Supercooled and glassy water: Metastable liquid(s), amorphous solid(s), and a no-man’s land

PubMed Central

Handle, Philip H.; Sciortino, Francesco

2017-01-01

We review the recent research on supercooled and glassy water, focusing on the possible origins of its complex behavior. We stress the central role played by the strong directionality of the water–water interaction and by the competition between local energy, local entropy, and local density. In this context we discuss the phenomenon of polyamorphism (i.e., the existence of more than one disordered solid state), emphasizing both the role of the preparation protocols and the transformation between the different disordered ices. Finally, we present the ongoing debate on the possibility of linking polyamorphism with a liquid–liquid transition that could take place in the no-man’s land, the temperature–pressure window in which homogeneous nucleation prevents the investigation of water in its metastable liquid form. PMID:29133419

Low-temperature kinetic measurements of microsecond freeze-hyperquench (MHQ) cytochrome oxidase monitored by UV-visible spectroscopy with a newly designed cuvette.

PubMed

Wiertz, F G M; de Vries, S

2006-02-01

A special cuvette was designed to measure optical changes of MHQ (microsecond freeze-hyperquench) powder samples at temperatures below approx. 250 K. Reduced cytochrome c oxidase from Paracoccus denitrificans was reacted with O(2) for 100 micros, frozen as a powder and transferred to the cuvette. Subsequently, cytochrome oxidase was allowed to react further following stepwise increments of the temperature from 100 K up to 250 K while recording spectra between 300 and 700 nm. The temperature was raised only when no further changes in the spectra could be detected. The experiment yielded spectra of the A, P(M), F and O intermediate states. This demonstrated that the catalytic cycle of cytochrome oxidase at low temperature is similar to that at room temperature and so verifies the suitability of this method for the study of enzymes with high catalytic-centre activity.

Generation of fine hydromagmatic ash by growth and disintegration of glassy rinds

USGS Publications Warehouse

Mastin, L.G.

2007-01-01

The deposits of mafic hydromagmatic eruptions are more fine grained and variable in vesicularity than dry magmatic deposits. Blocky, equant shapes of many hydromagmatic clasts also contrast with droplet, thread, and bubble wall morphology of dry magmatic fragments. Small (glassy rinds on pyroclast surfaces as they deform within turbulent flows. This process, termed "turbulent shedding", may occur during the expansion phase of vapor explosions or during turbulent but nonexplosive mixing of magma with water, steam, or water sprays. The occurrence of turbulent shedding and the resulting fragment sizes depend on the timescale for rind growth and the timescale between disturbances that remove or disintegrate glassy rinds. Turbulent shedding is directly observable in some small littoral jets at Kilauea. Calculations suggest that, in the presence of liquid water or water sprays, glassy rinds having a thickness of microns to millimeters should form in milliseconds to seconds. This is similar to the timescale between turbulent velocity fluctuations that can shred lava globules and remove such rinds. The fraction of a deposit consisting of fine ash should increase with the duration of this process: Large-scale Surtseyan jets generate hundreds or thousands of shedding events; bubble bursts or tephra jets at Kilauea's coast may produce only a few.

Observation of glassy state relaxation during annealing of frozen sugar solutions by X-ray computed tomography.

PubMed

Nakagawa, Kyuya; Tamiya, Shinri; Do, Gabsoo; Kono, Shinji; Ochiai, Takaaki

2018-06-01

Glassy phase formation in a frozen product determines various properties of the freeze-dried products. When an aqueous solution is subjected to freezing, a glassy phase forms as a consequence of freeze-concentration. During post-freezing annealing, the relaxation of the glassy phase and the ripening of ice crystals (i.e. Ostwald ripening) spontaneously occur, where the kinetics are controlled by the annealing and glass transition temperatures. This study was motivated to observe the progress of glassy state relaxation separate from ice coarsening during annealing. X-ray computed tomography (CT) was used to observe a frozen and post-freezing annealed solutions by using monochromatized X-ray from the synchrotron radiation. CT images were successfully obtained, and the frozen matrix were analyzed based on the gray level values that were equivalent to the linear X-ray attenuation coefficients of the observed matters. The CT images obtained from rapidly frozen sucrose and dextrin solutions with different concentrations gave clear linear relationships between the linear X-ray attenuation coefficients values and the solute concentrations. It was confirmed that the glassy state relaxation progressed as increasing annealing time, and this trend was larger in the order of the glass transition temperature of the maximally freeze-concentrated phase. The sucrose-water system required nearly 20 h of annealing time at -5 °C for the completion of the glassy phase relaxation, whereas dextrin-water systems required much longer periods because of their higher glass transition temperatures. The trends of ice coarsening, however, did not perfectly correspond to the trends of the relaxation, suggesting that the glassy phase relaxation and Ostwald ripening would jointly control the ice crystal growth/ripening kinetics, and the dominant mechanism differed by the annealing stage. Copyright © 2018 Elsevier B.V. All rights reserved.

Ultra-smooth glassy graphene thin films for flexible transparent circuits

PubMed Central

Dai, Xiao; Wu, Jiang; Qian, Zhicheng; Wang, Haiyan; Jian, Jie; Cao, Yingjie; Rummeli, Mark H.; Yi, Qinghua; Liu, Huiyun; Zou, Guifu

2016-01-01

Large-area graphene thin films are prized in flexible and transparent devices. We report on a type of glassy graphene that is in an intermediate state between glassy carbon and graphene and that has high crystallinity but curly lattice planes. A polymer-assisted approach is introduced to grow an ultra-smooth (roughness, <0.7 nm) glassy graphene thin film at the inch scale. Owing to the advantages inherited by the glassy graphene thin film from graphene and glassy carbon, the glassy graphene thin film exhibits conductivity, transparency, and flexibility comparable to those of graphene, as well as glassy carbon–like mechanical and chemical stability. Moreover, glassy graphene–based circuits are fabricated using a laser direct writing approach. The circuits are transferred to flexible substrates and are shown to perform reliably. The glassy graphene thin film should stimulate the application of flexible transparent conductive materials in integrated circuits. PMID:28138535

Constitutive modeling of glassy shape memory polymers

NASA Astrophysics Data System (ADS)

Khanolkar, Mahesh

The aim of this research is to develop constitutive models for non-linear materials. Here, issues related for developing constitutive model for glassy shape memory polymers are addressed in detail. Shape memory polymers are novel material that can be easily formed into complex shapes, retaining memory of their original shape even after undergoing large deformations. The temporary shape is stable and return to the original shape is triggered by a suitable mechanism such heating the polymer above a transition temperature. Glassy shape memory polymers are called glassy because the temporary shape is fixed by the formation of a glassy solid, while return to the original shape is due to the melting of this glassy phase. The constitutive model has been developed to capture the thermo-mechanical behavior of glassy shape memory polymers using elements of nonlinear mechanics and polymer physics. The key feature of this framework is that a body can exist stress free in numerous natural configurations, the underlying natural configuration of the body changing during the process, with the response of the body being elastic from these evolving natural configurations. The aim of this research is to formulate a constitutive model for glassy shape memory polymers (GSMP) which takes in to account the fact that the stress-strain response depends on thermal expansion of polymers. The model developed is for the original amorphous phase, the temporary glassy phase and transition between these phases. The glass transition process has been modeled using a framework that was developed recently for studying crystallization in polymers and is based on the theory of multiple natural configurations. Using the same frame work, the melting of the glassy phase to capture the return of the polymer to its original shape is also modeled. The effect of nanoreinforcement on the response of shape memory polymers (GSMP) is studied and a model is developed. In addition to modeling and solving boundary

Determining the critical relative humidity at which the glassy to rubbery transition occurs in polydextrose using an automatic water vapor sorption instrument.

PubMed

Yuan, Xiaoda; Carter, Brady P; Schmidt, Shelly J

2011-01-01

Similar to an increase in temperature at constant moisture content, water vapor sorption by an amorphous glassy material at constant temperature causes the material to transition into the rubbery state. However, comparatively little research has investigated the measurement of the critical relative humidity (RHc) at which the glass transition occurs at constant temperature. Thus, the central objective of this study was to investigate the relationship between the glass transition temperature (Tg), determined using thermal methods, and the RHc obtained using an automatic water vapor sorption instrument. Dynamic dewpoint isotherms were obtained for amorphous polydextrose from 15 to 40 °C. RHc was determined using an optimized 2nd-derivative method; however, 2 simpler RHc determination methods were also tested as a secondary objective. No statistical difference was found between the 3 RHc methods. Differential scanning calorimetry (DSC) Tg values were determined using polydextrose equilibrated from 11.3% to 57.6% RH. Both standard DSC and modulated DSC (MDSC) methods were employed, since some of the polydextrose thermograms exhibited a physical aging peak. Thus, a tertiary objective was to compare Tg values obtained using 3 different methods (DSC first scan, DSC rescan, and MDSC), to determine which method(s) yielded the most accurate Tg values. In general, onset and midpoint DSC first scan and MDSC Tg values were similar, whereas onset and midpoint DSC rescan values were different. State diagrams of RHc and experimental temperature and Tg and %RH were compared. These state diagrams, though obtained via very different methods, showed relatively good agreement, confirming our hypothesis that water vapor sorption isotherms can be used to directly detect the glassy to rubbery transition. Practical Application: The food polymer science (FPS) approach, pioneered by Slade and Levine, is being successfully applied in the food industry for understanding, improving, and

Loss of halogens from crystallized and glassy silicic volcanic rocks

USGS Publications Warehouse

Noble, D.C.; Smith, V.C.; Peck, L.C.

1967-01-01

One hundred and sixty-four F and Cl analyses of silicic welded tuffs and lavas and glass separates are presented. Comparison of the F and Cl contents of crystallized rocks with those of nonhydrated glass and hydrated glassy rocks from the same rock units shows that most of the halogens originally present were lost on crystallization. An average of about half of the F and four-fifths of the Cl originally present was lost. Analyses of hydrated natural glasses and of glassy rocks indicate that in some cases significant amounts of halogens may be removed from or added to hydrated glass through prolonged contact with ground water. The data show that the original halogen contents of the groundmass of a silicic volcanic rock can be reliably determined only from nonhydrated glass. ?? 1967.

Behavior of the Ru-bda water oxidation catalyst covalently anchored on glassy carbon electrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matheu, Roc; Francàs, Laia; Chernev, Petko

Electrochemical reduction of the dizaonium complex, [Ru II(bda)(NO)(N–N 2) 2] 3+, 2 3+ (N–N 2 2+ is 4-(pyridin-4-yl) benzenediazonium and bda 2– is [2,2'-bipyridine]-6,6'-dicarboxylate), in acetone produces the covalent grafting of this molecular complex onto glassy carbon (GC) electrodes. Multiple cycling voltammetric experiments on the GC electrode generates hybrid materials labeled as GC-4, with the corresponding Ru-aqua complex anchored on the graphite surface. GC-4 has been characterized at pH = 7.0 by electrochemical techniques and X-ray absorption spectroscopy (XAS) and has been shown to act as an active catalyst for the oxidation of water to dioxygen. This new hybrid materialmore » has a lower catalytic performance than its counterpart in homogeneous phase and progressively decomposes to form RuO 2 at the electrode surface. The resulting metal oxide attached at the GC electrode surface, GC-RuO 2, is a very fast and rugged heterogeneous water oxidation catalyst with TOF is of 300 s –1 and TONs >45000. The observed performance is comparable to the best electrocatalysts reported so far, at neutral pH.« less

Behavior of the Ru-bda water oxidation catalyst covalently anchored on glassy carbon electrodes

DOE PAGES

Matheu, Roc; Francàs, Laia; Chernev, Petko; ...

2015-05-07

Electrochemical reduction of the dizaonium complex, [Ru II(bda)(NO)(N–N 2) 2] 3+, 2 3+ (N–N 2 2+ is 4-(pyridin-4-yl) benzenediazonium and bda 2– is [2,2'-bipyridine]-6,6'-dicarboxylate), in acetone produces the covalent grafting of this molecular complex onto glassy carbon (GC) electrodes. Multiple cycling voltammetric experiments on the GC electrode generates hybrid materials labeled as GC-4, with the corresponding Ru-aqua complex anchored on the graphite surface. GC-4 has been characterized at pH = 7.0 by electrochemical techniques and X-ray absorption spectroscopy (XAS) and has been shown to act as an active catalyst for the oxidation of water to dioxygen. This new hybrid materialmore » has a lower catalytic performance than its counterpart in homogeneous phase and progressively decomposes to form RuO 2 at the electrode surface. The resulting metal oxide attached at the GC electrode surface, GC-RuO 2, is a very fast and rugged heterogeneous water oxidation catalyst with TOF is of 300 s –1 and TONs >45000. The observed performance is comparable to the best electrocatalysts reported so far, at neutral pH.« less

Shock-wave studies of anomalous compressibility of glassy carbon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Molodets, A. M., E-mail: molodets@icp.ac.ru; Golyshev, A. A.; Savinykh, A. S.

2016-02-15

The physico-mechanical properties of amorphous glassy carbon are investigated under shock compression up to 10 GPa. Experiments are carried out on the continuous recording of the mass velocity of compression pulses propagating in glassy carbon samples with initial densities of 1.502(5) g/cm{sup 3} and 1.55(2) g/cm{sup 3}. It is shown that, in both cases, a compression wave in glassy carbon contains a leading precursor with amplitude of 0.135(5) GPa. It is established that, in the range of pressures up to 2 GPa, a shock discontinuity in glassy carbon is transformed into a broadened compression wave, and shock waves are formedmore » in the release wave, which generally means the anomalous compressibility of the material in both the compression and release waves. It is shown that, at pressure higher than 3 GPa, anomalous behavior turns into normal behavior, accompanied by the formation of a shock compression wave. In the investigated area of pressure, possible structural changes in glassy carbon under shock compression have a reversible character. A physico-mechanical model of glassy carbon is proposed that involves the equation of state and a constitutive relation for Poisson’s ratio and allows the numerical simulation of physico-mechanical and thermophysical properties of glassy carbon of different densities in the region of its anomalous compressibility.« less

Graphene Reinforced Glassy Carbon (GRGC) Beam Windows

DOE Office of Scientific and Technical Information (OSTI.GOV)

Renomeron, Lynda L.

Secondary particle beams require beam windows that isolate the target (usually in air) from the primary particle beam vacuum. Advanced beam window solutions are needed that can withstand anticipated increases in beam power and intensity that will result in higher thermal shock on the window and increased oxidative erosion rates on the air-side caused by increased temperatures. Carbon-based windows, in particular, glassy carbon windows are of interest to minimize interaction with the beam. The attractive properties of glassy carbon are: 1. Low atomic number 2. Low thermal expansion 3. High strength and low Young's modulus 4. Low gas permeability andmore » low outgassing for ultrahigh vacuum use The one liability of glassy carbon is its low thermal conductivity, nominally 5 W/mK, which will exacerbate temperature rise, oxidation, and thermal shock concerns as beam powers increase. TA&T proposes the development of graphene reinforced glassy carbon (GRGC) composites to increase the thermal conductivity and address this Achilles heel of glassy carbon. Graphene as a reinforcing phase has shown the capability to increase the thermal conductivity of the matrix material by up to two orders of magnitude. For beam windows this would substantially increase heat spreading away from the beam zone of the window and improve thermal shock resistance, and reduce maximum temperature and air-side oxidation of the window. Increased thermal conductivity would also improve the effectiveness of edge-cooling schemes to minimize temperature increase. In the Phase I effort, graphene oxide (GO) particles were dispersed into glassy carbon precursor at different content levels and cast into solid shapes. The goal was to determine the effect of graphene concentration on the mechanical properties (flexure strength), and thermal (thermal conductivity). The Phase I results indicated that addition of graphene did have a significant effect on thermal conductivity; however the microstructural

Determination of fenitrothion in water using a voltammetric sensor based on a polymer-modified glassy carbon electrode.

PubMed

Amare, Meareg; Abicho, Samuel; Admassie, Shimelis

2014-01-01

A glassy carbon electrode (GCE) modified with poly(4-amino-3-hydroxynaphthalene sulfonic acid) (poly-AHNSA) was used for the selective and sensitive determination of fenitrothion (FT) organophosphorus pesticide in water. The electrochemical behavior of FT at the bare GCE and the poly-AHNSA/GCE were compared using cyclic voltammetry. Enhanced peak current response and shift to a lower potential at the polymer-modified electrode indicated the electrocatalytic activity of the polymer film towards FT. Under optimized solution and method parameters, the adsorptive stripping square wave voltammetric reductive peak current of FT was linear to FT concentration in the range of 0.001 to 6.6 x 10(-6) M, and the LOD obtained (3delta/m) was 7.95 x 10(-10) M. Recoveries in the range 96-98% of spiked FT in tap water and reproducible results with RSD of 2.6% (n = 5) were obtained, indicating the potential applicability of the method for the determination of trace levels of FT in environmental samples.

"Non-equilibrium" block copolymer micelles with glassy cores: a predictive approach based on theory of equilibrium micelles.

PubMed

Nagarajan, Ramanathan

2015-07-01

Micelles generated in water from most amphiphilic block copolymers are widely recognized to be non-equilibrium structures. Typically, the micelles are prepared by a kinetic process, first allowing molecular scale dissolution of the block copolymer in a common solvent that likes both the blocks and then gradually replacing the common solvent by water to promote the hydrophobic blocks to aggregate and create the micelles. The non-equilibrium nature of the micelle originates from the fact that dynamic exchange between the block copolymer molecules in the micelle and the singly dispersed block copolymer molecules in water is suppressed, because of the glassy nature of the core forming polymer block and/or its very large hydrophobicity. Although most amphiphilic block copolymers generate such non-equilibrium micelles, no theoretical approach to a priori predict the micelle characteristics currently exists. In this work, we propose a predictive approach for non-equilibrium micelles with glassy cores by applying the equilibrium theory of micelles in two steps. In the first, we calculate the properties of micelles formed in the mixed solvent while true equilibrium prevails, until the micelle core becomes glassy. In the second step, we freeze the micelle aggregation number at this glassy state and calculate the corona dimension from the equilibrium theory of micelles. The condition when the micelle core becomes glassy is independently determined from a statistical thermodynamic treatment of diluent effect on polymer glass transition temperature. The predictions based on this "non-equilibrium" model compare reasonably well with experimental data for polystyrene-polyethylene oxide diblock copolymer, which is the most extensively studied system in the literature. In contrast, the application of the equilibrium model to describe such a system significantly overpredicts the micelle core and corona dimensions and the aggregation number. The non-equilibrium model suggests ways to

Crystallization of the glassy grain boundary phase in silicon nitride ceramics

NASA Technical Reports Server (NTRS)

Drummond, Charles H., III

1991-01-01

The role was studied of the intergranular glassy phase in silicon nitride as-processed with yttria as a sintering aid. The microstructure, crystallization, and viscosity of the glassy phase were areas studied. Crystallization of the intergranular glassy phase to more refractory crystalline phases should improve the high temperature mechanical properties of the silicon nitride. The addition of a nucleating agent will increase the rate of crystallization. The measurement of the viscosity of the glassy phase will permit the estimation of the high temperature deformation of the silicon nitride.

Plastic flow modeling in glassy polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clements, Brad

2010-12-13

Glassy amorphous and semi-crystalline polymers exhibit strong rate, temperature, and pressure dependent polymeric yield. As a rule of thumb, in uniaxial compression experiments the yield stress increases with the loading rate and applied pressure, and decreases as the temperature increases. Moreover, by varying the loading state itself complex yield behavior can be observed. One example that illustrates this complexity is that most polymers in their glassy regimes (i.e., when the temperature is below their characteristic glass transition temperature) exhibit very pronounced yield in their uniaxial stress stress-strain response but very nebulous yield in their uniaxial strain response. In uniaxial compression,more » a prototypical glassy-polymer stress-strain curve has a stress plateau, often followed by softening, and upon further straining, a hardening response. Uniaxial compression experiments of this type are typically done from rates of 10{sup -5} s{sup -1} up to about 1 s{sup -1}. At still higher rates, say at several thousands per second as determined from Split Hopkinson Pressure Bar experiments, the yield can again be measured and is consistent with the above rule of thumb. One might expect that that these two sets of experiments should allow for a successful extrapolation to yet higher rates. A standard means to probe high rates (on the order of 105-107 S-I) is to use a uniaxial strain plate impact experiment. It is well known that in plate impact experiments on metals that the yield stress is manifested in a well-defined Hugoniot Elastic Limit (HEL). In contrast however, when plate impact experiments are done on glassy polymers, the HEL is arguably not observed, let alone observed at the stress estimated by extrapolating from the lower strain rate experiments. One might argue that polymer yield is still active but somehow masked by the experiment. After reviewing relevant experiments, we attempt to address this issue. We begin by first presenting our

Disconnecting structure and dynamics in glassy thin films

PubMed Central

Sussman, Daniel M.; Cubuk, Ekin D.; Liu, Andrea J.

2017-01-01

Nanometrically thin glassy films depart strikingly from the behavior of their bulk counterparts. We investigate whether the dynamical differences between a bulk and thin film polymeric glass former can be understood by differences in local microscopic structure. Machine learning methods have shown that local structure can serve as the foundation for successful, predictive models of particle rearrangement dynamics in bulk systems. By contrast, in thin glassy films, we find that particles at the center of the film and those near the surface are structurally indistinguishable despite exhibiting very different dynamics. Next, we show that structure-independent processes, already present in bulk systems and demonstrably different from simple facilitated dynamics, are crucial for understanding glassy dynamics in thin films. Our analysis suggests a picture of glassy dynamics in which two dynamical processes coexist, with relative strengths that depend on the distance from an interface. One of these processes depends on local structure and is unchanged throughout most of the film, while the other is purely Arrhenius, does not depend on local structure, and is strongly enhanced near the free surface of a film. PMID:28928147

SPM investigation of local aging effects in glassy polymers

NASA Astrophysics Data System (ADS)

Crider, Philip

2005-03-01

We investigate the cooperative and heterogeneous nature of glassy dynamics by nanometer-scale probing in a glassy polymer, Polyvinyl-Actetate (PVAc), with a Scanning Force Microscope (SFM). Using ultra-high-vacuum (UHV) Scanning Capacitive Force Microscopy techniques, nanometer-scale capacitive responses are probed. Dielectric relaxation near the glass transition is investigated, and scanning capabilities are utilized to analyze spatial response on a nanometer scale. The results of these studies may yield insight into the understanding of temperature-dependent cooperative length scales, local aging properties, and energy landscape properties of evolving dipole clusters on a mesoscopic scale. Results are used to test the validity and relevance of current models of glassy dynamics.

Determination of mutagenic amines in water and food samples by high pressure liquid chromatography with amperometric detection using a multiwall carbon nanotubes-glassy carbon electrode.

PubMed

Bueno, Ana María; Marín, Miguel Ángel; Contento, Ana María; Ríos, Ángel

2016-02-01

A chromatographic method, using amperometric detection, for the sensitive determination of six representative mutagenic amines was developed. A glassy carbon electrode (GCE), modified with multiwall carbon nanotubes (GCE-CNTs), was prepared and its response compared to a conventional glassy carbon electrode. The chromatographic method (HPLC-GCE-CNTs) allowed the separation and the determination of heterocyclic aromatic amines (HAAs) classified as mutagenic amines by the International Agency for Research of Cancer. The new electrode was systematically studied in terms of stability, sensitivity, and reproducibility. Statistical analysis of the obtained data demonstrated that the modified electrode provided better sensitivity than the conventional unmodified ones. Detection limits were in the 3.0 and 7.5 ng/mL range, whereas quantification limits ranged between 9.5 and 25.0 ng/mL were obtained. The applicability of the method was demonstrated by the determination of the amines in several types of samples (water and food samples). Recoveries indicate very good agreement between amounts added and those found for all HAAs (recoveries in the 92% and 105% range). Copyright © 2015 Elsevier Ltd. All rights reserved.

Thermodynamic behavior of glassy state of structurally related compounds.

PubMed

Kaushal, Aditya Mohan; Bansal, Arvind Kumar

2008-08-01

Thermodynamic properties of amorphous pharmaceutical forms are responsible for enhanced solubility as well as poor physical stability. The present study was designed to investigate the differences in thermodynamic parameters arising out of disparate molecular structures and associations for four structurally related pharmaceutical compounds--celecoxib, valdecoxib, rofecoxib, and etoricoxib. Conventional and modulated temperature differential scanning calorimetry were employed to study glass forming ability and thermodynamic behavior of the glassy state of model compounds. Glass transition temperature of four glassy compounds was in a close range of 327.6-331.8 K, however, other thermodynamic parameters varied considerably. Kauzmann temperature, strength parameter and fragility parameter showed rofecoxib glass to be most fragile of the four compounds. Glass forming ability of the compounds fared similar in the critical cooling rate experiments, suggesting that different factors were determining the glass forming ability and subsequent behavior of the compounds in glassy state. A comprehensive understanding of such thermodynamic facets of amorphous form would help in rationalizing the approaches towards development of stable glassy pharmaceuticals.

Secondary relaxations in supercooled and glassy sucrose-borate aqueous solutions.

PubMed

Longinotti, M Paula; Corti, Horacio R; Pablo, Juan J de

2008-10-13

The dielectric relaxation spectra of concentrated aqueous solutions of sucrose-borate mixtures have been measured in the supercooled and glassy regions in the frequency range of 40Hz to 2MHz. The secondary (beta) relaxation process was analyzed in the temperature range 183-233K at water contents between 20 and 30wt%. The relaxation times were obtained, and the activation energy of that process was calculated. In order to assess the effect of borate on the relaxation of disaccharide-water mixtures, we also studied the dielectric behavior of sucrose aqueous solutions in the same range of temperatures and water contents. Our findings support the view that, beyond a water content of approximately 20wt%, the secondary relaxation of water-sucrose and water-sucrose-borate mixtures adopts a universal character that can be explained in terms of a simple exponential function of the temperature scaled by the glass transition temperature (T(g)). The behavior observed for water-sucrose and water-sucrose-borate mixtures is compared with previous results obtained in other water-carbohydrate systems.

Effect of solute nature on the polyamorphic transition in glassy polyol aqueous solutions.

PubMed

Suzuki, Yoshiharu

2017-08-14

I examined the polyamorphic behavior of glassy dilute aqueous solutions of polyols (ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol) under pressure at low temperatures. Although the volume change of the glassy aqueous solution varied continuously against pressure, the rate of the volume change appeared to vary discontinuously at the onset pressure of the gradual polyamorphic transition. It is thought that low-density liquid-like solvent water and high-density liquid-like solvent water coexist during the transition. Moreover, the existence of a solute induces the shift of polyamorphic transition to the lower-pressure side. The effect of a solute on the polyamorphic transition becomes larger in the order ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol. Therefore, the solute can become a variable controlling the polyamorphic state of liquid water. This experimental result suggests that the metastable-equilibrium phase boundary between the low-density and the high-density amorphs for pure water is likely to be located at 0.22-0.23 GPa at about 150 K, which is slightly larger than the previously estimated pressure. Moreover, the solute-nature dependence on the polyamorphic transition seems to connect to that on the homogeneous nucleation temperature of polyol aqueous solution at ambient pressure. The region in which a low-density liquid appears coincides with the region in which the nucleus of ice Ih appears, suggesting that the formation of a low-density liquid is a precursory phenomenon of the nucleation of ice Ih.

Effect of solute nature on the polyamorphic transition in glassy polyol aqueous solutions

NASA Astrophysics Data System (ADS)

Suzuki, Yoshiharu

2017-08-01

I examined the polyamorphic behavior of glassy dilute aqueous solutions of polyols (ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol) under pressure at low temperatures. Although the volume change of the glassy aqueous solution varied continuously against pressure, the rate of the volume change appeared to vary discontinuously at the onset pressure of the gradual polyamorphic transition. It is thought that low-density liquid-like solvent water and high-density liquid-like solvent water coexist during the transition. Moreover, the existence of a solute induces the shift of polyamorphic transition to the lower-pressure side. The effect of a solute on the polyamorphic transition becomes larger in the order ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol. Therefore, the solute can become a variable controlling the polyamorphic state of liquid water. This experimental result suggests that the metastable-equilibrium phase boundary between the low-density and the high-density amorphs for pure water is likely to be located at 0.22-0.23 GPa at about 150 K, which is slightly larger than the previously estimated pressure. Moreover, the solute-nature dependence on the polyamorphic transition seems to connect to that on the homogeneous nucleation temperature of polyol aqueous solution at ambient pressure. The region in which a low-density liquid appears coincides with the region in which the nucleus of ice Ih appears, suggesting that the formation of a low-density liquid is a precursory phenomenon of the nucleation of ice Ih.

Glassy composition for hermetic seals

DOEpatents

Wilder, Jr., James A.

1980-01-01

The invention relates to a glassy composition adaptable for sealing to aluminum-based alloys to form a hermetically-sealed insulator body. The composition may either be employed as a glass or, after devitrifying heat treatment, as a glass-ceramic.

Solubility of gases and liquids in glassy polymers.

PubMed

De Angelis, Maria Grazia; Sarti, Giulio C

2011-01-01

This review discusses a macroscopic thermodynamic procedure to calculate the solubility of gases, vapors, and liquids in glassy polymers that is based on the general procedure provided by the nonequilibrium thermodynamics for glassy polymers (NET-GP) method. Several examples are presented using various nonequilibrium (NE) models including lattice fluid (NELF), statistical associating fluid theory (NE-SAFT), and perturbed hard sphere chain (NE-PHSC). Particular applications illustrate the calculation of infinite-dilution solubility coefficients in different glassy polymers and the prediction of solubility isotherms for different gases and vapors in pure polymers as well as in polymer blends. The determination of model parameters is discussed, and the predictive abilities of the models are illustrated. Attention is also given to the solubility of gas mixtures and solubility isotherms in nanocomposite mixed matrices. The fractional free volume determined from solubility data can be used to correlate solute diffusivities in mixed matrices.

Glassy dynamics of landscape evolution

PubMed Central

Ortiz, Carlos P.; Jerolmack, Douglas J.

2018-01-01

Soil creeps imperceptibly downhill, but also fails catastrophically to create landslides. Despite the importance of these processes as hazards and in sculpting landscapes, there is no agreed-upon model that captures the full range of behavior. Here we examine the granular origins of hillslope soil transport by discrete element method simulations and reanalysis of measurements in natural landscapes. We find creep for slopes below a critical gradient, where average particle velocity (sediment flux) increases exponentially with friction coefficient (gradient). At critical gradient there is a continuous transition to a dense-granular flow rheology. Slow earthflows and landslides thus exhibit glassy dynamics characteristic of a wide range of disordered materials; they are described by a two-phase flux equation that emerges from grain-scale friction alone. This glassy model reproduces topographic profiles of natural hillslopes, showing its promise for predicting hillslope evolution over geologic timescales. PMID:29686102

Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors.

PubMed

Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T; Evoy, Stephane

2016-03-14

Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors.

Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors

PubMed Central

Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T.; Evoy, Stephane

2016-01-01

Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors. PMID:26985910

Evaluation of grapevine as a host for the glassy-winged sharpshooter

USDA-ARS?s Scientific Manuscript database

Grapevine was evaluated as a feeding and oviposition host for the glassy-winged sharpshooter. Two sets of experiments were conducted. The first set compared performance and preference of glassy-winged sharpshooter females for grapevine (cv. Chardonnay) versus cowpea (Vigna unguiculata cultivar black...

Glassy dynamics of landscape evolution.

PubMed

Ferdowsi, Behrooz; Ortiz, Carlos P; Jerolmack, Douglas J

2018-05-08

Soil creeps imperceptibly downhill, but also fails catastrophically to create landslides. Despite the importance of these processes as hazards and in sculpting landscapes, there is no agreed-upon model that captures the full range of behavior. Here we examine the granular origins of hillslope soil transport by discrete element method simulations and reanalysis of measurements in natural landscapes. We find creep for slopes below a critical gradient, where average particle velocity (sediment flux) increases exponentially with friction coefficient (gradient). At critical gradient there is a continuous transition to a dense-granular flow rheology. Slow earthflows and landslides thus exhibit glassy dynamics characteristic of a wide range of disordered materials; they are described by a two-phase flux equation that emerges from grain-scale friction alone. This glassy model reproduces topographic profiles of natural hillslopes, showing its promise for predicting hillslope evolution over geologic timescales. Copyright © 2018 the Author(s). Published by PNAS.

Electrical properties of carbon nanotubes modified GaSe glassy system

NASA Astrophysics Data System (ADS)

Khan, Hana; Khan, Zubair M. S. H.; Islam, Shama; Rahman, Raja Saifu; Husain, M.; Zulfequar, M.

2018-05-01

In this paper we report the investigation of the effect of Carbon Nanotubes (CNT) addition on the electrical properties of GaSe Glassy system. Dielectric constant and dielectric loss of GaSe glassy system are found to increase on CNT addition. The conductivity of GaSe glasy systems is also found to increase on CNT addition. This behavior is attributed to the excellent conduction properties of Carbon Nanotube.

The superconducting state parameters of glassy superconductors

NASA Astrophysics Data System (ADS)

Vora, Aditya M.

2011-11-01

We present theoretical investigations of the superconducting state parameters (SSPs), i.e. the electron-phonon coupling strength, λ, Coulomb pseudopotential, μ*, transition temperature, Tc, isotope effect exponent, α, and effective interaction strength, N0V, of glassy superconductors by employing Ashcroft's well know empty core model potential for the first time using five screening functions proposed by Hartree (H), Taylor, Ichimaru-Utsumi (IU), Farid et al and Sarkar et al. The Tc obtained from the H and IU screening functions is found to be in excellent agreement with available experimental data. Also, the present results confirm the superconducting phase in bulk metallic glass superconductors. A strong dependency of the SSPs of the glassy superconductors on the 'Z' valence is found.

Glassy nature and glass-to-crystal transition in the binary metallic glass CuZr

NASA Astrophysics Data System (ADS)

Wei, Zi-Yang; Shang, Cheng; Zhang, Xiao-Jie; Liu, Zhi-Pan

2017-06-01

The prediction for the stability of glassy material is a key challenge in physical science. Here, we report a theoretical framework to predict the glass stability based on stochastic surface walking global optimization and reaction pathway sampling. This is demonstrated by revealing for the first time the global potential energy surface (PES) of two systems, CuZr binary metallic glass and nonglassy pure Cu systems, and establishing the lowest energy pathways linking glassy/amorphous structures with crystalline structures. The CuZr system has a significant number of glassy structures on PES that are ˜0.045 eV /atom above the crystal structure. Two clear trends are identified from global PES in the glass-to-crystal transition of the CuZr system: (i) the local Zr-Cu coordination (nearest neighbor) increases, and (ii) the local Zr bonding environment becomes homogeneous. This allows us to introduce quantitative structural and energetics conditions to distinguish the glassy structures from the crystalline structures. Because of the local Zr-Cu exchange in the glass-to-crystal transition, a high reaction barrier (>0.048 eV /atom ) is present to separate the glassy structures and the crystals in CuZr. By contrast, the Cu system, although it does possess amorphous structures that appear at much higher energy (˜0.075 eV /atom ) with respect to the crystal structure, has very low reaction barriers for the crystallization of amorphous structures, i.e. <0.011 eV /atom . The quantitative data on PES now available from global optimization techniques deepens our understanding on the microscopic nature of glassy material and might eventually facilitate the design of stable glassy materials.

Microwave enhanced electroanalysis of formulations: processes in micellar media at glassy carbon and at platinum electrodes.

PubMed

Ghanem, Mohamed A; Compton, Richard G; Coles, Barry A; Canals, Antonio; Marken, Frank

2005-10-01

The direct electroanalysis of complex formulations containing alpha-tocopherol (vitamin E) is possible in micellar solution and employing microwave-enhanced voltammetry. In the presence of microwave radiation substantial heating and current enhancement effects have been observed at 330 microm diameter glassy carbon electrodes placed into a micellar aqueous solution and both hydrophilic and highly hydrophobic redox systems are detected. For the water soluble Fe(CN)(6)(3-/4-) redox system in micellar aqueous solutions of 0.1 M NaCl and 0.1 M sodium dodecylsulfate (SDS) at low to intermediate microwave power, thermal effects and convection effects are observed. At higher microwave power, thermal cavitation is induced and dominates the mass transport at the electrode surface. For the micelle-soluble redox systems tert-butylferrocene and 2,5-di-tert-butyl-1,4-benzoquinone, strong and concentration dependent current responses are observed only in the presence of microwave radiation. For the oxidation of micelle-soluble alpha-tocopherol current responses at glassy carbon electrodes are affected by adsorption and desorption processes whereas at platinum electrodes, analytical limiting currents are obtained over a wide range of alpha-tocopherol concentrations. However, for the determination of alpha-tocopherol in a commercial formulation interference from proteins is observed at platinum electrodes and direct measurements are possible only over a limited concentration range and at glassy carbon electrodes.

Silicon-tin oxynitride glassy composition and use as anode for lithium-ion battery

DOEpatents

Neudecker, Bernd J.; Bates, John B.

2001-01-01

Disclosed are silicon-tin oxynitride glassy compositions which are especially useful in the construction of anode material for thin-film electrochemical devices including rechargeable lithium-ion batteries, electrochromic mirrors, electrochromic windows, and actuators. Additional applications of silicon-tin oxynitride glassy compositions include optical fibers and optical waveguides.

Graphitization of Glassy Carbon after Compression at Room Temperature

NASA Astrophysics Data System (ADS)

Shiell, T. B.; McCulloch, D. G.; McKenzie, D. R.; Field, M. R.; Haberl, B.; Boehler, R.; Cook, B. A.; de Tomas, C.; Suarez-Martinez, I.; Marks, N. A.; Bradby, J. E.

2018-05-01

Glassy carbon is a technologically important material with isotropic properties that is nongraphitizing up to ˜3000 °C and displays complete or "superelastic" recovery from large compression. The pressure limit of these properties is not yet known. Here we use experiments and modeling to show permanent densification, and preferred orientation occurs in glassy carbon loaded to 45 GPa and above, where 45 GPa represents the limit to the superelastic and nongraphitizing properties of the material. The changes are explained by a transformation from its s p2 rich starting structure to a s p3 rich phase that reverts to fully s p2 bonded oriented graphite during pressure release.

The viscoelastic behavior of notched glassy polymers

NASA Technical Reports Server (NTRS)

Crook, R. A.; Letton, Alan

1993-01-01

In the bulk, glassy polymers exhibit a nonlinear viscoelastic response during deformation. Stress or strain induced damage (i.e. crazing, microshear banding) results in the production of nonrecoverable work and observed nonlinearity. Stress or strain dependent shift factors have been used to mathematically model the mechanical behavior of these polymers. Glassy polymers that have been notched, may exhibit very different load displacement response compared to the same material under bulk deformation. If a sharp notch is introduced into the body then loaded, the load displacement trace may appear to be single-valued in the absence of viscoelasticity and crack growth. This suggests the volume of damaged material is small compared to the overall dimensions of the specimen. The ability to produce a single-valued load-load-line displacement trace through the use of the Correspondence Principle may prove to be useful for fracture of viscoelastic materials.

Scalable Synthesis of Cholesteric Glassy Liquid Crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wallace, Jason U.; Shestopalov, Alexander; Kosc, Tanya

2018-03-08

Capable of non-absorbing circular polarization of unpolarized incident light, cholesteric glassy liquid crystals consisting of hybrid chiral-nematic pendants to volume-excluding cores are potentially useful for the fabrication of various robust optical devices. As illustrated in this study, the well-oriented glassy film of enantiomeric Bz3ChN, with a glass transition at 73 oC and a cholesteric-to-isotropic transition at 295 oC, exhibits a selective reflection band centered at approximately 410 nm, an exceptional set of properties well suited for optical device exploration. To enable sustainable, large-scale synthesis of this material class for widespread applications, a productive strategy has been established, requiring a meremore » three-step scheme with an overall yield, atom economy, and reaction mass efficiency at 34, 33 and 12 %, respectively. While amenable to improvements, the resultant green chemistry metrics are encouraging as the first attempt.« less

The Erevan howardite: Petrology of glassy clasts and mineral chemistry

NASA Technical Reports Server (NTRS)

Nazarov, M. A.; Ariskin, A. A.

1993-01-01

The Erevan howardite is a polymict regolith breccia containing xenoliths of carbonaceous chondrites. In this work, we studied glassy clasts, which could be considered as primary quenched melts, and mineral chemistry of the breccia. The study reveals that the Erevan howardite consists of common rocks of the HED suite. However, unique glassy clasts, which are present in some eucritic melts, were identified. The mineral chemistry and the simulation of crystallization of the melts suggest that the compositions of the melts reflect those of some primary lithologies of EPB.

Development of the Ni-based Metallic glassy bipolar plates for Proton Exchange Membrane Fuel Cell (PEMFC)

NASA Astrophysics Data System (ADS)

Yamaura, S.; Yokoyama, M.; Kimura, H. M.; Inoue, A.

2009-01-01

Alloy optimization in the Ni80-xCrxP16B4 (x = 9-30 at%) alloy system was conducted in order to achieve low Tg, Tx and a large ΔTx. From this study, the Ni65Cr15P16B4 glassy alloy was found to be the optimal alloy. The static and potentiodynamic corrosion behaviours of this alloy were measured. As a result of polarization measurements, it was found that the current density of the non-polished glassy alloy sample was smaller than that of a SUS316L sample. By contrast, the current density of the surface-polished glassy sample was slightly larger than that of the SUS316L sample in the voltage range of 0.3-0.8 V. A bipolar plate was successfully produced by hot-pressing the glassy alloy sheet in a supercooled liquid state. The I-V characteristics of a single cell with the glassy bipolar plates were measured.

Optical and mechanical behaviors of glassy silicone networks derived from linear siloxane precursors

NASA Astrophysics Data System (ADS)

Jang, Heejun; Seo, Wooram; Kim, Hyungsun; Lee, Yoonjoo; Kim, Younghee

2016-01-01

Silicon-based inorganic polymers are promising materials as matrix materials for glass fiber composites because of their good process ability, transparency, and thermal property. In this study, for utilization as a matrix precursor for a glass-fiber-reinforced composite, glassy silicone networks were prepared via hydrosilylation of linear/pendant Si-H polysiloxanes and the C=C bonds of viny-lterminated linear/cyclic polysiloxanes. 13C nuclear magnetic resonance spectroscopy was used to determine the structure of the cross-linked states, and a thermal analysis was performed. To assess the mechanical properties of the glassy silicone networks, we performed nanoindentation and 4-point bending tests. Cross-linked networks derived from siloxane polymers are thermally and optically more stable at high temperatures. Different cross-linking agents led to final networks with different properties due to differences in the molecular weights and structures. After stepped postcuring, the Young's modulus and the hardness of the glassy silicone networks increased; however, the brittleness also increased. The characteristics of the cross-linking agent played an important role in the functional glassy silicone networks.

