for funding the research reported in this paper through the Center for Clean Water and Clean Energy at MIT and KFUPM.

  5. Launching droplets from a super-hydrophobic surface using electrowetting

    NASA Astrophysics Data System (ADS)

    Wang, Zhantao; Ende, Dirk Van Den; Cavalli, Andrea; Wijnperle, Daniel; Mugele, Frieder

    2015-11-01

    Electrowetting (EW) on super-hydrophobic surfaces in ambient air has been reported to be mostly irreversible due to the transition from the Cassie to the Wenzel state. By applying short voltage pulses using interdigitated electrodes, embedded in the substrate we demonstrate a reversible contact angle variation up to 70 degrees on a single-tier super-hydrophobic surface, which is much higher than previously reported. For a range of voltages and pulse durations the droplet can be launched from the substrate due to conversion of interfacial energy to kinetic energy of the center of mass. We have studied the jumping height as a function of the applied voltage and pulse duration and identified the parameters to maximize this height. The energy dissipation during the droplet detachment and subsequent bouncing was also analyzed by analyzing the drop shape and position from the side and bottom view recordings of the jumping drop. We also investigate the role of the ambient phase by considering the EW-actuated detachment of water drops in oils of different viscosities. We acknowledge financial support by the Dutch Technology Foundation STW.

  6. Electricity from Coal Combustion: Improving the hydrophobicity of oxidized coals

    NASA Astrophysics Data System (ADS)

    Seehra, Mohindar; Singh, Vivek

    2011-03-01

    To reduce pollution and improve efficiency, undesirable mineral impurities in coals are usually removed in coal preparation plants prior to combustion first by crushing and grinding coals followed by gravity separation using surfactant aided water flotation. However certain coals in the US are not amendable to this process because of their poor flotation characteristics resulting in a major loss of an energy resource. This problem has been linked to surface oxidation of mined coals which make these coals hydrophilic. In this project, we are investigating the surface and water flotation properties of the eight Argonne Premium (AP) coals using x-ray diffraction, IR spectroscopy and zeta potential measurements. The role of the surface functional groups, (phenolic -OH and carboxylic -COOH), produced as a result of chemisorptions of O2 on coals in determining their flotation behavior is being explored. The isoelectric point (IEP) in zeta potential measurements of good vs. poor floaters is being examined in order to improved the hydrophobicity of poor floating coals (e.g. Illinois #6). Results from XRD and IR will be presented along with recent findings from zeta potential measurements, and use of additives to improve hydrophobicity. Supported by USDOE/CAST, Contract #DE-FC26-05NT42457.

  7. Adsorption of Papain on solid substrates of different hydrophobicity.

    PubMed

    Lachmanová, Štěpánka; Kolivoška, Viliam; Pospíšil, Lubomír; Fanelli, Nicolangelo; Hromadová, Magdaléna

    2016-01-01

    Adsorption properties of protein Papain at the solid|liquid (0.1 M KCl) interfaces of different hydrophobicity [highly oriented pyrolytic graphite (HOPG), bare gold, CH3, OH, and COOH-terminated self-assembled monolayers on gold] were studied by a combined quartz crystal microbalance and atomic force microscopy techniques. It was found that Papain forms an incomplete monolayer at hydrophobic interfaces (HOPG and CH3-terminated substrate), whereas on more hydrophilic ones, a complete monolayer formation was always observed with either the onset of the formation of a second layer (bare gold substrate) or adsorption in a multilayer fashion, possibly a bilayer formation (OH-terminated substrate). The surface concentration and compact monolayer film thickness was much lower on the COOH-terminated substrate compared to other surfaces studied. This result was explained by partial dissociation of the interfacial COOH groups leading to additional electrostatic interactions between the positively charged protein domains and negatively charged carboxylate anions, as well as to local pH changes promoting protein denaturation. PMID:27405347

  8. Tuning hydrophobicity and water adhesion by electrospinning and silanization.

    PubMed

    Pisuchpen, Thanarath; Chaim-ngoen, Navarun; Intasanta, Narupol; Supaphol, Pitt; Hoven, Voravee P

    2011-04-01

    Electrospinning and silanization were synergistically employed to fabricate poly(vinyl alcohol) (PVA) and PVA/silica mixtures into flexible and chemically modifiable nanostructured surfaces with varying degrees of hydrophobicity and water adhesion. Surfaces possessing the greatest advancing water contact angle yet exhibiting a high level of water adhesion (θ(A)/θ(R) ≈ 168°/0°) were achieved by the reaction of PVA fiber mats with multiple cycles of SiCl(4)/H(2)O treatment, followed by silanization with (1H,1H,2H,2H-perfluorooctyl)trichlorosilane. It is postulated that the strong pinning effect and hence the water adhesion originated from the collapse of the underlying fibrous structures and the removal of air pockets. The addition of silica to the PVA matrix improved the rigidity and thus prevented the fibers from collapsing, allowing air to remain trapped within the fibrous structure and giving the surface greater water repellency. Throughout the investigation, the three wetting models--Wenzel's, Cassie-Baxter's, and the Cassie-impregnating--were regularly referred to as a conceptual framework. The hydrophobic surface that exhibited strong water adhesion, or the so-called "Petal effect", was elucidated in correlation with the fibrous structure of the film, as reviewed by microscopic analysis. In summary, electrospinning as a facile and cost-effective method provides promising opportunities for investigating the mechanistic character of nanowetting, nanoprinting, and nanocoating where the precise control of the dynamical three-phase contact line is of paramount importance. PMID:21401064

  9. Hydrophobicity of 43 potting media: Its implications for raising seedlings in revegetation programs

    NASA Astrophysics Data System (ADS)

    Gautam, Resham; Ashwath, Nanjappa

    2012-04-01

    SummaryThe practice of using nursery-raised seedlings is becoming popular in revegetation programs, as this will allow rapid establishment of plants. However, this practice often results in low survival of seedlings in the field, especially in the tropics under rain fed conditions. Part of this can be attributed to hydrophobicity of the media being used in raising the seedlings. Hydrophobicity is the property of potting media which make the media not able to readily absorb water from the surrounding soil once the media dry out. Thus, 41 commercially available potting media and media components and two soil samples (Control) were assessed for hydrophobicity at different moisture levels via Water Droplet Penetration Test (WDPT). At the driest state (oven dried samples), the tested media were classified into five hydrophobicity classes, viz., extremely hydrophobic (WDP time >3600 s, 28% of the tested media), severely hydrophobic (WDP time 600-3600 s, 35%), strongly hydrophobic (WDP time 60-600 s, 21%), slightly hydrophobic (WDP time 5-60 s, 12%) and non-hydrophobic (WDP time <5 s, 5%). The test showed that hydrophobicity decreased with an increase in moisture content of the media. For example, when samples were oven dried, 63% of the media were found severely to extremely hydrophobic whereas only 14% of the media remained in these categories when moisture content increased to 15%. Significant (P < 0.05) negative correlation was observed between hydrophobicity and pH (R2 = 0.92), and hydrophobicity and water holding capacity (P < 0.05) of the media (R2 = 0.89). However, no significant correlation was observed between hydrophobicity to electrical conductivity of the media (R2 = 0.03). The media wettability (ratio of hydrophilic and hydrophobic functional group of organic matter) as determined by FTIR spectroscopy was significantly (P < 0.001) higher in non-hydrophobic media than in hydrophobic media. Most Probable Number (MPN) adapted from a "Sheen Screen" method