Voltammetric pH sensing using carbon electrodes: glassy carbon behaves similarly to EPPG.

PubMed

Lu, Min; Compton, Richard G

2014-09-21

Developing and building on recent work based on a simple sensor for pH determination using unmodified edge plane pyrolytic graphite (EPPG) electrodes, we present a voltammetric method for pH determination using a bare unmodified glassy carbon (GC) electrode. By exploiting the pH sensitive nature of quinones present on carbon edge-plane like sites within the GC, we show how GC electrodes can be used to measure pH. The electro-reduction of surface quinone groups on the glassy carbon electrode was characterised using cyclic voltammetry (CV) and optimised with square-wave voltammetry (SWV) at 298 K and 310 K. At both temperatures, a linear correlation was observed, corresponding to a 2 electron, 2 proton Nernstian response over the aqueous pH range 1.0 to 13.1. As such, unmodified glassy carbon electrodes are seen to be pH dependent, and the Nernstian response suggests its facile use for pH sensing. Given the widespread use of glassy carbon electrodes in electroanalysis, the approach offers a method for the near-simultaneous measurement and monitoring of pH during such analyses.

Scalable Synthesis of Cholesteric Glassy Liquid Crystals

DOE PAGES

Wallace, Jason U.; Shestopalov, Alexander; Kosc, Tanya; ...

2018-03-15

Capable of non-absorbing circular polarization of unpolarized incident light, cholesteric glassy liquid crystals consisting of hybrid chiral-nematic pendants to volume-excluding cores are potentially useful for the fabrication of various robust optical devices. As illustrated in this study, the well-oriented glassy film of enantiomeric Bz3ChN, with a glass transition at 73 °C and a cholesteric-to-isotropic transition at 295 °C, exhibits a selective reflection band centered at approximately 410 nm, an exceptional set of properties well suited for optical device exploration. To enable sustainable, large-scale synthesis of this material class for widespread applications, a productive strategy has been established, requiring a meremore » three-step scheme with an overall yield, atom economy, and reaction mass efficiency at 34%, 33% and 12%, respectively. Lastly, while amenable to improvements, the resultant green chemistry metrics are encouraging as the first attempt.« less

Thermodynamic Modeling of Gas Transport in Glassy Polymeric Membranes.

PubMed

Minelli, Matteo; Sarti, Giulio Cesare

2017-08-19

Solubility and permeability of gases in glassy polymers have been considered with the aim of illustrating the applicability of thermodynamically-based models for their description and prediction. The solubility isotherms are described by using the nonequilibrium lattice fluid (NELF) (model, already known to be appropriate for nonequilibrium glassy polymers, while the permeability isotherms are described through a general transport model in which diffusivity is the product of a purely kinetic factor, the mobility coefficient, and a thermodynamic factor. The latter is calculated from the NELF model and mobility is considered concentration-dependent through an exponential relationship containing two parameters only. The models are tested explicitly considering solubility and permeability data of various penetrants in three glassy polymers, PSf, PPh and 6FDA-6FpDA, selected as the reference for different behaviors. It is shown that the models are able to calculate the different behaviors observed, and in particular the permeability dependence on upstream pressure, both when it is decreasing as well as when it is increasing, with no need to invoke the onset of additional plasticization phenomena. The correlations found between polymer and penetrant properties with the two parameters of the mobility coefficient also lead to the predictive ability of the transport model.

Thermodynamic Modeling of Gas Transport in Glassy Polymeric Membranes

PubMed Central

Minelli, Matteo; Sarti, Giulio Cesare

2017-01-01

Solubility and permeability of gases in glassy polymers have been considered with the aim of illustrating the applicability of thermodynamically-based models for their description and prediction. The solubility isotherms are described by using the nonequilibrium lattice fluid (NELF) (model, already known to be appropriate for nonequilibrium glassy polymers, while the permeability isotherms are described through a general transport model in which diffusivity is the product of a purely kinetic factor, the mobility coefficient, and a thermodynamic factor. The latter is calculated from the NELF model and mobility is considered concentration-dependent through an exponential relationship containing two parameters only. The models are tested explicitly considering solubility and permeability data of various penetrants in three glassy polymers, PSf, PPh and 6FDA-6FpDA, selected as the reference for different behaviors. It is shown that the models are able to calculate the different behaviors observed, and in particular the permeability dependence on upstream pressure, both when it is decreasing as well as when it is increasing, with no need to invoke the onset of additional plasticization phenomena. The correlations found between polymer and penetrant properties with the two parameters of the mobility coefficient also lead to the predictive ability of the transport model. PMID:28825619

Playback interference of glassy-winged sharp shooter communication

USDA-ARS?s Scientific Manuscript database

Animal communication is vital to reproduction, particularly for securing a mate. Insects commonly communicate by exchanging vibrational signals that are transmitted through host plants. The glassy-winged sharpshooter (GWSS), Homalodisca vitripennis, is an important vector of Xylella fastidiosa, a pl...

Mating interference of glassy-winged sharpshooters, Homalodisca vitripennis

USDA-ARS?s Scientific Manuscript database

Animal signaling is a complex behavior that is influenced by abiotic and biotic factors of the environment. Glassy-winged sharpshooters (GWSS), Homalodisca vitripennis (Hemiptera: Cicadellidae), primarily use vibrational signaling for courtship. Because GWSS is a major pest, transmitting the plant ...

Glassy selenium at high pressure: Le Chatelier's principle still works

NASA Astrophysics Data System (ADS)

Brazhkin, V. V.; Tsiok, O. B.

2017-10-01

Selenium is the only easily vitrified elementary substance. Numerous experimental studies of glassy Se (g -Se) at high pressures show a large spread in the data on the compressibility and electrical resistivity of g -Se. Furthermore, H. Liu et al. [Proc. Natl. Acad. Sci. USA 105, 13229 (2008), 10.1073/pnas.0806857105] have arrived at the surprising conclusion that the volume of glass increases during pressure-induced crystallization. We have performed high-precision measurements of the specific volume and electrical resistivity of glassy selenium (g -Se) at high hydrostatic pressures up to 9 GPa. The measured bulk modulus at normal pressure is B =(9.0 5 ±0.15 ) GPa and its pressure derivative is BP'=6.4 ±0.2 . In the pressure range P <3 GPa, glassy selenium has an anomalously large negative second derivative of the bulk modulus. The electrical resistivity of g -Se decreases almost exponentially with increasing pressure and reaches 20 Ω cm at a pressure of 8.75 GPa. The inelastic behavior and weak relaxation of the volume for g -Se begin at pressures above 3.5 GPa; the volume and logarithm of the electrical resistivity relax significantly (logarithmically with the time) at pressures above 8 GPa. Bulk measurements certainly indicate that the volume of g -Se glass in the crystallization pressure range is larger than the volumes of both appearing crystalline phases (by 2% and 4%). Therefore, the "volume expansion phenomenon" suggested in [H. Liu et al., Proc. Natl. Acad. Sci. USA 105, 13229 (2008), 10.1073/pnas.0806857105] is not observed, and the pressure-induced crystallization of glassy selenium is consistent with the laws of thermodynamics.

Glassy materials for lithium batteries: electrochemical properties and devices performances

NASA Astrophysics Data System (ADS)

Duclot, Michel; Souquet, Jean-Louis

Amorphous or glassy materials may be used as electrolyte or electrode materials for lithium primary or secondary batteries. A first generation proceeded from classical coin cells in which the organic electrolyte was replaced by a high lithium conductive glassy electrolyte. The solid components were assembled under isostatic pressure. The main advantages of such cells are a good storage stability and ability to operate until 200°C. Nevertheless, the high resistivity of the glassy electrolyte below room temperature and a limited depth for charge and discharge cycles makes these cells not competitive compared to conventional lithium-ion batteries. More promising, are the thin films solid state microbatteries realised by successive depositions of electrodes and electrolyte. The low resistance of the electrolyte amorphous layer allows cycling at temperatures as low as -10°C. The total thickness of thin film batteries, including packaging is less than 100 μm. A capacity of about 100 μAh cm -2 with over 10 4 charge-discharge cycles at 90% in depth of discharge is well suited for energy independent smart cards or intelligent labels, which represent for these devices a large and unrivalled market.

Subaqueous non-vesicular to poorly-vesicular shards: hydroclastic fragmentation on seamounts and summit calderas

NASA Astrophysics Data System (ADS)

Mueller, W. U.; Dingwell, D. B.; Downey, W. S.; Mastin, L. G.

2008-12-01

Recognizing pyroclastic deposits that originate directly from magmatic and phreatomagmatic explosions in a subaqueous setting is based upon sedimentary structures, such as massive, stratified, and graded beds as well as (pyro)clast size. Ideally such deposits form ordered fining-and thinning-upward sequences. Pumice, scoria, glass shards, euhedral and broken crystals, and lithic fragments are constituents that support an explosive heritage. Recent deep-sea ROV and submersible dives have retrieved non-vesicular to vesicle- poor, mm-scale, mafic shards in 5-15 cm-thick massive and/or graded (stratified) deposits, for which a subaqueous explosive origin has been inferred. These sheet hyaloclastites with variable shard shapes were first documented on Seamount 6 as deep-sea Limu O Pele at water depths > 1000 m. We identified in Seamount 6 samples equant to blocky shards with angular to subrounded terminations, but also subordinate hair-like and contorted glassy filaments, warped shards and irregular shards. Shards display internal laminations (flow-banding?) and have local perlitic fractures. Bubble wall shards derived from scoria burst were rare. In combination with all the above and a poor shard vesicularity (< 2%), a magmatic explosive origin seems improbable. Such small-volume deposits have been reported from seamounts and summit calderas associated with subaqueous drainage tubes and ponded magma in depths > 1000 m. We envision that hydrostatic pressure commensurate with water depth played a significant role. The deposits can be readily explained by a hydroclastic process whereby fragmentation occurred at the milli-second (Limu) to second scale (hyaloclastite). Hence, hyperquenched glass shards or thread-like glass filaments need not require magmatic explosivity. Constant surface interaction between aphyric, low-viscosity, high temperature, magma-lava at depth with seawater causes fragmentation (granulation) that can generate such delicate shards. The transfer of

Comment on ``Glassy Potts model: A disordered Potts model without a ferromagnetic phase''

NASA Astrophysics Data System (ADS)

Carlucci, Domenico M.

1999-10-01

We report the equivalence of the ``glassy Potts model,'' recently introduced by Marinari et al. and the ``chiral Potts model'' investigated by Nishimori and Stephen. Both models do not exhibit any spontaneous magnetization at low temperature, differently from the ordinary glass Potts model. The phase transition of the glassy Potts model is easily interpreted as the spin-glass transition of the ordinary random Potts model.

Spatial and mesoscopic fluctuations in glassy dynamics

NASA Astrophysics Data System (ADS)

Chamon, Claudio C.; Cugliandolo, Leticia F.

2004-05-01

One of the striking properties of a glassy system is that many material properties depend on its age, i.e., the time since the system entered its glassy phase. In this this talk we shall review some recent progress (work in collaboration with H. E. Castillo, P. Charbonneau, J. L. Iguain, M. P. Kennett, D. R. Reichman and M. Sellitto) in understanding local aging, through the study of local observable quantities, which reveal that there are spatial heterogeneities and fluctuations in the aging process of macroscopic systems. We show that a number of universal properties are shared by many non-equilibrium systems, both with and without quenched disorder, such as the 3D Edwards-Anderson model and some kinetically constrained non-interacting 2D and 3D spin models, for example. Similar scaling relations are found for mesoscopic sample-to-sample fluctuations of global quantities in small size systems. We discuss how the emergence of a symmetry in aging systems, time-reparametrization invariance, could be responsible for the observed universal behavior of the local and mesoscopic non-equilibrium fluctuations.

Shear-transformation-zone theory of linear glassy dynamics.

PubMed

Bouchbinder, Eran; Langer, J S

2011-06-01

We present a linearized shear-transformation-zone (STZ) theory of glassy dynamics in which the internal STZ transition rates are characterized by a broad distribution of activation barriers. For slowly aging or fully aged systems, the main features of the barrier-height distribution are determined by the effective temperature and other near-equilibrium properties of the configurational degrees of freedom. Our theory accounts for the wide range of relaxation rates observed in both metallic glasses and soft glassy materials such as colloidal suspensions. We find that the frequency-dependent loss modulus is not just a superposition of Maxwell modes. Rather, it exhibits an α peak that rises near the viscous relaxation rate and, for nearly jammed, glassy systems, extends to much higher frequencies in accord with experimental observations. We also use this theory to compute strain recovery following a period of large, persistent deformation and then abrupt unloading. We find that strain recovery is determined in part by the initial barrier-height distribution, but that true structural aging also occurs during this process and determines the system's response to subsequent perturbations. In particular, we find by comparison with experimental data that the initial deformation produces a highly disordered state with a large population of low activation barriers, and that this state relaxes quickly toward one in which the distribution is dominated by the high barriers predicted by the near-equilibrium analysis. The nonequilibrium dynamics of the barrier-height distribution is the most important of the issues raised and left unresolved in this paper.

Interplay between local dynamics and mechanical reinforcement in glassy polymer nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holt, Adam P.; Bocharova, Vera; Cheng, Shiwang

The modification of polymer dynamics in the presence of strongly interacting nanoparticles has been shown to significantly change themacroscopic properties above the glass transition temperature of polymer nanocomposites (PNCs). However, much less attention has been paid to changes in the dynamics of glassy PNCs. Analysis of neutron and light scattering data presented herein reveals a surprising enhancement of local dynamics, e.g., fast picosecond and secondary relaxations, in glassy PNCs accompanied with a strengthening of mechanical modulus. Here we ascribe this counter-intuitive behavior to the complex interplay between chain packing and stretching within the interfacial layer formed at the polymer-nanoparticle interface.

Interplay between local dynamics and mechanical reinforcement in glassy polymer nanocomposites

DOE PAGES

Holt, Adam P.; Bocharova, Vera; Cheng, Shiwang; ...

2017-11-17

The modification of polymer dynamics in the presence of strongly interacting nanoparticles has been shown to significantly change themacroscopic properties above the glass transition temperature of polymer nanocomposites (PNCs). However, much less attention has been paid to changes in the dynamics of glassy PNCs. Analysis of neutron and light scattering data presented herein reveals a surprising enhancement of local dynamics, e.g., fast picosecond and secondary relaxations, in glassy PNCs accompanied with a strengthening of mechanical modulus. Here we ascribe this counter-intuitive behavior to the complex interplay between chain packing and stretching within the interfacial layer formed at the polymer-nanoparticle interface.

Anomalous glassy dynamics in simple models of dense biological tissue

NASA Astrophysics Data System (ADS)

Sussman, Daniel M.; Paoluzzi, M.; Marchetti, M. Cristina; Manning, M. Lisa

2018-02-01

In order to understand the mechanisms for glassy dynamics in biological tissues and shed light on those in non-biological materials, we study the low-temperature disordered phase of 2D vertex-like models. Recently it has been noted that vertex models have quite unusual behavior in the zero-temperature limit, with rigidity transitions that are controlled by residual stresses and therefore exhibit very different scaling and phenomenology compared to particulate systems. Here we investigate the finite-temperature phase of two-dimensional Voronoi and Vertex models, and show that they have highly unusual, sub-Arrhenius scaling of dynamics with temperature. We connect the anomalous glassy dynamics to features of the potential energy landscape associated with zero-temperature inherent states.

Quantifying glassy and crystalline basalt partitioning in the oceanic crust

NASA Astrophysics Data System (ADS)

Moore, Rachael; Ménez, Bénédicte

2016-04-01

The upper layers of the oceanic crust are predominately basaltic rock, some of which hosts microbial life. Current studies of microbial life within the ocean crust mainly focus on the sedimentary rock fraction, or those organisms found within glassy basalts while the potential habitability of crystalline basalts are poorly explored. Recently, there has been recognition that microbial life develops within fractures and grain boundaries of crystalline basalts, therefore estimations of total biomass within the oceanic crust may be largely under evaluated. A deeper understanding of the bulk composition and fractionation of rocks within the oceanic crust is required before more accurate estimations of biomass can be made. To augment our understanding of glassy and crystalline basalts within the oceanic crust we created two end-member models describing basalt fractionation: a pillow basalt with massive, or sheet, flows crust and a pillow basalt with sheeted dike crust. Using known measurements of massive flow thickness, dike thickness, chilled margin thickness, pillow lava size, and pillow lava glass thickness, we have calculated the percentage of glassy versus crystalline basalts within the oceanic crust for each model. These models aid our understanding of textural fractionation within the oceanic crust, and can be applied with bioenergetics models to better constrain deep biomass estimates.

Broadband nanoindentation of glassy polymers: Part II. Viscoplasticity

Treesearch

Joseph E. Jakes; Rod S. Lakes; Don S. Stone

2012-01-01

The relationship between hardness and flow stress in glassy polymers is examined. Materials studied include poly(methylmethacrylate), polystyrene, and polycarbonate. Properties are strongly rate dependent, so broadband nanoindentation creep (BNC) is used to measure hardness across a broad range of indentation strain rates (10-4 to 10 s

Synthesis and characterization of Ag+ ion conducting glassy electrolytes

NASA Astrophysics Data System (ADS)

Chandra, Angesh; Bhatt, Alok; Chandra, Archana

2013-07-01

Synthesis and characterization of new Ag+ ion conducting glassy systems: x[0.75AgI:0.25AgC1]: (1 - x)[Ag2O:P2O5], where 0.1 < x < 1 in molar weight fraction, are reported. The present glassy electrolytes have been synthesized by melt-quench technique using a high-speed twin roller-quencher. An alternate host salt: "quenched [0.75AgI:0.25AgC1] mixed system/solid solution", has been used in place of the traditional host AgI. The compositional dependence conductivity studies on the glassy systems: x[0.75AgI:0.25AgC1]:(1 - x)[Ag2O:P2O5] as well as xAgI:(1 - x)[Ag2O:P2O5] prepared identically, indicated that the composition at x = 0.75 exhibited the highest room temperature conductivity (σ ~ 5.5 x 10-3 S cm-1). The composition: 0.75[0.75AgI:0.25AgC1]:0.25[Ag2O:P2O5] has been referred to as optimum conducting composition (OCC). The some basic ion transport parameters viz. ionic conductivity (σ), ionic mobility (μ), mobile ion concentration (n), ionic drift velocity (vd), ion transference number (tion) and activation energy (Ea) values have been characterized with the help of various experimental techniques. A solid state battery was fabricated and its basic cell parameters calculated.

Graphene oxide-mediated electrochemistry of glucose oxidase on glassy carbon electrodes.

PubMed

Castrignanò, Silvia; Valetti, Francesca; Gilardi, Gianfranco; Sadeghi, Sheila J

2016-01-01

Glucose oxidase (GOD) was immobilized on glassy carbon electrodes in the presence of graphene oxide (GO) as a model system for the interaction between GO and biological molecules. Lyotropic properties of didodecyldimethylammonium bromide (DDAB) were used to stabilize the enzymatic layer on the electrode surface resulting in a markedly improved electrochemical response of the immobilized GOD. Transmission electron microscopy images of the GO with DDAB confirmed the distribution of the GO in a two-dimensional manner as a foil-like material. Although it is known that glassy carbon surfaces are not ideal for hydrogen peroxide detection, successful chronoamperometric titrations of the GOD in the presence of GO with β-d-glucose were performed on glassy carbon electrodes, whereas no current response was detected upon β-d-glucose addition in the absence of GO. The GOD-DDAB-GO system displayed a high turnover efficiency and substrate affinity as a glucose biosensor. The simplicity and ease of the electrode preparation procedure of this GO/DDAB system make it a good candidate for immobilizing other biomolecules for fabrication of amperometric biosensors. © 2015 International Union of Biochemistry and Molecular Biology, Inc.

Broadband nanoindentation of glassy polymers: Part I Viscoelasticity

Treesearch

Joesph E. Jakes; Rod S. Lakes; Don S. Stone

2012-01-01

Protocols are developed to assess viscoelastic moduli from unloading slopes in Berkovich nanoindentation across four orders of magnitude in time scale (0.01-100 s unloading time). Measured viscoelastic moduli of glassy polymers poly(methyl methacrylate), polystyrene, and polycarbonate follow the same trends with frequency (1/unloading time) as viscoelastic moduli...

Structural and spectroscopic studies of a commercial glassy carbon

NASA Astrophysics Data System (ADS)

Parker, Stewart F.; Imberti, Silvia; Callear, Samantha K.; Albers, Peter W.

2013-12-01

Glassy carbon is a form of carbon made by heating a phenolic resin to high temperature in an inert atmosphere. It has been suggested that it is composed of fullerene-like structures. The aim of the present work was to characterize the material using both structural (neutron diffraction and transmission electron microscopy) and spectroscopic (inelastic neutron scattering, Raman and X-ray photoelectron spectroscopies) methods. We find no evidence to support the suggestion of fullerene-like material being present to a significant extent, rather the model that emerges from all of the techniques is that the material is very like amorphous carbon, consisting of regions of small graphite-like basic structural units of partly stacked but mismatched structure with the edges terminated by hydrogen or hydroxyls. We do find evidence for the presence of a small quantity of water trapped in the network and suggest that this may account for batch-to-batch variation in properties that may occur.

Permeation of Mixed Penetrants through Glassy Polymer Membranes.

DTIC Science & Technology

1985-03-15

and LOPE. Also, ESCA was used in conjunction with plasma etching to determine the effects of the gas phase fluorine concentration and fluorination...at 35 3C. ARD-AISS5 65 PERMEATION OF MIXED PENETRANTS THROUGH GLASSY POLYMER 213 MENBRANES (U) NORTH CAROLINA STATE UNIV AT RALEIGH R T CHERN ET AL. 15

The hydrophilic-to-hydrophobic transition in glassy silica is driven by the atomic topology of its surface

NASA Astrophysics Data System (ADS)

Yu, Yingtian; Krishnan, N. M. Anoop; Smedskjaer, Morten M.; Sant, Gaurav; Bauchy, Mathieu

2018-02-01

The surface reactivity and hydrophilicity of silicate materials are key properties for various industrial applications. However, the structural origin of their affinity for water remains unclear. Here, based on reactive molecular dynamics simulations of a series of artificial glassy silica surfaces annealed at various temperatures and subsequently exposed to water, we show that silica exhibits a hydrophilic-to-hydrophobic transition driven by its silanol surface density. By applying topological constraint theory, we show that the surface reactivity and hydrophilic/hydrophobic character of silica are controlled by the atomic topology of its surface. This suggests that novel silicate materials with tailored reactivity and hydrophilicity could be developed through the topological nanoengineering of their surface.

Glassy aging with modified Kohlrausch-Williams-Watts form

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sen Gupta, Bhaskar; Das, Shankar P.

2007-12-15

In this paper, we address the question of whether aging in the nonequilibrium glassy state is controlled by the equilibrium {alpha}-relaxation process, which occurs at temperatures above T{sub g}. Recently, Lunkenheimer et al. [Phys. Rev. Lett. 95, 055702 (2005)] proposed a model for the glassy aging data of dielectric relaxation using a modified Kohlrausch-Williams-Watts form exp[-(t{sub age}/{tau}{sub age}){sup {beta}{sub age}}]. The aging time t{sub age} dependence of the relaxation time {tau}{sub age} is defined by these authors through a functional relation involving the corresponding frequency {nu}(t{sub age})=1/(2{pi}{tau}{sub age}), but the stretching exponent {beta}{sub age} is the same as {beta}{sub {alpha}},more » the {alpha}-relaxation stretching exponent. We present here an alternative functional form for {tau}{sub age}(t{sub age}) directly involving the relaxation time itself. The proposed model fits the data of Lunkenheimer et al. perfectly with a stretching exponent {beta}{sub age} different from {beta}{sub {alpha}}.« less

Effects of nymphal diet and adult feeding on allocation of resources to glassy-winged sharpshooter egg production

USDA-ARS?s Scientific Manuscript database

The glassy-winged sharpshooter is an invasive insect capable of transmitting the bacterial pathogen Xylella fastidiosa. Pre-oviposition periods of laboratory reared glassy-winged sharpshooters are variable. Here, two questions were addressed: does nymphal diet affect pre-oviposition period and how d...

Equation of state of heated glassy carbon

NASA Technical Reports Server (NTRS)

Sekine, Toshimori; Ahrens, Thomas J.

1991-01-01

New Hugoniot data are presented for glassy carbon preheated to 1550 K and shocked to 20 GPa. The high-temperature Hugoniot is very similar to the principal Hugoniot. This results argues against the diffusional mechanism for the shock-induced transformaton of amorphous carbon to diamond, although the present results are obviously limited to below 20 GPa. This study provides the first Higoniot data for carbon preheated to significantly high temperatures.

Evidence for the absence of enzymatic reactions in the glassy state. A case study of xanthophyll cycle pigments in the desiccation-tolerant moss Syntrichia ruralis

PubMed Central

Fernández-Marín, Beatriz; Kranner, Ilse; Sebastián, María San; Artetxe, Unai; Laza, José Manuel; Vilas, José Luis; Pritchard, Hugh W.; Nadajaran, Jayanthi; Míguez, Fátima; Becerril, José María; García-Plazaola, José Ignacio

2013-01-01

Desiccation-tolerant plants are able to withstand dehydration and resume normal metabolic functions upon rehydration. These plants can be dehydrated until their cytoplasm enters a ‘glassy state’ in which molecular mobility is severely reduced. In desiccation-tolerant seeds, longevity can be enhanced by drying and lowering storage temperature. In these conditions, they still deteriorate slowly, but it is not known if deteriorative processes include enzyme activity. The storage stability of photosynthetic organisms is less studied, and no reports are available on the glassy state in photosynthetic tissues. Here, the desiccation-tolerant moss Syntrichia ruralis was dehydrated at either 75% or <5% relative humidity, resulting in slow (SD) or rapid desiccation (RD), respectively, and different residual water content of the desiccated tissues. The molecular mobility within dry mosses was assessed through dynamic mechanical thermal analysis, showing that at room temperature only rapidly desiccated samples entered the glassy state, whereas slowly desiccated samples were in a ‘rubbery’ state. Violaxanthin cycle activity, accumulation of plastoglobules, and reorganization of thylakoids were observed upon SD, but not upon RD. Violaxanthin cycle activity critically depends on the activity of violaxanthin de-epoxidase (VDE). Hence, it is proposed that enzymatic activity occurred in the rubbery state (after SD), and that in the glassy state (after RD) no VDE activity was possible. Furthermore, evidence is provided that zeaxanthin has some role in recovery apparently independent of its role in non-photochemical quenching of chlorophyll fluorescence. PMID:23761488

Understanding soft glassy materials using an energy landscape approach

NASA Astrophysics Data System (ADS)

Hwang, Hyun Joo; Riggleman, Robert A.; Crocker, John C.

2016-09-01

Many seemingly different soft materials--such as soap foams, mayonnaise, toothpaste and living cells--display strikingly similar viscoelastic behaviour. A fundamental physical understanding of such soft glassy rheology and how it can manifest in such diverse materials, however, remains unknown. Here, by using a model soap foam consisting of compressible spherical bubbles, whose sizes slowly evolve and whose collective motion is simply dictated by energy minimization, we study the foam's dynamics as it corresponds to downhill motion on an energy landscape function spanning a high-dimensional configuration space. We find that these downhill paths, when viewed in this configuration space, are, surprisingly, fractal. The complex behaviour of our model, including power-law rheology and non-diffusive bubble motion and avalanches, stems directly from the fractal dimension and energy function of these paths. Our results suggest that ubiquitous soft glassy rheology may be a consequence of emergent fractal geometry in the energy landscapes of many complex fluids.

Preparation and Relaxation of Very Stable Glassy States of a Simulated Liquid

NASA Astrophysics Data System (ADS)

Jack, Robert L.; Hedges, Lester O.; Garrahan, Juan P.; Chandler, David

2011-12-01

We prepare metastable glassy states in a model glass former made of Lennard-Jones particles by sampling biased ensembles of trajectories with low dynamical activity. These trajectories form an inactive dynamical phase whose “fast” vibrational degrees of freedom are maintained at thermal equilibrium by contact with a heat bath, while the “slow” structural degrees of freedom are located in deep valleys of the energy landscape. We examine the relaxation to equilibrium and the vibrational properties of these metastable states. The glassy states we prepare by our trajectory sampling method are very stable to thermal fluctuations and also more mechanically rigid than low-temperature equilibrated configurations.

Electrochemiluminescence of luminol at the titanate nanotubes modified glassy carbon electrode.

PubMed

Xu, Guifang; Zeng, Xiaoxue; Lu, Shuangyan; Dai, Hong; Gong, Lingshan; Lin, Yanyu; Wang, Qingping; Tong, Yuejin; Chen, Guonan

2013-01-01

A new strategy for the construction of a sensitive and stable electrochemiluminescent platform based on titanate nanotubes (TNTs) and Nafion composite modified electrode for luminol is described, TNTs contained composite modified electrodes that showed some photocatalytic activity toward luminol electrochemiluminescence emission, and thus could dramatically enhance luminol light emission. This extremely sensitive and stable platform allowed a decrease of the experiment electrochemiluminescence luminol reagent. In addition, in luminol solution at low concentrations, we compared the capabilities of a bare glassy carbon electrode with the TNT composite modified electrode for hydrogen peroxide detection. The results indicated that compared with glassy carbon electrode this platform was extraordinarily sensitive to hydrogen peroxide. Therefore, by combining with an appropriate enzymatic reaction, this platform would be a sensitive matrix for many biomolecules.

Electrochemical behavior of triflusal, aspirin and their metabolites at glassy carbon and boron doped diamond electrodes.

PubMed

Enache, Teodor Adrian; Fatibello-Filho, Orlando; Oliveira-Brett, Ana Maria

2010-08-01

The electrochemical behavior of triflusal (TRF) and aspirin (ASA), before and after hydrolysis in water and in alkaline medium using two different electrode surfaces, glassy carbon and boron doped diamond, was study by differential pulse voltammetry over a wide pH range. The hydrolysis products are 2-(hydroxyl)-4-(trifluoromethyl)-benzoic acid (HTB) for triflusal and salicylic acid (SA) for aspirin, which in vivo represent their main metabolites. The hydrolysis processes were also followed by spectrophotometry. The UV results showed complete hydrolysis after one hour for TRF and after two hours for ASA in alkaline solution. The glassy carbon electrode enables only indirect determination of TRF and ASA through the electrochemical detection of their hydrolysis products HTB and SA, respectively. The oxidation processes of HTB and SA are pH dependent and involve different numbers of electrons and protons. Moreover, the difference between the oxidation peak potential of SA and HTB was equal to 100 mV in the studied pH range from 1 to 8 due to the CF3 of the aromatic ring of HTB molecule. Due to its wider oxidation potential range, the boron doped diamond electrode was used to study the direct oxidation of TRF and ASA, as well as of their respective metabolites HTB and SA.

Disentangling the Role of Entanglement Density and Molecular Alignment in the Mechanical Response of Glassy Polymers

NASA Astrophysics Data System (ADS)

O'Connor, Thomas; Robbins, Mark

Glassy polymers are a ubiquitous part of modern life, but much about their mechanical properties remains poorly understood. Since chains in glassy states are hindered from exploring their conformational entropy, they can't be understood with common entropic network models. Additionally, glassy states are highly sensitive to material history and nonequilibrium distributions of chain alignment and entanglement can be produced during material processing. Understanding how these far-from equilibrium states impact mechanical properties is analytically challenging but essential to optimizing processing methods. We use molecular dynamics simulations to study the yield and strain hardening of glassy polymers as separate functions of the degree of molecular alignment and inter-chain entanglement. We vary chain alignment and entanglement with three different preparation protocols that mimic common processing conditions in and out of solution. We compare our results to common mechanical models of amorphous polymers and assess their applicability to different experimental processing conditions. This research was performed within the Center for Materials in Extreme Dynamic Environments (CMEDE) under the Hopkins Extreme Materials Institute at Johns Hopkins University. Financial support was provided by Grant W911NF-12-2-0022.

Compressed glassy carbon: An ultrastrong and elastic interpenetrating graphene network

PubMed Central

Hu, Meng; He, Julong; Zhao, Zhisheng; Strobel, Timothy A.; Hu, Wentao; Yu, Dongli; Sun, Hao; Liu, Lingyu; Li, Zihe; Ma, Mengdong; Kono, Yoshio; Shu, Jinfu; Mao, Ho-kwang; Fei, Yingwei; Shen, Guoyin; Wang, Yanbin; Juhl, Stephen J.; Huang, Jian Yu; Liu, Zhongyuan; Xu, Bo; Tian, Yongjun

2017-01-01

Carbon’s unique ability to have both sp2 and sp3 bonding states gives rise to a range of physical attributes, including excellent mechanical and electrical properties. We show that a series of lightweight, ultrastrong, hard, elastic, and conductive carbons are recovered after compressing sp2-hybridized glassy carbon at various temperatures. Compression induces the local buckling of graphene sheets through sp3 nodes to form interpenetrating graphene networks with long-range disorder and short-range order on the nanometer scale. The compressed glassy carbons have extraordinary specific compressive strengths—more than two times that of commonly used ceramics—and simultaneously exhibit robust elastic recovery in response to local deformations. This type of carbon is an optimal ultralight, ultrastrong material for a wide range of multifunctional applications, and the synthesis methodology demonstrates potential to access entirely new metastable materials with exceptional properties. PMID:28630918

Study of the physical properties of Ge-S-Ga glassy alloy

NASA Astrophysics Data System (ADS)

Rana, Anjli; Sharma, Raman

2018-05-01

In the present work, we have studied the effect of Ga doping on the physical properties of Ge20S80-xGax glassy alloy. The basic physical parameters which have important role in determining the structure and strength of the material viz. average coordination number, lone-pair electrons, mean bond energy, glass transition temperature, electro negativity, probabilities for bond distribution and cohesive energy have been computed theoretically for Ge-S-Ga glassy alloy. Here, the glass transition temperature and mean bond energy have been investigated using the Tichy-Ticha approach. The cohesive energy has been calculated by using chemical bond approach (CBA) method. It has been found that while average coordination number increases, all the other parameters decrease with the increase in Ga content in Ge-S-Ga system.

Effects of xylem-sap composition on glassy-winged sharpshooter egg maturation on high and low quality host plants

USDA-ARS?s Scientific Manuscript database

Glassy-winged sharpshooters must feed as adults to produce mature eggs. Cowpea and sunflower are both readily accepted by the glassy-winged sharpshooter for feeding, but egg production on sunflower was reported to be lower than egg production on cowpea. To better understand the role of adult diet in...

Glassy carbon electrode modified with polyanilne/ethylenediamine for detection of copper ions

NASA Astrophysics Data System (ADS)

Patil, Harshada K.; Deshmukh, Megha A.; Bodkhe, Gajanan A.; Shirsat, Mahendra D.

2018-05-01

Increasing water pollution is having high concern, since it creates the threats to all leaving organisms of existence. Industrial sewages have not only polluted the main stream lines of water, also the ground level water is having serious contaminations. Heavy metal ions are the pollutants which are not degradable and can be accumulated on living things ultimately the excess accumulation results into the serious concerns. Therefore, it is necessary to develop the sensors which can detect the heavy metal ions up to its maximum contamination limits. Conducting polymers are the materials which possess large application spectra. This investigation reports the electrochemically synthesized polyaniline (PANI) for modification of glassy carbon electrode (GCE). Ethylenediamine (EDA) - chelating ligand used for the modification of polyaniline so as to inculcate the selectivity toward copper ions Cu (II). The electrochemical cyclic voltammetry (CV) was used for the study of redox characteristics of PANI and influence of EDA modification. The result of CV has shown the reduced oxidation and reduction peak currents after modification indicating the domination of EDA. GCE modified with PANI/EDA was then employed for the detection of divalent copper ions and have shown the affinity toward Cu ions. The detection limit achieved was equal to 10mg/lit.

Isothermal enthalpy relaxation of glassy 1,2,6-hexanetriol

NASA Astrophysics Data System (ADS)

Fransson, Å.; Bäckström, G.

The isothermal enthalpy relaxation of glassy 1,2,6-hexanetriol has been measured at six temperatures. The relaxation time and the distribution parameters extracted from fits of the Williams-Watts relaxation function are compared with parameters obtained by other techniques and on other substances. A detailed comparison of the Williams-Watts and the Davidson-Cole relaxation functions is presented.

Asphaltene-laden interfaces form soft glassy layers in contraction experiments: a mechanism for coalescence blocking.

PubMed

Pauchard, Vincent; Rane, Jayant P; Banerjee, Sanjoy

2014-11-04

In previous studies, the adsorption kinetics of asphaltenes at the water-oil interface were interpreted utilizing a Langmuir equation of state (EOS) based on droplet expansion experiments.1-3 Long-term adsorption kinetics followed random sequential adsorption (RSA) theory predictions, asymptotically reaching ∼85% limiting surface coverage, which is similar to limiting random 2D close packing of disks. To extend this work beyond this slow adsorption process, we performed rapid contractions and contraction-expansions of asphaltene-laden interfaces using the pendant drop experiment to emulate a Langmuir trough. This simulates the rapid increase in interfacial asphaltene concentration that occurs during coalescence events. For the contraction of droplets aged in asphaltene solutions, deviation from the EOS consistently occurs at a surface pressure value ∼21 mN/m corresponding to a surface coverage ∼80%. At this point droplets lose the shape required for validity of the Laplace-Young equation, indicating solidlike surface behavior. On further contraction wrinkles appear, which disappear when the droplet is held at constant volume. Surface pressure also decreases down to an equilibrium value near that measured for slow adsorption experiments. This behavior appears to be due to a transition to a glassy interface on contraction past the packing limit, followed by relaxation toward equilibrium by desorption at constant volume. This hypothesis is supported by cycling experiments around the close-packed limit where the transition to and from a solidlike state appears to be both fast and reversible, with little hysteresis. Also, the soft glass rheology model of Sollich is shown to capture previously reported shear behavior during adsorption. The results suggest that the mechanism by which asphaltenes stabilize water-in-oil emulsions is by blocking coalescence due to rapid formation of a glassy interface, in turn caused by interfacial asphaltenes rapidly increasing in

Electrical resistivity in Zr48Nb8Cu12Fe8Be24 glassy and crystallized alloys

NASA Astrophysics Data System (ADS)

Bai, H. Y.; Tong, C. Z.; Zheng, P.

2004-02-01

The electrical resistivity of Zr48Nb8Cu12Fe8Be24 bulk metallic glassy and crystallized alloys in the temperature range of 4.2-293 K is investigated. It is found that the resistivity in glassy and crystallized states shows opposite temperature coefficients. For the metallic glass, the resistivity shows a negative logarithmic dependence at temperatures below 16 K, whereas it has more normal behavior for the crystallized alloy. At higher temperatures, the resistivity in both glassy and crystallized alloys shows dependence upon both T and T2, but the signs of the T and T2 terms are opposite. The results are interpreted in terms of scattering from two-level tunneling states in glasses and the generalized Ziman diffraction model.

Low substrate temperature deposition of diamond coatings derived from glassy carbon

DOEpatents

Holcombe, Jr., Cressie E.; Seals, Roland D.

1995-01-01

A process for depositing a diamond coating on a substrate at temperatures less than about 550.degree. C. A powder mixture of glassy carbon and diamond particles is passed through a high velocity oxy-flame apparatus whereupon the powders are heated prior to impingement at high velocity against the substrate. The powder mixture contains between 5 and 50 powder volume percent of the diamond particles, and preferably between 5 and 15 powder volume percent. The particles have a size from about 5 to about 100 micrometers, with the diamond particles being about 5 to about 30 micrometers. The flame of the apparatus provides a velocity of about 350 to about 1000 meters per second, with the result that upon impingement upon the substrate, the glassy carbon is phase transformed to diamond as coaxed by the diamond content of the powder mixture.

Unraveling the Mechanism of Nanoscale Mechanical Reinforcement in Glassy Polymer Nanocomposites

DOE PAGES

Cheng, Shiwang; Bocharova, Vera; Belianinov, Alex; ...

2016-05-20

The mechanical reinforcement of polymer nanocomposites (PNCs) above the glass transition temperature, T g, has been extensively researched. However, not much is known about the origin of this effect below T g. In this paper, we unravel the mechanism of PNC reinforcement within the glassy state by directly probing nanoscale mechanical properties with atomic force microscopy and macroscopic properties with Brillouin light scattering. Our results unambiguously show that the "glassy" Young's modulus in the interfacial polymer layer of PNCs is two-times higher than in the bulk polymer, which results in significant reinforcement below T g. We ascribe this phenomenon tomore » a high stretching of the chains within the interfacial layer. Since the interfacial chain packing is essentially temperature independent, these findings provide a new insight into the mechanical reinforcement of PNCs also above T g.« less

Low substrate temperature deposition of diamond coatings derived from glassy carbon

DOEpatents

Holcombe, C.E. Jr.; Seals, R.D.

1995-09-26

A process is disclosed for depositing a diamond coating on a substrate at temperatures less than about 550 C. A powder mixture of glassy carbon and diamond particles is passed through a high velocity oxy-flame apparatus whereupon the powders are heated prior to impingement at high velocity against the substrate. The powder mixture contains between 5 and 50 powder volume percent of the diamond particles, and preferably between 5 and 15 powder volume percent. The particles have a size from about 5 to about 100 micrometers, with the diamond particles being about 5 to about 30 micrometers. The flame of the apparatus provides a velocity of about 350 to about 1000 meters per second, with the result that upon impingement upon the substrate, the glassy carbon is phase transformed to diamond as coaxed by the diamond content of the powder mixture. 2 figs.

A Thermodynamic Theory of Solid Viscoelasticity. Part 3: Nonlinear Glassy Viscoelasticity, Stability Constraints, Specifications

NASA Technical Reports Server (NTRS)

Freed, Alan; Leonov, Arkady I.