  10. Critical water contents of hydrophobic soils in New Zealand

    NASA Astrophysics Data System (ADS)

    Landl, Magdalena; Holzinger, Ursula; Singh, Ranvir; Klik, Andreas

    2013-04-01

    Soil water repellency is an important problem for pasture farming in New Zealand which causes low infiltration rates and increased surface runoff. However, the real extent of this issue is not yet evaluated. Water repellency is thought to appear on dry soils, when the water content falls below a critical limit. The main objectives of this study was 1) to investigate the effects of different amounts of infiltration water on hydrophobicity of three selected soils under grassland in the North island of New Zealand, and 2) to determine the critical water content for ten sites with five different soil types. In April 2011 undisturbed and disturbed soil samples from a brown, gley and organic soil have been taken from sites around Mount Taranaki. Soil water repellency was determined using the Water Droplet Penetration Time Test (WDPT) and the Molarity of Ethanol Droplet Test (MED). During the lab experiment four amounts of water were applied to the 270 cm³ samples: 400, 800, 1600 and 2400 mL . One test was performed with cold and one with hot (80 °C) water. Each test was replicated four times. In the leachate the amount of dissolved organic carbon was analyzed. The experiments showed that only for the brown soil water repellency decreased significantly with increasing amount of infiltration water whereas for gley soils no correlation was found. Gley soil had initially a lower degree of hydrophobicity compared to the other soils. Possibly due to the higher bulk density of these soils, the carbon compounds directly surrounding the soil particles wre rearranged rather than leached. No clear pattern could be obtained for organic soils. This may be explained by the high initial carbon content of more than 20%. It may take a much greater amount of infiltration to affect hydrophobicity. The critical contact angle of investigated soils above which water repellency is moderately persistent, was 93.8°. In May 2012 ten more sites were sampled and five soil types were investigated

  11. Magnetic Bistability in a Discrete Organic Radical.

    PubMed

    Li, Tao; Tan, Gengwen; Shao, Dong; Li, Jing; Zhang, Zaichao; Song, You; Sui, Yunxia; Chen, Sheng; Fang, Yong; Wang, Xinping

    2016-08-17

    Molecular assembly with magnetic bistability has been of considerable interest for application as electronic devices. In contrast to transition-metal complexes, magnetic bistability so far observed in organic radical crystals is mainly caused by intermolecular electron-exchange interaction. We now report that the magnetic bistability in an organic radical can also be caused by intramolecular electron-exchange interaction. The diradical salt of 1,4-di(bisphenylamino)-2,3,5,6,-tetramethylbenzene undergoes a phase transition with a thermal hysteresis loop over the temperature range from 118 to 131 K. The phases above and below the loop correspond to two different singlet states of the diradical dication. The results provide a novel organic radical material as an unprecedented instance of an intramolecular magnetic bistability revalent to the design of functional materials. PMID:27479783

  12. Radical abdominoplasty, including body shaping: representative cases.

    PubMed

    Mühlbauer, W

    1989-01-01

    Even in the age of liposuction there exist certain situations for which abdominoplasty in its radical form is indicated--for example, redundant skin after radical weight loss, the stigmata of postpregnancy syndrome, and localized accumulation of adipose tissue--the lipodystrophies and resistant generalized obesity. Redundant skin after radical weight loss is resected simultaneously around the abdomen, the lumbar regions, the perineum, and the thighs. The typical stigmata of postpregnancy syndrome may be excised through an extended abdominoplasty combined with simultaneous excision and pexy of the inner aspects of the thighs leaving a "bikini" scar behind. A mastopexy may be added. Genetically predisposed localized lipodystrophies in the abdominal lumbar, and upper thigh region may be resected through a circular abdominoplasty with or without simultaneous resection of the perineum and inner thighs. Abdominal aprons often contain umbilical or ventral hernias that may need to be repaired simultaneously. Representative cases are presented and dangers and complications are discussed. PMID:2741749

  13. Resveratrol products resulting by free radical attack

    NASA Astrophysics Data System (ADS)

    Bader, Yvonne; Quint, R. M.; Getoff, Nikola

    2008-06-01

    Trans-resveratrol ( trans-3,4',5-trihydroxystilbene; RES), which is contained in red wine and many plants, is one of the most relevant and extensively investigated stilbenes with a broad spectrum of biological activities. Among other duties, RES has been reported to have anti-carcinogenetic activities, which could be attributed to its antioxidant properties. The degradation of RES was studied under various conditions. The products (aldehydes, carboxylic acids, etc.) generated from RES by the attack of free radicals were registered as a function of the radical concentration (absorbed radiation dose). Based on the obtained data it appears that the OH radicals are initiating the rather complicated process, which involves of the numerous consecutive reactions. A possible starting reaction mechanism is presented.

  14. Antioxidant and radical scavenging properties of curcumin.

    PubMed

    Ak, Tuba; Gülçin, Ilhami

    2008-07-10

    Curcumin (diferuoyl methane) is a phenolic compound and a major component of Curcuma longa L. In the present paper, we determined the antioxidant activity of curcumin by employing various in vitro antioxidant assays such as 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH*) scavenging, 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) radical scavenging activity, N,N-dimethyl-p-phenylenediamine dihydrochloride (DMPD) radical scavenging activity, total antioxidant activity determination by ferric thiocyanate, total reducing ability determination by the Fe(3+)-Fe(2+) transformation method, superoxide anion radical scavenging by the riboflavin/methionine/illuminate system, hydrogen peroxide scavenging and ferrous ions (Fe(2+)) chelating activities. Curcumin inhibited 97.3% lipid peroxidation of linoleic acid emulsion at 15 microg/mL concentration (20 mM). On the other hand, butylated hydroxyanisole (BHA, 123 mM), butylated hydroxytoluene (BHT, 102 mM), alpha-tocopherol (51 mM) and trolox (90 mM) as standard antioxidants indicated inhibition of 95.4, 99.7, 84.6 and 95.6% on peroxidation of linoleic acid emulsion at 45 microg/mL concentration, respectively. In addition, curcumin had an effective DPPH* scavenging, ABTS*(+) scavenging, DMPD*(+) scavenging, superoxide anion radical scavenging, hydrogen peroxide scavenging, ferric ions (Fe(3+)) reducing power and ferrous ions (Fe(2+)) chelating activities. Also, BHA, BHT, alpha-tocopherol and trolox, were used as the reference antioxidant and radical scavenger compounds. According to the present study, curcumin can be used in the pharmacological and food industry because of these properties. PMID:18547552

  15. Total radical yields from tropospheric ethene ozonolysis.

    PubMed

    Alam, Mohammed S; Camredon, Marie; Rickard, Andrew R; Carr, Timo; Wyche, Kevin P; Hornsby, Karen E; Monks, Paul S; Bloss, William J