2002-01-01

This paper, the last in the series, continues developing the nonlinear constitutive relations for non-isothermal, compressible, solid viscoelasticity. We initially discuss a single integral approach, more suitable for the glassy state of rubber-like materials, with basic functionals involved in the thermodynamic description for this type of viscoelasticity. Then we switch our attention to analyzing stability constraints, imposed on the general formulation of the nonlinear theory of solid viscoelasticity. Finally, we discuss specific (known from the literature or new) expressions for material functions that are involved in the constitutive formulations of both the rubber-like and glassy-like, complementary parts of the theory.

Cooperativity in glassy dynamics investigated by higher-harmonic dielectric spectroscopy

NASA Astrophysics Data System (ADS)

Bauer, Thomas; Lunkenheimer, Peter; Loidl, Alois; Experimental Physics V Team

2014-03-01

In recent years, due to experimental advances initiated by hole burning experiments, nonlinear dielectric spectroscopy has gained increasing interest in the field of glass-forming matter. For example, refining the technique of high-field permittivity measurements, we found a surprising lack of nonlinearity in the so-called excess wing region, that could not be accessed by this method before. In the present contribution, we report new, detailed measurements of the third-order nonlinear dielectric susceptibility χ3 of four glass-forming liquids for a broad temperature range. We find a significant hump in χ3(ν) , from which we deduce the number of correlated molecules Ncorr. We detect a continuous increase of Ncorr on approaching the glass-transition temperature. Comparing these results with the temperature-dependent apparent energy barriers in these systems, our experiments finally prove the old notion that intermolecular correlations of glassy systems are responsible for the non-canonical temperature development of glassy dynamics. This work was supported by the Deutsche Forschungsgemeinschaft via Research Unit FOR1394.

Relationship between local structure and relaxation in out-of-equilibrium glassy systems

DOE PAGES

Schoenholz, Samuel S.; Cubuk, Ekin D.; Kaxiras, Efthimios; ...

2016-12-27

The dynamical glass transition is typically taken to be the temperature at which a glassy liquid is no longer able to equilibrate on experimental timescales. Consequently, the physical properties of these systems just above or below the dynamical glass transition, such as viscosity, can change by many orders of magnitude over long periods of time following external perturbation. During this progress toward equilibrium, glassy systems exhibit a history dependence that has complicated their study. In previous work, we bridged the gap between structure and dynamics in glassy liquids above their dynamical glass transition temperatures by introducing a scalar field calledmore » “softness,” a quantity obtained using machine-learning methods. Softness is designed to capture the hidden patterns in relative particle positions that correlate strongly with dynamical rearrangements of particle positions. Here we show that the out-of-equilibrium behavior of a model glass-forming system can be understood in terms of softness. We first demonstrate that the evolution of behavior following a temperature quench is a primarily structural phenomenon: The structure changes considerably, but the relationship between structure and dynamics remains invariant. We then show that the relaxation time can be robustly computed from structure as quantified by softness, with the same relation holding both in equilibrium and as the system ages. Together, these results show that the history dependence of the relaxation time in glasses requires knowledge only of the softness in addition to the usual state variables.« less

Relationship between local structure and relaxation in out-of-equilibrium glassy systems.

PubMed

Schoenholz, Samuel S; Cubuk, Ekin D; Kaxiras, Efthimios; Liu, Andrea J

2017-01-10

The dynamical glass transition is typically taken to be the temperature at which a glassy liquid is no longer able to equilibrate on experimental timescales. Consequently, the physical properties of these systems just above or below the dynamical glass transition, such as viscosity, can change by many orders of magnitude over long periods of time following external perturbation. During this progress toward equilibrium, glassy systems exhibit a history dependence that has complicated their study. In previous work, we bridged the gap between structure and dynamics in glassy liquids above their dynamical glass transition temperatures by introducing a scalar field called "softness," a quantity obtained using machine-learning methods. Softness is designed to capture the hidden patterns in relative particle positions that correlate strongly with dynamical rearrangements of particle positions. Here we show that the out-of-equilibrium behavior of a model glass-forming system can be understood in terms of softness. To do this we first demonstrate that the evolution of behavior following a temperature quench is a primarily structural phenomenon: The structure changes considerably, but the relationship between structure and dynamics remains invariant. We then show that the relaxation time can be robustly computed from structure as quantified by softness, with the same relation holding both in equilibrium and as the system ages. Together, these results show that the history dependence of the relaxation time in glasses requires knowledge only of the softness in addition to the usual state variables.

Dielectric relaxation studies in super-cooled liquid and glassy phases of anti-cancerous alkaloid: Brucine

NASA Astrophysics Data System (ADS)

Afzal, Aboothahir; Shahin Thayyil, M.; Sulaiman, M. K.; Kulkarni, A. R.

2018-05-01

Brucine has good anti-tumor effects, on both liver cancer and breast cancer. It has bioavailability of 40.83%. Since the bioavailability of the drug is low, an alternative method to increase its bioavailability and solubility is by changing the drug into glassy form. We used Differential Scanning Calorimetry (DSC) for studying the glass forming ability of the drug. Brucine was found to be a very good glass former glass transition temperature 365 K. Based on the DSC analysis we have used broadband dielectric spectroscopy (BDS) for studying the drug in the super cooled and glassy state. BDS is an effective tool to probe the molecular dynamics in the super cooled and glassy state. Molecular mobility is found to be present even in the glassy state of this active pharmaceutical ingredient (API) which is responsible for the instability. Our aim is to study the factors responsible for instability of this API in amorphous form. Cooling curves for dielectric permittivity and dielectric loss revealed the presence of structural (α) and secondary relaxations (β and γ). Temperature dependence of relaxation time is fitted by Vogel-Fulcher-Tammann equation and found the values of activation energy of the α relaxation, fragility and glass transition temperature. Paluch's anti correlation is also verified, that the width of the α-loss peak at or near the glass transition temperature Tg is strongly anticorrelated with the polarity of the molecule. The larger the dielectric relaxation strength Δɛ (Tg) of the system, the narrower is the α-loss peak (higher value of βKWW).

Mating behavior and vibrational mimicry in the glassy-winged sharpshooter, Homalodisca vitripennis

USDA-ARS?s Scientific Manuscript database

Vibrational communication is widespread in insects, particularly in leafhoppers where the pair formation process is mediated by species-specific vibrational signals. One important pest using vibrational communication, glassy-winged sharpshooter (GWSS), Homalodisca vitripennis, is a vector of Xylella...

Substrate-borne vibrational signals in intraspecific communication of glassy-winged sharpshooters (GWSS)

USDA-ARS?s Scientific Manuscript database

Exploitation of vibrational signals for suppressing glassy-winged sharpshooter (GWSS) populations could prove to be a useful tool. However, existing knowledge on GWSS vibrational communication is insufficient to implement a management program for this pest in California. Therefore, the objective of ...

Elastic properties of aspirin in its crystalline and glassy phases studied by micro-Brillouin scattering

NASA Astrophysics Data System (ADS)

Ko, Jae-Hyeon; Lee, Kwang-Sei; Ike, Yuji; Kojima, Seiji

2008-11-01

The acoustic waves propagating along the direction perpendicular to the (1 0 0) cleavage plane of aspirin crystal were investigated using micro-Brillouin spectroscopy from which C11, C55 and C66 were obtained. The temperature dependence of the longitudinal acoustic waves could be explained by normal anharmonic lattice models, while the transverse acoustic waves showed an abnormal increase in the hypersonic attenuation at low temperatures indicating their coupling to local remnant dynamics. The sound velocity as well as the attenuation of the longitudinal acoustic waves of glassy aspirin showed a substantial change at ˜235 K confirming a transition from glassy to supercooled liquid state in vitreous aspirin.

Boson peak as a probe of quantum effects in a glassy state of biomolecules: the case of L-cysteine.

PubMed

Lima, T A; Ishikawa, M S; Martinho, H S

2014-02-01

Some physical properties of hydrated biomolecules, e.g., the occurrence of a boson peak, have been recognized to resemble those of glassy states. The present work shows that quantum fluctuations play a fundamental role in describing the glassy state of biomolecules, particularly at lower hydration levels. There is a linear relationship between the quantumness and the slope of the temperature dependence of the boson peak frequency, which is used to classify the extent of quantum contributions to the glassy state of glasses in general. Lastly, we demonstrate that the boson peak two-band spectral structure that is observed in some cases can be directly linked to the anisotropy of the elastic properties of the material. The amino acid L-cysteine is studied in detail. The findings are compared with previously reported data for other macromolecules.

Cooperative strings and glassy interfaces

PubMed Central

Salez, Thomas; Salez, Justin; Dalnoki-Veress, Kari; Raphaël, Elie; Forrest, James A.

2015-01-01

We introduce a minimal theory of glass formation based on the ideas of molecular crowding and resultant string-like cooperative rearrangement, and address the effects of free interfaces. In the bulk case, we obtain a scaling expression for the number of particles taking part in cooperative strings, and we recover the Adam–Gibbs description of glassy dynamics. Then, by including thermal dilatation, the Vogel–Fulcher–Tammann relation is derived. Moreover, the random and string-like characters of the cooperative rearrangement allow us to predict a temperature-dependent expression for the cooperative length ξ of bulk relaxation. Finally, we explore the influence of sample boundaries when the system size becomes comparable to ξ. The theory is in agreement with measurements of the glass-transition temperature of thin polymer films, and allows quantification of the temperature-dependent thickness hm of the interfacial mobile layer. PMID:26100908

Diazonium Chemistry for the Bio-Functionalization of Glassy Nanostring Resonator Arrays

PubMed Central

Zheng, Wei; Du, Rongbing; Cao, Yong; Mohammad, Mohammad A.; Dew, Steven K.; McDermott, Mark T.; Evoy, Stephane

2015-01-01

Resonant glassy nanostrings have been employed for the detection of biomolecules. These devices offer high sensitivity and amenability to large array integration and multiplexed assays. Such a concept has however been impaired by the lack of stable and biocompatible linker chemistries. Diazonium salt reduction-induced aryl grafting is an aqueous-based process providing strong chemical adhesion. In this work, diazonium-based linker chemistry was performed for the first time on glassy nanostrings, which enabled the bio-functionalization of such devices. Large arrays of nanostrings with ultra-narrow widths down to 10 nm were fabricated employing electron beam lithography. Diazonium modification was first developed on SiCN surfaces and validated by X-ray photoelectron spectroscopy. Similarly modified nanostrings were then covalently functionalized with anti-rabbit IgG as a molecular probe. Specific enumeration of rabbit IgG was successfully performed through observation of downshifts of resonant frequencies. The specificity of this enumeration was confirmed through proper negative control experiments. Helium ion microscopy further verified the successful functionalization of nanostrings. PMID:26263989

Diazonium Chemistry for the Bio-Functionalization of Glassy Nanostring Resonator Arrays.

PubMed

Zheng, Wei; Du, Rongbing; Cao, Yong; Mohammad, Mohammad A; Dew, Steven K; McDermott, Mark T; Evoy, Stephane

2015-07-30

Resonant glassy nanostrings have been employed for the detection of biomolecules. These devices offer high sensitivity and amenability to large array integration and multiplexed assays. Such a concept has however been impaired by the lack of stable and biocompatible linker chemistries. Diazonium salt reduction-induced aryl grafting is an aqueous-based process providing strong chemical adhesion. In this work, diazonium-based linker chemistry was performed for the first time on glassy nanostrings, which enabled the bio-functionalization of such devices. Large arrays of nanostrings with ultra-narrow widths down to 10 nm were fabricated employing electron beam lithography. Diazonium modification was first developed on SiCN surfaces and validated by X-ray photoelectron spectroscopy. Similarly modified nanostrings were then covalently functionalized with anti-rabbit IgG as a molecular probe. Specific enumeration of rabbit IgG was successfully performed through observation of downshifts of resonant frequencies. The specificity of this enumeration was confirmed through proper negative control experiments. Helium ion microscopy further verified the successful functionalization of nanostrings.

Temperature-dependent microindentation data of an epoxy composition in the glassy region

NASA Astrophysics Data System (ADS)

Minster, Jiří; Králík, Vlastimil

2015-02-01

The short-term instrumented microindentation technique was applied for assessing the influence of temperature in the glassy region on the time-dependent mechanical properties of an average epoxy resin mix near to its native state. Linear viscoelasticity theory with the assumption of time-independent Poisson ratio value forms the basis for processing the experimental results. The sharp standard Berkovich indenter was used to measure the local mechanical properties at temperatures 20, 24, 28, and 35 °C. The short-term viscoelastic compliance histories were defined by the Kohlrausch-Williams-Watts double exponential function. The findings suggest that depth-sensing indentation data of thermorheologically simple materials influenced by different temperatures in the glassy region can also be used, through the time-temperature superposition, to extract viscoelastic response functions accurately. This statement is supported by the comparison of the viscoelastic compliance master curve of the tested material with data derived from standard macro creep measurements under pressure on the material in a conformable state.

A thermo-chemo-mechanically coupled constitutive model for curing of glassy polymers

NASA Astrophysics Data System (ADS)

Sain, Trisha; Loeffel, Kaspar; Chester, Shawn

2018-07-01

Curing of a polymer is the process through which a polymer liquid transitions into a solid polymer, capable of bearing mechanical loads. The curing process is a coupled thermo-chemo-mechanical conversion process which requires a thorough understanding of the system behavior to predict the cure dependent mechanical behavior of the solid polymer. In this paper, a thermodynamically consistent, frame indifferent, thermo-chemo-mechanically coupled continuum level constitutive framework is proposed for thermally cured glassy polymers. The constitutive framework considers the thermodynamics of chemical reactions, as well as the material behavior for a glassy polymer. A stress-free intermediate configuration is introduced within a finite deformation setting to capture the formation of the network in a stress-free configuration. This work considers a definition for the degree of cure based on the chemistry of the curing reactions. A simplified version of the proposed model has been numerically implemented, and simulations are used to understand the capabilities of the model and framework.

A Novel Method for Electroplating Ultra-High-Strength Glassy Metals

NASA Technical Reports Server (NTRS)

Ramsey, Brian; Engelhaupt, Darell; Six, N. Frank (Technical Monitor)

2002-01-01

A novel method for electroplating ultra-high-strength glassy metals, nickel-phosphorous and nickel-cobalt-phosphorous, has been developed at NASA Marshall Space Flight Center, cooperatively with the University of Alabama in Huntsville. Traditionally, thin coatings of these metals are achieved via electroless deposition. Benefits of the new electrolytic process include thick, low-stress deposits, free standing shapes, lower plating temperature, low maintenance, and safer operation with substantially lower cost.

Topological structure and mechanics of glassy polymer networks.

PubMed

Elder, Robert M; Sirk, Timothy W

2017-11-22

The influence of chain-level network architecture (i.e., topology) on mechanics was explored for unentangled polymer networks using a blend of coarse-grained molecular simulations and graph-theoretic concepts. A simple extension of the Watts-Strogatz model is proposed to control the graph properties of the network such that the corresponding physical properties can be studied with simulations. The architecture of polymer networks assembled with a dynamic curing approach were compared with the extended Watts-Strogatz model, and found to agree surprisingly well. The final cured structures of the dynamically-assembled networks were nearly an intermediate between lattice and random connections due to restrictions imposed by the finite length of the chains. Further, the uni-axial stress response, character of the bond breaking, and non-affine displacements of fully-cured glassy networks were analyzed as a function of the degree of disorder in the network architecture. It is shown that the architecture strongly affects the network stability, flow stress, onset of bond breaking, and ultimate stress while leaving the modulus and yield point nearly unchanged. The results show that internal restrictions imposed by the network architecture alter the chain-level response through changes to the crosslink dynamics in the flow regime and through the degree of coordinated chain failure at the ultimate stress. The properties considered here are shown to be sensitive to even incremental changes to the architecture and, therefore, the overall network architecture, beyond simple defects, is predicted to be a meaningful physical parameter in the mechanics of glassy polymer networks.

Effects of energy reserves and diet on glassy-winged sharpshooter egg maturation

USDA-ARS?s Scientific Manuscript database

Effects of stored energy and diet quality on glassy-winged sharpshooter egg maturation were evaluated. To evaluate effects of diet quality on egg maturation, egg load weights of females at the end of a 6-day feeding period on cowpea or grapevine were compared. To estimate energy reserves available a...

Pair distribution function analysis of sulfide glassy electrolytes for all-solid-state batteries: Understanding the improvement of ionic conductivity under annealing condition.

PubMed

Shiotani, Shinya; Ohara, Koji; Tsukasaki, Hirofumi; Mori, Shigeo; Kanno, Ryoji

2017-08-01

In general, the ionic conductivity of sulfide glasses decreases with their crystallization, although it increases for a few sulphide glasses owing to the crystallization of a highly conductive new phase (e.g., Li 7 P 3 S 11 : 70Li 2 S-30P 2 S 5 ). We found that the ionic conductivity of 75Li 2 S-25P 2 S 5 sulfide glass, which consists of glassy and crystalline phases, is improved by optimizing the conditions of the heat treatment, i.e., annealing. A different mechanism of high ionic conductivity from the conventional mechanism is expected in the glassy phase. Here, we report the glassy structure of 75Li 2 S-25P 2 S 5 immediately before the crystallization by using the differential pair distribution function (d-PDF) analysis of high-energy X-ray diffraction. Even though the ionic conductivity increases during the optimum annealing, the d-PDF analysis indicated that the glassy structure undergoes no structural change in the sulfide glass-ceramic electrolyte at a crystallinity of 33.1%. We observed the formation of a nanocrystalline phase in the X-ray and electron diffraction patterns before the crystallization, which means that Bragg peaks were deformed. Thus, the ionic conductivity in the mixture of glassy and crystalline phases is improved by the coexistence of the nanocrystalline phase.

Laser micromilling of convex microfluidic channels onto glassy carbon for glass molding dies

NASA Astrophysics Data System (ADS)

Tseng, Shih-Feng; Chen, Ming-Fei; Hsiao, Wen-Tse; Huang, Chien-Yao; Yang, Chung-Heng; Chen, Yu-Sheng

2014-06-01

This study reports the fabrication of convex microfluidic channels on glassy carbon using an ultraviolet laser processing system to produce glass molding dies. The laser processing parameters, including various laser fluences and scanning speeds of galvanometers, were adjusted to mill a convex microchannel on a glassy carbon substrate to identify the effects of material removal. The machined glassy carbon substrate was then applied as a glass molding die to fabricate a glass-based microfluidic biochip. The surface morphology, milled width and depth, and surface roughness of the microchannel die after laser micromilling were examined using a three-dimensional confocal laser scanning microscope. This study also investigates the transcription rate of microchannels after the glass molding process. To produce a 180 μm high microchannel on the GC substrate, the optimal number of milled cycles, laser fluence, and scanning speed were 25, 4.9 J/cm2, and 200 mm/s, respectively. The width, height, and surface roughness of milled convex microchannels were 119.6±0.217 μm, 180.26±0.01 μm, and 0.672±0.08 μm, respectively. These measured values were close to the predicted values and suitable for a glass molding die. After the glass molding process, a typical glass-based microchannel chip was formed at a molding temperature of 660 °C and the molding force of 0.45 kN. The transcription rates of the microchannel width and depth were 100% and 99.6%, respectively. Thus, the proposed approach is suitable for performing in chemical, biochemical, or medical reactions.

Dynamical singularities of glassy systems in a quantum quench.

PubMed

Obuchi, Tomoyuki; Takahashi, Kazutaka

2012-11-01

We present a prototype of behavior of glassy systems driven by quantum dynamics in a quenching protocol by analyzing the random energy model in a transverse field. We calculate several types of dynamical quantum amplitude and find a freezing transition at some critical time. The behavior is understood by the partition-function zeros in the complex temperature plane. We discuss the properties of the freezing phase as a dynamical chaotic phase, which are contrasted to those of the spin-glass phase in the static system.

Molecular dynamics and crystallization phenomenon of supercooled and glassy DNA and RNA nucleosides: β-adenosine, β-thymidine, and β-uridine

NASA Astrophysics Data System (ADS)

Adrjanowicz, K.; Wojnarowska, Z.; Grzybowska, K.; Hawelek, L.; Kaminski, K.; Paluch, M.; Kasprzycka, A.; Walczak, K.

2011-11-01

Nucleosides are chemical compounds that have an extremely important biological role; they can be found in all types of living organisms. They are crucial components from which DNA and RNA acids are built. In addition, nucleosides are key regulators of many physiological processes. In this paper, the molecular dynamics in the liquid and glassy state of three selected nucleosides, β-adenosine, β-thymidine, and β-uridine, was investigated by means of dielectric spectroscopy. Our results revealed multiple relaxation processes associated with different types of molecular motions. Besides the primary α relaxation, two secondary modes in the glassy states of examined compounds were identified. Crystallization progress monitored by dielectric spectroscopy and x-ray diffraction technique at isostructural relaxation conditions revealed that the examined nucleosides possess completely different tendencies to recrystallize from the liquid as well as the glassy state. We have also made an attempt to predict the time scale of molecular motion below the glass transition temperatures of the respective nucleosides to discuss their potential stability at room temperature over prolonged storage time. Finally, combination of molecular mobility studies with evaluation of thermodynamic parameters from calorimetric measurements allowed us to discuss the fundamental roles of both kinetic and thermodynamic factors in governing the physical stability of the glassy state.

Relation between the Dynamics of Glassy Clusters and Characteristic Features of their Energy Landscape

NASA Astrophysics Data System (ADS)

De, Sandip; Schaefer, Bastian; Sadeghi, Ali; Sicher, Michael; Kanhere, D. G.; Goedecker, Stefan

2014-02-01

Based on a recently introduced metric for measuring distances between configurations, we introduce distance-energy (DE) plots to characterize the potential energy surface of clusters. Producing such plots is computationally feasible on the density functional level since it requires only a few hundred stable low energy configurations including the global minimum. By using standard criteria based on disconnectivity graphs and the dynamics of Lennard-Jones clusters, we show that the DE plots convey the necessary information about the character of the potential energy surface and allow us to distinguish between glassy and nonglassy systems. We then apply this analysis to real clusters at the density functional theory level and show that both glassy and nonglassy clusters can be found in simulations. It turns out that among our investigated clusters only those can be synthesized experimentally which exhibit a nonglassy landscape.

Electrochemical synthesis of gold nanoparticles on the surface of multi-walled carbon nanotubes with glassy carbon electrode and their application

NASA Astrophysics Data System (ADS)

Song, Y. Z.; Li, X.; Song, Y.; Cheng, Z. P.; Zhong, H.; Xu, J. M.; Lu, J. S.; Wei, C. G.; Zhu, A. F.; Wu, F. Y.; Xu, J.

2013-01-01

Gold nanoparticles on the surface of multi-walled carbon nanotubes with glassy carbon electrode were prepared using electrochemical synthesis method. The thin films of gold Nanoparticles/multi-walled carbon nanotubes were characterized by scanning electron microscopy, powder X-ray diffraction, and cyclic voltammetry. Electrochemical behavior of adrenaline hydrochloride at gold nanoparticles/multi-walled carbon nanotube modified glassy carbon electrode was investigated. A simple, sensitive, and inexpensive method for determination of adrenaline hydrochloride was proposed.

Glassy-winged sharpshooter can use a mechanical mechanism to inoculate Xylella fastidiosa into grapevines

USDA-ARS?s Scientific Manuscript database

Xylem-feeding leafhoppers such as the glassy-winged sharpshooter, Homalodisca vitripennis (Cicadellidae: Cicadellinae), are thought to inoculate the bacterium Xylella fastidiosa (Xf) from colonies bound to cuticle of the sharpshooter’s functional foregut (precibarium and cibarium). The mechanism of ...

Positronics of radiation-induced effects in chalcogenide glassy semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shpotyuk, O.; Kozyukhin, S. A., E-mail: sergkoz@igic.ras.ru; Shpotyuk, M.

2015-03-15

Using As{sub 2}S{sub 3} and AsS{sub 2} glasses as an example, the principal possibility of using positron annihilation spectroscopy methods for studying the evolution of the free volume of hollow nanoobjects in chalcogenide glassy semiconductors exposed to radiation is shown. The results obtained by measurements of the positron annihilation lifetime and Doppler broadening of the annihilation line in reverse chronological order are in full agreement with the optical spectroscopy data in the region of the fundamental absorption edge, being adequately described within coordination defect-formation and physical-aging models.

Glassy phase in quenched disordered crystalline membranes

NASA Astrophysics Data System (ADS)

Coquand, O.; Essafi, K.; Kownacki, J.-P.; Mouhanna, D.

2018-03-01

We investigate the flat phase of D -dimensional crystalline membranes embedded in a d -dimensional space and submitted to both metric and curvature quenched disorders using a nonperturbative renormalization group approach. We identify a second-order phase transition controlled by a finite-temperature, finite-disorder fixed point unreachable within the leading order of ɛ =4 -D and 1 /d expansions. This critical point divides the flow diagram into two basins of attraction: that associated with the finite-temperature fixed point controlling the long-distance behavior of disorder-free membranes and that associated with the zero-temperature, finite-disorder fixed point. Our work thus strongly suggests the existence of a whole low-temperature glassy phase for quenched disordered crystalline membranes and, possibly, for graphene and graphene-like compounds.

Molecular Factors Governing the Liquid and Glassy States Recrystallization of Celecoxib in Binary Mixtures with Excipients of Different Molecular Weights.

PubMed

Grzybowska, K; Chmiel, K; Knapik-Kowalczuk, J; Grzybowski, A; Jurkiewicz, K; Paluch, M

2017-04-03

Transformation of poorly water-soluble crystalline pharmaceuticals to the amorphous form is one of the most promising strategies to improve their oral bioavailability. Unfortunately, the amorphous drugs are usually thermodynamically unstable and may quickly return to their crystalline form. A very promising way to enhance the physical stability of amorphous drugs is to prepare amorphous compositions of APIs with certain excipients which can be characterized by significantly different molecular weights, such as polymers, acetate saccharides, and other APIs. By using different experimental techniques (broadband dielectric spectroscopy, differential scanning calorimetry, X-ray diffraction) we compare the effect of adding the large molecular weight polymer-polyvinylpyrrolidone (PVP K30)-and the small molecular weight excipient-octaacetylmaltose (acMAL)-on molecular dynamics as well as the tendency to recrystallization of the amorphous celecoxib (CEL) in the amorphous solid dispersions: CEL-PVP and CEL-acMAL. The physical stability investigations of the binary systems were performed in both the supercooled liquid and glassy states. We found that acMAL is a better inhibitor of recrystallization of amorphous CEL than PVP K30 deep in the glassy state (T < T g ). In contrast, PVP K30 is a better crystallization inhibitor of CEL than acMAL in the supercooled liquid state (at T > T g ). We discuss molecular factors governing the recrystallization of amorphous CEL in examined solid dispersions.

Glassy-winged sharpshooter oviposition effects on foliar grapevine and red-tipped photinia terpenoid levels

USDA-ARS?s Scientific Manuscript database

The glassy-winged sharpshooter (GWSS), Homalodisca vitripennis (Germar) (Hemiptera: Cicadellidae), is an important vector of Xylella fastidiosa, the bacterium that causes Pierce's disease of grapevine and is a threat to grape production throughout the United States. Female GWSS deposit egg masses be...

Egg maturation by the glassy-winged sharpshooter (Hemiptera: Cicadellidae); a vector of Xylella fastidiosa

USDA-ARS?s Scientific Manuscript database

Rates of spread of insect-transmitted plant pathogens are a function of vector abundance. Despite this, factors affecting population growth rates of insects that transmit plant pathogens have received limited attention. The glassy-winged sharpshooter (Homalodisca vitripennis) feeds on xylem-sap and ...

Polyamorphism in Water: Amorphous Ices and their Glassy States

NASA Astrophysics Data System (ADS)

Amann-Winkel, K.; Boehmer, R.; Fujara, F.; Gainaru, C.; Geil, B.; Loerting, T.

2015-12-01

Water is ubiquitous and of general importance for our environment. But it is also known as the most anomalous liquid. The fundamental origin of the numerous anomalies of water is still under debate. An understanding of these anomalous properties of water is closely linked to an understanding of the phase diagram of the metastable non-crystalline states of ice. The process of pressure induced amorphization of ice was first observed by Mishima et al. [1]. The authors pressurized hexagonal ice at 77 K up to a pressure of 1.6 GPa to form high density amorphous ice (HDA). So far three distinct structural states of amorphous water are known [2], they are called low- (LDA), high- (HDA) and very high density amorphous ice (VHDA). Since the discovery of multiple distinct amorphous states it is controversy discussed whether this phenomenon of polyamorphism at high pressures is connected to the occurrence of more than one supercooled liquid phase [3]. Alternatively, amorphous ices have been suggested to be of nanocrystalline nature, unrelated to liquids. Indeed inelastic X-ray scattering measurements indicate sharp crystal-like phonons in the amorphous ices [4]. In case of LDA the connection to the low-density liquid (LDL) was inferred from several experiments including the observation of a calorimetric glass-to-liquid transition at 136 K and ambient pressure [5]. Recently also the glass transition in HDA was observed at 116 K at ambient pressure [6] and at 140 K at elevated pressure of 1 GPa [7], using calorimetric measurements as well as dielectric spectroscopy. We discuss here the general importance of amorphous ices and their liquid counterparts and present calorimetric and dielectric measurements on LDA and HDA. The good agreement between dielectric and calorimetric results convey for a clearer picture of water's vitrification phenomenon. [1] O. Mishima, L. D. Calvert, and E. Whalley, Nature 314, 76, 1985 [2] D.T. Bowron, J. L. Finney, A. Hallbrucker, et al., J. Chem

A geochemical approach to constraining the formation of glassy fallout debris from nuclear tests

DOE PAGES

Bonamici, Chloë E.; Kinman, William S.; Fournelle, John H.; ...

2016-12-15

Reprocessed earth material is a glassy nuclear fallout debris from near-surface nuclear tests. A geochemical approach to analysis of glassy fallout is uniquely suited to determine the means of reprocessing and shed light on the mechanisms of fallout formation. An improved understanding of fallout formation is of interest both for its potential to guide post-detonation nuclear forensic investigations and in the context of possible affinities between glassy debris and other glasses generated by high-energy natural events, such as meteorite impacts and lightning strikes. Our study presents a large major-element compositional dataset for glasses within aerodynamic fallout from the Trinity nuclearmore » test (“trinitite”) and a geochemically based analysis of the glass compositional trends. Silica-rich and alkali-rich trinitite glasses show compositions and textures consistent with formation through melting of individual mineral grains—quartz and alkali feldspar, respectively—from the test-site sediment. Furthermore, the volumetrically dominant glass phase—called the CaMgFe glass—shows extreme major-element compositional variability. Compositional trends in the CaMgFe glass are most consistent with formation through volatility-controlled condensation from compositionally heterogeneous plasma. Radioactivity occurs only in CaMgFe glass, indicating that co-condensation of evaporated bulk ground material and trace device material was the main mechanism of radioisotope incorporation into trinitite. CaMgFe trinitite glasses overlap compositionally with basalts, rhyolites, fulgurites, tektites, and microtektites but display greater compositional diversity than all of these naturally formed glasses. Indeed, the most refractory CaMgFe glasses compositionally resemble early solar system condensates—specifically, CAIs.« less

A geochemical approach to constraining the formation of glassy fallout debris from nuclear tests

NASA Astrophysics Data System (ADS)

Bonamici, Chloë E.; Kinman, William S.; Fournelle, John H.; Zimmer, Mindy M.; Pollington, Anthony D.; Rector, Kirk D.

2017-01-01

Glassy nuclear fallout debris from near-surface nuclear tests is fundamentally reprocessed earth material. A geochemical approach to analysis of glassy fallout is uniquely suited to determine the means of reprocessing and shed light on the mechanisms of fallout formation. An improved understanding of fallout formation is of interest both for its potential to guide post-detonation nuclear forensic investigations and in the context of possible affinities between glassy debris and other glasses generated by high-energy natural events, such as meteorite impacts and lightning strikes. This study presents a large major-element compositional dataset for glasses within aerodynamic fallout from the Trinity nuclear test ("trinitite") and a geochemically based analysis of the glass compositional trends. Silica-rich and alkali-rich trinitite glasses show compositions and textures consistent with formation through melting of individual mineral grains—quartz and alkali feldspar, respectively—from the test-site sediment. The volumetrically dominant glass phase—called the CaMgFe glass—shows extreme major-element compositional variability. Compositional trends in the CaMgFe glass are most consistent with formation through volatility-controlled condensation from compositionally heterogeneous plasma. Radioactivity occurs only in CaMgFe glass, indicating that co-condensation of evaporated bulk ground material and trace device material was the main mechanism of radioisotope incorporation into trinitite. CaMgFe trinitite glasses overlap compositionally with basalts, rhyolites, fulgurites, tektites, and microtektites but display greater compositional diversity than all of these naturally formed glasses. Indeed, the most refractory CaMgFe glasses compositionally resemble early solar system condensates—specifically, CAIs.

Nucleation and growth of thin films of the organic conductor TTF-iodide over glassy carbon. Electrochemical and spectroelectrochemical study.

PubMed

Gómez, L; Rodríguez-Amaro, R

2009-04-21

On the basis of the electrochemical and spectroelectrochemical behavior of thin films of TTF over a glassy carbon electrode in iodide media, a new, more complete mechanism for the electrode processes involved is proposed. The voltammetric and chronoamperometric results for the films can be explained in light of a recently developed nucleation-growth model involving a layer-by-layer mechanism. Also, their in situ UV-vis spectral data expand the available knowledge about the overall mechanism and the nature of the compound formed over the glassy carbon electrode.

Electrochemical Detection of Ultratrace (Picomolar) Levels of Hg2+ Using a Silver Nanoparticle-Modified Glassy Carbon Electrode.

PubMed

Suherman, Alex L; Ngamchuea, Kamonwad; Tanner, Eden E L; Sokolov, Stanislav V; Holter, Jennifer; Young, Neil P; Compton, Richard G

2017-07-05

Ultratrace levels of Hg 2+ have been quantified by undertaking linear sweep voltammetry with a silver nanoparticle-modified glassy carbon electrode (AgNP-GCE) in aqueous solutions containing Hg 2+ . This is achieved by monitoring the change in the silver stripping peak with Hg 2+ concentration resulting from the galvanic displacement of silver by mercury: Ag(np) + 1/2Hg 2+ (aq) → Ag + (aq) + 1/2Hg(l). This facile and reproducible detection method exhibits an excellent linear dynamic range of 100.0 pM to 10.0 nM Hg 2+ concentration with R 2 = 0.982. The limit of detection (LoD) based on 3σ is 28 pM Hg 2+ , while the lowest detectable level for quantification purposes is 100.0 pM. This method is appropriate for routine environmental monitoring and drinking water quality assessment since the guideline value set by the US Environmental Protection Agency (EPA) for inorganic mercury in drinking water is 0.002 mg L -1 (10 nM).

Structural characterization and aging of glassy pharmaceuticals made using acoustic levitation.

PubMed

Benmore, Chris J; Weber, J K R; Tailor, Amit N; Cherry, Brian R; Yarger, Jeffery L; Mou, Qiushi; Weber, Warner; Neuefeind, Joerg; Byrn, Stephen R

2013-04-01

Here, we report the structural characterization of several amorphous drugs made using the method of quenching molten droplets suspended in an acoustic levitator. (13) C NMR, X-ray, and neutron diffraction results are discussed for glassy cinnarizine, carbamazepine, miconazole nitrate, probucol, and clotrimazole. The (13) C NMR results did not find any change in chemical bonding induced by the amorphization process. High-energy X-ray diffraction results were used to characterize the ratio of crystalline to amorphous material present in the glasses over a period of 8 months. All the glasses were stable for at least 6 months except carbamazepine, which has a strong tendency to crystallize within a few months. Neutron and X-ray pair distribution function analyses were applied to the glassy materials, and the results were compared with their crystalline counterparts. The two diffraction techniques yielded similar results in most cases and identified distinct intramolecular and intermolecular correlations. The intramolecular scattering was calculated based on the crystal structure and fit to the measured X-ray structure factor. The resulting intermolecular pair distribution functions revealed broad-nearest and next-nearest neighbor molecule-molecule correlations. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 102:1290-1300, 2013. Copyright © 2013 Wiley Periodicals, Inc.

Crystallization of the glassy phase of grain boundaries in silicon nitride

NASA Technical Reports Server (NTRS)

Jefferson, D. A.; Thomas, J. M.; Wen, S.

1984-01-01

Three types of hot-pressed silicon nitride specimens (containing 5wt% Y2O3 and 2wt% Al2O3 additives) which were subjected to different temperature heat treatments were studied by X-ray diffraction, X-ray microanalysis and high resolution electron microscopy. The results indicated that there were phase changes in the grain boundaries after heat treatment and the glassy phase at the grain boundaries was crystallized by heat treatment.

Glassiness versus Order in Densely Frustrated Josephson Arrays

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, P.; Teitel, S.; Gingras, M.J.

1998-01-01

We carry out extensive Monte Carlo simulations of the Coulomb gas dual to the uniformly frustrated two-dimensional XY model, for a sequence of frustrations f converging to the irrational (3{minus}{radical}(5))/ 2. We find in these systems a sharp first order equilibrium phase transition to an ordered vortex structure at a T{sub c} which varies only slightly with f . This ordered vortex structure remains, in general, phase incoherent until a lower vortex pinning transition T{sub p}(f) that varies with f. We argue that the glassy behaviors reported for this model in earlier simulations are dynamic effects. {copyright} {ital 1997} {italmore » The American Physical Society}« less

The glassy random laser: replica symmetry breaking in the intensity fluctuations of emission spectra

PubMed Central

Antenucci, Fabrizio; Crisanti, Andrea; Leuzzi, Luca

2015-01-01

The behavior of a newly introduced overlap parameter, measuring the correlation between intensity fluctuations of waves in random media, is analyzed in different physical regimes, with varying amount of disorder and non-linearity. This order parameter allows to identify the laser transition in random media and describes its possible glassy nature in terms of emission spectra data, the only data so far accessible in random laser measurements. The theoretical analysis is performed in terms of the complex spherical spin-glass model, a statistical mechanical model describing the onset and the behavior of random lasers in open cavities. Replica Symmetry Breaking theory allows to discern different kinds of randomness in the high pumping regime, including the most complex and intriguing glassy randomness. The outcome of the theoretical study is, eventually, compared to recent intensity fluctuation overlap measurements demonstrating the validity of the theory and providing a straightforward interpretation of qualitatively different spectral behaviors in different random lasers. PMID:26616194

Playback of natural vibrational signals in vineyard trellis for mating disruption of glassy-winged sharpshooter

USDA-ARS?s Scientific Manuscript database

The glassy-winged sharpshooter, Homalodisca vitripennis (Germar) (Hemiptera: Cicadellidae), is a vector of Xylella fastidiosa, an important bacterial pathogen of several crops in the Americas and Europe. Mating communication of this and many other cicadellid pests involves the exchange of substrate-...

Effect of osmotic dehydration pretreatment and glassy state storage on the quality attributes of frozen mangoes under long-term storage.

PubMed

Zhao, Jin-Hong; Xiao, Hong-Wei; Ding, Yang; Nie, Ying; Zhang, Yu; Zhu, Zhen; Tang, Xuan-Ming

2017-05-01

Changes in the quality of frozen mango cuboids were investigated during long-term glassy state storage with and without osmotic dehydration pretreatment. The mango cuboids were dehydrated in mixed solutions (sucrose: glucose: fructose in a ratio of 3.6:1:3) of different concentrations (30, 40, and 50% (wt/wt)) prior to freezing and then stored at -55 °C (in the glassy state) for 6 months. The results revealed that compared with the untreated samples, osmotic pretreatment decreased total color difference (reduced by 15.6-62.3%), drip loss (reduced by 8.2-29.5%) and titration acidity (reduced by 1.3-9.4%), while increasing hardness (increased by 48.8-82.3%), vitamin C content (increased by 72.5-120.6%) and total soluble solids (increased by 21.8-53.7%) of frozen mangoes after 6 months. Dehydration with a sugar concentration of 40% was considered as the optimal pretreatment condition. In addition, a storage temperature of -55 °C provided better retention of quality than rubbery state storage at -18 °C. With prolonged storage time, the quality of frozen mangoes continued to change, even in the glassy state. However, the changes in quality of the osmotic-dehydrated samples were less than those of the untreated samples. The current work indicates that osmotic pretreatment and glassy state storage significantly improved the quality of frozen mangoes during long-term storage.

Heating-induced glass-glass and glass-liquid transformations in computer simulations of water.