    2011-06-21

    The gas-phase reactions of ozone with alkenes can be significant sources of free radicals (OH, HO(2) and RO(2)) in the Earth's atmosphere. In this study the total radical production and degradation products from ethene ozonolysis have been measured, under conditions relevant to the troposphere, during a series of detailed simulation chamber experiments. Experiments were carried out in the European photoreactor EUPHORE (Valencia, Spain), utilising various instrumentation including a chemical-ionisation-reaction time-of-flight mass-spectrometer (CIR-TOF-MS) measuring volatile organic compounds/oxygenated volatile organic compounds (VOCs/OVOCs), a laser induced fluorescence (LIF) system for measuring HO(2) radical products and a peroxy radical chemical amplification (PERCA) instrument measuring HO(2) + ΣRO(2). The ethene + ozone reaction system was investigated with and without an OH radical scavenger, in order to suppress side reactions. Radical concentrations were measured under dry and humid conditions and interpreted through detailed chemical chamber box modelling, incorporating the Master Chemical Mechanism (MCMv3.1) degradation scheme for ethene, which was updated to include a more explicit representation of the ethene-ozone reaction mechanism.The rate coefficient for the ethene + ozone reaction was measured to be (1.45 ± 0.25) × 10(-18) cm(3) molecules(-1) s(-1) at 298 K, and a stabilised Criegee intermediate yield of 0.54 ± 0.12 was determined from excess CO scavenger experiments. An OH radical yield of 0.17 ± 0.09 was determined using a cyclohexane scavenger approach, by monitoring the formation of the OH-initiated cyclohexane oxidation products and HO(2). The results highlight the importance of knowing the [HO(2)] (particularly under alkene limited conditions and high [O(3)]) and scavenger chemistry when deriving radical yields. An averaged HO(2) yield of 0.27 ± 0.07 was determined by LIF/model fitting. The observed yields are interpreted in terms of

  16. Resonance ionization detection of combustion radicals

    SciTech Connect

    Cool, T.A.

    1993-12-01

    Fundamental research on the combustion of halogenated organic compounds with emphasis on reaction pathways leading to the formation of chlorinated aromatic compounds and the development of continuous emission monitoring methods will assist in DOE efforts in the management and disposal of hazardous chemical wastes. Selective laser ionization techniques are used in this laboratory for the measurement of concentration profiles of radical intermediates in the combustion of chlorinated hydrocarbon flames. A new ultrasensitive detection technique, made possible with the advent of tunable VUV laser sources, enables the selective near-threshold photoionization of all radical intermediates in premixed hydrocarbon and chlorinated hydrocarbon flames.

  17. Evolution of radical mastectomy for breast cancer

    PubMed Central

    Plesca, M; Bordea, C; El Houcheimi, B; Ichim, E; Blidaru, A

    2016-01-01

    Surgical treatment of breast cancer has been marked by a constant evolution since the Halsted radical mastectomy described in the late 19th century has become the current standard Madden radical mastectomy, a breast surgery that involves the ablation of tissue with the axillary lymphatic preserving both pectoral muscles. The purpose of this paper was to present the stages that have marked the evolution of this intervention and to provide an overview of the way breast cancer has been understood and treated in the last century. PMID:27453752

  18. Cell damage by oxygen free radicals.

    PubMed

    Bellomo, G

    1991-02-01

    The exposure of isolated and cultured cells to oxygen free radicals generated extracellularly or intracellularly during the metabolism of foreing compounds results in the development of damage that eventually lead to cell death. Multiple mechanisms are involved in these cytopathological processes, including direct attack of free radicals to macromolecules essential for cell life, as well as indirect activation of catabolic processes such as proteases, endonucleases and phospholipases. A key role in triggering these indirect events is played by Ca(2+) whose cytosolic concentration during oxidative stress raises well above the physiological limits. PMID:22358959

  19. [Robot-assisted radical prostatectomy: surgical techniques].

    PubMed

    Kojima, Yoshiyuki; Sato, Yuichi; Ogawa, Soichiro; Haga, Nobuhiro; Yanagida, Tomohiko

    2016-01-01

    Robot-assisted radical prostatectomy (RARP) for the patients with localized prostate cancer is increasingly being adopted around the world. The da Vinci surgical system (Intuitive Surgical, Sunnyvale, CA, USA) provides the advantages of simplification and precision of exposure and suturing because of allowing movements of the robotic arm in real time with increased degree of freedom and magnified 3-dimensional view. Therefore, RARP has been expected to provide superior therapeutic benefit to patients in terms of surgical outcome to open or laparoscopic radical prostatectomy. In this review, we provide our technical aspects and tips and tricks of RARP to improve surgical outcome and postoperative quality of life. PMID:26793888

  20. Radical Behaviorism and Buddhism: Complementarities and Conflicts

    PubMed Central

    Diller, James W; Lattal, Kennon A

    2008-01-01

    Comparisons have been made between Buddhism and the philosophy of science in general, but there have been only a few attempts to draw comparisons directly with the philosophy of radical behaviorism. The present review therefore considers heretofore unconsidered points of comparison between Buddhism and radical behaviorism in terms of their respective goals, conceptualization of human beings, and the outcomes of following either philosophy. From these comparisons it is concluded that the commonalities discerned between these two philosophies may enhance both philosophical systems. PMID:22478509

  1. Free-radical kinetics of coal liquefaction

    SciTech Connect

    Wang, M.; Smith, J.M.; McCoy, B.J.

    1994-07-16

    A rate expression with first- and second-order terms in the concentration of extractable compounds in solid coal particles is derived from a fundamental free-radical mechanism. The expression was suggested empirically by prior experiments for coal liquefaction in the presence of a hydrogen-donor solvent. Radical reactions are considered to occur in both coal and in solvent. The long-chain approximation justifies the neglect of initiation, hydrogen abstraction, and termination rates as quantitatively insignificant relative to propagation reaction rates.

  2. Resonant cavity spectroscopy of radical species

    NASA Astrophysics Data System (ADS)

    Ritchie, Grant

    2015-04-01

    Photo-oxidation in the troposphere is highly complex, being initiated by short lived radical species, in the daytime dominated by the hydroxyl radical, OH, with contributions from Cl atoms, and at night by either NO3 radicals or ozone. Chemical oxidation cycles, which couple OH, HO2 and peroxy (RO2) radical species, remove primary emitted trace species which are harmful to humans or to the wider environment. However, many of the secondary products produced by atmospheric photo-oxidation are also directly harmful, for example O3, NO2, acidic and multifunctional species, many of which are of low volatility and are able to partition effectively to the condensed phase, creating secondary organic aerosol (SOA), which contributes a significant fraction of tropospheric aerosol, with associated impacts on climate and human health. The accuracy of atmospheric models to predict these impacts necessarily requires accurate knowledge of the chemical oxidative cycling. Two of the simplest intermediates are the hydroperoxy radical, HO2, and the smallest and dominant organic peroxy radical, CH3O2, formed directly by the reactions of OH with CO/O2 and CH4/O2, respectively, and indirectly following the oxidation of larger VOCs. OH, HO2 and RO2 (collectively known as ROx) are rapidly cycled, being at the centre of tropospheric oxidation, and hence are some of the best targets for models to compare with field data. The reaction of HO2 and RO2 with NO constitutes the only tropospheric in-situ source of O3. Despite their importance, neither HO2 nor CH3O2 is measured directly in the atmosphere. HO2 is only measured indirectly following its conversion to OH and CH3O2 is not measured at all. Typically only the sum of RO2 radicals is measured, making no distinction between different organic peroxy radicals. This contribution will detail recent studies using (i) optical feedback cavity enhanced absorption spectroscopy with both quantum and inter-band cascade lasers in the mid-IR, and (ii