PubMed

Chiu, Janet; Starr, Francis W; Giovambattista, Nicolas

2014-03-21

Water exists in at least two families of glassy states, broadly categorized as the low-density (LDA) and high-density amorphous ice (HDA). Remarkably, LDA and HDA can be reversibly interconverted via appropriate thermodynamic paths, such as isothermal compression and isobaric heating, exhibiting first-order-like phase transitions. We perform out-of-equilibrium molecular dynamics simulations of glassy water using the ST2 model to study the evolution of LDA and HDA upon isobaric heating. Depending on pressure, glass-to-glass, glass-to-crystal, glass-to-vapor, as well as glass-to-liquid transformations are found. Specifically, heating LDA results in the following transformations, with increasing heating pressures: (i) LDA-to-vapor (sublimation), (ii) LDA-to-liquid (glass transition), (iii) LDA-to-HDA-to-liquid, (iv) LDA-to-HDA-to-liquid-to-crystal, and (v) LDA-to-HDA-to-crystal. Similarly, heating HDA results in the following transformations, with decreasing heating pressures: (a) HDA-to-crystal, (b) HDA-to-liquid-to-crystal, (c) HDA-to-liquid (glass transition), (d) HDA-to-LDA-to-liquid, and (e) HDA-to-LDA-to-vapor. A more complex sequence may be possible using lower heating rates. For each of these transformations, we determine the corresponding transformation temperature as function of pressure, and provide a P-T "phase diagram" for glassy water based on isobaric heating. Our results for isobaric heating dovetail with the LDA-HDA transformations reported for ST2 glassy water based on isothermal compression/decompression processes [Chiu et al., J. Chem. Phys. 139, 184504 (2013)]. The resulting phase diagram is consistent with the liquid-liquid phase transition hypothesis. At the same time, the glass phase diagram is sensitive to sample preparation, such as heating or compression rates. Interestingly, at least for the rates explored, our results suggest that the LDA-to-liquid (HDA-to-liquid) and LDA-to-HDA (HDA-to-LDA) transformation lines on heating are related

Heating-induced glass-glass and glass-liquid transformations in computer simulations of water

NASA Astrophysics Data System (ADS)

Chiu, Janet; Starr, Francis W.; Giovambattista, Nicolas

2014-03-01

Water exists in at least two families of glassy states, broadly categorized as the low-density (LDA) and high-density amorphous ice (HDA). Remarkably, LDA and HDA can be reversibly interconverted via appropriate thermodynamic paths, such as isothermal compression and isobaric heating, exhibiting first-order-like phase transitions. We perform out-of-equilibrium molecular dynamics simulations of glassy water using the ST2 model to study the evolution of LDA and HDA upon isobaric heating. Depending on pressure, glass-to-glass, glass-to-crystal, glass-to-vapor, as well as glass-to-liquid transformations are found. Specifically, heating LDA results in the following transformations, with increasing heating pressures: (i) LDA-to-vapor (sublimation), (ii) LDA-to-liquid (glass transition), (iii) LDA-to-HDA-to-liquid, (iv) LDA-to-HDA-to-liquid-to-crystal, and (v) LDA-to-HDA-to-crystal. Similarly, heating HDA results in the following transformations, with decreasing heating pressures: (a) HDA-to-crystal, (b) HDA-to-liquid-to-crystal, (c) HDA-to-liquid (glass transition), (d) HDA-to-LDA-to-liquid, and (e) HDA-to-LDA-to-vapor. A more complex sequence may be possible using lower heating rates. For each of these transformations, we determine the corresponding transformation temperature as function of pressure, and provide a P-T "phase diagram" for glassy water based on isobaric heating. Our results for isobaric heating dovetail with the LDA-HDA transformations reported for ST2 glassy water based on isothermal compression/decompression processes [Chiu et al., J. Chem. Phys. 139, 184504 (2013)]. The resulting phase diagram is consistent with the liquid-liquid phase transition hypothesis. At the same time, the glass phase diagram is sensitive to sample preparation, such as heating or compression rates. Interestingly, at least for the rates explored, our results suggest that the LDA-to-liquid (HDA-to-liquid) and LDA-to-HDA (HDA-to-LDA) transformation lines on heating are related

Exploring glassy-winged sharpshooter microbiota using deep 16S rRNA sequencing from individual insects

USDA-ARS?s Scientific Manuscript database

The glassy-winged sharpshooter (GWSS) is an invasive insect species that transmits Xylella fastidiosa, the bacterium causing Pierce’s disease of grapevine and other leaf scorch diseases. X. fastidiosa has been shown to colonize the anterior foregut (cibarium and precibarium) of sharpshooters, where ...

Glassy-winged sharpshooter Microbiota explored using deep 16S rRNA sequencing from individual insects

USDA-ARS?s Scientific Manuscript database

The glassy-winged sharpshooter (GWSS) is an invasive insect species that transmits Xylella fastidiosa, the bacterium causing Pierce’s disease of grapevine and other leaf scorch diseases. X. fastidiosa has been shown to colonize the anterior foregut (cibarium and precibarium) of sharpshooters, where ...

Grapevines respond to glassy-winged sharpshooter (Homalodisca vitripennis) oviposition by increasing local and systemic terpenoid levels

USDA-ARS?s Scientific Manuscript database

Grapevines (Vitis vinifera) have been observed to respond to oviposition by glassy-winged sharpshooters [Homalodisca vitripennis (Germar)(Hemiptera: Cicadellidae)] by producing volatile compounds that attract egg parasitoids such as Gonatocerus ashmeadi Girault (Hymenoptera: Mymaridae). Recent work ...

Environmental monitoring of carbaryl applied in urban areas to control the glassy-winged sharpshooter in California.

PubMed

Walters, Johanna; Goh, Kean S; Li, Linying; Feng, Hsiao; Hernandez, Jorge; White, Jane

2003-03-01

Carbaryl insecticide was applied by ground spray to plants in urban areas to control a serious insect pest the glassy-winged sharpshooter, Homalodisca coagulata (Say), newly introduced in California. To assure there are no adverse impacts to human health and the environment from the carbaryl applications, carbaryl was monitored in tank mixtures, air, surface water, foliage and backyard fruits and vegetables. Results from the five urban areas - Porterville, Fresno, Rancho Cordova, Brentwood and Chico - showed there were no significant human exposures or impacts on the environment. Spray tank concentrations ranged from 0.1-0.32%. Carbaryl concentrations in air ranged from none detected to 1.12 microg m(-3), well below the interim health screening level in air of 51.7 microg m(-3). There were three detections of carbaryl in surface water near application sites: 0.125 ppb (parts per billion) from a water treatment basin; 6.94 ppb from a gold fish pond; and 1737 ppb in a rain runoff sample collected from a drain adjacent to a sprayed site. The foliar dislodgeable residues ranged from 1.54-7.12 microg cm(-2), comparable to levels reported for safe reentry of 2.4 to 5.6 microg cm(-2) for citrus. Carbaryl concentrations in fruits and vegetables ranged from no detectable amounts to 7.56 ppm, which were below the U.S. EPA tolerance, allowable residue of 10 ppm.

Detection and typing of Xylella fastidiosa from glassy-winged sharpshooter for Pierce’s disease epidemiology

USDA-ARS?s Scientific Manuscript database

Epidemiology of Pierce’s disease of grape, caused by the bacterial pathogen Xylella fastidiosa (Xf), is largely dependent on populations of insect vectors such as the invasive glassy-winged sharpshooter (GWSS) (Homalodisca vitripennis). In the grape-growing regions of the southern San Joaquin Valley...

Electronic structure and bonding of intergranular glassy films in polycrystalline Si3 N4 : Ab initio studies and classical molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Rulis, P.; Chen, J.; Ouyang, L.; Ching, W.-Y.; Su, X.; Garofalini, S. H.

2005-06-01

The electronic structure and bonding of a realistic model of an intergranular glassy film (IGF) was studied with multiple computational methods. The model has a Si-O-N glassy region sandwiched between crystalline basal planes of β-Si3N4 and contains a total of 798 atoms. It was constructed with periodic boundary conditions via classical molecular dynamics (MD) techniques using an accurate multibody atomic potential. The model was then further relaxed by the VASP (Vienna ab initio simulation package) program. It is shown that the VASP-relaxed structure reduces the total energy from the MD-relaxed structure by only 47.38eV , validating the accuracy of the multiatom potential used. The calculated electronic structure shows the IGF model to be an insulator with a sizable gap of almost 3eV . Quasidefectlike states can be identified near the band edges arising from the more strained Si-N and Si-O bonds at the interface. Calculation of the Mulliken effective charge and bond order values indicates that the bonds in the glassy region and at the interface can be enhanced and weakened by distortions in the bond length and bond angle. The states at the top of the valence band are derived mostly from the crystalline part of the Si-N bonding while the states at the bottom of the conduction band are dominated by the Si-O bonding in the glassy region. Calculation of the electrostatic potential across the interface shows an average band offset of about 1.5eV between the crystalline β-Si3N4 and the glassy Si-O-N region which could be related to the space charge model for IGF.

Annealing effect on thermal conductivity and microhardness of carbon nanotube containing Se80Te16Cu4 glassy composites

NASA Astrophysics Data System (ADS)

Upadhyay, A. N.; Tiwari, R. S.; Singh, Kedar

2018-02-01

This study deals with the effect of thermal annealing on structural/microstructural, thermal and mechanical behavior of pristine Se80Te16Cu4 and carbon nanotubes (CNTs) containing Se80Te16Cu4 glassy composites. Pristine Se80Te16Cu4, 3 and 5 wt%CNTs-Se80Te16Cu4 glassy composites are annealed in the vicinity of glass transition temperature to onset crystallization temperature (340-380 K). X-ray diffraction (XRD) pattern revealed formation of polycrystalline phases of hexagonal CuSe and trigonal selenium. The indexed d-values in XRD patterns are in well conformity with the d-values obtained after the indexing of the ring pattern of selected area electron diffraction pattern of TEM images. The SEM investigation exhibited that the grain size of the CNTs containing Se80Te16Cu4 glassy composites increased with increasing annealing temperature and decreased at further higher annealing temperature. Thermal conductivity, microhardness exhibited a substantial increase with increasing annealing temperature of 340-360 K and slightly decreases for 380 K. The variation of thermal conductivity and microhardness can be explained by cross-linking formation and voids reduction.

A neutron-X-ray, NMR and calorimetric study of glassy Probucol synthesized using containerless techniques

NASA Astrophysics Data System (ADS)

Weber, J. K. R.; Benmore, C. J.; Tailor, A. N.; Tumber, S. K.; Neuefeind, J.; Cherry, B.; Yarger, J. L.; Mou, Q.; Weber, W.; Byrn, S. R.

2013-10-01

Acoustic levitation was used to trap 1-3 mm diameter drops of Probucol and other pharmaceutical materials in containerless conditions. Samples were studied in situ using X-ray diffraction and ex situ using neutron diffraction, NMR and DSC techniques. The materials were brought into non-equilibrium states by supersaturating solutions or by supercooling melts. The glass transition and crystallization temperatures of glassy Probucol were 29 ± 1 and 71 ± 1 °C respectively. The glassy form was stable with a shelf life of at least 8 months. A neutron/X-ray difference function of the glass showed that while molecular sub-groups remain rigid, many of the hydrogen correlations observed in the crystal become smeared out in the disordered material. The glass is principally comprised of slightly distorted Form I Probucol molecules with disordered packing rather than large changes in the individual molecular structure. Avoiding surface contact-induced nucleation provided access to highly non-equilibrium phases and enabled synthesis of phase-pure glasses.

Tellurium-nanowire-coated glassy carbon electrodes for selective and sensitive detection of dopamine.

PubMed

Tsai, Hsiang-Yu; Lin, Zong-Hong; Chang, Huan-Tsung

2012-05-15

Tellurium-nanowire-coated glassy carbon electrodes (TNGCEs) have been fabricated and employed for selective and sensitive detection of dopamine (DA). TNGCEs were prepared by direct deposition of tellurium nanowires, 600 ± 150 nm in length and 16 ± 3 nm in diameter, onto glassy carbon electrodes, which were further coated with Nafion to improve their selectivity and stability. Compared to the GCE, the TNGCE is more electroactive (by approximately 1.9-fold) for DA, and its selectivity toward DA over ascorbic acid (AA) and uric acid (UA) is also greater. By applying differential pulse voltammetry, at a signal-to-noise ratio of 3, the TNGCE provides a limit of detection of 1 nM for DA in the presence of 0.5mM AA and UA. Linearity (R(2)=0.9955) of the oxidation current at 0.19 V against the concentration of DA is found over the range 5 nM-1 μM. TNGCEs have been applied to determine the concentration of dopamine to be 0.59 ± 0.07 μM in PC12 cells. Copyright © 2012 Elsevier B.V. All rights reserved.

Mating vibrational signal transmission through and between plants of an agricultural pest, the Glassy-Winged Sharpshooter

USDA-ARS?s Scientific Manuscript database

The agricultural pest, glassy-winged sharpshooter (GWSS), Homalodisca vitripennis, relies primarily on successful vibrational communication across its home plant. Males and females engage in a vibrational duet to identify correct species, attractiveness of mate, and location on the plant. The signal...

Solute induced relaxation in glassy polymers: Experimental measurements and nonequilibrium thermodynamic model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Minelli, Matteo; Doghieri, Ferruccio

2014-05-15

Data for kinetics of mass uptake from vapor sorption experiments in thin glassy polymer samples are here interpreted in terms of relaxation times for volume dilation. To this result, both models from non-equilibrium thermodynamics and from mechanics of volume relaxation contribute. Different kind of sorption experiments have been considered in order to facilitate the direct comparison between kinetics of solute induced volume dilation and corresponding data from process driven by pressure or temperature jumps.

Adsorption stripping voltammetry of phenol at Nafion-modified glassy carbon electrode in the presence of surfactants.

PubMed

Yi, H; Wu, K; Hu, S; Cui, D

2001-12-24

In this paper, a new voltammetric method for the determination of phenol is described. In pH 8.00 phosphate buffer and in the presence of long-chain cationic surfactant-cetyltrimethylammonium bromide-phenol has a very sensitive oxidation peak at 0.47 V (vs. SCE) on the Nafion-modified glassy carbon electrode (GCE). The experimental parameters, such as supporting electrolyte and pH values, amounts of Nafion, varieties and concentration of surfactants, accumulation potential and time, as well as scan rate were optimized. The peak current is linear with the concentration of phenol in the range from 8x10(-9) to 1x10(-5) M, and the detection limit is 1x10(-9) M after being accumulated at -0.50 V (vs. SCE) for 3 min. Trace levels of phenol in water samples were determined by using this voltammetric method, the average recovery was calculated to be 99.56%.

Dynamic actuation of glassy polymersomes through isomerization of a single azobenzene unit at the block copolymer interface

NASA Astrophysics Data System (ADS)

Molla, Mijanur Rahaman; Rangadurai, Poornima; Antony, Lucas; Swaminathan, Subramani; de Pablo, Juan J.; Thayumanavan, S.

2018-06-01

Nature has engineered exquisitely responsive systems where molecular-scale information is transferred across an interface and propagated over long length scales. Such systems rely on multiple interacting, signalling and adaptable molecular and supramolecular networks that are built on dynamic, non-equilibrium structures. Comparable synthetic systems are still in their infancy. Here, we demonstrate that the light-induced actuation of a molecularly thin interfacial layer, assembled from a hydrophilic- azobenzene -hydrophobic diblock copolymer, can result in a reversible, long-lived perturbation of a robust glassy membrane across a range of over 500 chemical bonds. We show that the out-of-equilibrium actuation is caused by the photochemical trans-cis isomerization of the azo group, a single chemical functionality, in the middle of the interfacial layer. The principles proposed here are implemented in water-dispersed nanocapsules, and have implications for on-demand release of embedded cargo molecules.

Glassy dynamics of dense particle assemblies on a spherical substrate.

PubMed

Vest, Julien-Piera; Tarjus, Gilles; Viot, Pascal

2018-04-28

We study by molecular dynamics simulation a dense one-component system of particles confined on a spherical substrate. We more specifically investigate the evolution of the structural and dynamical properties of the system when changing the control parameters, the temperature and the curvature of the substrate. We find that the dynamics become glassy at low temperature, with a strong slowdown of the relaxation and the emergence of dynamical heterogeneity. The prevalent local 6-fold order is frustrated by curvature and we analyze in detail the role of the topological defects in the statics and the dynamics of the particle assembly.

Application of neural networks with novel independent component analysis methodologies to a Prussian blue modified glassy carbon electrode array.

PubMed

Wang, Liang; Yang, Die; Fang, Cheng; Chen, Zuliang; Lesniewski, Peter J; Mallavarapu, Megharaj; Naidu, Ravendra

2015-01-01

Sodium potassium absorption ratio (SPAR) is an important measure of agricultural water quality, wherein four exchangeable cations (K(+), Na(+), Ca(2+) and Mg(2+)) should be simultaneously determined. An ISE-array is suitable for this application because its simplicity, rapid response characteristics and lower cost. However, cross-interferences caused by the poor selectivity of ISEs need to be overcome using multivariate chemometric methods. In this paper, a solid contact ISE array, based on a Prussian blue modified glassy carbon electrode (PB-GCE), was applied with a novel chemometric strategy. One of the most popular independent component analysis (ICA) methods, the fast fixed-point algorithm for ICA (fastICA), was implemented by the genetic algorithm (geneticICA) to avoid the local maxima problem commonly observed with fastICA. This geneticICA can be implemented as a data preprocessing method to improve the prediction accuracy of the Back-propagation neural network (BPNN). The ISE array system was validated using 20 real irrigation water samples from South Australia, and acceptable prediction accuracies were obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

Design of a candidate vibrational signal for mating disruption against the glassy-winged sharpshooter, Homalodisca Vitripennis

USDA-ARS?s Scientific Manuscript database

The glassy-winged sharpshooter (GWSS), Homalodisca vitripennis, is an important pest of grapevines due to its ability to transmit Xylella fastidiosa, the causal agent of Pierce’s disease. GWSS mating communication is based on vibrational signals; therefore, vibrational mating disruption could be an ...

Evidence for a glassy state in strongly driven carbon

DOE PAGES

Brown, C. R. D.; Gericke, D. O.; Cammarata, M.; ...

2014-06-09

Here, we report results of an experiment creating a transient, highly correlated carbon state using a combination of optical and x-ray lasers. Scattered x-rays reveal a highly ordered state with an electrostatic energy significantly exceeding the thermal energy of the ions. Strong Coulomb forces are predicted to induce nucleation into a crystalline ion structure within a few picoseconds. However, we observe no evidence of such phase transition after several tens of picoseconds but strong indications for an over-correlated fluid state. The experiment suggests a much slower nucleation and points to an intermediate glassy state where the ions are frozen closemore » to their original positions in the fluid.« less

Ion beam promoted lithium absorption in glassy polymeric carbon

NASA Astrophysics Data System (ADS)

Ila, D.; Zimmerman, R. L.; Jenkins, G. M.; Maleki, H.; Poker, D. B.

1995-12-01

Glassy Polymeric Carbon (GPC) samples prepared from a precursor possess accessible pore volume that depends on the heat treatment temperature. We have shown that lithium percolates without diffusion into the accessible pores of GPC samples immersed in a molten lithium salt bath at 700°C. Ion bombardment with 10 MeV Au atoms increases the total pore volume available for lithium occupation even for samples normally impermeable to lithium. The lithium concentration depth profile is measured using Li7(p,2α) nuclear reaction analysis. We will report on lithium percolation into GPC prepared at temperatures between 500°C and 1000°C and activated by a 10 MeV gold ion bombardment.

Salivary enzymes are injected into xylem by the glassy-winged sharpshooter, a vector of Xylella fastidiosa

USDA-ARS?s Scientific Manuscript database

Certain hemipteran insects such as the glassy-winged sharpshooter, Homalodisca vitripennis, subsist entirely on xylem fluid, notwithstanding the poor nutrition of such food. Among many adaptations enabling xylem-feeding are aspects of the insect’s salivation that may also allow these insects to tra...

Exceptional effect of glassy lithium fluorophosphate on Mn-rich olivine cathode material for high-performance Li ion batteries

NASA Astrophysics Data System (ADS)

Kim, Jongsoon; Kim, Hyungsub; Myung, Seung-Taek; Yoo, Jung-Keun; Lee, Seongsu

2018-01-01

Mn-rich olivine LiFe0.3Mn0.7PO4 is homogenously encapsulated by an ∼3-nm-thick conductive nanolayer composed of the glassy lithium fluorophosphate through simple non-stoichiometric synthesis using additives of small amounts of LiF and a phosphorus source. The coating of the glassy lithium fluorophosphate nanolayer is clearly verified using transmission electron microscopy and X-ray photoelectron spectroscopy. It enables significant decrease in charge transfer resistance of LiFe0.3Mn0.7PO4 and improvement of its sluggish Li diffusion. At a rate of 10C, the LiFe0.3Mn0.7PO4 encapsulated by conductive glassy lithium fluorophosphate (LiFe0.3Mn0.7PO4-GLFP) electrode delivers a capacity of ∼130 mAh g-1, which is ∼77% of its theoretical capacity (∼170 mAh g-1) and ∼1.5 times higher than that of the pristine counterpart at 10C. Furthermore, LiFe0.3Mn0.7PO4-GLFP achieves outstanding cycle stability (∼75% retention of its initial capacity over 500 cycles at 1C). The proposed olivine LiFe0.3Mn0.7PO4-GLFP battery is thus expected to be a promising candidate for large-scale energy storage applications.

Highly Selective Membranes For The Separation Of Organic Vapors Using Super-Glassy Polymers

DOEpatents

Pinnau, Ingo; Lokhandwala, Kaaeid; Nguyen, Phuong; Segelke, Scott

1997-11-18

A process for separating hydrocarbon gases of low boiling point, particularly methane, ethane and ethylene, from nitrogen. The process is performed using a membrane made from a super-glassy material. The gases to be separated are mixed with a condensable gas, such as a C.sub.3+ hydrocarbon. In the presence of the condensable gas, improved selectivity for the low-boiling-point hydrocarbon gas over nitrogen is achieved.

Diffusion of liquid polystyrene into glassy poly(phenylene oxide) characterized by DSC

NASA Astrophysics Data System (ADS)

Li, Linling; Wang, Xiaoliang; Zhou, Dongshan; Xue, Gi

2013-03-01

We report a diffusion study on the polystyrene/poly(phenylene oxide) (PS/PPO) mixture consisted by the PS and PPO nanoparticles. Diffusion of liquid PS into glassy PPO (l-PS/g-PPO) is promoted by annealing the PS/PPO mixture at several temperatures below Tg of the PPO. By tracing the Tgs of the PS-rich domain behind the diffusion front using DSC, we get the relationships of PS weight fractions and diffusion front advances with the elapsed diffusion times at different diffusion temperatures using the Gordon-Taylor equation and core-shell model. We find that the plots of weight fraction of PS vs. elapsed diffusion times at different temperatures can be converted to a master curve by Time-Temperature superposition, and the shift factors obey the Arrhenius equation. Besides, the diffusion front advances of l-PS into g-PPO show an excellent agreement with the t1/2 scaling law at the beginning of the diffusion process, and the diffusion coefficients of different diffusion temperatures also obey the Arrhenius equation. We believe the diffusion mechanism for l-PS/g-PPO should be the Fickean law rather than the Case II, though there are departures of original linearity at longer diffusion times due to the limited liquid supply system. Diffusion of liquid polystyrene into glassy poly(phenylene oxide) characterized by DSC

Structural modifications of polymethacrylates: impact on thermal behavior and release characteristics of glassy solid solutions.

PubMed

Claeys, Bart; De Coen, Ruben; De Geest, Bruno G; de la Rosa, Victor R; Hoogenboom, Richard; Carleer, Robert; Adriaensens, Peter; Remon, Jean Paul; Vervaet, Chris

2013-11-01

Polymethacrylates such as Eudragit® polymers are well established as drug delivery matrix. Here, we synthesize several Eudragit E PO (n-butyl-, dimethylaminoethyl-, methyl-methacrylate-terpolymer) analogues via free radical polymerization. These polymers are processed via hot melt extrusion, followed by injection molding and evaluated as carriers to produce immediate release solid solution tablets. Three chemical modifications increased the glass transition temperature of the polymer: (a) substitution of n-butyl by t-butyl groups, (b) reduction of the dimethylaminoethyl methacrylate (DMAEMA) content, and (c) incorporation of a bulky isobornyl repeating unit. These structural modifications revealed the possibility to increase the mechanical stability of the tablets via altering the polymer Tg without influencing the drug release characteristics and glassy solid solution forming properties. The presence of DMAEMA units proved to be crucial with respect to API/polymer interaction (essential in creating glassy solid solutions) and drug release characteristics. Moreover, these chemical modifications accentuate the need for a more rational design of (methacrylate) polymer matrix excipients for drug formulation via hot melt extrusion and injection molding. Copyright © 2013 Elsevier B.V. All rights reserved.

Glassy and Metastable Crystalline BaTi2O5 by Containerless Processing

NASA Astrophysics Data System (ADS)

Yoda, Shinichi; Kentei Yu, Yu; Kumar, Vijaya; Kameko, Masashi

Many efforts have been devoted to forming bulk glass from the melt of ferroelectric crystalline materials without adding any network-forming oxides such as SiO2 due to the potential for producing transparent glass ceramics with high dielectric constant and enhanced piezoelectric, pyroelectric and electro-optic use. The containerless processing is an attractive synthesis tech-nique as it can prevent melt contamination, minimize heterogeneous nucleation, and allow melt to achieve deep undercooling for forming metastable and glassy materials. We have fabricated a new ferroelectric materiel BaTi2 O5 [1] as bulk glass from melt by us-ing containerless processing and studied the phase relationship between microstructure and ferroelectric properties of BaTi2 O5 [2]. The structures of glassy and metastable crystalline BaTi2 O5 fabricated by the containerless pro-cessing were comprehensively investigated by combined X-ray and neutron diffractions, XANES analyses and computer simulations [3]. The 3-dimensional atomic structure of glassy BaTi2 O5 (g-BaTi2 O5 ), simulated by Reverse Monte Carlo (RMC) modelling on diffraction data, shows that extremely distorted TiO5 polyhedra interconnected with both corner-and edge-shared oxy-gen, formed a higher packing density structure than that of conventional silicate glass linked with only corner-sharing of SiO4 polyhedra. In addition, XANES measurement reveales that five-coordinated TiO5 polyhedra were formable in the crystallized metastable a-and b-BaTi2 O5 phases. The structure of metastable b-BaTi2 O5 was solved by ab initio calculation, and refined by Rietveld refinement as group Pnma with unit lattices a = 10.23784 ˚, b = 3.92715 ˚, c A A = 10.92757 A ˚. Our results show that the glass-forming ability enhanced by containerless pro-cessing, not by `strong glass former', fabricated new bulk oxide glasses with peculiar structures and properties. The intermediate-range structure of g-BaTi2 O5 and the crystalline structure of

Effects of Xylem-Sap Composition on Glassy-Winged Sharpshooter (Hemiptera: Cicadellidae) Egg Maturation on High- and Low-Quality Host Plants.

PubMed

Sisterson, Mark S; Wallis, Christopher M; Stenger, Drake C

2017-04-01

Glassy-winged sharpshooters must feed as adults to produce mature eggs. Cowpea and sunflower are both readily accepted by the glassy-winged sharpshooter for feeding, but egg production on sunflower was reported to be lower than egg production on cowpea. To better understand the role of adult diet in egg production, effects of xylem-sap chemistry on glassy-winged sharpshooter egg maturation was compared for females confined to cowpea and sunflower. Females confined to cowpea consumed more xylem-sap than females held on sunflower. In response, females held on cowpea produced more eggs, had heavier bodies, and greater lipid content than females held on sunflower. Analysis of cowpea and sunflower xylem-sap found that 17 of 19 amino acids were more concentrated in cowpea xylem-sap than in sunflower xylem-sap. Thus, decreased consumption of sunflower xylem-sap was likely owing to perceived lower quality, with decreased egg production owing to a combination of decreased feeding and lower return per unit volume of xylem-sap consumed. Examination of pairwise correlation coefficients among amino acids indicated that concentrations of several amino acids within a plant species were correlated. Principal component analyses identified latent variables describing amino acid composition of xylem-sap. For females held on cowpea, egg maturation was affected by test date, volume of excreta produced, and principal components describing amino acid composition of xylem-sap. Principal component analyses aided in identifying amino acids that were positively or negatively associated with egg production, although determining causality with respect to key nutritional requirements for glassy-winged sharpshooter egg production will require additional testing. Published by Oxford University Press on behalf of Entomological Society of America 2017. This work is written by US Government employees and is in the public domain in the US.

Evaluation of a method to quantify glassy-winged sharpshooter (Hemiptera: Cicadellidae) egg maturation during a feeding assay

USDA-ARS?s Scientific Manuscript database

Methods to improve an assay relating adult feeding to egg maturation by the glassy-winged sharpshooter (Hemiptera: Cicadellidae) were evaluated. The assay consisted of confining adult females to cowpea stems in parafilm enclosures and quantifying adult feeding and egg maturation. Adult feeding was...

Sterilization Resistance of Bacterial Spores Explained with Water Chemistry.

PubMed

Friedline, Anthony W; Zachariah, Malcolm M; Middaugh, Amy N; Garimella, Ravindranath; Vaishampayan, Parag A; Rice, Charles V

2015-11-05

Bacterial spores can survive for long periods without nutrients and in harsh environmental conditions. This survival is influenced by the structure of the spore, the presence of protective compounds, and water retention. These compounds, and the physical state of water in particular, allow some species of bacterial spores to survive sterilization schemes with hydrogen peroxide and UV light. The chemical nature of the spore core and its water has been a subject of some contention and the chemical environment of the water impacts resistance paradigms. Either the spore has a glassy core, where water is immobilized along with other core components, or the core is gel-like with mobile water diffusion. These properties affect the movement of peroxide and radical species, and hence resistance. Deuterium solid-state NMR experiments are useful for examining the nature of the water inside the spore. Previous work in our lab with spores of Bacillus subtilis indicate that, for spores, the core water is in a more immobilized state than expected for the gel-like core theory, suggesting a glassy core environment. Here, we report deuterium solid-state NMR observations of the water within UV- and peroxide-resistant spores from Bacillus pumilus SAFR-032. Variable-temperature NMR experiments indicate no change in the line shape after heating to 50 °C, but an overall decrease in signal after heating to 100 °C. These results show glass-like core dynamics within B. pumilus SAFR-032 that may be the potential source of its known UV-resistance properties. The observed NMR traits can be attributed to the presence of an exosporium containing additional labile deuterons that can aid in the deactivation of sterilizing agents.

In-Vivo Characterization of Glassy Carbon Micro-Electrode Arrays for Neural Applications and Histological Analysis of the Brain Tissue

NASA Astrophysics Data System (ADS)

Vomero, Maria

The aim of this work is to fabricate and characterize glassy carbon Microelectrode Arrays (MEAs) for sensing and stimulating neural activity, and conduct histological analysis of the brain tissue after the implant to determine long-term performance. Neural applications often require robust electrical and electrochemical response over a long period of time, and for those applications we propose to replace the commonly used noble metals like platinum, gold and iridium with glassy carbon. We submit that such material has the potential to improve the performances of traditional neural prostheses, thanks to better charge transfer capabilities and higher electrochemical stability. Great interest and attention is given in this work, in particular, to the investigation of tissue response after several weeks of implants in rodents' brain motor cortex and the associated materials degradation. As part of this work, a new set of devices for Electrocorticography (ECoG) has been designed and fabricated to improve durability and quality of the previous generation of devices, designed and manufactured by the same research group in 2014. In-vivo long-term impedance measurements and brain activity recordings were performed to test the functionality of the neural devices. In-vitro electrical characterization of the carbon electrodes, as well as the study of the adhesion mechanisms between glassy carbon and different substrates is also part of the research described in this book.

Carbon nanotube modified glassy carbon electrode for electrochemical oxidation of alkylphenol ethoxylate.

PubMed

Patiño, Yolanda; Díaz, Eva; Lobo-Castañón, María Jesús; Ordóñez, Salvador

2018-06-01

Electrochemical oxidation of an emerging pollutant, 2-(4-methylphenoxy)ethanol (MPET), from water has been studied by cyclic voltammetry (CV). Multiwall carbon nanotubes glassy carbon electrodes (MWCNT-GCE) were used as working electrode due to their extraordinary properties. The oxidation process is irreversible, since no reduction peaks were observed in the reverse scan. The electrocatalytic effect of MWCNT was confirmed as the oxidation peak intensity increases in comparison to bare-GCE. The effect of functional groups on MWCNT was also studied by MWCNT functionalized with NH 2 (MWCNT-NH 2 ) and COOH (MWCNT-COOH) groups. The oxidation peak current decreases in the following order: MWCNT > MWCNT-NH 2 > MWCNT-COOH. Taking into account the normalized peak current, MWCNT-NH 2 exhibits the best results due to its strong interaction with MPET. Under optimal conditions (pH = 5.0 and volume of MWCNT = 10 μL), degradation was studied for MWCNT-GCE and MWCNT-NH 2 -GCE. A complete MPET removal was observed using MWCNT-GCE after four CV cycles, for a volume/area (V/A) ratio equal to 19. In the case of MWCNT-NH 2 -GCE, the maximum MPET removal was close to 90% for V/A = 37, higher than that obtained for MWCNT-GCE at the same conditions (≈80%). In both cases, no organic by-products were detected.

In situ AFM investigation of slow crack propagation mechanisms in a glassy polymer

NASA Astrophysics Data System (ADS)

George, M.; Nziakou, Y.; Goerke, S.; Genix, A.-C.; Bresson, B.; Roux, S.; Delacroix, H.; Halary, J.-L.; Ciccotti, M.

2018-03-01

A novel experimental technique based on in situ AFM monitoring of the mechanisms of damage and the strain fields associated to the slow steady-state propagation of a fracture in glassy polymers is presented. This micron-scale investigation is complemented by optical measurements of the sample deformation up to the millimetric macroscopic scale of the sample in order to assess the proper crack driving conditions. These multi-scale observations provide important insights towards the modeling of the fracture toughness of glassy polymers and its relationship with the macromolecular structure and non-linear rheological properties. This novel technique is first tested on a standard PMMA thermoplastic in order to both evaluate its performance and the richness of this new kind of observations. Although the fracture propagation in PMMA is well known to proceed through crazing in the bulk of the samples, our observations provide a clear description and quantitative evaluation of a change of fracture mechanism towards shear yielding fracture accompanied by local necking close to the free surface of the sample, which can be explained by the local change of stress triaxiality. Moreover, this primary surface necking mechanism is shown to be accompanied by a network of secondary grooves that can be related to surface crazes propagating towards the interior of the sample. This overall scenario is validated by post-mortem fractographic investigations by scanning electron microscopy.

Structural and surface changes in glassy carbon due to strontium implantation and heat treatment

NASA Astrophysics Data System (ADS)

Odutemowo, O. S.; Malherbe, J. B.; Prinsloo, L. C.; Njoroge, E. G.; Erasmus, R.; Wendler, E.; Undisz, A.; Rettenmayr, M.

2018-01-01

There are still questions around the microstructure of glassy carbon (GC), like the observation of the micropores. These were proposed to explain the low density of GC. This paper explains the effect of ion bombardment (200 keV Sr+, 1 × 1016 Sr+/cm2 at RT) on the microstructure of GC. TEM and AFM show that micropores in pristine GC are destroyed leading to densification of GC from 1.42 g/cm3 to 2.03 g/cm3. The amorphisation of glassy carbon was also not complete with graphitic strands embedded within the GC. These were relatively few, as Raman analysis showed that the Sr implantation resulted in a typical amorphous Raman spectrum. Annealing of the sample at 900 °C only resulted in a slight recovery of the GC structure. AFM and SEM analysis showed that the surface of the sample became rougher after Sr implantation. The roughness increased after the sample was annealed at 600 °C due to segregation of Sr towards the surface of the GC. SEM measurements of a sample with both implanted and un-implanted edges after annealing at 900 °C, showed that the high temperature heat treatment did not affect the surface topography of un-irradiated GC.

Mediatorless solar energy conversion by covalently bonded thylakoid monolayer on the glassy carbon electrode.

PubMed

Lee, Jinhwan; Im, Jaekyun; Kim, Sunghyun

2016-04-01

Light reactions of photosynthesis that take place in thylakoid membranes found in plants or cyanobacteria are among the most effective ways of utilizing light. Unlike most researches that use photosystem I or photosystem II as conversion units for converting light to electricity, we have developed a simple method in which the thylakoid monolayer was covalently immobilized on the glassy carbon electrode surface. The activity of isolated thylakoid membrane was confirmed by measuring evolving oxygen under illumination. Glassy carbon surfaces were first modified with partial or full monolayers of carboxyphenyl groups by reductive C-C coupling using 4-aminobenzoic acid and aniline and then thylakoid membrane was bioconjugated through the peptide bond between amine residues of thylakoid and carboxyl groups on the surface. Surface properties of modified surfaces were characterized by cyclic voltammetry, contact angle measurements, and electrochemical impedance spectroscopy. Photocurrent of 230 nA cm(-2) was observed when the thylakoid monolayer was formed on the mixed monolayer of 4-carboxylpheny and benzene at applied potential of 0.4V vs. Ag/AgCl. A small photocurrent resulted when the 4-carboxyphenyl full monolayer was used. This work shows the possibility of solar energy conversion by directly employing the whole thylakoid membrane through simple surface modification. Copyright © 2015 Elsevier B.V. All rights reserved.

Temperature and frequency response of conductivity in Ag2S doped chalcogenide glassy semiconductor

NASA Astrophysics Data System (ADS)

Ojha, Swarupa; Das, Anindya Sundar; Roy, Madhab; Bhattacharya, Sanjib

2018-06-01

The electric conductivity of chalcogenide glassy semiconductor xAg2S-(1-x)(0.5S-0.5Te) has been presented here as a function of temperature and frequency. Formation of different nanocrystallites has been confirmed from X-ray diffraction study. It is also noteworthy that average size of nanocrystallites decreases with the increase of dislocation density. Dc conductivity data have been interpreted using Mott's model and Greaves's model in low and high temperature regions respectively. Ac conductivity above the room temperature has been analyzed using Meyer-Neldel (MN) conduction rule. It is interestingly noted that Correlated Barrier Hopping (CBH) model is the most appropriate conduction mechanism for x = 0.35, where pairs of charge carrier are considered to hop over the potential barrier between the sites via thermal activation. To interpret experimental data for x = 0.45, modified non-overlapping small polaron tunnelling (NSPT) model is supposed to be appropriate model due to tunnelling through grain boundary. The conductivity spectra at various temperatures have been analyzed using Almond-West Formalism (power law model). Scaling of conductivity spectra reveals that electrical relaxation process of charge carriers (polaron) is temperature independent but depends upon the composition of the present chalcogenide glassy system.

Electrochemical behavior of an antiviral drug acyclovir at fullerene-C(60)-modified glassy carbon electrode.

PubMed

Shetti, Nagaraj P; Malode, Shweta J; Nandibewoor, Sharanappa T

2012-12-01

Electrochemical oxidation of acyclovir at fullerene-C(60)-modified glassy carbon electrode has been investigated using cyclic and differential pulse voltammetry. In pH 7.4 phosphate buffer, acyclovir showed an irreversible oxidation peak at about 0.96V. The cyclic voltammetric results showed that fullerene-C(60)-modified glassy carbon electrode can remarkably enhance electrocatalytic activity towards the oxidation of acyclovir. The electrocatalytic behavior was further exploited as a sensitive detection scheme for the acyclovir determination by differential pulse voltammetry. Effects of anodic peak potential (E(p)/V), anodic peak current (I(p)/μA) and heterogeneous rate constant (k(0)) have been discussed. Under optimized conditions, the concentration range and detection limit were 9.0×10(-8) to 6.0×10(-6)M and 1.48×10(-8)M, respectively. The proposed method was applied to acyclovir determination in pharmaceutical samples and human biological fluids such as urine and blood plasma as a real sample. This method can also be employed in quality control and routine determination of drugs in pharmaceutical formulations. Copyright © 2012 Elsevier B.V. All rights reserved.

Novel Heating-Induced Reversion during Crystallization of Al-based Glassy Alloys

NASA Astrophysics Data System (ADS)

Han, F. F.; Inoue, A.; Han, Y.; Kong, F. L.; Zhu, S. L.; Shalaan, E.; Al-Marzouki, F.; Greer, A. L.

2017-04-01

Thermal stability and crystallization of three multicomponent glassy alloys, Al86Y7Ni5Co1Fe0.5Pd0.5, Al85Y8Ni5Co1Fe0.5Pd0.5 and Al84Y9Ni4Co1.5Fe0.5Pd1, were examined to assess the ability to form the mixture of amorphous (am) and fcc-aluminum (α-Al) phases. On heating, the glass transition into the supercooled liquid is shown by the 85Al and 84Al glasses. The crystallization sequences are [am] → [am + α-Al] → [α-Al + compounds] for the 86Al and 85Al alloys, and [am] → [am + α-Al + cubic AlxMy (M = Y, Ni, Co, Fe, Pd)] → [am + α-Al] → [α-Al + Al3Y + Al9(Co, Ni)2 + unknown phase] for the 84Al alloy. The glass transition appears even for the 85Al alloy where the primary phase is α-Al. The heating-induced reversion from [am + α-Al + multicomponent AlxMy] to [am + α-Al] for the 84Al alloy is abnormal, not previously observed in crystallization of glassy alloys, and seems to originate from instability of the metastable AlxMy compound, in which significant inhomogeneous strain is caused by the mixture of solute elements. This novel reversion phenomenon is encouraging for obtaining the [am + α-Al] mixture over a wide range of high temperature effective for the formation of Al-based high-strength nanostructured bulk alloys by warm working.

Early Stage Anodic Instability of Glassy Carbon Electrodes in Propylene Carbonate Solvent Containing Lithium Hexafluorophosphate.

PubMed

Carino, Emily V; Newman, Daniel J; Connell, Justin G; Kim, Chaerin; Brushett, Fikile R

2017-10-31

Irreversible changes to the morphology of glassy carbon (GC) electrodes at potentials between 3.5 and 4.5 V vs Li/Li + in propylene carbonate (PC) solvent containing lithium hexafluorophosphate (LiPF 6 ) are reported. Analysis of cyclic voltammetry (CV) experiments in the range of 3.0 to 6.0 V shows that the capacitance of the electrochemical double-layer increased irreversibly beginning at potentials as low as 3.5 V. These changes resulted from nonfaradaic interactions, and were not due to oxidative electrochemical decomposition of the electrode and electrolyte, anion intercalation, nor caused by the presence of water, a common impurity in organic electrolyte solutions. Atomic force microscopy (AFM) images revealed that increasing the potential of a bare GC surface from 3.0 to 4.5 V resulted in a 6× increase in roughness, in good agreement with the changes in double-layer capacitance. Treating the GC surface via exposure to trichloromethylsilane vapors resulted in a stable double-layer capacitance between 3.0 and 4.5 V, and this treatment also correlated with less roughening. These results inform future efforts aimed at controlling surface composition and morphology of carbon electrodes.

An experimental study of hydromagmatic fragmentation through energetic, non-explosive magma-water mixing

USGS Publications Warehouse

Mastin, L.G.; Spieler, O.; Downey, W.S.