  3. Synergistic radical scavenging potency of curcumin-in-β-cyclodextrin-in-nanomagnetoliposomes.

    PubMed

    Aadinath, W; Bhushani, Anu; Anandharamakrishnan, C

    2016-07-01

    Curcumin is a highly potent nutraceutical associated with various health benefits. However, its hydrophobic nature affects its bioavailability and bioactivity, and limits nutraceutical applications. Drug-in-cyclodextrin-in-liposome has the ability to mask the hydrophobic nature of drug and achieve better encapsulation. Also, encapsulating iron oxide nanoparticles (IONPs) within liposomes endow additional beneficial functionalities of IONPs. In the present study, curcumin-β-cyclodextrin inclusion complex (IC) and IONPs were co-encapsulated within liposomes (curcumin-in-β-cyclodextrin-in-nanomagnetoliposomes) to achieve the synergistic antioxidant potential of curcumin and IONPs. IC of curcumin-β-cyclodextrin was prepared by a simple rapid method and successful inclusion was confirmed by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). Mean diameter of IONPs was found to be 180nm and X-ray diffraction pattern confirmed the formation of hematite nanoparticles. Band gap energy calculated using absorption spectra was 2.25eV, which falls in close proximity with the theoretically calculated values of hematite. Mean diameter of curcumin-in-β-cyclodextrin-in-nanomagnetoliposomes was 67nm and encapsulation efficiency of curcumin was found to be 71%. Further, the co-encapsulated particles possessed significantly low IC50 value (64.7791μg/ml, p<0.01) compared to conventional curcumin liposome and IONPs, indicating its synergistically enhanced radical scavenging property. PMID:27127056

  4. Application of surface enzyme treatments using laccase and a hydrophobic compound to paper-based media.

    PubMed

    Cusola, Oriol; Valls, Cristina; Vidal, Teresa; Roncero, M Blanca

    2013-03-01

    A new approach for the hydrophobization of finished cellulosic substrates based on a previously reported enzymatic technique is proposed. Commercial finished paper was hydrophobized by using laccase from Trametes villosa in combination with lauryl gallate (LG) as hydrophobic compound. The efficiency of the method was increased by the use of a lignosulfonate as a natural dispersant to improve the surface distribution of LG on the paper, raise its hydrophobicity and help preserve the enzyme activity. No similar threefold effect from a single compound for the improvement of enzymatic treatments was previously reported. The influence of processing conditions including the LG dose, treatment time and temperature was also examined, resulting in further increased hydrophobicity. Efficient fiber bonding and chemical functionalization were confirmed by thorough washing and Soxhlet extraction of the paper. As shown here for the first time, enzyme treatments have the potential to improve the surface hydrophobicity of paper-based media. PMID:23453234

  5. Inhibitory effect of super-hydrophobicity on silver release and antibacterial properties of super-hydrophobic Ag/TiO2 nanotubes.

    PubMed

    Zhang, Licheng; Zhang, Lihai; Yang, Yun; Zhang, Wei; Lv, Houchen; Yang, Fei; Lin, Changjian; Tang, Peifu

    2016-07-01

    The antibacterial properties of super-hydrophobic silver (Ag) on implant surface have not yet to be fully illuminated. In our study, we investigate the protective effects of super-hydrophobic coating of silver/titanium dioxide (Ag/TiO2 ) nanotubes against bacterial pathogens, as well as its pattern of Ag release. Ag/TiO2 nanotubes are prepared by a combination of electrochemical anodization and pulse electrodeposition. The super-hydrophobic coating is prepared by modifying the surface of Ag/TiO2 nanotubes with 1H, 1H, 2H, 2H-perfluorooctyl-triethoxysilane (PTES). Surface features and Ag release are examined by SEM, X-ray photoelectron spectroscopy, contact-angle measurement, and inductively coupled plasma-mass spectrometry (ICP-MS). The antibacterial activity of super-hydrophobic coating Ag/TiO2 nanotubes is investigated both in vitro and in vivo. Consequently, the super-hydrophobic coating on Ag/TiO2 nanotubes shows a regularly arranged structure; and nano-Ag particles (10-30 nm) are evenly distributed on the surface or inside the nanotubes. The contact angles of water on the super-hydrophobic coating Ag/TiO2 nanotubes are all above 150°. In addition, the super-hydrophobic character displays a certain conserved effect that contributes to the sustained release of Ag. The super-hydrophobic Ag/TiO2 nanotubes are also effective in inhibiting bacterial adhesion, killing the adhering bacteria and preventing postoperative infection in rabbits. Therefore, it is expected that the super-hydrophobic Ag/TiO2 nanotubes which can contain the release of Ag, leading to stable release, may show a consistent surface antibacterial capability. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1004-1012, 2016. PMID:25995046

  6. [Preparation of honeycombed monolithic zeolite and hydrophobic modification with SiCl4].

    PubMed

    Wang, Xi-Qin; Li, Kai; Wei, Bing; Luan, Zhi-Qiang

    2011-12-01

    A kind of hydrophobic zeolitic monolith were prepared by mixing HY/ZSM-5, additives and water, followed by processes of extrusion and drying, and then hydrophobic modification with SiCl4. The structures and properties of the adsorbent were examined by nitrogen adsorption and desorption measurement, XRD, and benzene adsorption experiment. The results show that those adsorbents possess hierarchical pore structures and excellent hydrophobicity. PMID:22468534

  7. Glutathione--hydroxyl radical interaction: a theoretical study on radical recognition process.

    PubMed

    Fiser, Béla; Jójárt, Balázs; Csizmadia, Imre G; Viskolcz, Béla

    2013-01-01

    Non-reactive, comparative (2 × 1.2 μs) molecular dynamics simulations were carried out to characterize the interactions between glutathione (GSH, host molecule) and hydroxyl radical (OH(•), guest molecule). From this analysis, two distinct steps were identified in the recognition process of hydroxyl radical by glutathione: catching and steering, based on the interactions between the host-guest molecules. Over 78% of all interactions are related to the catching mechanism via complex formation between anionic carboxyl groups and the OH radical, hence both terminal residues of GSH serve as recognition sites. The glycine residue has an additional role in the recognition of OH radical, namely the steering. The flexibility of the Gly residue enables the formation of further interactions of other parts of glutathione (e.g. thiol, α- and β-carbons) with the lone electron pair of the hydroxyl radical. Moreover, quantum chemical calculations were carried out on selected GSH/OH(•) complexes and on appropriate GSH conformers to describe the energy profile of the recognition process. The relative enthalpy and the free energy changes of the radical recognition of the strongest complexes varied from -42.4 to -27.8 kJ/mol and from -21.3 to 9.8 kJ/mol, respectively. These complexes, containing two or more intermolecular interactions, would be the starting configurations for the hydrogen atom migration to quench the hydroxyl radical via different reaction channels. PMID:24040010

  8. Radical scavenging ability of some compounds isolated from Piper cubeba towards free radicals.

    PubMed

    Aboul-Enein, Hassan Y; Kładna, Aleksandra; Kruk, Irena

    2011-01-01

    The purpose of this study was to identify the antioxidant activity of 16 compounds isolated from Piper cubeba (CNCs) through the extent of their capacities to scavenge free radicals, hydroxyl radical (HO(•)), superoxide anion radical O•(2)(-) and 2,2-diphenyl-1-picrylhydrazyl radical (DPPH(•)), in different systems. Electron paramagnetic resonance (EPR) and 5,5-dimethyl-1-pyrroline-N-oxide, DMPO, as the spin trap, and chemiluminescence techniques were applied. Using the Fenton-like reaction [Fe(II) + H(2)O(2)], CNCs were found to inhibit DMPO-OH radical formation ranging from 5 to 57% at 1.25 mmol L(-1) concentration. The examined CNCs also showed a high DPPH antiradical activity (ranging from 15 to 99% at 5 mmol L(-1) concentration). Furthermore, the results indicated that seven of the 16 tested compounds may catalyse the conversion of superoxide radicals generated in the potassium superoxide/18-crown-6 ether system, thus showing superoxide dismutase-like activity. The data obtained suggest that radical scavenging properties of CNCs might have potential application in many plant medicines. PMID:21681910

  9. Impact of particle nanotopology on water transport through hydrophobic soils.

    PubMed

    Truong, Vi Khanh; Owuor, Elizabeth A; Murugaraj, Pandiyan; Crawford, Russell J; Mainwaring, David E

    2015-12-15

    The impact of non- and poorly wetting soils has become increasingly important, due to its direct influence on the water-limited potential yield of rain-fed grain crops at a time of enhanced global competition for fresh water. This study investigates the physical and compositional mechanisms underlying the influence of soil organic matter (SOM) on the wetting processes of model systems. These model systems are directly related to two sandy wheat-producing soils that have contrasting hydrophobicities. Atomic force microscopy (AFM), contact angle and Raman micro-spectroscopy measurements on model planar and particulate SOM-containing surfaces demonstrated the role of the hierarchical surface structure on the wetting dynamics of packed particulate beds. It was found that a nanoscale surface topology is superimposed over the microscale roughness of the packed particles, and this controls the extent of water ingress into particulate packed beds of these particles. Using two of the dominant component organic species found in the SOM of the two soils used in this study, it was found that the specific interactions taking place between the SOM components, rather than their absolute quantities, dictated the formation of highly hydrophobic surface nanotopologies. This hydrophobicity was demonstrated, using micro-Raman imaging, to arise from the surface being in a composite Cassie-Baxter wetting state. Raman imaging demonstrated that the particle surface nanotopography influenced the degree of air entrapment in the interstices within the particle bed. The influence of a conventional surfactant on the wetting kinetics of both the model planar surfaces and packed particulate beds was quantified in terms of their respective advancing contact angles and the capillary wetting force vector. The information obtained for all of the planar and particulate surfaces, together with that obtained for the two soils, allowed linear relationships to be obtained in plots of the contact angle

  10. Sweeping Gas Membrane Desalination Using Commercial Hydrophobic Hollow Fiber Membranes

    SciTech Connect

    EVANS, LINDSEY; MILLER, JAMES E.

    2002-01-01

    Water shortages affect 88 developing countries that are home to half of the world's population. In these places, 80-90% of all diseases and 30% of all deaths result from poor water quality. Furthermore, over the next 25 years, the number of people affected by severe water shortages is expected to increase fourfold. Low cost methods of purifying freshwater, and desalting seawater are required to contend with this destabilizing trend. Membrane distillation (MD) is an emerging technology for separations that are traditionally accomplished via conventional distillation or reverse osmosis. As applied to desalination, MD involves the transport of water vapor from a saline solution through the pores of a hydrophobic membrane. In sweeping gas MD, a flowing gas stream is used to flush the water vapor from the permeate side of the membrane, thereby maintaining the vapor pressure gradient necessary for mass transfer. Since liquid does not penetrate the hydrophobic membrane, dissolved ions are completely rejected by the membrane. MD has a number of potential advantages over conventional desalination including low temperature and pressure operation, reduced membrane strength requirements, compact size, and 100% rejection of non-volatiles. The present work evaluated the suitability of commercially available technology for sweeping gas membrane desalination. Evaluations were conducted with Celgard Liqui-Cel{reg_sign} Extra-Flow 2.5X8 membrane contactors with X-30 and X-40 hydrophobic hollow fiber membranes. Our results show that sweeping gas membrane desalination systems are capable of producing low total dissolved solids (TDS) water, typically 10 ppm or less, from seawater, using low grade heat. However, there are several barriers that currently prevent sweeping gas MD from being a viable desalination technology. The primary problem is that large air flows are required to achieve significant water yields, and the costs associated with transporting this air are prohibitive. To

  11. Study on Super-Hydrophobic and Oleophobic Surfaces Prepared by Chemical Adsorption Technique

    NASA Astrophysics Data System (ADS)

    Tsuji, Issei; Ohkubo, Yuji; Ogawa, Kazufumi

    2009-04-01

    Preparation techniques for super-hydrophobic and oleophobic surfaces were studied by forming a fractally roughened surface and preparing a hydrophobic monolayer. In this study, the fractal structure on the surface of an aluminum substrate was formed by combining sand-blasting with electrolytical etching. Then, a hydrophobic monolayer was prepared on the roughened surface, without decreasing roughness. The surface of the treated substrate can be evaluated by contact angle measurement and field emission scanning electron microscopy (FE-SEM). The surface treated by a technique combining chemical adsorption, sandblasting, and electrolytical etching was super-hydrophobic and highly oleophobic.

  12. Use of hydrophobic constants of molecular fragments for characterizing analytical systems

    SciTech Connect

    Tselik, E.I.; Polvektov, N.S.

    1985-06-10

    The authors attempt to clarify the applicability of the proposed hydrophobicity parameters to a description of the behavior of complex compounds with organic ligands in extractional systems, and to establish quantitative relationships between the properties of the complex and hydrophobicity of the ligand. It was found that the stability constants of the ionic associates of lanthanum, neodymium, and erbium with certain derivatives of salicylic acid, dihalogenated derivatives of 8-hydroxyquinoline, and Rhodamine B correlate with the hydrophobicity of the ligands. The quantitative expressions of these serve as empirical hydrophobic constants of molecular fragments of organic compounds.

  13. On-demand microfluidic droplet manipulation using hydrophobic ferrofluid as a continuous-phase.

    PubMed

    Zhang, Kai; Liang, Qionglin; Ai, Xiaoni; Hu, Ping; Wang, Yiming; Luo, Guoan

    2011-04-01

    Multiple essential microdroplet operation units, including splitting, dispensing, oil-phase exchange, trapping, release and demulsification, were successfully implemented by combining hydrophobic ferrofluid with microfluidic chips. PMID:21327251

  14. Bioconcentration kinetics of hydrophobic chemicals in different densities of Chlorella pyrenoidosa

    SciTech Connect

    Sijm, D.T.H.M.; Broersen, K.W.; Roode, D.F. de; Mayer, P.

    1998-09-01

    Algal density-dependent bioconcentration factors and rate constants were determined for a series of hydrophobic compounds in Chlorella pyrenoidosa. The apparent uptake rate constants of the hydrophobic compounds in algae varied between 200 and 710,000 L/kg/d, slightly increased with hydrophobicity within an experiment, were relatively constant for each algal density, and fitted fairly within existing allometric relationships. The bioavailability of the hydrophobic test compounds was significantly reduced by sorption by algal exudates. The sorption coefficients of the hydrophobic compounds to the algal exudates were between 80 and 1,200 L/kg, and were for most algal densities in the same order of magnitude as the apparent bioconcentration factors to the algae, that is, between 80 and 60,200 L/kg. In typical field situations, however, no significant reduction in bioavailability due to exudates is expected. The apparent elimination rate constants of the hydrophobic compounds were high and fairly constant for each algal density and varied between 2 and 190/d. Because the apparent elimination rate constants were higher than the growth rate constant, and were independent of hydrophobicity, the authors speculated that other factors dominate excretion, such as exudate excretion-enhanced elimination. Bioconcentration factors increased less than proportional with hydrophobicity, i.e., the octanol-water partition coefficient [K{sub ow}]. The role of algal composition in bioconcentration is evaluated. Bioconcentrations (kinetics) of hydrophobic compounds that are determined at high algal densities should be applied with caution to field situations.