2009-01-01

In this paper we report the first experimental investigation of non-explosive hydromagmatic fragmentation during energetic mixing with water. We mix magma and water by two methods: (1) pouring a basaltic melt between two converging water sprays; and (2) jetting basaltic melt at high pressure (3??MPa) through a nozzle into a tank of stagnant water. These experiments involved shear at relative velocities of ~ 5-16??m/s and vigorous mixing for less than a second, providing sufficient time for glassy rinds to grow but insufficient time for clot interiors to cool. In resulting fragments, we examined the gross morphology, which reflects fluid deformation during mixing, and surface textures, which reflect the growth and disruption of glassy rinds. We find major differences in both fragment morphology and surface texture between experiments. Water-spray experiments produced Pele's hair, thin bubble shards, melt droplets, and angular, fracture-bound droplet pieces. Melt-jet experiments produced mostly coarse (> 1??mm diameter), wavy fluidal fragments with broken ends. Fluidal surfaces of fragments produced by water-spray experiments were generally shiny under reflected light and, in microscopic examination, smooth down to micron scale, implying no disruption of glassy rinds, except for (a) rare flaking on Pele's hair that was bent prior to solidification; or (b) cracking and alligator-skin textures on segments of melt balls that had expanded before complete cooling. In contrast, textures of fluidal surfaces on fragments produced by melt-jet experiments are dull in reflected light and, in scanning electron images, exhibit ubiquitous discontinuous skins ("rinds") that are flaked, peeled, or smeared away in stripes. Adhering to these surfaces are flakes, blocks, and blobs of detached material microns to tens of microns in diameter. In the water-spray fragments, we interpret the scarcity of disrupted surface rinds to result from lack of bending after surfaces formed. In the

Non-enzymatic browning kinetics analysed through water-solids interactions and water mobility in dehydrated potato.

PubMed

Acevedo, Nuria C; Schebor, Carolina; Buera, Pilar

2008-06-01

Non-enzymatic browning (NEB) development was studied in dehydrated potato at 70°C. It was related to the macroscopic and molecular properties and to water-solid interactions over a wide range of water activities. Time resolved (1)H NMR, thermal transitions and water sorption isotherms were evaluated. Although non-enzymatic browning could be detected in the glassy state; colour development was higher in the supercooled state. The reaction rate increased up to a water content of 26g/100g of solids (aw=0.84) and then decreased at higher water contents, concomitantly with the increase of water proton mobility. The joint analyses of NEB kinetics, water sorption isotherm and proton relaxation behaviour made it evident that the point at which the reaction rate decreased, after a maximum value, could be related to the appearance of highly mobile water. The results obtained in this work indicate that the prediction of chemical reaction kinetics can be performed through the integrated analysis of water sorption, water and solids mobility and the physical state of the matrix. Copyright © 2007 Elsevier Ltd. All rights reserved.

VNIR reflectance spectroscopy of glassy igneous material with variable oxidation states

NASA Astrophysics Data System (ADS)

Carli, Cristian; Di Genova, Danilo; Roush, Ted L.; Ertel-Ingrisch, Werner; Capaccioni, Fabrizio; Dingwell, Donald B.

2017-04-01

Silicate glasses with igneous compositions may represent an abundant component of planetary surface material via effusive volcanism or impact cratering processes. Several planetary surfaces are mapped with hyper-spectrometers in the visible and near-infrared (VNIR). In this spectral range, crystal field (C.F.) absorptions are useful to discriminate iron-bearing silicate components. At the same time, in the VNIR reflectance spectroscopy iron bearing glasses may exhibit a C.F. absorption at ˜1.1 μm. A weak C.F. absorption is also present at ˜1.9 μm. These absorptions can be therefore diagnostic for glassy component and can also affect the C.F. absorptions of mafic minerals when mixed in the regolith. So far, few studies investigated the spectral properties of systematic glasses compositions and at different oxygen fucacity. For these reasons studying glassy materials, and their optical constants, represents an important effort to document and to interpret, spectral features of Solar System silicate crusts where glasses are present, but may be difficult to map. In previous work Carli et al. (2016) considered the composition of glassy igneous materials produced in Earth-like atmospheric conditions (i.e. oxidized conditions). Here, we expand on that effort by including glasses formed under more reducing condition. In this study, glasses were produced at -9.3 log fO2 and 1400 ˚ C for a duration of 4 h at the Department of Earth and Environmental Sciences at the University of Munich using a gas-mixing furnace. The major element composition, sample homogeneity, and the Fe3+/Fetot. ratio of run products were analytically determined. Moreover, Raman spectra of the same samples were also acquired. Afterwards, powders were produced with nine-grain size from 250-224 μm to 50-20 μm and measured in bidirectional reflectance at Spectroscopy LABoratory (IAPS-INAF, Rome). Reflectance spectra were acquired from 0.35 to 2.5 μm with a Field-Pro Spectrometer mounted on a

Glassy carbon/multi walled carbon nanotube/cadmium sulphide photoanode for light energy storage in vanadium photoelectrochemical cell

NASA Astrophysics Data System (ADS)

Peimanifard, Zahra; Rashid-Nadimi, Sahar

2015-12-01

The aim of this study is utilizing the artificial photosynthesis, which is an attractive and challenging theme in the photoelectrocatalytic water splitting, to charge the vanadium redox flow battery (VRFB). In this work multi walled carbon nanotube/cadmium sulphide hybrid is employed as a photoanode material to oxidize VO2+ toVO2+ for charging the positive vanadium redox flow battery's half-cell. Characterization studies are also described using the scanning electron microscopic-energy-dispersive X-ray spectroscopy (SEM-EDS), inductively coupled plasma atomic emission spectroscopy (ICP-AES) and UV-Visible methods. The phtoelectrochemical performance is characterized by cyclic voltammetry and chronoamperometry. Applied bias photon-to-current efficiency (ABPE) is achieved for both two and three-electrode configurations. The glassy carbon/multi walled carbon nanotube/cadmium sulphide yields high maximum ABPE of 2.6% and 2.12% in three and two-electrode setups, respectively. These results provide a useful guideline in designing photoelectrochemical cells for charging the vanadium redox flow batteries by sunlight as a low cost, free and abundant energy source, which does not rely on an external power input.

Evaluation of the relevance of the glassy state as stability criterion for freeze-dried bacteria by application of the Arrhenius and WLF model.

PubMed

Aschenbrenner, Mathias; Kulozik, Ulrich; Foerst, Petra

2012-12-01

The aim of this work was to describe the temperature dependence of microbial inactivation for several storage conditions and protective systems (lactose, trehalose and dextran) in relation to the physical state of the sample, i.e. the glassy or non-glassy state. The resulting inactivation rates k were described by applying two models, Arrhenius and Williams-Landel-Ferry (WLF), in order to evaluate the relevance of diffusional limitation as a protective mechanism. The application of the Arrhenius model revealed a significant decrease in activation energy E(a) for storage conditions close to T(g). This finding is an indication that the protective effect of a surrounding glassy matrix can, at least, partly be ascribed to its inherent restricted diffusion and mobility. The application of the WLF model revealed that the temperature dependence of microbial inactivation above T(g) is significantly weaker than predicted by the universal coefficients. Thus, it can be concluded that microbial inactivation is not directly linked with the mechanical relaxation behavior of the surrounding matrix as it was reported for viscosity and crystallization phenomena in case of disaccharide systems. Copyright © 2012. Published by Elsevier Inc.

A 3D Microfluidic Chip for Electrochemical Detection of Hydrolysed Nucleic Bases by a Modified Glassy Carbon Electrode

PubMed Central

Vlachova, Jana; Tmejova, Katerina; Kopel, Pavel; Korabik, Maria; Zitka, Jan; Hynek, David; Kynicky, Jindrich; Adam, Vojtech; Kizek, Rene

2015-01-01

Modification of carbon materials, especially graphene-based materials, has wide applications in electrochemical detection such as electrochemical lab-on-chip devices. A glassy carbon electrode (GCE) modified with chemically alternated graphene oxide was used as a working electrode (glassy carbon modified by graphene oxide with sulphur containing compounds and Nafion) for detection of nucleobases in hydrolysed samples (HCl pH = 2.9, 100 °C, 1 h, neutralization by NaOH). It was found out that modification, especially with trithiocyanuric acid, increased the sensitivity of detection in comparison with pure GCE. All processes were finally implemented in a microfluidic chip formed with a 3D printer by fused deposition modelling technology. As a material for chip fabrication, acrylonitrile butadiene styrene was chosen because of its mechanical and chemical stability. The chip contained the one chamber for the hydrolysis of the nucleic acid and another for the electrochemical detection by the modified GCE. This chamber was fabricated to allow for replacement of the GCE. PMID:25621613

A 3D microfluidic chip for electrochemical detection of hydrolysed nucleic bases by a modified glassy carbon electrode.

PubMed

Vlachova, Jana; Tmejova, Katerina; Kopel, Pavel; Korabik, Maria; Zitka, Jan; Hynek, David; Kynicky, Jindrich; Adam, Vojtech; Kizek, Rene

2015-01-22

Modification of carbon materials, especially graphene-based materials, has wide applications in electrochemical detection such as electrochemical lab-on-chip devices. A glassy carbon electrode (GCE) modified with chemically alternated graphene oxide was used as a working electrode (glassy carbon modified by graphene oxide with sulphur containing compounds and Nafion) for detection of nucleobases in hydrolysed samples (HCl pH = 2.9, 100 °C, 1 h, neutralization by NaOH). It was found out that modification, especially with trithiocyanuric acid, increased the sensitivity of detection in comparison with pure GCE. All processes were finally implemented in a microfluidic chip formed with a 3D printer by fused deposition modelling technology. As a material for chip fabrication, acrylonitrile butadiene styrene was chosen because of its mechanical and chemical stability. The chip contained the one chamber for the hydrolysis of the nucleic acid and another for the electrochemical detection by the modified GCE. This chamber was fabricated to allow for replacement of the GCE.

Novel Heating-Induced Reversion during Crystallization of Al-based Glassy Alloys.

PubMed

Han, F F; Inoue, A; Han, Y; Kong, F L; Zhu, S L; Shalaan, E; Al-Marzouki, F; Greer, A L

2017-04-13

Thermal stability and crystallization of three multicomponent glassy alloys, Al 86 Y 7 Ni 5 Co 1 Fe 0.5 Pd 0.5 , Al 85 Y 8 Ni 5 Co 1 Fe 0.5 Pd 0.5 and Al 84 Y 9 Ni 4 Co 1.5 Fe 0.5 Pd 1 , were examined to assess the ability to form the mixture of amorphous (am) and fcc-aluminum (α-Al) phases. On heating, the glass transition into the supercooled liquid is shown by the 85Al and 84Al glasses. The crystallization sequences are [am] → [am + α-Al] → [α-Al + compounds] for the 86Al and 85Al alloys, and [am] → [am + α-Al + cubic Al x M y (M = Y, Ni, Co, Fe, Pd)] → [am + α-Al] → [α-Al + Al 3 Y + Al 9 (Co, Ni) 2  + unknown phase] for the 84Al alloy. The glass transition appears even for the 85Al alloy where the primary phase is α-Al. The heating-induced reversion from [am + α-Al + multicomponent Al x M y ] to [am + α-Al] for the 84Al alloy is abnormal, not previously observed in crystallization of glassy alloys, and seems to originate from instability of the metastable Al x M y compound, in which significant inhomogeneous strain is caused by the mixture of solute elements. This novel reversion phenomenon is encouraging for obtaining the [am + α-Al] mixture over a wide range of high temperature effective for the formation of Al-based high-strength nanostructured bulk alloys by warm working.

A wrinkling-based method for investigating glassy polymer film relaxation as a function of film thickness and temperature.

PubMed

Chung, Jun Young; Douglas, Jack F; Stafford, Christopher M

2017-10-21

We investigate the relaxation dynamics of thin polymer films at temperatures below the bulk glass transition T g by first compressing polystyrene films supported on a polydimethylsiloxane substrate to create wrinkling patterns and then observing the slow relaxation of the wrinkled films back to their final equilibrium flat state by small angle light scattering. As with recent relaxation measurements on thin glassy films reported by Fakhraai and co-workers, we find the relaxation time of our wrinkled films to be strongly dependent on film thickness below an onset thickness on the order of 100 nm. By varying the temperature between room temperature and T g (≈100 °C), we find that the relaxation time follows an Arrhenius-type temperature dependence to a good approximation at all film thicknesses investigated, where both the activation energy and the relaxation time pre-factor depend appreciably on film thickness. The wrinkling relaxation curves tend to cross at a common temperature somewhat below T g , indicating an entropy-enthalpy compensation relation between the activation free energy parameters. This compensation effect has also been observed recently in simulated supported polymer films in the high temperature Arrhenius relaxation regime rather than the glassy state. In addition, we find that the film stress relaxation function, as well as the height of the wrinkle ridges, follows a stretched exponential time dependence and the short-time effective Young's modulus derived from our modeling decreases sigmoidally with increasing temperature-both characteristic features of glassy materials. The relatively facile nature of the wrinkling-based measurements in comparison to other film relaxation measurements makes our method attractive for practical materials development, as well as fundamental studies of glass formation.

A wrinkling-based method for investigating glassy polymer film relaxation as a function of film thickness and temperature

NASA Astrophysics Data System (ADS)

Chung, Jun Young; Douglas, Jack F.; Stafford, Christopher M.

2017-10-01

We investigate the relaxation dynamics of thin polymer films at temperatures below the bulk glass transition Tg by first compressing polystyrene films supported on a polydimethylsiloxane substrate to create wrinkling patterns and then observing the slow relaxation of the wrinkled films back to their final equilibrium flat state by small angle light scattering. As with recent relaxation measurements on thin glassy films reported by Fakhraai and co-workers, we find the relaxation time of our wrinkled films to be strongly dependent on film thickness below an onset thickness on the order of 100 nm. By varying the temperature between room temperature and Tg (≈100 °C), we find that the relaxation time follows an Arrhenius-type temperature dependence to a good approximation at all film thicknesses investigated, where both the activation energy and the relaxation time pre-factor depend appreciably on film thickness. The wrinkling relaxation curves tend to cross at a common temperature somewhat below Tg, indicating an entropy-enthalpy compensation relation between the activation free energy parameters. This compensation effect has also been observed recently in simulated supported polymer films in the high temperature Arrhenius relaxation regime rather than the glassy state. In addition, we find that the film stress relaxation function, as well as the height of the wrinkle ridges, follows a stretched exponential time dependence and the short-time effective Young's modulus derived from our modeling decreases sigmoidally with increasing temperature—both characteristic features of glassy materials. The relatively facile nature of the wrinkling-based measurements in comparison to other film relaxation measurements makes our method attractive for practical materials development, as well as fundamental studies of glass formation.

The Planck-Benzinger thermal work function in the condensation of water vapor

NASA Astrophysics Data System (ADS)

Chun, Paul W.

Based on the Planck-Benzinger thermal work function using Chun's method, the innate temperature-invariant enthalpy at 0 K, ?H0(T0), for the condensation of water vapor as well as the dimer, trimer, tetramer, and pentamer form in the vapor phase, was determined to be 0.447 kcal mol-1 for vapor, 1.127 for the dimer, 0.555 for the trimer, 0.236 for the tetramer, and 0.079 kcal mol-1 for the pentamer using ?G(T) data reported by Kell et al. in 1968 and Kell and McLaurin in 1969. These results suggest that the predominant dimeric form is the most stable of these n-mers. Using Nemethy and Scheraga's 1962 data for the Helmholtz free energy of liquid water, the value of ?H0(T0) was determined to be 1.21 kcal mol-1. This is very close to the value for the energy of the hydrogen bond EH of 1.32 kcal mol-1 reported by Nemethy and Scheraga, using statistical thermodynamics. It seems clear that very little energy is required for interconversion between the hypothetical supercooled water vapor and glassy water at 0 K. A hypothetical supercooled water vapor at 0 K is apparently almost as highly associated as glassy water at that temperature, suggesting a dynamic equilibrium between vapor and liquid. This water vapor condensation is highly similar in its thermodynamic behavior to that of sequence-specific pairwise (dipeptide) hydrophobic interaction, except that the negative Gibbs free energy change minimum at ?Ts?, the thermal setpoint for vapor condensation, where T?S = 0, occurs at a considerably lower temperature, 270 K (below 0°C) compared with ?350 K. The temperature of condensation ?Tcond? at which ?G(T) = 0, where water vapor begins to condense, was found to be 383 K. In the case of a sequence-specific pairwise hydrophobic interaction, the melting temperature, ?Tm?, where ?G(Tm) = 0 was found to be 460 K. Only between two temperature limits, ?Th? = 99 K and ?Tcond? = 383 K, where ?G(Tcond) = 0, is the net chemical driving force favorable for polymorphism of glassy water

Electrochemical reduction of nalidixic acid at glassy carbon electrode modified with multi-walled carbon nanotubes.

PubMed

Patiño, Yolanda; Pilehvar, Sanaz; Díaz, Eva; Ordóñez, Salvador; De Wael, Karolien

2017-02-05

The aqueous phase electrochemical degradation of nalidixic acid (NAL) is studied in this work, using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) as instrumental techniques. The promotional effect of multi-walled carbon nanotubes (MWCNT) on the performance of glassy carbon electrodes is demonstrated, being observed that these materials catalyze the NAL reduction. The effect of surface functional groups on MWCNT -MWCNT-COOH and MWCNT-NH 2 -was also studied. The modification of glassy carbon electrode (GCE) with MWCNT leads to an improved performance for NAL reduction following the order of MWCNT>MWCNT-NH 2 >MWCNT-COOH. The best behavior at MWCNT-GCE is mainly due to both the increased electrode active area and the enhanced MWCNT adsorption properties. The NAL degradation was carried out under optimal conditions (pH=5.0, deposition time=20s and volume of MWCNT=10μL) using MWCNT-GCE obtaining an irreversible reduction of NAL to less toxic products. Paramaters as the number of DPV cycles and the volume/area (V/A) ratio were optimized for maximize pollutant degradation. It was observed that after 15 DPV scans and V/A=8, a complete reduction was obtained, obtaining two sub-products identified by liquid chromatography-mass spectrometry (LC-MS). Copyright © 2016 Elsevier B.V. All rights reserved.

Glassy behavior and dynamic tweed in defect-free multiferroics

NASA Astrophysics Data System (ADS)

Wang, Xiaofei; Salje, Ekhard K. H.; Sun, Jun; Ding, Xiangdong

2018-01-01

Multiferroics often show significant elastic fluctuations even when the transition is strongly stepwise. Molecular dynamics simulations of a generic toy model show the appearance of tweed nanostructures (cross hatched patterns) in the paraelastic phase just above the transition point. This tweed lowers the elastic modulus C12 when approaching the transition temperature. The spatial and temporal correlations of the tweed structure follow the Vogel-Fulcher relationship, and the Vogel-Fulcher temperature is slightly below the transition temperature Ttrans, preventing this glassy state to freeze completely. Spatial correlations of shear strain show that the size of tweed patches reaches about eight lattice spacings near Ttrans. Cross- and rod-shaped diffuse scattering, similar to that in relaxors, emerges around {hh0}* and {h00}* Bragg reflections. The viscosity of the sample increases dramatically at the transition point with a significant precursor increase in the tweed regime.

Thermodynamics and glassy phase transition of regular black holes

NASA Astrophysics Data System (ADS)

Javed, Wajiha; Yousaf, Z.; Akhtar, Zunaira

2018-05-01

This paper is aimed to study thermodynamical properties of phase transition for regular charged black holes (BHs). In this context, we have considered two different forms of BH metrics supplemented with exponential and logistic distribution functions and investigated the recent expansion of phase transition through grand canonical ensemble. After exploring the corresponding Ehrenfest’s equation, we found the second-order background of phase transition at critical points. In order to check the critical behavior of regular BHs, we have evaluated some corresponding explicit relations for the critical temperature, pressure and volume and draw certain graphs with constant values of Smarr’s mass. We found that for the BH metric with exponential configuration function, the phase transition curves are divergent near the critical points, while glassy phase transition has been observed for the Ayón-Beato-García-Bronnikov (ABGB) BH in n = 5 dimensions.

Manufacturing of glassy thin shell for adaptive optics: results achieved

NASA Astrophysics Data System (ADS)

Poutriquet, F.; Rinchet, A.; Carel, J.-L.; Leplan, H.; Ruch, E.; Geyl, R.; Marque, G.

2012-07-01

Glassy thin shells are key components for the development of adaptive optics and are part of future & innovative projects such as ELT. However, manufacturing thin shells is a real challenge. Even though optical requirements for the front face - or optical face - are relaxed compared to conventional passive mirrors, requirements concerning thickness uniformity are difficult to achieve. In addition, process has to be completely re-defined as thin mirror generates new manufacturing issues. In particular, scratches and digs requirement is more difficult as this could weaken the shell, handling is also an important issue due to the fragility of the mirror. Sagem, through REOSC program, has recently manufactured different types of thin shells in the frame of European projects: E-ELT M4 prototypes and VLT Deformable Secondary Mirror (VLT DSM).

Dielectric Relaxation of Water and Water-Plasticized Biomolecules in Relation to Cellular Water Organization, Cytoplasmic Viscosity, and Desiccation Tolerance in Recalcitrant Seed Tissues1

PubMed Central

Sun, Wendell Q.

2000-01-01

To understand the relationship between the organization of cellular water, molecular interactions, and desiccation tolerance, dielectric behaviors of water and water-plasticized biomolecules in red oak (Quercus rubra) seeds were studied during dehydration. The thermally stimulated current study showed three dielectric dispersions: (a) the relaxation of loosely-bound water and small polar groups, (b) the relaxation of tightly-bound water, carbohydrate chains, large polar groups of macromolecules, and (c) the “freezing in” of molecular mobility (glassy state). Seven discrete hydration levels (water contents of 1.40, 0.55, 0.41, 0.31, 0.21, 0.13, and 0.08 g/g dry weight, corresponding to −1.5, −8, −11, −14, −24, −74, and −195 MPa, respectively) were identified according to the changes in thermodynamic and dielectric properties of water and water-plasticized biomolecules during dehydration. The implications of intracellular water organization for desiccation tolerance were discussed. Cytoplasmic viscosity increased exponentially at water content < 0.40 g/g dry weight, which was correlated with the great relaxation slowdown of water-plasticized biomolecules, supporting a role for viscosity in metabolic shutdown during dehydration. PMID:11080297

To enhance the efficiency of a power supply circuit by the use of Fe-P-B-Nb-type ultralow loss glassy metal core

NASA Astrophysics Data System (ADS)

Matsumoto, H.; Urata, A.; Yamada, Y.; Makino, A.

2009-04-01

The inductor in a power supply is required to be capable of dealing satisfactorily with the high-current supply and to improve the power loss characteristic. A novel glassy metal powder with a chemical composition Fe77P7B13Nb3 features both a high saturated magnetic flux density of 1.3 T and a low coercive force of 2.0 A/m, which has a stable amorphous structure suitable for glassy metal composite cores. Hence there is no magnetic saturation even under a high-current supply, and it is confirmed to have significantly low magnetic loss resulting from the low coercive force. As a result of using the glassy metal alloy Fe77P7B13Nb3 powder in an inductor core, we have achieved improvement in power supply efficiency by up to roughly 2.0%. Moreover, the reduction in the standby power requirement by the improvement in the power supply efficiency in the low load current case, where the core loss occupies a high ratio in the entire loss, can be expected. Additionally, heat generation in a core is suppressed by using the low loss powder, and it becomes easy to design a temperature rise in the entire power supply circuit.

Anterior foregut microbiota of the glassy-winged sharpshooter explored using deep 16S rRNA gene sequencing from individual insects

USDA-ARS?s Scientific Manuscript database

The glassy-winged sharpshooter (GWSS) is an invasive insect species that transmits Xylella fastidiosa, the bacterium causing Pierce’s disease of grapevine and other leaf scorch diseases. X. fastidiosa has been shown to colonize the anterior foregut (cibarium and precibarium) of sharpshooters, where ...

Early Stage Anodic Instability of Glassy Carbon Electrodes in Propylene Carbonate Solvent Containing Lithium Hexafluorophosphate

DOE PAGES

Carino, Emily V.; Newman, Daniel J.; Connell, Justin G.; ...

2017-09-19

In this paper, irreversible changes to the morphology of glassy carbon (GC) electrodes at potentials between 3.5 and 4.5 V vs Li/Li + in propylene carbonate (PC) solvent containing lithium hexafluorophosphate (LiPF 6) are reported. Analysis of cyclic voltammetry (CV) experiments in the range of 3.0 to 6.0 V shows that the capacitance of the electrochemical double -layer increased irreversibly beginning at potentials as low as 3.5 V. These changes resulted from nonfaradaic interactions, and were not due to oxidative electrochemical decomposition of the electrode and electrolyte, anion intercalation, nor caused by the presence of water, a common impurity inmore » organic electrolyte solutions. Atomic force microscopy (AFM) images revealed that increasing the potential of a bare GC surface from 3.0 to 4.5 V resulted in a 6X increase in roughness, in good agreement with the changes in double -layer capacitance. Treating the GC surface via exposure to trichloromethylsilane vapors resulted in a stable double -layer capacitance between 3.0 and 4.5 V, and this treatment also correlated with less roughening. Lastly, these results inform future efforts aimed at controlling surface composition and morphology of carbon electrodes.« less

Determination of Fracture Patterns in Glass and Glassy Polymers.

PubMed

Baca, Allison C; Thornton, John I; Tulleners, Frederic A

2016-01-01

The study of fractures of glass, glassy-type materials, and plastic has long been of interest to the forensic community. The focus of this interest has been the use of glass and polymer fractures to associate items of evidence under the assumption that each fracture is different. Generally, it is well-accepted that deviations exist; however, the emphasis has been on classifying and predicting fracture rather than determining that each fracture is different. This study documented the controlled fracture patterns of 60 glass panes, 60 glass bottles, and 60 plastic tail light lens covers using both dynamic impact and static pressure methods under closely controlled conditions. Each pattern was intercompared, and based on the limited specimens tested in this study, the results illustrate that the fracture patterns are different. Further repetitive studies, under controlled conditions, will be needed to provide more statistical significance to the theory that each fracture forms a nonreproducible fracture pattern. © 2015 American Academy of Forensic Sciences.

Crystallization of probucol from solution and the glassy state.

PubMed

Kawakami, Kohsaku; Ohba, Chie

2017-01-30

Crystallization of probucol (PBL) from both solution and glassy solid state was investigated. In the crystallization study from solution, six solvents and three methods, i.e., evaporation, addition of a poor solvent, and cooling on ice, were used to obtain various crystal forms. In addition to common two crystal forms (forms I and II), two further forms (forms III and cyclohexane-solvate) were found in this study, and their thermodynamic relationships were determined. Forms I and II are likely to be enantiotropically related with thermodynamic transition temperature below 5°C. Isothermal crystallization studies revealed that PBL glass initially crystallized into form III between 25 and 50°C, and then transformed to form I. The isothermal crystallization appears to be a powerful option to find uncommon crystal forms. The crystallization of PBL was identified to be pressure controlled, thus the physical stability of PBL glass is higher than that of typical compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

Ion beam promoted lithium absorption in glassy polymeric carbon

NASA Astrophysics Data System (ADS)

Zimmerman, R. L.; Ila, D.; Jenkins, G. M.; Maleki, H.; Poker, D. B.

1995-12-01

Glassy Polymeric Carbon (GPC) samples prepared from a precursor possess accessible pore volume that depends on the heat treatment temperature [G.M. Jenkins and K. Kawamura, Polymeric Carbons - Carbon Fiber, Glass and Char (Cambridge University Press, Cambridge, 1976) p. 140]. We have shown that lithium percolates without diffusion into the accessible pores of GPC samples immersed in a molten lithium salt bath at 700°C [D. Ila, G.M. Jenkins, L.R. Holland, A.L. Evelyn and H. Jena, Vacuum 45 (1994) 451]. Ion bombardment with 10 MeV Au atoms increases the total pore volume available for lithium occupation even for samples normally impermeable to lithium. The lithium concentration depth profile is measured using Li 7(p,2α) nuclear reaction analysis. We will report on lithium percolation into GPC prepared at temperatures between 500°C and 1000°C and activated by a 10 MeV gold ion bombardment.

A novel highly selective and sensitive detection of serotonin based on Ag/polypyrrole/Cu2O nanocomposite modified glassy carbon electrode.

PubMed

Selvarajan, S; Suganthi, A; Rajarajan, M

2018-06-01

A silver/polypyrrole/copper oxide (Ag/PPy/Cu 2 O) ternary nanocomposite was prepared by sonochemical and oxidative polymerization simple way, in which Cu 2 O was decorated with Ag nanoparticles, and covered by polyprrole (PPy) layer. The as prepared materials was characterized by UV-vis-spectroscopy (UV-vis), FT-IR, X-ray diffraction (XRD), thermo-gravimetric analysis (TGA), scanning electron microscopy (SEM) with EDX, high resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS). Sensing of serotonin (5HT) was evaluated electrocatalyst using polypyrrole/glassy carbon electrode (PPy/GCE), polypyrrole/copper oxide/glassy carbon electrode (PPy/Cu 2 O/GCE) and silver/polypyrrole/copper oxide/glassy carbon electrode (Ag/PPy/Cu 2 O/GCE). The Ag/PPy/Cu 2 O/GCE was electrochemically treated in 0.1MPBS solution through cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The peak current response increases linearly with 5-HT concentration from 0.01 to 250 µmol L -1 and the detection limit was found to be 0.0124 μmol L -1 . It exhibits high electrocatalytic activity, satisfactory repeatability, stability, fast response and good selectivity against potentially interfering species, which suggests its potential in the development of sensitive, selective, easy-operation and low-cost serotonin sensor for practical routine analyses. The proposed method is potential to expand the possible applied range of the nanocomposite material for detection of various concerned electro active substances. Copyright © 2018 Elsevier B.V. All rights reserved.

Fundamental differences between glassy dynamics in two and three dimensions.

PubMed

Flenner, Elijah; Szamel, Grzegorz

2015-06-12

The two-dimensional freezing transition is very different from its three-dimensional counterpart. In contrast, the glass transition is usually assumed to have similar characteristics in two and three dimensions. Using computer simulations, here we show that glassy dynamics in supercooled two- and three-dimensional fluids are fundamentally different. Specifically, transient localization of particles on approaching the glass transition is absent in two dimensions, whereas it is very pronounced in three dimensions. Moreover, the temperature dependence of the relaxation time of orientational correlations is decoupled from that of the translational relaxation time in two dimensions but not in three dimensions. Last, the relationships between the characteristic size of dynamically heterogeneous regions and the relaxation time are very different in two and three dimensions. These results strongly suggest that the glass transition in two dimensions is different than in three dimensions.

Fundamental differences between glassy dynamics in two and three dimensions

PubMed Central

Flenner, Elijah; Szamel, Grzegorz

2015-01-01

The two-dimensional freezing transition is very different from its three-dimensional counterpart. In contrast, the glass transition is usually assumed to have similar characteristics in two and three dimensions. Using computer simulations, here we show that glassy dynamics in supercooled two- and three-dimensional fluids are fundamentally different. Specifically, transient localization of particles on approaching the glass transition is absent in two dimensions, whereas it is very pronounced in three dimensions. Moreover, the temperature dependence of the relaxation time of orientational correlations is decoupled from that of the translational relaxation time in two dimensions but not in three dimensions. Last, the relationships between the characteristic size of dynamically heterogeneous regions and the relaxation time are very different in two and three dimensions. These results strongly suggest that the glass transition in two dimensions is different than in three dimensions. PMID:26067877

Electrochemical Determination of Caffeine Content in Ethiopian Coffee Samples Using Lignin Modified Glassy Carbon Electrode.

PubMed

Amare, Meareg; Aklog, Senait

2017-01-01

Lignin film was deposited at the surface of glassy carbon electrode potentiostatically. In contrast to the unmodified glassy carbon electrode, an oxidative peak with an improved current and overpotential for caffeine at modified electrode showed catalytic activity of the modifier towards oxidation of caffeine. Linear dependence of peak current on caffeine concentration in the range 6 × 10 -6 to 100 × 10 -6  mol L -1 with determination coefficient and method detection limit (LoD = 3 s/slope) of 0.99925 and 8.37 × 10 -7  mol L -1 , respectively, supplemented by recovery results of 93.79-102.17% validated the developed method. An attempt was made to determine the caffeine content of aqueous coffee extracts of Ethiopian coffees grown in four coffee cultivating localities (Wonbera, Wolega, Finoteselam, and Zegie) and hence to evaluate the correlation between users preference and caffeine content. In agreement with reported works, caffeine contents (w/w%) of 0.164 in Wonbera coffee; 0.134 in Wolega coffee; 0.097 in Finoteselam coffee; and 0.089 in Zegie coffee were detected confirming the applicability of the developed method for determination of caffeine in a complex matrix environment. The result indicated that users' highest preference for Wonbera and least preference for Zegie cultivated coffees are in agreement with the caffeine content.

Development and Validation of Chronopotentiometric Method for Imidacloprid Determination in Pesticide Formulations and River Water Samples

PubMed Central

Đurović, Ana; Stojanović, Zorica; Kravić, Snežana; Grahovac, Nada; Bursić, Vojislava; Vuković, Gorica; Suturović, Zvonimir

2016-01-01

A new electrochemical method for determination of imidacloprid using chronopotentiometry on thin film mercury and glassy carbon electrode was presented. The most important experimental parameters of chronopotentiometry were examined and optimized with respect to imidacloprid analytical signal. Imidacloprid provided well-defined reduction peak in Britton-Robinson buffer on thin film mercury electrode at −1.0 V (versus Ag/AgCl (KCl, 3.5 mol/L)) and on glassy carbon electrode at −1.2 V (versus Ag/AgCl (KCl, 3.5 mol/L)). The reduction time was linearly proportional to concentrations from 0.8 to 30.0 mg/L on thin film mercury electrode and from 7.0 to 70.0 mg/L on glassy carbon electrode. The detection limits were 0.17 mg/L and 0.93 mg/L for thin film mercury and glassy carbon electrode, respectively. The estimation of method precision as a function of repeatability and reproducibility showed relative standard deviations values lower than 3.73%. Recovery values from 97.3 to 98.1% confirmed the accuracy of the proposed method, while the constancy of the transition time with deliberated small changes in the experimental parameters indicated a very good robustness. A minor influence of possible interfering compounds proved good selectivity of the method. Developed method was applied for imidacloprid determination in commercial pesticide formulations and river water samples. PMID:27042181

Low Young's modulus Ti-based porous bulk glassy alloy without cytotoxic elements.

PubMed

Nicoara, M; Raduta, A; Parthiban, R; Locovei, C; Eckert, J; Stoica, M

2016-05-01

A new a biocompatible Ti42Zr40Ta3Si15 (atomic %) porous bulk glassy alloy was produced by combination of rapid solidification and powder metallurgy techniques. Amorphous alloy ribbons were fabricated by melt spinning, i.e. extremely fast quenching the molten alloy with 10(6)K/s from T=1973K down to room temperature. The ribbons were then cryo-milled at liquid nitrogen temperature in order to produce powder, which was subsequently hot pressed. The resulting thick pellets have a porosity of about 14vol%, a high compression strength of 337MPa and a Young's modulus of about E=52GPa, values very close to those characteristic of cortical bone. Moreover, the morphology of the samples is very similar to that of cortical bone. The biocompatibility, which is due to the absence of any toxic element in the chemical composition, together with the suitable mechanical behavior, make these samples promising for orthopedic and dentistry applications. Ti-based alloys are nowadays the standard solution for biomedical implants. However, both the conventional crystalline and amorphous alloys have higher rigidity as the human bone, leading to the damage of the bone at the interface, and contains harmful elements like vanadium, aluminum, nickel or beryllium. The hierarchical porous structures based on glassy alloys with biocompatible elements is a much better alternative. This work presents for the first time the manufacturing of such porous bodies starting from Ti-based amorphous alloy ribbons, which contains only non-harmful elements. The morphology and the compressive mechanical properties of these new products are analyzed in regard with those characteristic to the cortical bone. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Water-clear cell adenoma of the parathyroid. A case report with immunohistochemistry and electron microscopy.

PubMed

Grenko, R T; Anderson, K M; Kauffman, G; Abt, A B

1995-11-01

We report a water-clear cell adenoma of the parathyroid gland, a lesion which to our knowledge has not been described previously. Like its rare but well-described hyperplastic counterpart, water-clear cell hyperplasia, this adenoma is composed of cells with abundant foamy-to-granular cytoplasm and mild nuclear pleomorphism. The cells form glandular structures and cell nests separated by fine fibrovascular septae. The tumor cells stain positively with anti-parathyroid hormone and show characteristic glassy and flocculate material by electron microscopy. Unlike water-clear cell hyperplasia, water-clear cell adenoma is a solitary lesion that compresses the residual nonneoplastic parathyroid gland.

Cryptoachneliths: Hidden glassy ash in composite spheroidal lapilli

NASA Astrophysics Data System (ADS)

Carracedo Sánchez, M.; Arostegui, J.; Sarrionandia, F.; Larrondo, E.; Gil Ibarguchi, J. I.

2010-09-01

Cryptoachneliths, perceptible by means of electron microscopy but unresolved under the optical microscope, occur unnoticed inside spheroidal lapilli of ultrabasic composition of the Cabezo Segura volcano (Calatrava volcanic province, Spain). The cryptoachneliths are glassy spherical particles that have compositions of Al-rich silicate with minor amounts of Fe, Ca and other elements. The smallest cryptoachneliths of < 1 μm in diameter (nanoachneliths) joined by coalescence to form microspheres > 1 μm (microachneliths) and homogeneous less regular masses of similar composition. Nano and microachneliths welded each other or to other types of volcanic particles (crystals, crystal fragments, spinning droplets, cognate lithic clasts, etc.) to form spheroidal lapilli and even bomb size clasts within proximal fall deposits of the Cabezo Segura volcano. The welding processes took place inside the eruptive column, previous to the fall of the spheroidal lapilli on top of the volcanic cone. The presence of the cryptoachneliths implies that lapilli and even bomb size tephra within deposits formed during explosive eruptions of low-viscosity basic to ultrabasic magmas should be carefully examined in order to establish key parameters of eruption dynamics, like size, amount and distribution of juvenile fine particles.

Electronic Transport Behaviors due to Charge Density Waves in Ni-Nb-Zr-H Glassy Alloys

NASA Astrophysics Data System (ADS)

Fukuhara, Mikio; Umemori, Yoshimasa

2013-11-01

The amorphous Ni-Nb-Zr-H glassy alloy containing subnanometer-sized icosahedral Zr5 Nb5Ni3 clusters exhibited four types of electronic phenomena: a metal/insulator transition, an electric current-induced voltage oscillation (Coulomb oscillation), giant capacitor behavior and an electron avalanche with superior resistivity. These findings could be excluded by charge density waves that the low-dimensional component of clusters, in which the atoms are lined up in chains along the [130] direction, plays important roles in various electron transport phenomena.

Retardation of Bulk Water Dynamics by Disaccharide Osmolytes

NASA Astrophysics Data System (ADS)

Shukla, Nimesh; Chen, Lee; Pomarico, Enrico; Chergui, Majed; Othon, Christina

Bioprotective nature of disaccharides is hypothesized to derive from the modification of the hydrogen bonding network of water which protects biomolecules through lowered water activity at the protein interface. Using ultrafast fluorescence spectroscopy, we measured the relaxation of bulk water dynamics around the induced dipole moment of two fluorescent probes (Lucifer Yellow Ethylenediamine and Tryptophan). Our results indicate a reduction in bulk water reorganization rate of approximately 30%. We observe this retardation in the low concentration regime measured at 0.1 and 0.25 M, far below the onset of glassy dynamics. This water structuring should be significant in crowded biological systems, contributing to a global change in protein energy landscape, resulting in a significant enhancement of protein stability under environmental stress. We observed similar dynamic reduction for two disaccharide osmolytes, sucrose and trehalose, with trehalose being the more effective in reducing solvation dynamics.

Differences in Stylet Penetration Behaviors of Glassy-winged Sharpshooters on Xylella-Resistant Vitis candicans vs. Susceptible Vitis vinifera cv. ‘Chardonnay’

USDA-ARS?s Scientific Manuscript database

Electrical penetration graph (EPG) monitoring was used to compare stylet penetration behaviors of glassy-winged sharpshooter (GWSS), a vector of Xylella fastidiosa (Xf), on Xf-resistant Vitis candicans grape vs. susceptible V. vinifera cv. ‘Chardonnay.’ Frequency of occurrence of X waves (represent...

Electrocatalytic activity of spots of electrodeposited noble-metal catalysts on carbon nanotubes modified glassy carbon.

PubMed

Chen, Xingxing; Eckhard, Kathrin; Zhou, Min; Bron, Michael; Schuhmann, Wolfgang

2009-09-15

A strategy for the screening of the electrocatalytic activity of electrocatalysts for possible application in fuel cells and other devices is presented. In this approach, metal nanoclusters (Pt, Au, Ru, and Rh and their codeposits) were prepared using a capillary-based droplet-cell by pulsed electrodeposition in a diffusion-restricted viscous solution. A glassy carbon surface was modified with carbon nanotubes (CNTs) by electrophoretic accumulation and was used as substrate for metal nanoparticle deposition. The formed catalyst spots on the CNT-modified glassy carbon surface were investigated toward their catalytic activity for oxygen reduction as a test reaction employing the redox competition mode of scanning electrochemical microscopy (RC-SECM). Qualitative information on the electrocatalytic activity of the catalysts was obtained by varying the potential applied to the substrate; semiquantitative evaluation was based on the determination of the electrochemically deposited catalyst loading by means of the charge transferred during the metal nanoparticle deposition. Qualitatively, Au showed the highest electrocatalytic activity toward the oxygen reduction reaction (ORR) in phosphate buffer among all investigated single metal catalysts which was attributed to the much higher loading of Au achieved during electrodeposition. Coelectrodeposited Au-Pt catalysts showed a more positive onset potential (-150 mV in RC-SECM experiments) of the ORR in phosphate buffer at pH 6.7. After normalizing the SECM image by the charge during the metal nanocluster deposition which represents the mass loading of the catalyst, Ru showed a higher electrocatalytic activity toward the ORR than Au.

Atomistic interpretation of the ac-dc crossover frequency in crystalline and glassy ionic conductors

NASA Astrophysics Data System (ADS)

Marple, M. A. T.; Avila-Paredes, H.; Kim, S.; Sen, S.

2018-05-01

A comprehensive analysis of the ionic dynamics in a wide variety of crystalline and glassy ionic conductors, obtained in recent studies using a combination of electrochemical impedance and nuclear magnetic resonance spectroscopic techniques, is presented. These results demonstrate that the crossover frequency, between the frequency-independent dc conductivity and the frequency-dependent ac conductivity, corresponds to the time scale of "successful" diffusive hops of the mobile ions between the trapping sites in the structure. These inter-site hops are typically compound in nature and consist of several elementary hops in the intervening region between the neighboring trapping sites.

Atomistic interpretation of the ac-dc crossover frequency in crystalline and glassy ionic conductors.