  15. RadicalLocator: A software tool for identifying the radicals in Chinese characters.

    PubMed

    Yu, Lili; Reichle, Erik D; Jones, Mathew; Liversedge, Simon P

    2015-09-01

    This article describes a new software tool called RadicalLocator that can be used to automatically identify (e.g., for visual inspection) individual target radicals (i.e., groups of strokes) in written Chinese characters. We first briefly clarify why this software is useful for research purposes and discuss the factors that make this pattern recognition task so difficult. We then describe how the software can be downloaded and installed, and used to identify the radicals in characters for the purposes of, for example, selecting materials for psycholinguistic experiments. Finally, we discuss several known limitations of the software and heuristics for addressing them. PMID:25169830

  16. Radical Negativity: Music Education for Social Justice

    ERIC Educational Resources Information Center

    McLaren, Peter

    2011-01-01

    According to Hedges (2010), the real enemies of the liberal class are radical thinkers such as Noam Chomsky and Ralph Nader, iconoclastic intellectuals who possess the moral autonomy to defy the power elite. While this author agrees with Hedges, he would take this argument even further. In this article, the author argues that the real enemy of…

  17. Radical Agendas? The Politics of Adult Education.

    ERIC Educational Resources Information Center

    Westwood, Sallie, Ed.; Thomas, J. E., Ed.

    This book brings together eight of the most significant papers published in the journal "Studies in the Education of Adults" from the 1970s and 1980s, together with three new essays that place the earlier material in context. It examines the changes in British adult education between 1970 and 1990 and is concerned with the place of radicalism in…

  18. Serendipitous findings while researching oxygen free radicals.

    PubMed

    Floyd, Robert A

    2009-04-15

    This review is based on the honor of receiving the Discovery Award from the Society of Free Radical Biology and Medicine. The review is reflective and presents our thinking that led to experiments that yielded novel observations. Critical questioning of our understanding of oxygen free radicals in biomedical problems led us to use and develop more direct and extremely sensitive methods. This included nitrone free radical spin trapping and HPLC-electrochemical detection. This technology led to the pioneering use of salicylate to trap hydroxyl free radicals and show increased flux in ischemia/reperfused brain regions and also to first sensitively detect 8-hydroxyl-2-deoxyguanosine in oxidatively damaged DNA and help assess its role in cancer development. We demonstrated that methylene blue (MB) photoinduces formation of 8-hydroxyguanine in DNA and RNA and discovered that MB sensitively photoinactivates RNA viruses, including HIV and the West Nile virus. Studies in experimental stroke led us serendipitously to discover that alpha-phenyl-tert-butylnitrone (PBN) was neuroprotective if given after the stroke. This led to extensive commercial development of NXY-059, a PBN derivative, for the treatment of stroke. More recently we discovered that PBN nitrones have potent anti-cancer activity and are active in preventing hearing loss caused by acute acoustical trauma. PMID:19439210

  19. DNP with Trityl Radicals in Deuterated Polyethylene

    NASA Astrophysics Data System (ADS)

    Wang, Li; Meyer, W.; Berlin, A.; Herick, J.; Hess, C.; Reicherz, G.

    2016-02-01

    Chemically doping with trityl radicals was performed in fully deuterated polyethylene. The behavior of paramagnetic centers has been investigated by ESR X-band spectrometer. The highest deuteron polarization was 8% at 2.5 T and 1 K with a spin concentration of 3 × 1019 spins/g.

  20. Unimolecular reaction dynamics of free radicals

    SciTech Connect

    Terry A. Miller

    2006-09-01

    Free radical reactions are of crucial importance in combustion and in atmospheric chemistry. Reliable theoretical models for predicting the rates and products of these reactions are required for modeling combustion and atmospheric chemistry systems. Unimolecular reactions frequently play a crucial role in determining final products. The dissociations of vinyl, CH2= CH, and methoxy, CH3O, have low barriers, about 13,000 cm-1 and 8,000 cm-1, respectively. Since barriers of this magnitude are typical of free radicals these molecules should serve as benchmarks for this important class of reactions. To achieve this goal, a detailed understanding of the vinyl and methoxy radicals is required. Results for dissociation dynamics of vinyl and selectively deuterated vinyl radical are reported. Significantly, H-atom scrambling is shown not to occur in this reaction. A large number of spectroscopic experiments for CH3O and CHD2O have been performed. Spectra recorded include laser induced fluorescence (LIF), laser excited dispersed fluorescence (LEDF), fluorescence dip infrared (FDIR) and stimulated emission pumping (SEP). Such results are critical for implementing dynamics experiments involving the dissociation of methoxy.

  1. Radical Constructivism, and the Sin of Relativism

    ERIC Educational Resources Information Center

    Quale, Andreas

    2007-01-01

    The epistemology of "relativism" that is featured by the theory of radical constructivism is addressed. In particular, I examine several objections, all based on this epistemic position of relativism, that are often raised by critics of the theory: the charge of "reality denial" (which, it is often claimed, must lead ultimately to the…

  2. Radical Feminism and the Subject of Writing.

    ERIC Educational Resources Information Center

    Rhodes, Jacqueline

    The radical feminists of the late 1960s and early 1970s, as well as their online counterparts today, offer provocative examples of networked textuality, a discourse dependent on the constant and visible contextualization of self and writing within the discourses of hegemony. Given its potential use for liberatory writing pedagogies, it seems…

  3. Density functional calculations on model tyrosyl radicals.

    PubMed Central

    Himo, F; Gräslund, A; Eriksson, L A

    1997-01-01

    A gradient-corrected density functional theory approach (PWP86) has been applied, together with large basis sets (IGLO-III), to investigate the structure and hyperfine properties of model tyrosyl free radicals. In nature, these radicals are observed in, e.g., the charge transfer pathways in photosystem II (PSII) and in ribonucleotide reductases (RNRs). By comparing spin density distributions and proton hyperfine couplings with experimental data, it is confirmed that the tyrosyl radicals present in the proteins are neutral. It is shown that hydrogen bonding to the phenoxyl oxygen atom, when present, causes a reduction in spin density on O and a corresponding increase on C4. Calculated proton hyperfine coupling constants for the beta-protons show that the alpha-carbon is rotated 75-80 degrees out of the plane of the ring in PSII and Salmonella typhimurium RNR, but only 20-30 degrees in, e.g., Escherichia coli, mouse, herpes simplex, and bacteriophage T4-induced RNRs. Furthermore, based on the present calculations, we have revised the empirical parameters used in the experimental determination of the oxygen spin density in the tyrosyl radical in E. coli RNR and of the ring carbon spin densities, from measured hyperfine coupling constants. Images FIGURE 1 FIGURE 5 PMID:9083661

  4. Dynamics of poly(4-hydroxystyrene) radical cation

    NASA Astrophysics Data System (ADS)

    Okamoto, Kazumasa; Kozawa, Takahiro; Tagawa, Seiichi

    2008-03-01

    Poly(4-hydroxystyrene) (PHS) has been used in KrF excimer laser (248 nm) lithography as a backbone polymer, and is also a promising material for EUV or electron beam lithography. Analysis of the intermediate species is important for the control of reactions in resist materials. Since the size of integrated circuits fabricated for mass production will decrease below 30 nm and the size error must also be decreased to the molecular level, the elucidation of proton dynamics at the molecular level is also important for reducing the deviation of the resist pattern size. In this study, the dynamics of PHS radical cations were studied, because PHS radical cation is main source of proton. The transient absorption of PHS was observed in the near-infrared region (NIR) in p-dioxane solutions by pulse radiolysis. The intramolecular PHS dimer radical cation (M2 +.) were observed, whereas p-cresol shows no distinct CR band. Although the radical cations of phenol derivatives are known to be easily deprotonated, it was found that M2 +. formation prevents deprotonation by its charge resonance stabilization.

  5. The Radical Faculty -- What Are Its Goals?

    ERIC Educational Resources Information Center

    Kampf, Louis

    According to radical faculty members and students, universities have been contradicting their humanistic educational ideals by concentrating on competitive professionalism and non-academic research in a struggle for institutional power in a preponderantly capitalistic society. It is their belief that meaningful education provides intellectual…

  6. Emerging themes in radical SAM chemistry

    PubMed Central

    Shisler, Krista A; Broderick, Joan B

    2014-01-01

    Enzymes in the radical SAM (RS) superfamily catalyze a wide variety of reactions through unique radical chemistry. The characteristic markers of the superfamily include a [4Fe–4S] cluster coordinated to the protein via a cysteine triad motif, typically CX3CX2C, with the fourth iron coordinated by S-adenosylmethionine (SAM). The SAM serves as a precursor for a 5′-deoxyadenosyl radical, the central intermediate in nearly all RS enzymes studied to date. The SAM-bound [4Fe–4S] cluster is located within a partial or full triosephosphate isomerase (TIM) barrel where the radical chemistry occurs protected from the surroundings. In addition to the TIM barrel and a RS [4Fe–4S] cluster, many members of the superfamily contain additional domains and/or additional Fe–S clusters. Recently characterized superfamily members are providing new examples of the remarkable range of reactions that can be catalyzed, as well as new structural and mechanistic insights into these fascinating reactions. PMID:23141873

  7. Neurotoxins: Free Radical Mechanisms and Melatonin Protection

    PubMed Central

    Reiter, Russel J.; Manchester, Lucien C.; Tan, Dun-Xian

    2010-01-01

    Toxins that pass through the blood-brain barrier put neurons and glia in peril. The damage inflicted is usually a consequence of the ability of these toxic agents to induce free radical generation within cells but especially at the level of the mitochondria. The elevated production of oxygen and nitrogen-based radicals and related non-radical products leads to the oxidation of essential macromolecules including lipids, proteins and DNA. The resultant damage is referred to as oxidative and nitrosative stress and, when the molecular destruction is sufficiently severe, it causes apoptosis or necrosis of neurons and glia. Loss of brain cells compromises the functions of the central nervous system expressed as motor, sensory and cognitive deficits and psychological alterations. In this survey we summarize the publications related to the following neurotoxins and the protective actions of melatonin: aminolevulinic acid, cyanide, domoic acid, kainic acid, metals, methamphetamine, polychlorinated biphenyls, rotenone, toluene and 6-hydroxydopamine. Given the potent direct free radical scavenging activities of melatonin and its metabolites, their ability to indirectly stimulate antioxidative enzymes and their efficacy in reducing electron leakage from mitochondria, it would be expected that these molecules would protect the brain from oxidative and nitrosative molecular mutilation. The studies summarized in this review indicate that this is indeed the case, an action that is obviously assisted by the fact that melatonin readily crosses the blood brain barrier. PMID:21358970

  8. Praxis: Implication for "Really" Radical Education.

    ERIC Educational Resources Information Center

    Allman, Paula; Wallis, John

    1990-01-01

    Explicates the concept of praxis in Marx's dialectical analysis of capitalism and relates it to radical education: issues of access to educational opportunities, the challenge to the status quo through curriculum change, the role of the intellectual, and the relationship between knowledge and action. (SK)

  9. Reactive intermediates: Radicals with multiple personalities

    NASA Astrophysics Data System (ADS)

    Forbes, Malcolm D. E.

    2013-06-01

    A combined theoretical and experimental approach has revealed that radicals can be significantly stabilized by the presence of a remote anionic site in the same molecule. This finding has implications for understanding and potentially controlling the reactivity of these important reactive intermediates.

  10. Snowballing radical generation leads to ultrahigh molecular weight polymers.

    PubMed

    Laurino, Paola; Hernandez, Hugo F; Bräuer, Judith; Krüger, Kathleen; Grützmacher, Hansjörg; Tauer, Klaus; Seeberger, Peter H

    2012-10-26

    Styrene is the classical monomer obeying zero-one kinetics in radical emulsion polymerization. Accordingly, particles that are less than 100 nm in diameter contain either one or no growing radical(s). We describe a unique photoinitiated polymerization reaction accelerated by snowballing radical generation in a continuous flow reactor. Even in comparison to classical emulsion polymerization, these unprecedented snowballing reactions are rapid and high-yielding, with each particle simultaneously containing more than one growing radical. This is a consequence of photoinitiator incorporation into the nascent polymer backbone and repeated radical generation upon photo-irradiation. PMID:22837041

  11. Hydrophobic statins induce autophagy in cultured human rhabdomyosarcoma cells.

    PubMed

    Araki, Makoto; Motojima, Kiyoto

    2008-03-01

    Statins are widely used to treat hypercholesterolemia, but they are associated with muscle-related adverse events, by as yet, inadequately resolved mechanisms. In this study, we report that statins induced autophagy in cultured human rhabdomyosarcoma A204 cells. Potency differed widely among the statins: cerivastatin induced autophagy at 0.1muM, simvastatin at 10muM but none was induced by pravastatin. Addition of mevalonate, but not cholesterol, blocked induction of autophagy by cerivastatin, suggesting that this induction is dependent on modulation of isoprenoid metabolic pathways. The statin-induced autophagy was not observed in other types of cells, such as human hepatoma HepG2 or embryonic kidney HEK293 cells. Muscle-specific abortive induction of autophagy by hydrophobic statins is a possible mechanism for statin-induced muscle-related side effects. PMID:18178158

  12. Modification of Deeply Buried Hydrophobic Interfaces by Ionic Surfactants

    SciTech Connect

    Ocko, B.M.; Tamam, L.; Pontoni, D.; Sapir, Z.; Yefet, S.; Sloutskin, E.; Reichert, H.; Deutsch, M.

    2011-04-05

    Hydrophobicity, the spontaneous segregation of oil and water, can be modified by surfactants. The way this modification occurs is studied at the oil-water interface for a range of alkanes and two ionic surfactants. A liquid interfacial monolayer, consisting of a mixture of alkane molecules and surfactant tails, is found. Upon cooling, it freezes at T{sub s}, well above the alkane's bulk freezing temperature, T{sub b}. The monolayer's phase diagram, derived by surface tensiometry, is accounted for by a mixtures-based theory. The monolayer's structure is measured by high-energy X-ray reflectivity above and below T{sub s}. A solid-solid transition in the frozen monolayer, occurring approximately 3 C below T{sub s}, is discovered and tentatively suggested to be a rotator-to-crystal transition.

  13. Modification of Deeply Buried Hydrophobic Interfaces by Ionic Surfactants

    SciTech Connect

    L Tamam; D Pontoni Z Sapir; S Yefet; S Sloutskin; B Ocko; H Reichert; M Deutsch

    2011-12-31

    Hydrophobicity, the spontaneous segregation of oil and water, can be modified by surfactants. The way this modification occurs is studied at the oil-water interface for a range of alkanes and two ionic surfactants. A liquid interfacial monolayer, consisting of a mixture of alkane molecules and surfactant tails, is found. Upon cooling, it freezes at T{sub s}, well above the alkane's bulk freezing temperature, T{sub b}. The monolayer's phase diagram, derived by surface tensiometry, is accounted for by a mixtures-based theory. The monolayer's structure is measured by high-energy X-ray reflectivity above and below T{sub s}. A solid-solid transition in the frozen monolayer, occurring approximately 3 C below T{sub s}, is discovered and tentatively suggested to be a rotator-to-crystal transition.