PubMed

Marple, M A T; Avila-Paredes, H; Kim, S; Sen, S

2018-05-28

A comprehensive analysis of the ionic dynamics in a wide variety of crystalline and glassy ionic conductors, obtained in recent studies using a combination of electrochemical impedance and nuclear magnetic resonance spectroscopic techniques, is presented. These results demonstrate that the crossover frequency, between the frequency-independent dc conductivity and the frequency-dependent ac conductivity, corresponds to the time scale of "successful" diffusive hops of the mobile ions between the trapping sites in the structure. These inter-site hops are typically compound in nature and consist of several elementary hops in the intervening region between the neighboring trapping sites.

Thermal and Compositional Variation of Glassy Metal Structure Factors.

NASA Astrophysics Data System (ADS)

From, Milton

The x-ray total structure factor of the glassy -metal alloys Mg_{70}Zn_ {30}, Ca_{70}Mg_{30 } and Mg_{85.5}Cu _{14.5} has been measured at three temperatures: 9K, 150K, and 300K. The data have a statistical precision of about.8% and an absolute accuracy of roughly 3%. Percus-Yevick hard sphere structure factors may be fitted quite accurately to the data in the region of the first peak. In addition, the variation of the experimental structure factor with composition is found to be consistent with the Percus-Yevick theory. At low k values, Percus -Yevick and other theoretical model structure factors are in poor agreement with the data. Within experimental error, the temperature dependence of the structure factors is in agreement with the Debye plane wave phonon model of atomic vibrations. The measured structure factors are used to calculate the electrical resistivity from the Faber-Ziman equation. In most cases, the calculations yield both the correct magnitude of resistivity and sign of the temperature coefficient of resistivity.

A glassy carbon electrode modified with poly(2,4-dinitrophenylhydrazine) for simultaneous detection of dihydroxybenzene isomers.

PubMed

Lopa, Nasrin Siraj; Rahman, Md Mahbubur; Jang, Hohyoun; Sutradhar, Sabuj Chandra; Ahmed, Faiz; Ryu, Taewook; Kim, Whangi

2017-12-06

2,4-Dinitrophenylhydrazine (DNPH) was electropolymerized on the surface of an anodized glassy carbon electrode by cyclic voltammetry. The anodized electrode has a highly electroactive surface due to the creation of chemically functionalized graphitic nanoparticles, and this facilitates the formation of poly-DNPH via radical polymerization. Poly-DNPH displays excellent redox activity due to the presence of nitro groups on its backbone. These catalyze the electro-oxidation of hydroquinone (HQ) and catechol (CT). The peak-to-peak separation is around 109 mV, while a bare GCE cannot resolve the peaks (located at 165 and 274 mV vs. Ag/AgCl). Sensitivity is also enhanced to ∼1.20 and 1.19 μA·cm -2 ·μM -1 , respectively. The sensor has a linear response that covers the 20-250 μM concentration range for both HQ and CT, with 0.75 and 0.76 μM detection limits, respectively, at simultaneous detection. Commonly present species do not interfere. Graphical abstract A novel conducting poly(2,4-dinitrophenylhydrazine)-modified anodized glassy carbon electrode (pDNPH/AGCE) was developed by electrochemical method. The electro-catalytic activity of pDNPH/AGCE sensor was investigated for the selective and simultaneous electrochemical detection of hydroquinone (HQ) and catechol (CT), which revealed high sensitivities and low detection limits with excellent stability.

New Scenario of Dynamical Heterogeneity in Supercooled Liquid and Glassy States of 2D Monatomic System.

PubMed

Van Hoang, Vo; Teboul, Victor; Odagaki, Takashi

2015-12-24

Via analysis of spatiotemporal arrangements of atoms based on their dynamics in supercooled liquid and glassy states of a 2D monatomic system with a double-well Lennard-Jones-Gauss (LJG) interaction potential, we find a new scenario of dynamical heterogeneity. Atoms with the same or very close mobility have a tendency to aggregate into clusters. The number of atoms with high mobility (and size of their clusters) increases with decreasing temperature passing over a maximum before decreasing down to zero. Position of the peak moves toward a lower temperature if mobility of atoms in clusters is lower together with an enhancement of height of the peak. In contrast, the number of atoms with very low mobility or solidlike atoms (and size of their clusters) has a tendency to increase with decreasing temperature and then it suddenly increases in the vicinity of the glass transition temperature leading to the formation of a glassy state. A sudden increase in the number of strongly correlated solidlike atoms in the vicinity of a glass transition temperature (Tg) may be an origin of a drastical increase in viscosity of the glass-forming systems approaching the glass transition. In fact, we find that the diffusion coefficient decays exponentially with a fraction of solidlike atoms exhibiting a sudden decrease in the vicinity of the glass transition region.

Viscous organic aerosol particles in the upper troposphere: diffusivity-controlled water uptake and ice nucleation?

DOE PAGES

Lienhard, D. M.; Huisman, A. J.; Krieger, U. K.; ...

2015-01-01

New measurements of water diffusion in secondary organic aerosol (SOA) material produced by oxidation of α-pinene and in a number of organic/inorganic model mixtures (3-methylbutane-1,2,3-tricarboxylic acid (3-MBTCA), levoglucosan, levoglucosan/NH 4HSO 4, raffinose) are presented. These indicate that water diffusion coefficients are determined by several properties of the aerosol substance and cannot be inferred from the glass transition temperature or bouncing properties. Our results suggest that water diffusion in SOA particles is faster than often assumed and imposes no significant kinetic limitation on water uptake and release at temperatures above 220 K. The fast diffusion of water suggests that heterogeneous icemore » nucleation on a glassy core is very unlikely in these systems. At temperatures below 220 K, model simulations of SOA particles suggest that heterogeneous ice nucleation may occur in the immersion mode on glassy cores which remain embedded in a liquid shell when experiencing fast updraft velocities. The particles absorb significant quantities of water during these updrafts which plasticize their outer layers such that these layers equilibrate readily with the gas phase humidity before the homogeneous ice nucleation threshold is reached. Glass formation is thus unlikely to restrict homogeneous ice nucleation. Only under most extreme conditions near the very high tropical tropopause may the homogeneous ice nucleation rate coefficient be reduced as a consequence of slow condensed-phase water diffusion. Since the differences between the behavior limited or non limited by diffusion are small even at the very high tropical tropopause, condensed-phase water diffusivity is unlikely to have significant consequences on the direct climatic effects of SOA particles under tropospheric conditions.« less

Hydrogen and Sulfur from Hydrogen Sulfide. 5. Anodic Oxidation of Sulfur on Activated Glassy Carbon

DTIC Science & Technology

1988-12-05

electrolyses of H S can probably be carried out at high rates with modest cell voltages in the range 1-1.5 V. The variation in anode current densities...of H2S from solutions of NaSH in aqueous NaOH was achieved using suitably ac- tivated glassy carbon anodes. Thus electrolyses of H2S can probably be...passivation by using a basic solvent at 850C. Using an H2S-saturated 6M NaOH solution, they conducted electrolyses for extended periods at current densities

Plutonium segregation in glassy aerodynamic fallout from a nuclear weapon test

DOE PAGES

Holliday, K. S.; Dierken, J. M.; Monroe, M. L.; ...

2017-01-11

Our study combines electron microscopy equipped with energy dispersive spectroscopy to probe major element composition and autoradiography to map plutonium in order to examine the spatial relationships between plutonium and fallout composition in aerodynamic glassy fallout from a nuclear weapon test. We interrogated a sample set of 48 individual fallout specimens in order to reveal that the significant chemical heterogeneity of this sample set could be described compositionally with a relatively small number of compositional endmembers. Furthermore, high concentrations of plutonium were never associated with several endmember compositions and concentrated with the so-called mafic glass endmember. Our result suggests thatmore » it is the physical characteristics of the compositional endmembers and not the chemical characteristics of the individual component elements that govern the un-burnt plutonium distribution with respect to major element composition in fallout.« less

Protein/ionic liquid/glassy carbon sensors following analyte focusing by ionic liquid micelle collapse for simultaneous determination of water soluble vitamins in plasma matrices.

PubMed

Abd El-Hady, D; Albishri, H M

2015-07-01

Two novel sensors based on human serum albumin (HSA)-ionic liquid (IL) and bovine serum albumin (BSA)-ionic liquid (IL) composites modified glassy carbon electrode (GCE) were produced for simultaneous determination of water soluble vitamins B2, B6 and C in human plasma following analytes focusing by IL micelles collapse (AFILMC). For selective and efficient extraction, vitamins were dissolved in 3.0molL(-1) micellar solution of 1-octyl-3-methyl imidazolium bromide IL. The extracted vitamins were hydrodynamically injected by 25mbar for 20s into a running buffer of 12.5mmolL(-1) phosphate at pH 6.0 followed by electrochemical detection (ECD) on protein/1-octyl-3-methyl imidazolium hexafluorophosphate IL/GC sensors. The chemical stability of proposed sensors was achieved up to 7 days without any decomposition of PF6-based IL/protein and adsorption of interfering ions. In the current work, the sensitivity enhancement factor (SEF) up to 5000-fold was achieved using the AFILMC/ECD setup compared to conventional CE/UV. Under optimal conditions, linear calibration graphs were obtained from 0.5, 0.5 and 1.0 to 1500.0µgmL(-1) of vitamins B2, B6 and C, respectively. Detection limits of analytes were ranged from 180.0 to 520.0ngmL(-1). The proposed AFILMC/ECD setup was successfully applied to the assay of trace level quantification of vitamins in human plasma samples and also their binding constants with HSA and BSA were determined. The concurrent use of IL micelles for the proposed separation and detection processes exhibited some advantages, such as, a reduction of use toxic solvents, an efficient extraction and a direct injection of samples with a short-single run. Furthermore, IL micelles, having variable possibility of interactions, facilitated the successful achievements of AFILMC/ECD setup for the quantification of vitamins in plasma matrices. Copyright © 2015 Elsevier B.V. All rights reserved.

Recrystallization of water in non-water-soluble (meth)acrylate polymers is not rare and is not devitrification.

PubMed

Gemmei-Ide, Makoto; Ohya, Atsushi; Kitano, Hiromi

2012-02-16

Change in the state of water sorbed into four kinds of non-water-soluble poly(meth)acrylates with low water content by temperature (T) perturbation was examined on the basis of T variable mid-infrared (MIR) spectroscopy. Many studies using differential scanning calorimetry suggested that there was no change in the state. T dependence of their MIR spectra, however, clearly demonstrated various changes in the state. Furthermore, recrystallization, which was crystallization during heating, was observed in all four polymers. The recrystallization observed in this study was not devitrification, which is the change in the state from glassy water to crystalline water, but vapor deposition during heating (vapor re-deposition). There were only two reports about recrystallization of water in a non-water-soluble polymer before this report; therefore, it might be considered to be a rare phenomenon. However, as demonstrated in this study, it is not a rare phenomenon. Recrystallization (vapor re-deposition) of water in the polymer matrices is related to a balance between flexibility and strength of the electrostatic interaction sites of polymer matrices but might not be related to the biocompatibility of polymers.

Plant water stress effects on stylet probing behaviors of Homalodisca vitripennis (Hemiptera: Cicadellidae) associated with acquisition and inoculation of the bacterium Xylella fastidiosa

USDA-ARS?s Scientific Manuscript database

The glassy-winged sharpshooter, Homalodisca vitripennis, is a xylem fluid-ingesting leafhopper that transmits Xylella fastidiosa, the causal agent of several plant diseases in the Americas. While the role of plant water stress on the population density and dispersal of H. vitripennis has been studie...

Scanning Electron Microscopy and Petrography of Glassy Particles Produced by Lava Fountain Eruptions. Ph.D. Thesis - Final Report

NASA Technical Reports Server (NTRS)

Ladle, G. H.

1978-01-01

A conceptual model of a lava fountain consists of a vent, spatter ramparts, fountain column, downwind plume and associated pumice deposits. Glassy particles produced by lava fountain eruptions consist primarily of sideromelane glass and minor to moderate amounts of vesicles and crystals. Particles are classified on the basis of morphology as: (1) spherical, (2) elongate, (3) glass-coated mineral grain, (4) shard, (5) reticulite, (6) composite particle, and (7) lithic fragment.

Mode coupling theory for nonequilibrium glassy dynamics of thermal self-propelled particles.

PubMed

Feng, Mengkai; Hou, Zhonghuai

2017-06-28

We present a mode coupling theory study for the relaxation and glassy dynamics of a system of strongly interacting self-propelled particles, wherein the self-propulsion force is described by Ornstein-Uhlenbeck colored noise and thermal noises are included. Our starting point is an effective Smoluchowski equation governing the distribution function of particle positions, from which we derive a memory function equation for the time dependence of density fluctuations in nonequilibrium steady states. With the basic assumption of the absence of macroscopic currents and standard mode coupling approximation, we can obtain expressions for the irreducible memory function and other relevant dynamic terms, wherein the nonequilibrium character of the active system is manifested through an averaged diffusion coefficient D[combining macron] and a nontrivial structural function S 2 (q) with q being the magnitude of wave vector q. D[combining macron] and S 2 (q) enter the frequency term and the vertex term for the memory function, and thus influence both the short time and the long time dynamics of the system. With these equations obtained, we study the glassy dynamics of this thermal self-propelled particle system by investigating the Debye-Waller factor f q and relaxation time τ α as functions of the persistence time τ p of self-propulsion, the single particle effective temperature T eff as well as the number density ρ. Consequently, we find the critical density ρ c for given τ p shifts to larger values with increasing magnitude of propulsion force or effective temperature, in good accordance with previously reported simulation work. In addition, the theory facilitates us to study the critical effective temperature T for fixed ρ as well as its dependence on τ p . We find that T increases with τ p and in the limit τ p → 0, it approaches the value for a simple passive Brownian system as expected. Our theory also well recovers the results for passive systems and can be

Seasonal population dynamics of Homalodisca vitripennis (Hemiptera: Cicadellidae) in sweet orange trees maintained under continuous deficit irrigation.

PubMed

Krugner, Rodrigo; Groves, Russell L; Johnson, Marshall W; Flores, Arnel P; Hagler, James R; Morse, Joseph G

2009-06-01

A 2-yr study was conducted in a citrus orchard (Citrus sinensis L. Osbeck cultivar Valencia) to determine the influence of plant water stress on the population dynamics of glassy-winged sharpshooter, Homalodisca vitripennis (Germar). Experimental treatments included irrigation at 100% of the crop evapotranspiration rate (ET(c)) and continuous deficit-irrigation regimens at 80 and 60% ET(c). Microclimate and plant conditions monitored included temperature and humidity in the tree canopy, leaf surface temperature, water potential, and fruit quality and yield. Glassy-winged sharpshooter population densities and activity were monitored weekly by a combination of visual inspections, beat net sampling, and trapping. Glassy-winged sharpshooter populations were negatively affected by severe plant water stress; however, population densities were not linearly related to decreasing water availability in plants. Citrus trees irrigated at 60% ET(c) had significantly warmer leaves, lower xylem water potential, and consequently hosted fewer glassy-winged sharpshooter eggs, nymphs, and adults than trees irrigated at 80% ET(c). Citrus trees irrigated at 100% ET(c) hosted similar numbers of glassy-winged sharpshooter stages as trees irrigated at 60% ET(c) and a lower number of glassy-winged sharpshooter nymphs than the 80% ET(c) treatment, specifically during the nymphal density peak in mid-April to early July. Irrigation treatments did not affect populations of monitored natural enemies. Although the adult glassy-winged sharpshooter population was reduced, on average, by 50% in trees under severe water stress, the total number of fruit and number of fruit across several fruit grade categories were significantly lower in the 60% ET(c) than in the 80 and 100% ET(c) irrigation treatments.

Anomalous Dynamics of Water Confined in Protein-Protein and Protein-DNA Interfaces.

PubMed

Chong, Song-Ho; Ham, Sihyun

2016-10-06

Confined water often exhibits anomalous properties not observable in the bulk phase. Although water in hydrophobic confinement has been the focus of intense investigation, the behavior of water confined between hydrophilic surfaces, which are more frequently found in biological systems, has not been fully explored. Here, we investigate using molecular dynamics simulations dynamical properties of the water confined in hydrophilic protein-protein and protein-DNA interfaces. We find that the interfacial water exhibits glassy slow relaxations even at 300 K. In particular, the rotational dynamics show a logarithmic decay that was observed in glass-forming liquids at deeply supercooled states. We argue that such slow water dynamics are indeed induced by the hydrophilic binding surfaces, which is in opposition to the picture that the hydration water slaves protein motions. Our results will significantly impact the view on the role of water in biomolecular interactions.

Potential applications of cold sprayed Cu50Ti20Ni30 metallic glassy alloy powders for antibacterial protective coating in medical and food sectors.

PubMed

El-Eskandrany, M Sherif; Al-Azmi, Ahmed

2016-03-01

Mechanical alloying was utilized for synthesizing of metallic glassy Cu50Ti20Ni30 alloy powders, using a low energy ball milling technique. The metallic glassy powders obtained after 100 h of ball milling had an average particle size of 1.7 mm in diameter and possessed excellent thermal stability, indexed by a relatively high glass transition temperature (358.3 °C) with a wide supercooled liquid region (61 °C). This amorphous phase crystallized into Ti2Cu and CuTiNi2 ordered phases through two overlapped crystallization temperatures at 419.3 °C and 447.5 °C, respectively. The total enthalpy change of crystallization was -4.8 kJ/mol. The glassy powders were employed as feedstock materials to double-face coating the surface of SUS 304 substrate, using cold spraying process under helium gas pressure at 400 °C. This coating material had an extraordinary high nanohardness value of 3.1 GPa. Moreover, it showed a high resistance to wear with a low value of the coefficient of friction ranging from 0.45 to 0.45. Biofilms were grown on 20-mm(2) SUS304 sheets coated coupons inoculated with 1.5 × 10(8) CFU ml(-1)E. coli. Significant biofilm inhibition (p The inhibition of biofilm formation by nanocrystalline powders of Cu-based provides a practical approach to achieve the inhibition of biofilms formation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Selective electrochemical detection of 2,4,6-trinitrotoluene (TNT) in water based on poly(styrene-co-acrylic acid) PSA/SiO2/Fe3O4/AuNPs/lignin-modified glassy carbon electrode.

PubMed

Mahmoud, Khaled A; Abdel-Wahab, Ahmed; Zourob, Mohammed

2015-01-01

A new versatile electrochemical sensor based on poly(styrene-co-acrylic acid) PSA/SiO2/Fe3O4/AuNPs/lignin (L-MMS) modified glassy carbon electrode (GCE) was developed for the selective detection of trace trinitrotoluene (TNT) from aqueous media with high sensitivity. The fabricated magnetic microspheres were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). L-MMS films were cast on the GCE surface to fabricate the TNT sensing electrode. The limit of detection (LOD) of TNT determined by the amperometric i-t curve reached 35 pM. The lignin film and well packed Fe3O4/AuNPs facilitated the pre-concentration of trace TNT on the electrode surface resulting in a fast amperometric response of 3 seconds near the detection limit. The high sensitivity and excellent catalytic activity of the modified electrode could be attributed to the lignin layer and highly packed Fe3O4/AuNPs on the electrode surface. The total recovery of TNT from tapwater and seawater matrices was 98% and 96%, respectively. The electrode film was highly stable after five repeated adsorption/desorption cycles. The new electrochemical sensing scheme provides a highly selective, sensitive and versatile assay for the in-situ detection of TNT in complex water media.

Water Retention in Mature and Immature Lunar Regolith

NASA Astrophysics Data System (ADS)

Flom, A. J.; Kramer, G. Y.; Combe, J. P.

2017-12-01

The study of water and hydroxyl (HOH/OH) in lunar regolith and how it is retained has important implications for understanding how the Solar System and the Moon were formed. As a "hydration" phenomenon, understanding the process may provide a vital resource in space exploration. This study looks at how the amount of surface HOH/OH changes over time (eons) in lunar regolith. This is done by comparing the spectral absorption feature in the 3 micron area in Moon Mineralogy Mapper (M3) data [1]. This area of the spectrum is affected by thermal emission and it is known that the initial M3 correction for this is was not sufficient. To correct for this, a new thermal correction has been done on the data using a surface roughness model. With this correction, the 3 micron area spectral absorption feature between mature regolith (that has been exposed to weathering processes on the surface) against immature regolith (in fresh crater ejecta which has been mostly unaffected by these processes) [2]. It is commonly believed that HOH/OH is being formed due to hydrogen atoms from the solar wind interacting with oxygen in lunar minerals. There are a couple competing hypotheses about the process that dominates retaining this HOH/OH once it forms. The first suggests that the exposed oxygen atoms on freshly fractured mineral surfaces facilitate adsorption of protons. Alternately, a second proposes that HOH/OH is trapped in vesicles in the glassy parts of more mature regolith. The first hypothesis would lead to the mature regolith having a weaker HOH/OH absorption than immature regolith, because its weathered glassy coating would prevent it from capturing hydrogen atoms as efficiently. The second hypothesis would lead to the mature regolith having a stronger absorption because the glassy component of the regolith increases with maturity, and therefore so do the vesicles in that glassy coating. This study looks at fresh craters across Crisium, South Pole Aitken, and Reiner Gamma in

Highly Stable Glassy Carbon Interfaces for Long-Term Neural Stimulation and Low-Noise Recording of Brain Activity

PubMed Central

Vomero, Maria; Castagnola, Elisa; Ciarpella, Francesca; Maggiolini, Emma; Goshi, Noah; Zucchini, Elena; Carli, Stefano; Fadiga, Luciano; Kassegne, Sam; Ricci, Davide

2017-01-01

We report on the superior electrochemical properties, in-vivo performance and long term stability under electrical stimulation of a new electrode material fabricated from lithographically patterned glassy carbon. For a direct comparison with conventional metal electrodes, similar ultra-flexible, micro-electrocorticography (μ-ECoG) arrays with platinum (Pt) or glassy carbon (GC) electrodes were manufactured. The GC microelectrodes have more than 70% wider electrochemical window and 70% higher CTC (charge transfer capacity) than Pt microelectrodes of similar geometry. Moreover, we demonstrate that the GC microelectrodes can withstand at least 5 million pulses at 0.45 mC/cm2 charge density with less than 7.5% impedance change, while the Pt microelectrodes delaminated after 1 million pulses. Additionally, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) was selectively electrodeposited on both sets of devices to specifically reduce their impedances for smaller diameters (<60 μm). We observed that PEDOT-PSS adhered significantly better to GC than Pt, and allowed drastic reduction of electrode size while maintaining same amount of delivered current. The electrode arrays biocompatibility was demonstrated through in-vitro cell viability experiments, while acute in vivo characterization was performed in rats and showed that GC microelectrode arrays recorded somatosensory evoked potentials (SEP) with an almost twice SNR (signal-to-noise ratio) when compared to the Pt ones. PMID:28084398

Dielectric relaxation studies in Se{sub 90}Cd{sub 8}Sb{sub 2} glassy alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shukla, Nitesh; Rao, Vandita; Dwivedi, D. K.

2016-05-06

Se{sub 90}Cd{sub 8}Sb{sub 2} chalcogenide semiconducting alloy was prepared by melt quench technique. The prepared glassy alloy has been characterized by techniques such as scanning electron microscopy (SEM) and energy dispersive X-ray (EDAX).Dielectric properties of Se{sub 90}Cd{sub 8}Sb{sub 2} chalcogenide semiconductor have been studied using impedance spectroscopic technique in the frequency range 5×10{sup 2}Hz - 1×10{sup 5}Hz and in temperature range 303-318K. It is found that dielectric constant ε′ and dielectric loss factor ε″ are dependent on frequency and temperature.

Energy barriers, entropy barriers, and non-Arrhenius behavior in a minimal glassy model.

PubMed

Du, Xin; Weeks, Eric R

2016-06-01

We study glassy dynamics using a simulation of three soft Brownian particles confined to a two-dimensional circular region. If the circular region is large, the disks freely rearrange, but rearrangements are rarer for smaller system sizes. We directly measure a one-dimensional free-energy landscape characterizing the dynamics. This landscape has two local minima corresponding to the two distinct disk configurations, separated by a free-energy barrier that governs the rearrangement rate. We study several different interaction potentials and demonstrate that the free-energy barrier is composed of a potential-energy barrier and an entropic barrier. The heights of both of these barriers depend on temperature and system size, demonstrating how non-Arrhenius behavior can arise close to the glass transition.

Understanding glass-forming ability through sluggish crystallization of atomically thin metallic glassy films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Y. T.; Cao, C. R.; Huang, K. Q.

2014-08-04

The glass-forming ability (GFA) of an alloy, closely related to its ability to resist crystallization, is a crucial issue in condensed matter physics. So far, the studies on GFA are mostly statistical and empirical guides. Benefiting from the ultrahigh thermal stability of ultrathin metallic glassy film and high resolution spherical aberration-corrected transmission electron microscope, the crystallization of atomically thin ZrCu and its microalloyed ZrCuAl glasses with markedly different GFA was investigated at the atomic scale. We find the Zr diffusivity estimated from the density of nuclei is dramatically decreased by adding of Al, which is the major reason for themore » much better GFA of the ZrCuAl metallic glass.« less

Pressure-induced positive electrical resistivity coefficient in Ni-Nb-Zr-H glassy alloy

NASA Astrophysics Data System (ADS)

Fukuhara, M.; Gangli, C.; Matsubayashi, K.; Uwatoko, Y.

2012-06-01

Measurements under hydrostatic pressure of the electrical resistivity of (Ni0.36Nb0.24Zr0.40)100-xHx (x = 9.8, 11.5, and 14) glassy alloys have been made in the range of 0-8 GPa and 0.5-300 K. The resistivity of the (Ni0.36Nb0.24Zr0.40)86H14 alloy changed its sign from negative to positive under application of 2-8 GPa in the temperature range of 300-22 K, coming from electron-phonon interaction in the cluster structure under pressure, accompanied by deformation of the clusters. In temperature region below 22 K, the resistivity showed negative thermal coefficient resistance by Debye-Waller factor contribution, and superconductivity was observed at 1.5 K.

Poly(amidosulfonic acid) modified glassy carbon electrode for determination of isoniazid in pharmaceuticals.

PubMed

Yang, Gongjun; Wang, Cunxiao; Zhang, Rui; Wang, Chenying; Qu, Qishu; Hu, Xiaoya

2008-06-01

Amidosulfonic acid was electropolymerized by cyclic voltammetry onto the surface of glassy carbon electrode (GCE) to fabricate the chemically modified electrode, which showed high stability, good selectivity and reproducibility for determination of isoniazid. The modified electrode showed an excellent electrocatalytical effect on the oxidation of isoniazid. Under the optimum conditions, there was a good linear relationship between anodic peak current and isoniazid concentration in the range of 5.0 x 10(-8)- 1.0 x 10(-5) M, and a detection limit of 1.0 x 10(-8) M (S/N = 3) was obtained after 120 s at the accumulation potential of - 0.2 V (vs. SCE). This developed method had been applied to the direct determination of isoniazid in injection and tablet samples with satisfactory results.

Confinement-Induced Glassy Dynamics in a Model for Chromosome Organization

NASA Astrophysics Data System (ADS)

Kang, Hongsuk; Yoon, Young-Gui; Thirumalai, D.; Hyeon, Changbong

2015-11-01

Recent experiments showing scaling of the intrachromosomal contact probability, P (s )˜s-1 with the genomic distance s , are interpreted to mean a self-similar fractal-like chromosome organization. However, scaling of P (s ) varies across organisms, requiring an explanation. We illustrate dynamical arrest in a highly confined space as a discriminating marker for genome organization, by modeling chromosomes inside a nucleus as a homopolymer confined to a sphere of varying sizes. Brownian dynamics simulations show that the chain dynamics slows down as the polymer volume fraction (ϕ ) inside the confinement approaches a critical value ϕc. The universal value of ϕc∞≈0.44 for a sufficiently long polymer (N ≫1 ) allows us to discuss genome dynamics using ϕ as the sole parameter. Our study shows that the onset of glassy dynamics is the reason for the segregated chromosome organization in humans (N ≈3 ×109, ϕ ≳ϕc∞), whereas chromosomes of budding yeast (N ≈108, ϕ <ϕc∞) are equilibrated with no clear signature of such organization.

Gold nanoparticles embedded electropolymerized thin film of pyrimidine derivative on glassy carbon electrode for highly sensitive detection of l-cysteine.

PubMed

Kannan, Ayyadurai; Sevvel, Ranganathan

2017-09-01

This paper demonstrates the fabrication of novel gold nanoparticles incorporated poly (4-amino-6-hydroxy-2-mercaptopyrimidine) (Nano-Au/Poly-AHMP) film modified glassy carbon electrode and it is employed for highly sensitive detection of l-cysteine (CYS). The modified electrode was characterized by scanning electron microscope (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). SEM images of modified electrode revealed the homogeneous distribution of gold nanoparticles on poly (4-amino-6-hydroxy-2-mercaptopyrimidine) thin film modified glassy carbon electrode. The modified electrode was successfully utilized for highly selective and sensitive determination of l-cysteine at physiological pH7.0. The present electrochemical sensor successfully resolved the voltammetric signals of ascorbic acid (AA) and l-cysteine with peak separation of 0.510V. To the best of our knowledge, this is the first report of larger peak separation between AA and CYS. Wide linear concentration ranges (2μM-500μM), low detection limit (0.020μM), an excellent reproducibility and stability are achieved for cysteine sensing with this Nano-Au/Poly-AHMP/GCE. Copyright © 2017 Elsevier B.V. All rights reserved.

Molecular dynamics simulation of melting of 2D glassy monatomic system

NASA Astrophysics Data System (ADS)

Nhu Tranh, Duong Thi; Van Hoang, Vo; Thu Hanh, Tran Thi

2018-01-01

The melting of two-dimensional (2D) glassy monatomic systems is studied using the molecular dynamics simulation with Lennard-Jones-Gauss interaction potential. The temperature dependence of various structural and dynamical properties of the systems during heating is analyzed and discussed via the radial distribution functions, the coordination number distributions, the ring statistics, the mobility of atoms and their clustering. Atomic mechanism of melting is also analyzed via tendency to increase mobility and breaking clusters of atoms upon heating. We found that melting of a 2D glass does not follow any theory of the melting of 2D crystals proposed in the past. The melting exhibits a homogeneous nature, i.e. liquid-like atoms occur homogeneously throughout the system and melting proceeds further leading to the formation of an entire liquid phase. In addition, we found a defined transition temperature region in which structural and dynamical properties of systems strongly change with increasing temperature.

An Easily Fabricated Electrochemical Sensor Based on a Graphene-Modified Glassy Carbon Electrode for Determination of Octopamine and Tyramine

PubMed Central

Zhang, Yang; Zhang, Meiqin; Wei, Qianhui; Gao, Yongjie; Guo, Lijuan; Al-Ghanim, Khalid A.; Mahboob, Shahid; Zhang, Xueji

2016-01-01

A simple electrochemical sensor has been developed for highly sensitive detection of octopamine and tyramine by electrodepositing reduced graphene oxide (ERGO) nanosheets onto the surface of a glassy carbon electrode (GCE). The electrocatalytic oxidation of octopamine and tyramine is individually investigated at the surface of the ERGO modified glassy carbon electrode (ERGO/GCE) by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Several essential factors including the deposition cycle of reduced graphene oxide nanosheets and the pH of the running buffer were investigated in order to determine the optimum conditions. Furthermore, the sensor was applied to the quantification of octopamine and tyramine by DPV in the concentration ranges from 0.5 to 40 μM and 0.1 to 25 μM, respectively. In addition, the limits of detection of octopamine and tyramine were calculated to be 0.1 μM and 0.03 μM (S/N = 3), respectively. The sensor showed good reproducibility, selectivity and stability. Finally, the sensor successfully detected octopamine and tyramine in commercially available beer with satisfactory recovery ranges which were 98.5%–104.7% and 102.2%–103.1%, respectively. These results indicate the ERGO/GCE based sensor is suitable for the detection of octopamine and tyramine. PMID:27089341

Water Oxidation Catalysis by Co(II) Impurities in Co(III) 4O 4 Cubanes

DOE PAGES

Ullman, Andrew M.; Liu, Yi; Huynh, Michael; ...

2014-11-18

Here, the observed water oxidation activity of the compound class Co 4O 4(OAc) 4(Py–X) 4 emanates from a Co(II) impurity. This impurity is oxidized to produce the well-known Co-OEC heterogeneous cobaltate catalyst, which is an active water oxidation catalyst. We present results from electron paramagnetic resonance spectroscopy, nuclear magnetic resonance line broadening analysis, and electrochemical titrations to establish the existence of the Co(II) impurity as the major source of water oxidation activity that has been reported for Co 4O 4 molecular cubanes. Differential electrochemical mass spectrometry is used to characterize the fate of glassy carbon at water oxidizing potentials andmore » demonstrate that such electrode materials should be used with caution for the study of water oxidation catalysis.« less

Glassy-winged sharpshooter feeding does not cause air embolisms in xylem of well-watered plants.

USDA-ARS?s Scientific Manuscript database

Plant xylem vessels are under negative hydrostatic pressure (tension) as evapotranspiration of water from the leaf surface pulls the column of water in xylem upwards. When xylem fluid flux is under extreme tension, any puncture or breakage of the xylem vessel wall can cause formation of air embolis...

Glassy dynamics of polymethylphenylsiloxane in one- and two-dimensional nanometric confinement—A comparison

NASA Astrophysics Data System (ADS)

Kipnusu, Wycliffe K.; Elsayed, Mohamed; Krause-Rehberg, Reinhard; Kremer, Friedrich

2017-05-01

Glassy dynamics of polymethylphenylsiloxane (PMPS) is studied by broadband dielectric spectroscopy in one-dimensional (1D) and two-dimensional (2D) nanometric confinement; the former is realized in thin polymer layers having thicknesses down to 5 nm, and the latter in unidirectional (thickness 50 μm) nanopores with diameters varying between 4 and 8 nm. Based on the dielectric measurements carried out in a broad spectral range at widely varying temperatures, glassy dynamics is analyzed in detail in 1D and in 2D confinements with the following results: (i) the segmental dynamics (dynamic glass transition) of PMPS in 1D confinement down to thicknesses of 5 nm is identical to the bulk in the mean relaxation rate and the width of the relaxation time distribution function; (ii) additionally a well separated surface induced relaxation is observed, being assigned to adsorption and desorption processes of polymer segments with the solid interface; (iii) in 2D confinement with native inner pore walls, the segmental dynamics shows a confinement effect, i.e., the smaller the pores are, the faster the segmental dynamics; on silanization, this dependence on the pore diameter vanishes, but the mean relaxation rate is still faster than in 1D confinement; (iv) in a 2D confinement, a pronounced surface induced relaxation process is found, the strength of which increases with the decreasing pore diameter; it can be fully removed by silanization of the inner pore walls; (v) the surface induced relaxation depends on its spectral position only negligibly on the pore diameter; (vi) comparing 1D and 2D confinements, the segmental dynamics in the latter is by about two orders of magnitude faster. All these findings can be comprehended by considering the density of the polymer; in 1D it is assumed to be the same as in the bulk, hence the dynamic glass transition is not altered; in 2D it is reduced due to a frustration of packaging resulting in a higher free volume, as proven by ortho

Electric resistivity and thermoelectricity of Ni-Nb-Zr and Ni-Nb-Zr-H glassy alloys

NASA Astrophysics Data System (ADS)

Fukuhara, Mikio; Inoue, Akihisa

2010-09-01

Electric resistivity ρ and thermoelectric power S of Ni 36Nb 24Zr 40 and (Ni 0.36Nb 0.24Zr 0.4) 90H 10 glassy alloys were investigated in temperature region between 1.5 and 300 K. After resistivity curves of both alloys increase gradually with decreasing temperature down to around 6 K, they dropped suddenly and then reached zero resistivity at 2.1 K, leading to superconductivity. Linear curve with negative TCR of ρ vs T2 and slight increase of S/ T in temperature region down to around 6 K clearly reveal Fermi-liquid phenomenon in electronic state for both alloys independent of hydrogen content.

Persistent optical hole-burning spectroscopy of nano-confined dye molecules in liquid at room temperature: Spectral narrowing due to a glassy state and extraordinary relaxation in a nano-cage

NASA Astrophysics Data System (ADS)

Murakami, Hiroshi

2018-04-01

Persistent optical hole-burning spectroscopy has been conducted for a dye molecule within a very small (˜1 nm) reverse micelle at room temperature. The spectra show a spectral narrowing due to site-selective excitation. This definitely demonstrates that the surroundings of the dye molecule are in a glassy state regardless of a solution at room temperature. On the other hand, the hole-burning spectra exhibit large shifts from excitation frequencies, and their positions are almost independent of excitation frequencies. The hole-burning spectra have been theoretically calculated by taking account of a vibronic absorption band of the dye molecule under the assumption that the surroundings of the dye molecule are in a glassy state. The calculated results agree with the experimental ones that were obtained for the dye molecule in a polymer glass for comparison, where it has been found that the ratio of hole-burning efficiencies of vibronic- to electronic-band excitations is quite high. On the other hand, the theoretical results do not explain the large spectral shift from the excitation frequency and small spectral narrowing observed in the hole-burning spectra measured for the dye-containing reverse micelle. It is thought that the spectral shift and broadening occur within the measurement time owing to the relaxation process of the surroundings that are hot with the thermal energy deposited by the dye molecule optically excited. Furthermore, the relaxation should be temporary because the cooling of the inside of the reverse micelle takes place with the dissipation of the excess thermal energy to the outer oil solvent, and so the surroundings of the dye molecule return to the glassy state and do not attain the thermal equilibrium. These results suggest that a very small reverse micelle provides a unique reaction field in which the diffusional motion can be controlled by light in a glassy state.

Analysis of water sorption isotherms of amorphous food materials by solution thermodynamics with relevance to glass transition: evaluation of plasticizing effect of water by the thermodynamic parameters.

PubMed

Shimazaki, Eriko; Tashiro, Akiko; Kumagai, Hitomi; Kumagai, Hitoshi

2017-04-01

Relation between the thermodynamic parameters obtained from water sorption isotherms and the degree of reduction in the glass transition temperature (T g ), accompanied by water sorption, was quantitatively studied. Two well-known glassy food materials namely, wheat gluten and maltodextrin were used as samples. The difference between the chemical potential of water in a solution and that of pure water ([Formula: see text]), the difference between the chemical potential of solid in a solution and that of a pure solid ([Formula: see text]), and the change in the integral Gibbs free energy ([Formula: see text]) were obtained by analyzing the water sorption isotherms using solution thermodynamics. The parameter [Formula: see text] correlated well with ΔT g (≡T g  - T g0 ; where T g0 is the glass transition temperature of dry material), which had been taken to be an index of plasticizing effect. This indicates that plasticizing effect of water on foods can be evaluated through the parameter [Formula: see text].

Glucose biosensing using glassy carbon electrode modified with polyhydroxy-C60, glucose oxidase and ionic-liquid.

PubMed

Yang, Tian; Yang, Xiao-Lu; Zhang, Yu-Shuai; Xiao, BaoLin; Hong, Jun

2014-01-01

Direct electrochemistry of glucose oxidase (GOD) was achieved when an ionic liquid/GOD-Polyhydroxy-C60 functional membrane was confined on a glassy carbon electrode (GCE). The cyclic voltammograms (CVs) of the modified GCE showed a pair of redox peaks with a formal potential (E°') of - 329 ± 2 mV. The heterogeneous electron transfer constant (k(s)) was 1.43 s-1. The modified GCE response to glucose was linear in the range from 0.02 to 2.0 mM. The detection limit was 1 μM. The apparent Michaelis-Menten constant (K(m)(app)) was 1.45 mM.

Water dynamics in hardened ordinary Portland cement paste or concrete: from quasielastic neutron scattering.

PubMed

Bordallo, Heloisa N; Aldridge, Laurence P; Desmedt, Arnaud

2006-09-14

Portland cement reacts with water to form an amorphous paste through a chemical reaction called hydration. In concrete the formation of pastes causes the mix to harden and gain strength to form a rock-like mass. Within this process lies the key to a remarkable peculiarity of concrete: it is plastic and soft when newly mixed, strong and durable when hardened. These qualities explain why one material, concrete, can build skyscrapers, bridges, sidewalks and superhighways, houses, and dams. The character of the concrete is determined by the quality of the paste. Creep and shrinkage of concrete specimens occur during the loss and gain of water from cement paste. To better understand the role of water in mature concrete, a series of quasielastic neutron scattering (QENS) experiments were carried out on cement pastes with water/cement ratio varying between 0.32 and 0.6. The samples were cured for about 28 days in sealed containers so that the initial water content would not change. These experiments were carried out with an actual sample of Portland cement rather than with the components of cement studied by other workers. The QENS spectra differentiated between three different water interactions: water that was chemically bound into the cement paste, the physically bound or "glassy water" that interacted with the surface of the gel pores in the paste, and unbound water molecules that are confined within the larger capillary pores of cement paste. The dynamics of the "glassy" and "unboud" water in an extended time scale, from a hundred picoseconds to a few nanoseconds, could be clearly differentiated from the data. While the observed motions on the picosecond time scale are mainly stochastic reorientations of the water molecules, the dynamics observed on the nanosecond range can be attributed to long-range diffusion. Diffusive motion was characterized by diffusion constants in the range of (0.6-2) 10(-9) m(2)/s, with significant reduction compared to the rate of diffusion

Molecular motions in glassy crystal cyanoadamantane : a proton spin-lattice relaxation study

NASA Astrophysics Data System (ADS)

Amoureux, J. P.; Decressain, R.; Sahour, M.; Cochon, E.