  14. Super-hydrophobic bandages and method of making the same

    SciTech Connect

    Simpson, John T.; D'Urso, Brian R.

    2012-06-05

    A bandage that includes a material, which can be breathable, having a first surface, and a plurality of superhydrophobic particles attached to the first surface. The plurality of superhydrophobic particles ranging in size from about 100 nanometers to about 10 micrometers. The superhydrophobic particles including a protrusive material defining a plurality of nanopores and a plurality of spaced apart nanostructures that define an external boundary of the hydrophobic particles. The nanopores providing a flow through porosity. The first surface can be rendered superhydrophobic by the attached superhydrophobic particles. The material can have a second surface opposite the first surface that is hydrophilic. The superhydrophobic particles can be adhered to the first surface by a binder. Also included is a method of making the bandages described herein.

  15. Hydrophobic actuation of a DNA origami bilayer structure.

    PubMed

    List, Jonathan; Weber, Michael; Simmel, Friedrich C

    2014-04-14

    Amphiphilic compounds have a strong tendency to form aggregates in aqueous solutions. It is shown that such aggregation can be utilized to fold cholesterol-modified, single-layered DNA origami structures into sandwich-like bilayer structures, which hide the cholesterol modifications in their interior. The DNA bilayer structures unfold after addition of the surfactant Tween 80, and also in the presence of lipid bilayer membranes, with opening kinetics well described by stretched exponentials. It is also demonstrated that by combination with an appropriate lock and key mechanism, hydrophobic actuation of DNA sandwiches can be made conditional on the presence of an additional molecular input such as a specific DNA sequence. PMID:24616083

  16. Hydrophobic conjugated microporous polymers for sorption of human serum albumin

    NASA Astrophysics Data System (ADS)

    Zheng, Chunli; Du, Miaomiao; Feng, Shanshan; Sun, Hanxue; Li, An; He, Chi; Zhang, TianCheng; Wang, Qiaorui; Wei, Wei

    2016-02-01

    This paper investigated the sorption of human serum albumin (HSA) from water by three kinds of conjugated microporous polymers (CMPs) with surface hydrophobicity and intrinsic porosity. It was found that the three CMPs captured HSA with fast sorption kinetics and good working capacity. Equilibrium was obtained at 80 min for all the tests, and the maximum sorption quantity (qm) ranged from 0.07 to 0.14 mg/mg. With the increase in the particle external surface area of the CMPs, a greater extent of HSA sorption was achieved. Moreover, promoting the dispersion of CMPs in HSA aqueous solution was also beneficial to the extraction. Attenuated Total Reflection Fourier Transform Infrared spectroscopy verified the interactions between the CMPs and the Nsbnd H, Cdbnd O, and Csbnd N groups of HSA. This paper might provide fundamental guidance for the practical application of CMPs to proteins separation and recovery.

  17. Droplet coalescence and freezing on hydrophilic, hydrophobic, and biphilic surfaces

    NASA Astrophysics Data System (ADS)

    Van Dyke, Alexander S.; Collard, Diane; Derby, Melanie M.; Betz, Amy Rachel

    2015-10-01

    Frost and ice formation can have severe negative consequences, such as aircraft safety and reliability. At atmospheric pressure, water heterogeneously condenses and then freezes at low temperatures. To alter this freezing process, this research examines the effects of biphilic surfaces (surfaces which combine hydrophilic and hydrophobic regions) on heterogeneous water nucleation, growth, and freezing. Silicon wafers were coated with a self-assembled monolayer and patterned to create biphilic surfaces. Samples were placed on a freezing stage in an environmental chamber at atmospheric pressure, at a temperature of 295 K, and relative humidities of 30%, 60%, and 75%. Biphilic surfaces had a significant effect on droplet dynamics and freezing behavior. The addition of biphilic patterns decreased the temperature required for freezing by 6 K. Biphilic surfaces also changed the size and number of droplets on a surface at freezing and delayed the time required for a surface to freeze. The main mechanism affecting freezing characteristics was the coalescence behavior.

  18. Charged hydrophobic colloids at an oil-aqueous phase interface

    NASA Astrophysics Data System (ADS)

    Kelleher, Colm P.; Wang, Anna; Guerrero-García, Guillermo Iván; Hollingsworth, Andrew D.; Guerra, Rodrigo E.; Krishnatreya, Bhaskar Jyoti; Grier, David G.; Manoharan, Vinothan N.; Chaikin, Paul M.

    2015-12-01

    Hydrophobic poly(methyl methacrylate) (PMMA) colloidal particles, when dispersed in oil with a relatively high dielectric constant, can become highly charged. In the presence of an interface with a conducting aqueous phase, image-charge effects lead to strong binding of colloidal particles to the interface, even though the particles are wetted very little by the aqueous phase. We study both the behavior of individual colloidal particles as they approach the interface and the interactions between particles that are already interfacially bound. We demonstrate that using particles which are minimally wetted by the aqueous phase allows us to isolate and study those interactions which are due solely to charging of the particle surface in oil. Finally, we show that these interactions can be understood by a simple image-charge model in which the particle charge q is the sole fitting parameter.

  19. Hysteresis free carbon nanotube thin film transistors comprising hydrophobic dielectrics

    NASA Astrophysics Data System (ADS)

    Lefebvre, J.; Ding, J.; Li, Z.; Cheng, F.; Du, N.; Malenfant, P. R. L.

    2015-12-01

    We present two examples of carbon nanotube network thin film transistors with strongly hydrophobic dielectrics comprising either Teflon-AF or a poly(vinylphenol)/poly(methyl silsesquioxane) (PVP/pMSSQ) blend. In the absence of encapsulation, bottom gated transistors in air ambient show no hysteresis between forward and reverse gate sweep direction. Device threshold gate voltage and On-current present excellent time dependent stability even under dielectric stress. Furthermore, threshold gate voltage for hole conduction is negative upon device encapsulation with PVP/pMSSQ enabling much improved current On/Off ratio at 0 V. This work addresses two major challenges impeding solution based fabrication of relevant thin film transistors with printable single-walled carbon nanotube channels.

  20. Overcoming solubility limits in overloaded gradient hydrophobic interaction chromatography.

    PubMed

    Poplewska, Izabela; Piątkowski, Wojciech; Antos, Dorota

    2015-03-20

    The impact of the solubility limits on the performance of gradient protein chromatography has been studied. As a case study elution of model protein, i.e., lysozyme, on hydrophobic interaction media has been selected. A dependence of the protein solubility and crystallization kinetics on the content of cosmotropic salt in the mobile phase has been determined. Moreover, adsorption properties of the protein versus the mobile phase composition have been quantified. A model of chromatographic column dynamics has been developed which incorporated the mass transport kinetics accompanying both adsorption and crystallization processes. The model was used to study the influence of operating parameters such as flowrate and concentration loading on the solubility pattern inside the column and the separation performance. The analysis performed indicated existence of supersaturation regions for which, due to slow kinetics of crystallization, chromatographic process could be performed under conditions of strong concentration overloading while avoiding undesirable effects of flow blockage in chromatographic systems. PMID:25687455