1992-02-01

Cyanoadamantane C{10}H{15}CN exhibits four different solid phases : two cubic plastic (I and I'), one cubic glassy (Ig) and one monoclinic ordered (II). In cubic plastic phases (I, I') three types of motion coexist : a uniaxial rotation of the molecule around its C—CequivN axis, a tumbling reorientation of this dipolar axis between the <~ngle 001rangle directions and a vacancy self-diffusion. In the cubic glassy state (Ig) the tumbling motion is frozen and therefore only the uniaxial rotation survives. In the ordered phase (II), the molecules only perform a 3-fold uniaxial rotation among identical positions. These different molecular motions in the four solid phases have been studied by the analysis of the T_{1 z} and T_{1 ρ} spin-lattice relaxation times in ^1H-NMR. The derived residence time are compared, when possible, to values previously deduced from quasi-elastic neutron scattering, dielectric relaxation and second moment of the ^1H-NMR lineshape. Le cyanoadamantane C{10}H{15}CN possède quatre phases solides différentes : deux plastiques cubiques (I et I'), une vitreuse cubique (Ig) et une ordonnée monoclinique (II). Dans les phases plastiques cubiques (I, I') trois types de mouvements coexistent : une rotation uniaxiale de la molécule autour de son axe C—CequivN, un basculement de cet axe dipolaire entre les directions <~ngle 001rangle et une diffusion moléculaire. Dans l'état vitreux cubique (Ig), le mouvement de basculement est gelé et seule la rotation uniaxiale subsiste. Enfin dans la phase ordonnée (II), les molécules effectuent une rotation uniaxiale d'ordre 3 entre positions indiscernables. Ces différents mouvements dans les quatre phases solides ont été évalués par l'analyse des temps de relaxation spin-réseau T_{1 z} et T_{1 ρ} en ^1H-RMN. Les temps de résidence qui en sont déduits sont comparés (lorsque cela est possible) aux valeurs correspondantes déduites précédemment par diffusion quasi-élastique des neutrons, par

Pressure Dependence of the Boson Peak of Glassy Glycerol

DOE PAGES

Ahart, Muhtar; Aihaiti, Dilare; Hemley, Russell J.; ...

2017-05-31

The pressure dependence of the Boson peak (BP) of glycerol, including its behavior across the liquid-glass transition, has been studied under pressure using Raman scattering. A significant increase of the BP frequency was observed with pressure up to 11 GPa at room temperature. The pressure dependence of BP frequency ν BP is proportional to (1+P/P 0) 1/3, where P and P 0 are the pressure and a constant, respectively, the spectra are consistent with a soft potential model. The characteristic length of medium range order is close in size to a cyclic trimer of glycerol molecules, which is predicted asmore » the medium range order of a BP vibration using molecular dynamics simulations. The pressure dependence of a characteristic length of medium range order is nearly constant. The pressure induced structural changes in glycerol can be understood in terms of the shrinkage of voids with cyclic trimers remaining up to at least 11 GPa. Lastly, the pressure dependence of intermolecular O-H stretching mode indicates that the intermolecular hydrogen bond distance gradually decreases below the glass transition pressure of ~5 GPa, while it becomes nearly constant in the glassy state indicating the disappearance of the free volume in the dense glass.« less

Electrochemical and spectroelectrochemical behavior of the TCNQ(0/)(-) couple on a glassy carbon electrode. Layer-by-layer nucleation and growth.

PubMed

Gómez, L; Rodríguez-Amaro, R

2006-08-15

On the basis of the electrochemical results obtained for thin films of 7,7,8,8- tetracyanoquinodimethane (TCNQ) on a glassy carbon electrode, the reduction and oxidation of the [TCNQ](0/)(-) couple in KCl aqueous media occurs via a mechanism involving layer-by-layer nucleation and growth. In situ recorded UV-visible spectroelectrochemical data allow two different crystal structures for the oxidized form of TCNQ to be discriminated.

Water in silicate melts

NASA Astrophysics Data System (ADS)

McMillan, Paul; Stolper, Edward

Water is one of the more important volatile species in magmas, both in terms of its abundance and its influence on the properties of a given magma. Many workers in the geological sciences have measured, modeled, and speculated on the interaction of water with silicate melts as a function of pressure. At the same time, glass and materials scientists have collected a considerable body of data on the effect of water on the properties of liquid and glassy silicates at 1 atmosphere (1.01325×105 N m-2) and below. A special session on “Solubility and Transport Properties of Water in Silicate Melts” was held during the 1983 AGU Spring Meeting, May 30-June 3, in Baltimore. The session had three main objectives: (1) review the present data base and discuss the status of current models in order to identify areas where further work is needed; (2) introduce interested geologists to the large body of work being carried out in the glass and materials sciences; and (3) consider static properties, such as thermodynamic relations, structure of hydrous melts, and dynamic properties including diffusion and viscosity. This report summarizes the major topics discussed. More detailed information may be found in the published abstracts (Eos, May 3, 1983, pp. 338-343).

Humidity-dependent compression-induced glass transition of the air-water interfacial Langmuir films of poly(D,L-lactic acid-ran-glycolic acid) (PLGA).

PubMed

Kim, Hyun Chang; Lee, Hoyoung; Jung, Hyunjung; Choi, Yun Hwa; Meron, Mati; Lin, Binhua; Bang, Joona; Won, You-Yeon

2015-07-28

Constant rate compression isotherms of the air-water interfacial Langmuir films of poly(D,L-lactic acid-ran-glycolic acid) (PLGA) show a distinct feature of an exponential increase in surface pressure in the high surface polymer concentration regime. We have previously demonstrated that this abrupt increase in surface pressure is linked to the glass transition of the polymer film, but the detailed mechanism of this process is not fully understood. In order to obtain a molecular-level understanding of this behavior, we performed extensive characterizations of the surface mechanical, structural and rheological properties of Langmuir PLGA films at the air-water interface, using combined experimental techniques including the Langmuir film balance, X-ray reflectivity and double-wall-ring interfacial rheometry methods. We observed that the mechanical and structural responses of the Langmuir PLGA films are significantly dependent on the rate of film compression; the glass transition was induced in the PLGA film only at fast compression rates. Surprisingly, we found that this deformation rate dependence is also dependent on the humidity of the environment. With water acting as a plasticizer for the PLGA material, the diffusion of water molecules through the PLGA film seems to be the key factor in the determination of the glass transformation properties and thus the mechanical response of the PLGA film against lateral compression. Based on our combined results, we hypothesize the following mechanism for the compression-induced glass transformation of the Langmuir PLGA film; (1) initially, a humidified/non-glassy PLGA film is formed in the full surface-coverage region (where the surface pressure shows a plateau) during compression; (2) further compression leads to the collapse of the PLGA chains and the formation of new surfaces on the air side of the film, and this newly formed top layer of the PLGA film is transiently glassy in character because the water evaporation rate

Anodic stripping voltammetric determination of mercury using multi-walled carbon nanotubes film coated glassy carbon electrode.

PubMed

Yi, Hongchao

2003-10-01

An electrochemical method for the determination of trace levels of mercury based on a multi-walled carbon nanotubes (MWNT) film coated glassy carbon electrode (GCE) is described. In 0.1 mol L(-1) HCl solution containing 0.02 mol L(-1) KI, Hg(2+) was firstly preconcentrated at the MWNT film and then reduced at -0.60 V. During the anodic potential sweep, reduced mercury was oxidized, and then a sensitive and well-defined stripping peak at about -0.20 V appeared. Under identical conditions, a MWNT film coated GCE greatly enhances the stripping peak current of mercury in contrast to a bare GCE. Low concentrations of I(-) remarkably improve the determining sensitivity, since this increases the accumulation efficiency of Hg(2+) at the MWNT film coated GCE. The stripping peak current is proportional to the concentration of Hg(2+) over the range 8 x 10(-10)-5 x 10(-7) mol L(-1). The lowest detectable concentration of Hg(2+) is 2 x 10(-10) mol L(-1) at 5 min accumulation. The relative standard deviation (RSD) at 1 x 10(-8) mol L(-1) Hg(2+) was about 6% ( n=10). By using this proposed method, Hg(2+) in some water samples was determined, and the results were compared with those obtained by atomic absorption spectrometry (AAS). The two results are similar, suggesting that the MWNT-film coated GCE has great potential in practical analysis.

Glassy phases and driven response of the phase-field-crystal model with random pinning.

PubMed

Granato, E; Ramos, J A P; Achim, C V; Lehikoinen, J; Ying, S C; Ala-Nissila, T; Elder, K R

2011-09-01

We study the structural correlations and the nonlinear response to a driving force of a two-dimensional phase-field-crystal model with random pinning. The model provides an effective continuous description of lattice systems in the presence of disordered external pinning centers, allowing for both elastic and plastic deformations. We find that the phase-field crystal with disorder assumes an amorphous glassy ground state, with only short-ranged positional and orientational correlations, even in the limit of weak disorder. Under increasing driving force, the pinned amorphous-glass phase evolves into a moving plastic-flow phase and then, finally, a moving smectic phase. The transverse response of the moving smectic phase shows a vanishing transverse critical force for increasing system sizes.

Modification of glassy carbon electrode with poly(hydroxynaphthol blue)/multi-walled carbon nanotubes composite and construction a new voltammetric sensor for the simultaneous determination of hydroquinone, catechol, and resorcinol

NASA Astrophysics Data System (ADS)

Daneshinejad, Hassan; Arab Chamjangali, Mansour; Goudarzi, Nasser; Hossain Amin, Amir

2018-03-01

A novel voltammetric sensor is developed based on a poly(hydroxynaphthol blue)/multi-walled carbon nanotubes-modified glassy carbon electrode for the simultaneous determination of the dihydroxybenzene isomers hydroquinone (HQ), catechol (CC), and resorcinol (RS). The preparation and basic electrochemical performance of the sensor are investigated in details. The electrochemical behavior of the dihydroxybenzene isomers at the sensor is studied by the cyclic and differential pulse voltammetric techniques. The results obtained show that this new electrochemical sensor exhibits an excellent electro-catalytic activity towards oxidation of the three isomers. The mechanism of this electro-catalytic activity is discussed. Using the optimum parameters, limit of detection obtained 0.24, 0.24, and 0.26 μmol L-1 for HQ, CC, and RS, respectively. The modified electrode is also successfully applied to the simultaneous determination of dihydroxybenzene in water samples.

Experimental characterization and modeling of isothermal and nonisothermal physical aging in glassy polymer films

NASA Astrophysics Data System (ADS)

Guo, Yunlong

This dissertation focuses on nonisothermal physical aging of polymers from both experimental and theoretical aspects. The study concentrates on pure polymers rather than fiber-reinforced composites; this step removes several complicating factors to simplify the study. It is anticipated that the findings of this work can then be applied to composite materials applications. The physical aging tests in this work are performed using a dynamic mechanical analyzer (DMA). The viscoelastic response of glassy polymers under various loading and thermal histories are observed as stress-strain data at a series of time points. The first stage of the experimental work involves the characterization of the isothermal physical aging behavior of two advanced thermoplastics. The second stage conducts tests on the same materials with varying thermal histories and with long-term test duration. This forms the basis to assess and modify a nonisothermal physical aging model (KAHR-ate model). Based on the experimental findings, the KAHR-ate model has been revised by new correlations between aging shift factors and volume response; this revised model performed well in predicting the nonisothermal physical aging behavior of glassy polymers. In the work on isothermal physical aging, short-term creep and stress relaxation tests were performed at several temperatures within 15-35°C below the glass transition temperature (Tg) at various aging times, using the short-term test method established by Struik. Stress and strain levels were such that the materials remained in the linear viscoelastic regime. These curves were then shifted together to determine momentary master curves and shift rates. In order to validate the obtained isothermal physical aging behavior, the results of creep and stress relaxation testing were compared and shown to be consistent with one another using appropriate interconversion of the viscoelastic material functions. Time-temperature superposition of the master curves

Electrocatalytic oxidation of hydrazine and hydroxylamine by graphene oxide-Pd nanoparticle-modified glassy carbon electrode.

PubMed

Lee, Eunhee; Kim, Daekun; You, Jung-Min; Kim, Seul Ki; Yun, Mira; Jeon, Seungwon

2012-12-01

Pd nanoparticle catalysts supported by thiolated graphene oxide (tGO) on a glassy carbon electrode (GCE), and denoted as tGO-Pd/GCE, are used in this study for the electrochemical determination of hydroxylamine and hydrazine. The physicochemical properties of tGO-Pd were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). They showed strong catalytic activity toward the oxidation of hydroxylamine and hydrazine. Cyclic voltammetry (CV) and amperometry were used to characterize the sensors' performances. The detection limits of hydroxylamine and hydrazine by tGO-Pd/GCE were 0.31 and 0.25 microM (s/n = 3), respectively. The sensors' sensitivity, selectivity, and stability were also investigated.

Amperometric sensing of hydrogen peroxide using glassy carbon electrode modified with copper nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sophia, J.; Muralidharan, G., E-mail: muraligru@gmail.com

2015-10-15

In this paper, fabrication of glassy carbon electrode (GCE) modified with nano copper particles is discussed. The modified electrode has been tested for the non-enzymatic electrochemical detection of hydrogen peroxide (H{sub 2}O{sub 2}). The copper nanoparticles (Cu NPs) were prepared employing a simple chemical reduction method. The presence of Cu NPs was confirmed through UV–visible (UV–vis) absorption spectroscopy and X-ray diffraction (XRD) analysis. The size and morphology of the particles were investigated using transmission electron microscopy (TEM). The electrochemical properties of the fabricated sensor were studied via cyclic voltammetry (CV), chronoamperometry and electrochemical impedance spectroscopy (EIS). The electrochemical sensor displayedmore » excellent performance features towards H{sub 2}O{sub 2} detection exhibiting wide linear range, low detection limit, swift response time, good reproducibility and stability.« less

Polymer modified glassy carbon electrode for the electrochemical determination of caffeine in coffee.

PubMed

Amare, Meareg; Admassie, Shimelis

2012-05-15

4-Amino-3-hydroxynaphthalene sulfonic acid (AHNSA) was electropolymerized on a glassy carbon electrode. The deposited film showed electrocatalytic activity towards the oxidation of caffeine. The polymer-modified electrode showed high sensitivity, selectivity and stability in the determination of caffeine in coffee. The peak current increased linearly with the concentration of caffeine in the range of 6 × 10(-8) to 4 × 10(-5) mol L(-1), with a detection limit of 1.37 × 10(-7) mol L(-1) (LoD = 3δ/slope). Analysis of caffeine in coffee was affected neither by sample matrices nor by structurally similar compounds. Recoveries ranging between 93.75 ± 2.32 and 100.75 ± 3.32 were achieved from coffee extracts indicating the applicability of the developed method for real sample analyses. Copyright © 2012 Elsevier B.V. All rights reserved.

Reduced electronegativity difference as a factor leading to the formation of Al-based glassy alloys with a large supercooled liquid region of 50 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Louzguine-Luzgin, Dmitri V.; Inoue, Akihisa; Botta, Walter Jose

2006-01-02

The influence of the electronegativity difference among the constituent elements on the stability of the supercooled liquid in two Al-based glassy alloys is studied. A record-large value of the supercooled liquid region of about 50 K is obtained based on the electronegativity difference concept within a certain composition range.

Spinodals with Disorder: From Avalanches in Random Magnets to Glassy Dynamics

NASA Astrophysics Data System (ADS)

Nandi, Saroj Kumar; Biroli, Giulio; Tarjus, Gilles

2016-04-01

We revisit the phenomenon of spinodals in the presence of quenched disorder and develop a complete theory for it. We focus on the spinodal of an Ising model in a quenched random field (RFIM), which has applications in many areas from materials to social science. By working at zero temperature in the quasistatically driven RFIM, thermal fluctuations are eliminated and one can give a rigorous content to the notion of spinodal. We show that the latter is due to the depinning and the subsequent expansion of rare droplets. We work out the associated critical behavior, which, in any finite dimension, is very different from the mean-field one: the characteristic length diverges exponentially and the thermodynamic quantities display very mild nonanalyticities much like in a Griffith phenomenon. From the recently established connection between the spinodal of the RFIM and glassy dynamics, our results also allow us to conclusively assess the physical content and the status of the dynamical transition predicted by the mean-field theory of glass-forming liquids.

MIP-graphene-modified glassy carbon electrode for the determination of trimethoprim.

PubMed

da Silva, Hélder; Pacheco, João G; Magalhães, Júlia M C S; Viswanathan, Subramanian; Delerue-Matos, Cristina

2014-02-15

A novel sensitive electrochemical sensor was developed by electropolymerization of pyrrole (PY) and molecularly imprinted polymer (MIP) which was synthesized onto a glassy carbon electrode (GCE) in aqueous solution using cyclic voltammetry in the presence of Trimethoprim (TMP) as template molecules. Furthermore, a previous electrode modification was performed by deposition of a suspension of graphene on the electrode's surface. The performance of the imprinted and non-imprinted (NIP) films was evaluated by impedance spectroscopy (EIS) and cyclic voltammetry (CV) of a ferric solution. The molecularly imprinted film exhibited a high selectivity and sensitivity toward TMP. The sensor presented a linear range, between peak current intensity and logarithm of TMP concentration between 1.0 × 10(-6) and 1.0 × 10(-4)M. The results were accurate (with recoveries higher than 94%), precise (with standard deviations less than 5%) and the detection limit was 1.3 × 10(-7)M. The new sensor is selective, simple to construct and easy to operate. The MIP sensor was successfully applied to quantify TMP in urine samples. © 2013 Elsevier B.V. All rights reserved.

Effects of kaolin particle film and imidacloprid on glassy-winged sharpshooter (Homalodisca vitripennis) (Hemiptera: Cicadellidae)populations and the prevention of spread of Xylella fastidiosa in grape

USDA-ARS?s Scientific Manuscript database

The glassy-winged sharpshooter (GWSS), Homalodisca coagulata (Say), was introduced into California and soon became a major pest of important agronomic, horticultural, landscape, ornamental crops and native trees in California. This pest feeds readily on grape and, in doing so, transmits X. fastidio...

A glassy carbon electrode modified with cerium phosphate nanotubes for the simultaneous determination of hydroquinone, catechol and resorcinol.

PubMed

Li, Zhen; Yue, Yuhua; Hao, Yanjun; Feng, Shun; Zhou, Xianli

2018-03-12

A nafion film containing cerium phosphate nanotubes was pasted onto a glassy carbon electrode (GCE) to obtain a sensor for hydroquinone (HQ). The morphologies and components of the coating were characterized by transmission electron microscopy, scanning electron microscopy and energy-dispersive spectroscopy. Cyclic voltammetry and differential pulse voltammetry (DPV) showed the specific surface of the electrode to be significantly increased and the electron transfer rate to be accelerated. The modified GCE was applied to the determination of hydroquinone (HQ) via DPV. The oxidation current increases linearly in the 0.23 μM to 16 mM HQ concentration range which is as wide as five orders of magnitude. The limit of detection is 0.12 μM (based on a signal-to-noise ratio of 3), and the sensitivity is 1.41 μA·μM -1  cm -2 . The method was further applied to the simultaneous determination of HQ, catechol and resorcinol. The potentials for the three species are well separated (20, 134, and 572 mV vs SCE). Average recoveries from (spiked) real water samples are between 95.2 and 107.0%, with relative standard deviations of 0.9~2.7% (for n = 3) at three spiking levels. The method was validated by independent assays using HPLC. Graphical abstract ᅟ.

The Quench Control of Water Estimates in Convergent Margin Magmas

NASA Astrophysics Data System (ADS)

Gavrilenko, M.; Krawczynski, M.; Ruprecht, P.

2017-12-01

Mineral-hosted glassy melt inclusions (MIs) have been used to quantify magma volatile contents for several decades. Despite the growing number of volatile studies utilizing MIs, it has not been tested whether there is a physical limit on how much dissolved volatiles a glassy MI can contain. We explored the limits of MIs as hydrous magma recorders in an experimental study, showing that there is a limit of dissolved H2O that glassy MIs cannot exceed. These results show there is potential bias in the glassy MI data set; they can only faithfully record pre-eruptive H2O contents in the upper-most part of the Earth's crust where H2O-solubility is low. The current MI database cannot be used to robustly estimate the full range of arc magmas and therefore assess volatile budgets in primitive or evolved compositions. Such magmas may contain much larger amounts of H2O than currently recognized and the diversity of magma evolutionary pathways in subduction zones is likely being significantly underappreciated.

Effect of chain rigidity on network architecture and deformation behavior of glassy polymer networks

NASA Astrophysics Data System (ADS)

Knowles, Kyler Reser

Processing carbon fiber composite laminates creates molecular-level strains in the thermoset matrix upon curing and cooling which can lead to failures such as geometry deformations, micro-cracking, and other issues. It is known strain creation is attributed to the significant volume and physical state changes undergone by the polymer matrix throughout the curing process, though storage and relaxation of cure-induced strains remain poorly understood. This dissertation establishes two approaches to address the issue. The first establishes testing methods to simultaneously measure key volumetric properties of a carbon fiber composite laminate and its polymer matrix. The second approach considers the rigidity of the polymer matrix in regards to strain storage and relaxation mechanisms which ultimately control composite performance throughout manufacturing and use. Through the use of a non-contact, full-field strain measurement technique known as digital image correlation (DIC), we describe and implement useful experiments which quantify matrix and composite parameters necessary for simulation efforts and failure models. The methods are compared to more traditional techniques and show excellent correlation. Further, we established relationships which represent matrix-fiber compatibility in regards to critical processing constraints. The second approach involves a systematic study of epoxy-amine networks which are chemically-similar but differ in chain segment rigidity. Prior research has investigated the isomer effect of glassy polymers, showing sizeable differences in thermal, volumetric, physical, and mechanical properties. This work builds on these themes and shows the apparent isomer effect is rather an effect of chain rigidity. Indeed, it was found that structurally-dissimilar polymer networks exhibit very similar properties as a consequence of their shared average network rigidity. Differences in chain packing, as a consequence of chain rigidity, were shown to

Corrosion fatigue studies on a bulk glassy Zr-based alloy under three-point bending

NASA Astrophysics Data System (ADS)

Grell, Daniel; Wilkin, Yannic; Gostin, Petre F.; Gebert, Annett; Kerscher, Eberhard

2016-12-01

Corrosion fatigue (CF) tests were carried out on bulk glassy Zr52.5Cu17.9Al10Ni14.6Ti5 (Vitreloy 105) samples under load-controlled three-point bending conditions with a load ratio of R = 0.1 in 0.01 M Na2SO4 + 0.01 M NaCl electrolyte. During cyclic testing, the bar-shaped specimens were polarized in situ at constant potentials and the current was monitored. Three different anodic potentials within the interval between the pitting potential EP and the repassivation potential ER, and three different load amplitudes were applied. In some cases, in situ microscopic observations revealed the formation of black corrosion products in the vicinity of the crack tip during anodic polarization. Fractographic analysis revealed a clear distinction between two modes of crack growth characterized by smooth dissolution induced regions on the one hand and slim fast fracture areas on the other hand. Both alternating features contributed to a broad striated corrosion fatigue fracture surface. Moreover, further fatigue tests were carried out under free corrosion conditions yielding additional information on crack initiation and crack propagation period by means of the open circuit potential (OCP) changes. Thereby, a slight increase in OCP was detected after rupture of the passive layer due to bare metal exposed to the electrolyte. The electrochemical response increased continuously according to stable crack propagation until fracture occurred. Finally, the fracture surfaces of the corrosion fatigue samples were investigated by energy dispersive X-ray with the objective of analyzing the elemental distribution after anodic dissolution. Interestingly, anodic polarization at a near repassivation potential of -50 mV vs. SCE (Saturated Calomel Electrode, E = 0.241 V vs. SHE, Standard Hydrogen Electrode) led to favorable effects on the fatigue lifetime. In conclusion, all results are conflated to a corrosion fatigue model for bulk glassy Vitreloy 105 under anodic polarization in chloride

Ab initio tensile experiment on a model of an intergranular glassy film in β-Si3N4 with prismatic surfaces

NASA Astrophysics Data System (ADS)

Ching, W. Y.; Rulis, Paul; Ouyang, Lizhi; Misra, A.

2009-02-01

We report the results of a large-scale ab initio simulation of an intergranular glassy film (IGF) model in β-Si3N4. It is shown that the stress-strain behavior under uniaxial load in the model with prismatic surfaces and few defective bonds is very different from an earlier IGF model with basal planes. The results are explained by the fundamental electronic structure of the model.

Glass polymorphism in glycerol-water mixtures: I. A computer simulation study.

PubMed

Jahn, David A; Wong, Jessina; Bachler, Johannes; Loerting, Thomas; Giovambattista, Nicolas

2016-04-28

We perform out-of-equilibrium molecular dynamics (MD) simulations of water-glycerol mixtures in the glass state. Specifically, we study the transformations between low-density (LDA) and high-density amorphous (HDA) forms of these mixtures induced by compression/decompression at constant temperature. Our MD simulations reproduce qualitatively the density changes observed in experiments. Specifically, the LDA-HDA transformation becomes (i) smoother and (ii) the hysteresis in a compression/decompression cycle decreases as T and/or glycerol content increase. This is surprising given the fast compression/decompression rates (relative to experiments) accessible in MD simulations. We study mixtures with glycerol molar concentration χ(g) = 0-13% and find that, for the present mixture models and rates, the LDA-HDA transformation is detectable up to χ(g) ≈ 5%. As the concentration increases, the density of the starting glass (i.e., LDA at approximately χ(g) ≤ 5%) rapidly increases while, instead, the density of HDA remains practically constant. Accordingly, the LDA state and hence glass polymorphism become inaccessible for glassy mixtures with approximately χ(g) > 5%. We present an analysis of the molecular-level changes underlying the LDA-HDA transformation. As observed in pure glassy water, during the LDA-to-HDA transformation, water molecules within the mixture approach each other, moving from the second to the first hydration shell and filling the first interstitial shell of water molecules. Interestingly, similar changes also occur around glycerol OH groups. It follows that glycerol OH groups contribute to the density increase during the LDA-HDA transformation. An analysis of the hydrogen bond (HB)-network of the mixtures shows that the LDA-HDA transformation is accompanied by minor changes in the number of HBs of water and glycerol. Instead, large changes in glycerol and water coordination numbers occur. We also perform a detailed analysis of the effects that

Multiscale simulations of PS-SiO2 nanocomposites: from melt to glassy state.

PubMed

Mathioudakis, I G; Vogiatzis, G G; Tzoumanekas, C; Theodorou, D N

2016-09-28

The interaction energetics, molecular packing, entanglement network properties, segmental dynamics, and elastic constants of atactic polystyrene-amorphous silica nanocomposites in the molten and the glassy state are studied via molecular simulations using two interconnected levels of representation: (a) a coarse-grained one, wherein each polystyrene repeat unit is mapped onto a single "superatom" and the silica nanoparticle is viewed as a solid sphere. Equilibration at all length scales at this level is achieved via connectivity-altering Monte Carlo simulations. (b) A united-atom (UA) level, wherein the polymer chains are represented in terms of a united-atom forcefield and the silica nanoparticle is represented in terms of a simplified, fully atomistic model. Initial configurations for UA molecular dynamics (MD) simulations are obtained by reverse mapping well-equilibrated coarse-grained configurations. By analysing microcanonical UA MD trajectories, the polymer density profile is studied and the polymer is found to exhibit layering in the vicinity of the nanoparticle surface. An estimate of the enthalpy of mixing between polymer and nanoparticles, derived from the UA simulations, compares favourably against available experimental values. The dynamical behaviour of polystyrene (in neat and filled melt systems) is characterized in terms of bond orientation and dihedral angle time autocorrelation functions. At low concentration in the molten polymer matrix, silica nanoparticles are found to cause a slight deceleration of the segmental dynamics close to their surface compared to the bulk polymer. Well-equilibrated coarse-grained long-chain configurations are reduced to entanglement networks via topological analysis with the CReTA algorithm, yielding a slightly lower density of entanglements in the filled than in the neat systems. UA melt configurations are glassified by MD cooling. The elastic moduli of the resulting glassy nanocomposites are computed through an

Impedimetric PSA aptasensor based on the use of a glassy carbon electrode modified with titanium oxide nanoparticles and silk fibroin nanofibers.

PubMed

Benvidi, Ali; Banaei, Maryam; Tezerjani, Marzieh Dehghan; Molahosseini, Hosein; Jahanbani, Shahriar

2017-12-14

This article describes an impedimetric aptasensor for the prostate specific antigen (PSA), a widely accepted prostate cancer biomarker. A glassy carbon electrode (GCE) was modified with titanium oxide nanoparticles (TiO 2 ) and silk fibroin nanofiber (SF) composite. The aptasensor was obtained by immobilizing a PSA-binding aptamer on the AuNP-modified with 6-mercapto-1-hexanol. The single fabrication steps were characterized by cyclic voltammetry and electrochemical impedance spectroscopy. The assay has two linear response ranges (from 2.5 fg.mL -1 to 25 pg.mL -1 , and from 25 pg.mL -1 to 25 ng.mL -1 ) and a 0.8 fg.mL -1 detection limit. After optimization of experimental conditions, the sensor is highly selective for PSA over bovine serum albumin and lysozyme. It was successfully applied to the detection of PSA in spiked serum samples. Graphical abstract Schematic of the fabrication of an aptasensor for the prostate specific antigen (PSA). It is based on the use of a glassy carbon electrode modified with gold nanoparticles and titanium oxide-silk fibroin. The immobilization process of aptamer and interaction with PSA were followed by electrochemical impedance spectroscopy technique.

Gas Permeation in Thin Glassy Polymer Films

NASA Astrophysics Data System (ADS)

Paul, Donald

2011-03-01

The development of asymmetric and composite membranes with very thin dense ``skins'' needed to achieve high gas fluxes enabled the commercial use of membranes for molecular level separations. It has been generally assumed that these thin skins, with thicknesses of the order of 100 nm, have the same permeation characteristics as films with thicknesses of 25 microns or more. Thick films are easily made in the laboratory and have been used extensively for measuring permeation characteristics to evaluate the potential of new polymers for membrane applications. There is now evidence that this assumption can be in very significant error, and use of thick film data to select membrane materials or predict performance should be done with caution. This presentation will summarize our work on preparing films of glassy polymers as thin as 20 nm and characterizing their behavior by gas permeation, ellipsometry and positron annihilation lifetime spectroscopy. Some of the most important polymers used commercially as gas separation membranes, i.e., Matrimid polyimide, polysulfone (PSF) and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), have been made into well-defined thin films in our laboratories by spin casting techniques and their properties studied using the techniques we have developed. These thin films densify (or physically age) much faster than thicker films, and, as result, the permeability decreases, sometimes by several-fold over weeks or months for thin films. This means that the properties of these thin films can be very different from bulk films. The techniques, interpretations and implications of these observations will be discussed. In a broader sense, gas permeation measurements can be a powerful way of developing a better understanding of the effects of polymer chain confinement and/or surface mobility on the behavior of thin films.

Amperometric biosensor based on glassy carbon electrode modified with long-length carbon nanotube and enzyme

NASA Astrophysics Data System (ADS)

Furutaka, Hajime; Nemoto, Kentaro; Inoue, Yuki; Hidaka, Hiroki; Muguruma, Hitoshi; Inoue, Hitoshi; Ohsawa, Tatsuya

2016-05-01

An amperometric biosensor based on a glassy carbon electrode modified with long-length multiwalled carbon nanotubes (MWCNTs) and enzyme nicotinamide-adenine-dinucleotide-dependent glucose dehydrogenase (GDH) is presented. We demonstrate the effect of the MWCNT length on the amperometric response of the enzyme biosensor. The long length of MWCNT is 200 µm (average), whereas the normal length of MWCNT is 1 µm (average). The response of the long MWCNT-GDH electrode is 2 times more sensitive than that of the normal-length MWCNT-GDH electrode in the concentration range from 0.25-35 mM. The result of electrochemical impedance spectroscopy measurements suggest that the long-length MWCNT-GDH electrode formed a better electron transfer network than the normal-length one.

Unusual strain glassy phase in Fe doped Ni2Mn1.5In0.5

NASA Astrophysics Data System (ADS)

Nevgi, R.; Priolkar, K. R.

2018-01-01

Fe doped Ni2Mn1.5In0.5, particularly, Ni2Mn1.4Fe0.1In0.5, despite having an incommensurate, modulated 7M martensitic structure at room temperature exhibits frequency dependent behavior of storage modulus and loss which obeys the Vogel-Fulcher law as well as shows ergodicity breaking between zero field cooled and field cooled strain measurements just above the transition temperature. Both frequency dependence and ergodicity breaking are characteristics of a strain glassy phase and occur due to the presence of strain domains which are large enough to present signatures of long range martensitic order in diffraction but are non-interacting with other strain domains due to the presence of Fe impurities.

ac impedance analysis of a Ni-Nb-Zr-H glassy alloy with femtofarad capacitance tunnels

NASA Astrophysics Data System (ADS)

Fukuhara, M.; Seto, M.; Inoue, A.

2010-01-01

A Nyquist diagram of a (Ni0.36Nb0.24Zr0.40)90H10 glassy alloy shows a semitrue circle, indicating that it is a conducting material with a total capacitance of 17.8 μF. The Bode plots showing the dependencies of its real and imaginary impedances, and phase on frequency suggest a simpler equivalent circuit having a resistor in parallel with a capacitor. Dividing the total capacitance (17.8 μF) by the capacitance of a single tunnel (0.9 fF), we deduced that this material has a high number of dielectric tunnels, which can be regarded as regular prisms separated from the electric-conducting distorted icosahedral Zr5Ni5Nb3 clusters by an average of 0.225 nm.

Origin of maar volcanoes: external water, internal volatiles, or both?

NASA Astrophysics Data System (ADS)

Rausch, J.; Schmincke, H.-U.

2012-04-01

The origin of maar volcanoes has been interpreted as due to explosive magma-water interaction for more than 40 years (Fisher and Waters 1970; Lorenz 1973 and Fisher and Schmincke 1984). Earlier suspicions that CO2-degassing plays a role in maar formation (Schmincke 1977) are now followed up by re-examining maar deposits of four different compositions in the maar-type locality (Eifel, Germany). These four compositions comprise: (1) melilite-nephelinites (West Eifel), (2) leucitites/nephelinites (West Eifel), (3) Na-rich basanites (West Eifel), and (4) K-rich basanites (East Eifel). At present, we focus on high-resolution stratigraphy, sedimentology, grain-size distribution, component analysis (accidental vs. juvenile clasts), and morphological and textural particle studies, accompanied by standard glass and bulk chemical and mineralogical analyses. Interestingly, maar deposits of highly silica-undersaturated and - by inference - CO2-rich composition (melilite-nephelinites and leucitites/nephelinites) show features contrasting with the classical catalogue of criteria for hydroclastic fragmentation (Fisher and Schmincke 1984). Their deposits are medium- to coarse-grained (MdØ mainly: 2 - 8 mm), mostly moderate- to well-sorted (σØ mainly: 1 - 2.5) and in some cases juvenile-rich (up to 50-70 wt. %). Transport and depositional mechanisms comprise a mixture of surge and fallout differing from the general assumption that maar deposits are dominated by surges. Additionally, features of juvenile clasts of highly silica-undersaturated composition largely differ from the features of "classic" hydroclastic particles (e.g.: dense, blocky, glassy shards). Juvenile clasts of highly silica-undersaturated composition show: (a) round- to semiround morphologies, (b) slight- to moderate vesicularities, (c) near absence of glassy material, (d) abundance of deep-seated xenoliths (mantle and lower crust), (e) agglutinated lava rinds enveloping the mantle- and crust-xenoliths, and (f

Rheological observation of glassy dynamics of dilute polymer solutions near the coil-stretch transition in elongational flows.

PubMed

Sridhar, T; Nguyen, D A; Prabhakar, R; Prakash, J Ravi

2007-04-20

It has long been conjectured that the macroscopic dynamics of dilute polymer solutions may exhibit a glasslike slowdown caused by ergodicity breaking, in the vicinity of the coil-stretch transition in elongational flows. We report experimental observations using a filament stretching rheometer that confirm the existence of such glassy states. It is observed that different time-dependent elongational strain-rate profiles lead to a pronounced history dependence and aging effects within a narrow range of strain rates. The results have a direct bearing on the analysis and design of processes employing dilute polymer solutions, such as ink-jet printing, surface coating, and turbulent-drag reduction.

The effect of hydrogen content on ballistic transport behaviors in the Ni-Nb-Zr-H glassy alloys.

PubMed

Fukuhara, Mikio; Umemori, Yoshimasa

2012-01-01

The electronic transport behaviors of (Ni(0.39)Nb(0.25)Zr(0.35))(100-) (x)H(x) (0 ≤ x < 23.5) glassy alloys with subnanostructural icosahedral Zr(5)Nb(5)Ni(3) clusters have been studied as a function of hydrogen content. These alloys show semiconducting, electric current-induced voltage (Coulomb) oscillation and ballistic transport behaviors. Coulomb oscillation and ballistic transport occur at hydrogen contents between 6.7 and 13.5 at% and between 13.5 and 21.2 at%, respectively. These results suggest that the localization effect of hydrogen in the clusters plays an important role in various electron transport phenomena.

The Effect of Hydrogen Content on Ballistic Transport Behaviors in the Ni-Nb-Zr-H Glassy Alloys

PubMed Central

Fukuhara, Mikio; Umemori, Yoshimasa

2012-01-01

The electronic transport behaviors of (Ni0.39Nb0.25Zr0.35)100−xHx (0 ≤ x < 23.5) glassy alloys with subnanostructural icosahedral Zr5Nb5Ni3 clusters have been studied as a function of hydrogen content. These alloys show semiconducting, electric current-induced voltage (Coulomb) oscillation and ballistic transport behaviors. Coulomb oscillation and ballistic transport occur at hydrogen contents between 6.7 and 13.5 at% and between 13.5 and 21.2 at%, respectively. These results suggest that the localization effect of hydrogen in the clusters plays an important role in various electron transport phenomena. PMID:22312246

Dispersion of the refractive index of a samarium-doped Se{sup 95}Te{sup 5} chalcogenide glassy semiconductor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Atayeva, S. U., E-mail: seva-atayeva@mail.ru; Mekhtiyeva, S. I.; Isayev, A. I.

2015-07-15

The transmission spectrum of a Se{sup 95}Te{sup 5} chalcogenide glassy semiconductor doped with samarium (0.05, 0.1, 0.25, 0.5, and 1 at %) is studied; the Swanepoel method and the single-oscillator model are used to determine the oscillator energy E{sup 0}, dispersion energy E{sup d}, optical width of the band gap E{sup g}, and linear (n) and nonlinear (n{sup 2}) refractive indices. The changes in the values of these parameters as a result of doping are attributed to modification of the local structure and to a change in the concentration of defect states.

Analysis of features of stainless steels in dissimilar welded joints in chloride inducted corrosion

NASA Astrophysics Data System (ADS)

Topolska, S.; Łabanowski, J.

2017-08-01

Stainless steels of femtic-austenitic microstructure that means the duplex Cr-Ni-Mo steels, in comparison with austenitic steel includes less expensive nickel and has much better mechanical properties with good formability and corrosion resistance, even in environments containing chloride ions. Similar share of high chromium ferrite and austenite, which is characterized by high ductility, determines that the duplex steels have good crack resistance at temperatures up to approximately -40°C. The steels containing approximately 22% Cr, 5% Ni, 3% Mo and 0.2% N crystallizes as a solid solution δ, partially transforming from the temperature of about 1200°C to 850°C into the phase α. The stable structure of considered steels, at temperatures above 850°C, is ferrite, and at lower temperatures the mixture of phase γ+α +σ. The two-phase structure α+γ the duplex steel obtains after hyperquenching at the temperature of stability of the mixture of α+γ phases, and the share of the phases depends on the hyper quenching attributes. Hyperquenching in water, with a temperature close to 1200°C, ensures the instance in the microstructure of the steel a large share of ferrite and a small share of the high chromium austenite. This causes the increase of strength properties and reducing the plasticity of the steel and its resistance ability to cracking and corrosion. Slower cooling from the mentioned temperature, for example in the air, enables the partial transformation of the a phase into the γ one (α → γ) and increasing the share of austenite in the steel structure. It leads to improvement of plasticity properties. In the paper are presented the results of investigations of heteronymous welded joints of duplex steel and austenitic one. The results include the relation between the chemical composition of steels and their weldability.

Wetting of a Charged Surface of Glassy Carbon by Molten Alkali-Metal Chlorides

NASA Astrophysics Data System (ADS)

Stepanov, V. P.

2018-03-01

Values of the contact angle of wetting of a surface of glassy carbon by molten chlorides of lithium, sodium, potassium, and cesium are measured by the meniscus weight method to determine the common factors of wettability of solid surfaces by ionic melts upon a change in the salt phase composition and a jump in electric potential. It is found that with a potential shift in the positive direction the shape of the curve of the contact angle's dependence on the potential varies upon substitution of one salt by another: the angle of wetting shrinks monotonously in lithium chloride but remains constant in molten cesium chloride. This phenomenon is explained by the hypothesis that the nature of the halide anion adsorption on the positively charged surface of an electrode is chemical and not electrostatic. It is shown that the adsorption process is accompanied by charge transfer through the interface, with covalent bonding between the adsorbent and adsorbate.

Vapor annealing synthesis of non-epitaxial MgB2 films on glassy carbon

NASA Astrophysics Data System (ADS)

Baker, A. A.; Bayu Aji, L. B.; Bae, J. H.; Stavrou, E.; Steich, D. J.; McCall, S. K.; Kucheyev, S. O.

2018-05-01

We describe the fabrication and characterization of 25–800 nm thick MgB2 films on glassy carbon substrates by Mg vapor annealing of sputter-deposited amorphous B films. Results demonstrate a critical role of both the initial B film thickness and the temperature–time profile on the microstructure, elemental composition, and superconducting properties of the resultant MgB2 films. Films with thicknesses of 55 nm and below exhibit a smooth surface, with a roughness of 1.1 nm, while thicker films have surface morphology consisting of elongated nano-crystallites. The suppression of the superconducting transition temperature for thin films scales linearly with the oxygen impurity concentration and also correlates with the amount of lattice disorder probed by Raman scattering. The best results are obtained by a rapid (12 min) anneal at 850 °C with large temperature ramp and cooling rates of ∼540 °C min‑1. Such fast processing suppresses the deleterious oxygen uptake.

Local Structure and Ion Transport in Glassy Poly(ethylene oxide styrene) Copolymers

NASA Astrophysics Data System (ADS)

Yang, Han-Chang; Mays, Jimmy; Sokolov, Alexei P.; Winey, Karen I.

2014-03-01

Polymer electrolytes have attracted attention for a wide variety of applications in energy production such as lithium-ion batteries and fuel cells. The concept of free volume provides important information about ion mobility and chain dynamics in the polymer matrix. Researchers have recently demonstrated that ion transport in glassy polymer can be improved by designing a system with high free volume. We have studied the effect of temperature and humidity on the intermolecular correlations of poly(ethylene oxide styrene-block-styrene) (PEOSt- b-St) block copolymer and poly(ethylene oxide styrene) (PEOSt) homopolymer using in situ multi-angle x-ray scattering across a wide range of scattering angles (q = 0.007-1.5 Å-1) . An increase in backbone-to-backbone distance is observed, indicating an increase in free volume between different polymer main chains. Structural characterization of the polymer segments will be discussed together with conductivity and dielectric results to better understand the ion transport mechanism in the local environment of the polymer system. Department of Chemistry, University of Tennessee.

Calorimetric study of water's two glass transitions in the presence of LiCl

PubMed Central

Ruiz, Guadalupe N.; Amann-Winkel, Katrin; Bove, Livia E.; Corti, Horacio R.

2018-01-01

A DSC study of dilute glassy LiCl aqueous solutions in the water-dominated regime provides direct evidence of a glass-to-liquid transition in expanded high density amorphous (eHDA)-type solutions. Similarly, low density amorphous ice (LDA) exhibits a glass transition prior to crystallization to ice Ic. Both glass transition temperatures are independent of the salt concentration, whereas the magnitude of the heat capacity increase differs. By contrast to pure water, the glass transition endpoint for LDA can be accessed in LiCl aqueous solutions above 0.01 mole fraction. Furthermore, we also reveal the endpoint for HDA's glass transition, solving the question on the width of both glass transitions. This suggests that both equilibrated HDL and LDL can be accessed in dilute LiCl solutions, supporting the liquid–liquid transition scenario to understand water's anomalies. PMID:29442107

Electrochemical study of ricin at glassy carbon electrode.

PubMed

Ribeiro, Williame F; da Costa, Daniel J E; Lourenço, Anabel S; Lopes, Ilanna C; de Medeiros, Everaldo P; Salazar-Banda, Giancarlo R; do Nascimento, Valberes B; de Araújo, Mário C U

2013-08-21

Ricin, Ricinus communis agglutinin 60 - RCA 60, is a deadly phytotoxic protein which inhibits ribosomes (class II), and there is no known effective antidote in living organisms. Ricin is composed of two polypeptide chains, A and B, linked covalently by a single disulfide bond. The analytical methods for the detection of RCA 60 are commonly laborious, expensive, require skilled labor, and involve sophisticated equipment. Aimed at the development of electroanalytical methods for RCA 60 detection, here we studied the electrochemical oxidation of RCA 60 on a glassy carbon (GC) electrode over a wide pH range, using cyclic voltammetry, differential pulse voltammetry (DPV) and square wave voltammetry (SWV). Two quasi-reversible electrochemical RCA 60 oxidation peaks were identified on the GC electrode by SWV. For values of 2.2 ≤ pH ≤ 10.2, DPV studies revealed that the peak potentials, EP1 and EP2, display a linear dependence with pH and the reaction mechanism involves the transfer of 2H⁺/2e⁻ (peak 1) and 1H⁺/1e⁻ (peak 2). The first and second RCA 60 oxidation steps may correspond to the oxidation of cysteine and tyrosine-tryptophan residues, respectively. The oxidation product of the second RCA 60 oxidation step appears at 7.0 ≤ pH ≤ 11.8. For pH ≥ 10.2, both processes are pH independent, resulting in a pKa of ca. 10.2. A third RCA 60 oxidation peak only appears at acidic pH. RCA 60 samples extracted from different castor seed cultivars showed similar electrochemical behavior, enabling the implementation of an analytical voltammetric method.

Molecular dynamics in supercooled liquid and glassy states of antibiotics: azithromycin, clarithromycin and roxithromycin studied by dielectric spectroscopy. Advantages given by the amorphous state.

PubMed

Adrjanowicz, K; Zakowiecki, D; Kaminski, K; Hawelek, L; Grzybowska, K; Tarnacka, M; Paluch, M; Cal, K

2012-06-04

Antibiotics are chemical compounds of extremely important medical role. Their history can be traced back more than one hundred years. Despite the passing time and significant progress made in pharmacy and medicine, treatment of many bacterial infections without antibiotics would be completely impossible. This makes them particularly unique substances and explains the unflagging popularity of antibiotics within the medical community. Herein, using dielectric spectroscopy we have studied the molecular mobility in the supercooled liquid and glassy states of three well-known antibiotic agents: azithromycin, clarithromycin and roxithromycin. Dielectric studies revealed a number of relaxation processes of different molecular origin. Besides the primary α-relaxation, observed above the respective glass transition temperatures of antibiotics, two secondary relaxations in the glassy state were identified. Interestingly, the fragility index as well as activation energies of the secondary processes turned out to be practically the same for all three compounds, indicating probably much the same molecular dynamics. Long-term stability of amorphous antibiotics at room temperature was confirmed by X-ray diffraction technique, and calorimetric studies were performed to evaluate the basic thermodynamic parameters. Finally, we have also checked the experimental solubility advantages given by the amorphous form of the examined antibiotics.

Electrografting of diazonium-functionalized polyoxometalates: synthesis, immobilisation and electron-transfer characterisation from glassy carbon.

PubMed

Rinfray, Corentin; Izzet, Guillaume; Pinson, Jean; Gam Derouich, Sarra; Ganem, Jean-Jacques; Combellas, Catherine; Kanoufi, Frédéric; Proust, Anna

2013-10-04

Polyoxometalates (POMs) are attractive candidates for the rational design of multi-level charge-storage materials because they display reversible multi-step reduction processes in a narrow range of potentials. The functionalization of POMs allows for their integration in hybrid complementary metal oxide semiconductor (CMOS)/molecular devices, provided that fine control of their immobilisation on various substrates can be achieved. Owing to the wide applicability of the diazonium route to surface modification, a functionalized Keggin-type POM [PW11 O39 {Ge(p-C6 H4 -CC-C6 H4 -${{\\rm N}{{+\\hfill \\atop 2\\hfill}}}$)}](3-) bearing a pending diazonium group was prepared and subsequently covalently anchored onto a glassy carbon electrode. Electron transfer with the immobilised POM was thoroughly investigated and compared to that of the free POM in solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Classification of heavy metal ions present in multi-frequency multi-electrode potable water data using evolutionary algorithm

NASA Astrophysics Data System (ADS)

Karkra, Rashmi; Kumar, Prashant; Bansod, Baban K. S.; Bagchi, Sudeshna; Sharma, Pooja; Krishna, C. Rama

2017-11-01

Access to potable water for the common people is one of the most challenging tasks in the present era. Contamination of drinking water has become a serious problem due to various anthropogenic and geogenic events. The paper demonstrates the application of evolutionary algorithms, viz., particle swan optimization and genetic algorithm to 24 water samples containing eight different heavy metal ions (Cd, Cu, Co, Pb, Zn, Ar, Cr and Ni) for the optimal estimation of electrode and frequency to classify the heavy metal ions. The work has been carried out on multi-variate data, viz., single electrode multi-frequency, single frequency multi-electrode and multi-frequency multi-electrode water samples. The electrodes used are platinum, gold, silver nanoparticles and glassy carbon electrodes. Various hazardous metal ions present in the water samples have been optimally classified and validated by the application of Davis Bouldin index. Such studies are useful in the segregation of hazardous heavy metal ions found in water resources, thereby quantifying the degree of water quality.

Magnetic resonance imaging and image analysis for assessment of HPMC matrix tablets structural evolution in USP Apparatus 4.

PubMed

Kulinowski, Piotr; Dorożyński, Przemysław; Młynarczyk, Anna; Węglarz, Władysław P

2011-05-01

The purpose of the study was to present a methodology for the processing of Magnetic Resonance Imaging (MRI) data for the quantification of the dosage form matrix evolution during drug dissolution. The results of the study were verified by comparison with other approaches presented in literature. A commercially available, HPMC-based quetiapine fumarate tablet was studied with a 4.7T MR system. Imaging was performed inside an MRI probe-head coupled with a flow-through cell for 12 h in circulating water. The images were segmented into three regions using threshold-based segmentation algorithms due to trimodal structure of the image intensity histograms. Temporal evolution of dry glassy, swollen glassy and gel regions was monitored. The characteristic features were observed: initial high expansion rate of the swollen glassy and gel layers due to initial water uptake, dry glassy core disappearance and maximum area of swollen glassy region at 4 h, and subsequent gel layer thickness increase at the expense of swollen glassy layer. The temporal evolution of an HPMC-based tablet by means of noninvasive MRI integrated with USP Apparatus 4 was found to be consistent with both the theoretical model based on polymer disentanglement concentration and experimental VIS/FTIR studies.

Surface temperatures and glassy state investigations in tribology, part 1

NASA Technical Reports Server (NTRS)

Winer, W. O.; Sanborn, D. M.

1978-01-01

The research in this report is divided into two categories: (1) lubricant rheological behavior, and (2) thermal behavior of a simulated elastohydrodynamic contact. The studies of the lubricant rheological behavior consists of high pressure, low shear rate viscosity measurements, viscoelastic transition measurements, by volume dilatometry, dielectric transitions at atmospheric pressure and light scattering transitions. Lubricant shear stress-strain behavior in the amorphous glassy state was measured on several fluids. It appears clear from these investigations that many lubricants undergo viscoplastic transitions in typical EHD contacts and that the lubricant has a limiting maximum shear stress it can support which in turn will determine the traction in the contact except in cases of very low slide-roll ratio. Surface temperature measurements were made for a naphthenic mineral oil and a polyphenyl ether. The maximum surface temperature in these experiments was approximately symmetrical about the zero slide-roll ration except for absolute values of slide-roll ratio greater than about 0.9. Additional surface temperature measurements were made in contacts with rough surfaces where the composite surface roughness was approximately equal to the EHD film thickness. A regression analysis was done to obtain a predictive equation for surface temperatures as a function of pressure, sliding speed, and surface roughness. A correction factor for surface roughness effects to the typical flash temperature analysis was found.

Nanomolar determination of 4-nitrophenol based on a poly(methylene blue)-modified glassy carbon electrode.

PubMed

Giribabu, Krishnamoorthy; Suresh, Ranganathan; Manigandan, Ramadoss; Munusamy, Settu; Kumar, Sivakumar Praveen; Muthamizh, Selvamani; Narayanan, Vengidusamy

2013-10-07

A poly(methylene blue)-modified glassy carbon electrode (PMB/GCE) was fabricated by electropolymerisation of methylene blue on a GCE and further utilized to investigate the electrochemical determination of 4-nitrophenol (4-NP) by cyclic voltammetry (CV), differential pulse voltammetry and chronocoulometry. The morphology of the PMB on GCE was examined using a scanning electron microscope (SEM). An oxidation peak of 4-NP at the PMB modified electrode was observed at 0.28 V, and in the case of bare GCE, no oxidation peak was observed, which indicates that PMB/GCE exhibits a remarkable effect on the electrochemical determination of 4-NP. Due to this remarkable effect of PMB/GCE, a sensitive and simple electrochemical method was proposed for the determination of 4-NP. The effect of the scan rate and pH was investigated to determine the optimum conditions at which the PMB/GCE exhibits a higher sensitivity with a lower detection limit. Moreover, kinetic parameters such as the electron transfer number, proton transfer number and standard heterogeneous rate constant were calculated. Under optimum conditions, the oxidation current of 4-NP is proportional to its concentration in the range of 15-250 nM with a correlation coefficient of 0.9963. The detection limit was found to be 90 nM (S/N = 3). The proposed method based on PMB/GCE is simple, easy and cost effective. To further confirm its possible application, the proposed method was successfully used for the determination of 4-NP in real water samples with recoveries ranging from 97% to 101.6%. The interference due to sodium, potassium, calcium, magnesium, copper, zinc, iron, sulphate, carbonate, chloride, nitrate and phosphate was found to be almost negligible.

Heterogeneous ice nucleation on phase-separated organic-sulfate particles: effect of liquid vs. glassy coatings

NASA Astrophysics Data System (ADS)

Schill, G. P.; Tolbert, M. A.

2013-05-01

Atmospheric ice nucleation on aerosol particles relevant to cirrus clouds remains one of the least understood processes in the atmosphere. Upper tropospheric aerosols as well as sub-visible cirrus residues are known to be enhanced in both sulfates and organics. The hygroscopic phase transitions of organic-sulfate particles can have an impact on both the cirrus cloud formation mechanism and resulting cloud microphysical properties. In addition to deliquescence and efflorescence, organic-sulfate particles are known to undergo another phase transition known as liquid-liquid phase separation. The ice nucleation properties of particles that have undergone liquid-liquid phase separation are unknown. Here, Raman microscopy coupled with an environmental cell was used to study the low temperature deliquescence, efflorescence, and liquid-liquid phase separation behavior of 2 : 1 mixtures of organic polyols (1,2,6-hexanetriol and 1 : 1 1,2,6-hexanetriol + 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol) and ammonium sulfate from 240-265 K. Further, the ice nucleation efficiency of these organic-sulfate systems after liquid-liquid phase separation and efflorescence was investigated from 210-235 K. Raman mapping and volume-geometry analysis indicate that these particles contain solid ammonium sulfate cores fully engulfed in organic shells. For the ice nucleation experiments, we find that if the organic coatings are liquid, water vapor diffuses through the shell and ice nucleates on the ammonium sulfate core. In this case, the coatings minimally affect the ice nucleation efficiency of ammonium sulfate. In contrast, if the coatings become semi-solid or glassy, ice instead nucleates on the organic shell. Consistent with recent findings that glasses can be efficient ice nuclei, the phase-separated particles are nearly as efficient at ice nucleation as pure crystalline ammonium sulfate.

Heterogeneous ice nucleation on phase-separated organic-sulfate particles: effect of liquid vs. glassy coatings

NASA Astrophysics Data System (ADS)

Schill, G. P.; Tolbert, M. A.

2012-12-01

Atmospheric ice nucleation on aerosol particles relevant to cirrus clouds remains one of the least understood processes in the atmosphere. Upper tropospheric aerosols as well as sub-visible cirrus residues are known to be enhanced in both sulfates and organics. The hygroscopic phase transitions of organic-sulfate particles can have an impact on both the cirrus cloud formation mechanism and resulting cloud microphysical properties. In addition to deliquescence and efflorescence, organic-sulfate particles are known to undergo another phase transition known as liquid-liquid phase separation. The ice nucleation properties of particles that have undergone liquid-liquid phase separation are unknown. Here, Raman microscopy coupled with an environmental cell was used to study the low temperature deliquescence, efflorescence, and liquid-liquid phase separation behavior of 2:1 mixtures of organic polyols (1,2,6-hexanetriol, and 1:1 1,2,6-hexanetriol +2,2,6,6-tetrakis(hydroxymethyl)cycohexanol) and ammonium sulfate from 240-265 K. Further, the ice nucleation efficiency of these organic-sulfate systems after liquid-liquid phase separation and efflorescence was investigated from 210-235 K. Raman mapping and volume-geometry analysis indicates that these particles contain solid ammonium sulfate cores fully engulfed in organic shells. For the ice nucleation experiments, we find that if the organic coatings are liquid, water vapor diffuses through the shell and ice nucleates on the ammonium sulfate core. In this case, the coatings minimally affect the ice nucleation efficiency of ammonium sulfate. In contrast, if the coatings become semi-solid or glassy, ice instead nucleates on the organic shell. Consistent with recent findings that glasses can be efficient ice nuclei, the phase separated particles are nearly as efficient at ice nucleation as pure crystalline ammonium sulfate.

Anomalous Capacitance Maximum of the Glassy Carbon-Ionic Liquid Interface through Dilution with Organic Solvents.

PubMed

Bozym, David J; Uralcan, Betül; Limmer, David T; Pope, Michael A; Szamreta, Nicholas J; Debenedetti, Pablo G; Aksay, Ilhan A

2015-07-02

We use electrochemical impedance spectroscopy to measure the effect of diluting a hydrophobic room temperature ionic liquid with miscible organic solvents on the differential capacitance of the glassy carbon-electrolyte interface. We show that the minimum differential capacitance increases with dilution and reaches a maximum value at ionic liquid contents near 5-10 mol% (i.e., ∼1 M). We provide evidence that mixtures with 1,2-dichloroethane, a low-dielectric constant solvent, yield the largest gains in capacitance near the open circuit potential when compared against two traditional solvents, acetonitrile and propylene carbonate. To provide a fundamental basis for these observations, we use a coarse-grained model to relate structural variations at the double layer to the occurrence of the maximum. Our results reveal the potential for the enhancement of double-layer capacitance through dilution.

Hysteresis, reentrance, and glassy dynamics in systems of self-propelled rods

NASA Astrophysics Data System (ADS)

Kuan, Hui-Shun; Blackwell, Robert; Hough, Loren E.; Glaser, Matthew A.; Betterton, M. D.

2015-12-01

Nonequilibrium active matter made up of self-driven particles with short-range repulsive interactions is a useful minimal system to study active matter as the system exhibits collective motion and nonequilibrium order-disorder transitions. We studied high-aspect-ratio self-propelled rods over a wide range of packing fractions and driving to determine the nonequilibrium state diagram and dynamic properties. Flocking and nematic-laning states occupy much of the parameter space. In the flocking state, the average internal pressure is high and structural and mechanical relaxation times are long, suggesting that rods in flocks are in a translating glassy state despite overall flock motion. In contrast, the nematic-laning state shows fluidlike behavior. The flocking state occupies regions of the state diagram at both low and high packing fraction separated by nematic-laning at low driving and a history-dependent region at higher driving; the nematic-laning state transitions to the flocking state for both compression and expansion. We propose that the laning-flocking transitions are a type of glass transition that, in contrast to other glass-forming systems, can show fluidization as density increases. The fluid internal dynamics and ballistic transport of the nematic-laning state may promote collective dynamics of rod-shaped micro-organisms.

Hysteresis, reentrance, and glassy dynamics in systems of self-propelled rods.

PubMed

Kuan, Hui-Shun; Blackwell, Robert; Hough, Loren E; Glaser, Matthew A; Betterton, M D

2015-01-01

Nonequilibrium active matter made up of self-driven particles with short-range repulsive interactions is a useful minimal system to study active matter as the system exhibits collective motion and nonequilibrium order-disorder transitions. We studied high-aspect-ratio self-propelled rods over a wide range of packing fractions and driving to determine the nonequilibrium state diagram and dynamic properties. Flocking and nematic-laning states occupy much of the parameter space. In the flocking state, the average internal pressure is high and structural and mechanical relaxation times are long, suggesting that rods in flocks are in a translating glassy state despite overall flock motion. In contrast, the nematic-laning state shows fluidlike behavior. The flocking state occupies regions of the state diagram at both low and high packing fraction separated by nematic-laning at low driving and a history-dependent region at higher driving; the nematic-laning state transitions to the flocking state for both compression and expansion. We propose that the laning-flocking transitions are a type of glass transition that, in contrast to other glass-forming systems, can show fluidization as density increases. The fluid internal dynamics and ballistic transport of the nematic-laning state may promote collective dynamics of rod-shaped micro-organisms.

Amperometric ascorbic acid sensor based on doped ferrites nanoparticles modified glassy carbon paste electrode.

PubMed

Dimitrijević, Teodora; Vulić, Predrag; Manojlović, Dragan; Nikolić, Aleksandar S; Stanković, Dalibor M

2016-07-01

In this study, a novel electrochemical sensor for quantification of ascorbic acid with amperometric detection in physiological conditions was constructed. For this purpose, cobalt and nickel ferrites were synthesized using microwave and ultrasound assistance, characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and X-ray powder diffraction (XRPD), and used for modification of glassy carbon paste electrode (GCPE). It was shown that introducing these nanoparticles to the structure of GCPE led to increasing analytical performance. Co ferrite modified GCPE (CoFeGCPE) showed better characteristics toward ascorbic acid sensing. The limit of detection (LOD) obtained by sensor was calculated to be 0.0270 mg/L, with linear range from 0.1758 to 2.6010 mg/L. This sensor was successfully applied for practical analysis, and the obtained results demonstrated that the proposed procedure could be a promising replacement for the conventional electrode materials and time-consuming and expensive separation methods. Copyright © 2016 Elsevier Inc. All rights reserved.

Age determination of the glassy-winged sharpshooter, Homalodisca vitripennis, using wing pigmentation.

PubMed

Timmons, Chris; Hassell, Aaron; Lauziere, Isabelle; Bextine, Blake

2011-01-01

A red pigment is contained in the wing veins of the glassy-winged sharpshooter, Homalodisca vitripennis (Hemiptera: Cicadellidae). This insect is the main vector of the plant-pathogenic bacterium Xylella fastidiosa Wells (Xanthomonadales: Xanthomonadaceae), the causal agent of Pierce's disease of grapevines. Over the course of the H. vitripennis lifespan, the red pigment darkens and eventually becomes brown/black in color. These pigments are believed to be pheomelanin and eumelanin, respectively. The age of H. vitripennis can be determined by calculating the amount of red pigment found in the wings by analyzing high resolution wing photographs with image analysis software. In this study, a standard curve for the age determination of H. vitripennis was developed using laboratory-reared insects of known ages varying from 1 to 60 days. The impact of three environmental conditions on these readings was also investigated and found to have little effect on the age determination, and could be easily accounted for. Finally, field collected insects from several Central Texas vineyards were successfully analyzed for age determination suggesting that the annually reported influx of H. vitripennis was composed almost entirely of older insects.

New biosensing platforms based on the layer-by-layer self-assembling of polyelectrolytes on Nafion/carbon nanotubes-coated glassy carbon electrodes.

PubMed

Rivas, Gustavo A; Miscoria, Silvia A; Desbrieres, Jacques; Barrera, Gustavo D

2007-01-15

We are proposing for the first time the use of a Nafion/multi-walled carbon nanotubes dispersion deposited on glassy carbon electrodes (GCE) as a new platform for developing enzymatic biosensors based on the self-assembling of a chitosan derivative and different oxidases. The electrodes are obtained by deposition of a layer of Nafion/multi-wall carbon nanotubes dispersion on glassy carbon electrodes, followed by the adsorption of a chitosan derivative as polycation and glucose oxidase, l-aminoacid oxidase or polyphenol oxidase, as polyanions and biorecognition elements. The optimum configuration for glucose biosensors has allowed a highly sensitive (sensitivity=(0.28+/-0.02)muAmM(-1), r=0.997), fast (4s in reaching the maximum response), and highly selective (0% interference of ascorbic acid and uric acid at maximum physiological levels) glucose quantification at 0.700V with detection and quantification limits of 0.035 and 0.107mM, respectively. The repetitivity for 10 measurements was 5.5%, while the reproducibility was 8.4% for eight electrodes. The potentiality of the new platform was clearly demonstrated by using the carbon nanotubes/Nafion layer as a platform for the self-assembling of l-aminoacid oxidase and polyphenol oxidase. Therefore, the platform we are proposing here, that combines the advantages of nanostructured materials with those of the layer-by-layer self-assembling of polyelectrolytes, opens the doors to new and exciting possibilities for the development of enzymatic and affinity biosensors using different transdution modes.

Glass polymorphism in glycerol–water mixtures: I. A computer simulation study

PubMed Central

Jahn, David A.; Wong, Jessina; Bachler, Johannes; Loerting, Thomas

2016-01-01

We perform out-of-equilibrium molecular dynamics (MD) simulations of water–glycerol mixtures in the glass state. Specifically, we study the transformations between low-density (LDA) and high-density amorphous (HDA) forms of these mixtures induced by compression/decompression at constant temperature. Our MD simulations reproduce qualitatively the density changes observed in experiments. Specifically, the LDA–HDA transformation becomes (i) smoother and (ii) the hysteresis in a compression/decompression cycle decreases as T and/or glycerol content increase. This is surprising given the fast compression/decompression rates (relative to experiments) accessible in MD simulations. We study mixtures with glycerol molar concentration χ g = 0–13% and find that, for the present mixture models and rates, the LDA–HDA transformation is detectable up to χ g ≈ 5%. As the concentration increases, the density of the starting glass (i.e., LDA at approximately χ g ≤ 5%) rapidly increases while, instead, the density of HDA remains practically constant. Accordingly, the LDA state and hence glass polymorphism become inaccessible for glassy mixtures with approximately χ g > 5%. We present an analysis of the molecular-level changes underlying the LDA–HDA transformation. As observed in pure glassy water, during the LDA-to-HDA transformation, water molecules within the mixture approach each other, moving from the second to the first hydration shell and filling the first interstitial shell of water molecules. Interestingly, similar changes also occur around glycerol OH groups. It follows that glycerol OH groups contribute to the density increase during the LDA–HDA transformation. An analysis of the hydrogen bond (HB)-network of the mixtures shows that the LDA–HDA transformation is accompanied by minor changes in the number of HBs of water and glycerol. Instead, large changes in glycerol and water coordination numbers occur. We also perform a detailed analysis of the

Determination of heavy metals in mussel and oyster samples with tris (2,2‧-bipyridyl) ruthenium (II)/graphene/Nafion® modified glassy carbon electrodes

NASA Astrophysics Data System (ADS)

Palisoc, Shirley T.; Uy, Donald Jans S.; Natividad, Michelle T.; Lopez, Toni Beth G.

2017-11-01

Tris (2,2‧-bipyridyl)ruthenium(II)/graphene/Nafion® modified glassy carbon electrodes (GCEs) were fabricated using the drop coating method. The modified electrode was used as the working electrode in differential pulse voltammetry (DPV) for the determination of lead, cadmium, and copper in mussel and oyster samples. The concentration of Tris (2,2‧-bipyridyl) ruthenium (II) and graphene were varied while those of Nafion®, methanol, and ethanol were held constant in the coating solution. The morphology and elemental composition of the fabricated electrodes were analyzed by scanning electron microscopy and energy-dispersive x-ray spectroscopy. Cyclic voltammetry (CV) was done to investigate the reversibility and stability of the modified electrodes. The modified electrode with the best figures of merit was utilized for the detection of copper (Cu2+), lead (Pb2+) and cadmium (Cd2+) via DPV. This was the electrode modified with 4 mg [Ru (bpy)3]2+ and 3 mg graphene. The anodic current and metal concentration showed linear relationship in the range of 48 ppb-745 ppb for Pb2+, 49 ppb-613 ppb for Cd2+, and 28 ppb-472 ppb for Cu2+. The limits of detection for lead, cadmium, and copper were 48 ppb, 49 ppb, and 28 ppb, respectively. Results from atomic absorption spectrometry (AAS) were compared with those measured with DPV. Lead, cadmium, and copper were in mussels, oysters, and sea water. In addition, DPV was able to detect other metals such as zinc, iron, tin and mercury in sea water samples and some samples of oysters.

Network approach towards understanding the crazing in glassy amorphous polymers

NASA Astrophysics Data System (ADS)

Venkatesan, Sudarkodi; Vivek-Ananth, R. P.; Sreejith, R. P.; Mangalapandi, Pattulingam; Hassanali, Ali A.; Samal, Areejit

2018-04-01

We have used molecular dynamics to simulate an amorphous glassy polymer with long chains to study the deformation mechanism of crazing and associated void statistics. The Van der Waals interactions and the entanglements between chains constituting the polymer play a crucial role in crazing. Thus, we have reconstructed two underlying weighted networks, namely, the Van der Waals network and the entanglement network from polymer configurations extracted from the molecular dynamics simulation. Subsequently, we have performed graph-theoretic analysis of the two reconstructed networks to reveal the role played by them in the crazing of polymers. Our analysis captured various stages of crazing through specific trends in the network measures for Van der Waals networks and entanglement networks. To further corroborate the effectiveness of network analysis in unraveling the underlying physics of crazing in polymers, we have contrasted the trends in network measures for Van der Waals networks and entanglement networks in the light of stress-strain behaviour and voids statistics during deformation. We find that the Van der Waals network plays a crucial role in craze initiation and growth. Although, the entanglement network was found to maintain its structure during craze initiation stage, it was found to progressively weaken and undergo dynamic changes during the hardening and failure stages of crazing phenomena. Our work demonstrates the utility of network theory in quantifying the underlying physics of polymer crazing and widens the scope of applications of network science to characterization of deformation mechanisms in diverse polymers.

Water Behavior in Bacterial Spores by Deuterium NMR Spectroscopy

PubMed Central

2015-01-01

Dormant bacterial spores are able to survive long periods of time without nutrients, withstand harsh environmental conditions, and germinate into metabolically active bacteria when conditions are favorable. Numerous factors influence this hardiness, including the spore structure and the presence of compounds to protect DNA from damage. It is known that the water content of the spore core plays a role in resistance to degradation, but the exact state of water inside the core is a subject of discussion. Two main theories present themselves: either the water in the spore core is mostly immobile and the core and its components are in a glassy state, or the core is a gel with mobile water around components which themselves have limited mobility. Using deuterium solid-state NMR experiments, we examine the nature of the water in the spore core. Our data show the presence of unbound water, bound water, and deuterated biomolecules that also contain labile deuterons. Deuterium–hydrogen exchange experiments show that most of these deuterons are inaccessible by external water. We believe that these unreachable deuterons are in a chemical bonding state that prevents exchange. Variable-temperature NMR results suggest that the spore core is more rigid than would be expected for a gel-like state. However, our rigid core interpretation may only apply to dried spores whereas a gel core may exist in aqueous suspension. Nonetheless, the gel core, if present, is inaccessible to external water. PMID:24950158

IUPAC-NIST Solubility Data Series 70. The Solubility of Gases in Glassy Polymers

NASA Astrophysics Data System (ADS)

Paterson, Russell; Yampol'Skii, Yuri P.; Fogg, Peter G. T.; Bokarev, Alexandre; Bondar, Valerii; Ilinich, Oleg; Shishatskii, Sergey

1999-09-01

Solubility of gases in polymers is an important property of polymeric materials relevant to many practical applications. Sorption of small molecules in polymers is a fundamental concern in such areas as food packaging, beverage storage, and polymer processing. However, by far the main interest in the solubility of gases in polymers, and especially in glassy polymers, is related to development of novel advanced materials for gas separation membranes. This is because the concentration gradient of a dissolved gas is the driving force of membrane processes. Development of these novel separation methods resulted in a rapid accumulation, in the recent literature, of thermodynamic data related to the solubility of gases in polymers at different temperatures and pressures. Polymers can be regarded as special cases of media intermediate between liquids and solids. As a consequence, modeling of gas sorption in polymers is very difficult and presents a permanent challenge to theoreticians and experimenters. The collection and critical evaluation of solubility data for various gas-polymer systems is relevant to both practical aspects of polymer applications and to fundamental studies of polymer behavior. This volume of the IUPAC-NIST Solubility Data Series summarizes the compilations and critical evaluations of the data on solubility of gases in glassy polymers. It is implied in this edition that "gases" are the components that are either permanent gases (supercitical fluids) or have saturated vapor pressure more than 1 atm at ambient conditions (298 K). The polymeric components of compilations and critical evaluations are primarily high molecular mass, amorphous, linear (noncross-linked) compounds that have the glass transition temperatures above ambient temperature. The data for each gas-polymer system have been evaluated, if the results of at least three independent and reliable studies have been reported. Where the data of sufficient accuracy and reliability are available

The relevance of the amorphous state to pharmaceutical dosage forms: glassy drugs and freeze dried systems.

PubMed

Craig, D Q; Royall, P G; Kett, V L; Hopton, M L

1999-03-15

Many pharmaceuticals, either by accident or design, may exist in a total or partially amorphous state. Consequently, it is essential to have an understanding of the physico-chemical principles underpinning the behaviour of such systems. In this discussion, the nature of the glassy state will be described, with particular emphasis on the molecular processes associated with glass transitional behaviour and the use of thermal methods for characterising the glass transition temperature, Tg. The practicalities of such measurements, the significance of the accompanying relaxation endotherm and plasticization effects are considered. The advantages and difficulties associated with the use of amorphous drugs will be outlined, with discussion given regarding the problems associated with physical and chemical stability. Finally, the principles of freeze drying will be described, including discussion of the relevance of glass transitional behaviour to product stability. Copyright

Novel Signal-Amplified Fenitrothion Electrochemical Assay, Based on Glassy Carbon Electrode Modified with Dispersed Graphene Oxide

NASA Astrophysics Data System (ADS)

Wang, Limin; Dong, Jinbo; Wang, Yulong; Cheng, Qi; Yang, Mingming; Cai, Jia; Liu, Fengquan

2016-03-01

A novel signal-amplified electrochemical assay for the determination of fenitrothion was developed, based on the redox behaviour of organophosphorus pesticides on a glassy carbon working electrode. The electrode was modified using graphene oxide dispersion. The electrochemical response of fenitrothion at the modified electrode was investigated using cyclic voltammetry, current-time curves, and square-wave voltammetry. Experimental parameters, namely the accumulation conditions, pH value, and volume of dispersed material, were optimised. Under the optimum conditions, a good linear relationship was obtained between the oxidation peak current and the fenitrothion concentration. The linear range was 1-400 ng·mL-1, with a detection limit of 0.1 ng·mL-1 (signal-to-nose ratio = 3). The high sensitivity of the sensor was demonstrated by determining fenitrothion in pakchoi samples.

Interplay of the Glass Transition and the Liquid-Liquid Phase Transition in Water

PubMed Central

Giovambattista, Nicolas; Loerting, Thomas; Lukanov, Boris R.; Starr, Francis W.

2012-01-01

Water has multiple glassy states, often called amorphous ices. Low-density (LDA) and high-density (HDA) amorphous ice are separated by a dramatic, first-order like phase transition. It has been argued that the LDA-HDA transformation connects to a first-order liquid-liquid phase transition (LLPT) above the glass transition temperature Tg. Direct experimental evidence of the LLPT is challenging to obtain, since the LLPT occurs at conditions where water rapidly crystallizes. In this work, we explore the implications of a LLPT on the pressure dependence of Tg(P) for LDA and HDA by performing computer simulations of two water models – one with a LLPT, and one without. In the absence of a LLPT, Tg(P) for all glasses nearly coincide. When there is a LLPT, different glasses exhibit dramatically different Tg(P) which are directly linked with the LLPT. Available experimental data for Tg(P) are only consistent with the scenario including a LLPT. PMID:22550566

Interplay of the Glass Transition and the Liquid-Liquid Phase Transition in Water

NASA Astrophysics Data System (ADS)

Giovambattista, Nicolas; Loerting, Thomas; Lukanov, Boris R.; Starr, Francis W.

2012-05-01

Water has multiple glassy states, often called amorphous ices. Low-density (LDA) and high-density (HDA) amorphous ice are separated by a dramatic, first-order like phase transition. It has been argued that the LDA-HDA transformation connects to a first-order liquid-liquid phase transition (LLPT) above the glass transition temperature Tg. Direct experimental evidence of the LLPT is challenging to obtain, since the LLPT occurs at conditions where water rapidly crystallizes. In this work, we explore the implications of a LLPT on the pressure dependence of Tg(P) for LDA and HDA by performing computer simulations of two water models - one with a LLPT, and one without. In the absence of a LLPT, Tg(P) for all glasses nearly coincide. When there is a LLPT, different glasses exhibit dramatically different Tg(P) which are directly linked with the LLPT. Available experimental data for Tg(P) are only consistent with the scenario including a LLPT.

A model for complex flows of soft glassy materials with application to flows through fixed fiber beds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sarkar, Arijit; Koch, Donald L., E-mail: dlk15@cornell.edu

2015-11-15

The soft glassy rheology (SGR) model has successfully described the time dependent simple shear rheology of a broad class of complex fluids including foams, concentrated emulsions, colloidal glasses, and solvent-free nanoparticle-organic hybrid materials (NOHMs). The model considers a distribution of mesoscopic fluid elements that hop from trap to trap at a rate which is enhanced by the work done to strain the fluid element. While an SGR fluid has a broad exponential distribution of trap energies, the rheology of NOHMs is better described by a narrower energy distribution and we consider both types of trap energy distributions in this study.more » We introduce a tensorial version of these models with a hopping rate that depends on the orientation of the element relative to the mean stress field, allowing a range of relative strengths of the extensional and simple shear responses of the fluid. As an application of these models we consider the flow of a soft glassy material through a dilute fixed bed of fibers. The dilute fixed bed exhibits a range of local linear flows which alternate in a chaotic manner with time in a Lagrangian reference frame. It is amenable to an analytical treatment and has been used to characterize the strong flow response of many complex fluids including fiber suspensions, dilute polymer solutions and emulsions. We show that the accumulated strain in the fluid elements has an abrupt nonlinear growth at a Deborah number of order one in a manner similar to that observed for polymer solutions. The exponential dependence of the hopping rate on strain leads to a fluid element deformation that grows logarithmically with Deborah number at high Deborah numbers. SGR fluids having a broad range of trap energies flowing through fixed beds can exhibit a range of rheological behaviors at small Deborah numbers ranging from a yield stress, to a power law response and finally to Newtonian behavior.« less

Thermodynamic parameters of bonds in glassy materials from viscosity-temperature relationships.

PubMed

Ojovan, Michael I; Travis, Karl P; Hand, Russell J

2007-10-17

Doremus's model of viscosity assumes that viscous flow in amorphous materials is mediated by broken bonds (configurons). The resulting equation contains four coefficients, which are directly related to the entropies and enthalpies of formation and motion of the configurons. Thus by fitting this viscosity equation to experimental viscosity data these enthalpy and entropy terms can be obtained. The non-linear nature of the equation obtained means that the fitting process is non-trivial. A genetic algorithm based approach has been developed to fit the equation to experimental viscosity data for a number of glassy materials, including SiO 2 , GeO 2 , B 2 O 3 , anorthite, diopside, xNa 2 O-(1-x)SiO 2 , xPbO-(1-x)SiO 2 , soda-lime-silica glasses, salol, and α-phenyl-o-cresol. Excellent fits of the equation to the viscosity data were obtained over the entire temperature range. The fitting parameters were used to quantitatively determine the enthalpies and entropies of formation and motion of configurons in the analysed systems and the activation energies for flow at high and low temperatures as well as fragility ratios using the Doremus criterion for fragility. A direct anti-correlation between fragility ratio and configuron percolation threshold, which determines the glass transition temperature in the analysed materials, was found.

Detection of Guanine and Adenine Using an Aminated Reduced Graphene Oxide Functional Membrane-Modified Glassy Carbon Electrode

PubMed Central

Li, Di; Yang, Xiao-Lu; Xiao, Bao-Lin; Geng, Fang-Yong; Hong, Jun; Sheibani, Nader; Moosavi-Movahedi, Ali Akbar

2017-01-01

A new electrochemical sensor based on a Nafion, aminated reduced graphene oxide and chitosan functional membrane-modified glassy carbon electrode was proposed for the simultaneous detection of adenine and guanine. Fourier transform-infrared spectrometry (FTIR), transmission electron microscopy (TEM), and electrochemical methods were utilized for the additional characterization of the membrane materials. The prepared electrode was utilized for the detection of guanine (G) and adenine (A). The anodic peak currents to G and A were linear in the concentrations ranging from 0.1 to 120 μM and 0.2 to 110 μM, respectively. The detection limits were found to be 0.1 μM and 0.2 μM, respectively. Moreover, the modified electrode could also be used to determine G and A in calf thymus DNA. PMID:28718793

Evaluation in a Dog Model of Three Antimicrobial Glassy Coatings: Prevention of Bone Loss around Implants and Microbial Assessments

PubMed Central

López-Píriz, Roberto; Solá-Linares, Eva; Rodriguez-Portugal, Mercedes; Malpica, Beatriz; Díaz-Güemes, Idoia; Enciso, Silvia; Esteban-Tejeda, Leticia; Cabal, Belén; Granizo, Juan José; Moya, José Serafín; Torrecillas, Ramón

2015-01-01

Objectives The aim of the present study is to evaluate, in a ligature-induced peri-implantitis model, the efficacy of three antimicrobial glassy coatings in the prevention of biofilm formation, intrasulcular bacterial growth and the resulting peri-implant bone loss. Methods Mandibular premolars were bilaterally extracted from five beagle dogs. Four dental implants were inserted on each hemiarch. Eight weeks after, one control zirconia abutment and three with different bactericidal coatings (G1n-Ag, ZnO35, G3) were connected. After a plaque control period, bacterial accumulation was allowed and biofilm formation on abutments was observed by Scanning Electron Microscopy (SEM). Peri-implantitis was induced by cotton ligatures. Microbial samples and peri-implant crestal bone levels of all implant sites were obtained before, during and after the breakdown period. Results During experimental induce peri-implantitis: colony forming units counts from intrasulcular microbial samples at implants with G1n-Ag coated abutment remained close to the basal inoculum; G3 and ZnO35 coatings showed similar low counts; and anaerobic bacterias counts at control abutments exhibited a logarithmic increase by more than 2. Bone loss during passive breakdown period was no statistically significant. Additional bone loss occurred during ligature-induce breakdown: 0.71 (SD 0.48) at G3 coating, 0.57 (SD 0.36) at ZnO35 coating, 0.74 (SD 0.47) at G1n-Ag coating, and 1.29 (SD 0.45) at control abutments; and statistically significant differences (p<0.001) were found. The lowest bone loss at the end of the experiment was exhibited by implants dressing G3 coated abutments (mean 2.1; SD 0.42). Significance Antimicrobial glassy coatings could be a useful tool to ward off, diminish or delay peri-implantitis progression. PMID:26489088

Evaluation in a Dog Model of Three Antimicrobial Glassy Coatings: Prevention of Bone Loss around Implants and Microbial Assessments.

PubMed

López-Píriz, Roberto; Solá-Linares, Eva; Rodriguez-Portugal, Mercedes; Malpica, Beatriz; Díaz-Güemes, Idoia; Enciso, Silvia; Esteban-Tejeda, Leticia; Cabal, Belén; Granizo, Juan José; Moya, José Serafín; Torrecillas, Ramón

2015-01-01

The aim of the present study is to evaluate, in a ligature-induced peri-implantitis model, the efficacy of three antimicrobial glassy coatings in the prevention of biofilm formation, intrasulcular bacterial growth and the resulting peri-implant bone loss. Mandibular premolars were bilaterally extracted from five beagle dogs. Four dental implants were inserted on each hemiarch. Eight weeks after, one control zirconia abutment and three with different bactericidal coatings (G1n-Ag, ZnO35, G3) were connected. After a plaque control period, bacterial accumulation was allowed and biofilm formation on abutments was observed by Scanning Electron Microscopy (SEM). Peri-implantitis was induced by cotton ligatures. Microbial samples and peri-implant crestal bone levels of all implant sites were obtained before, during and after the breakdown period. During experimental induce peri-implantitis: colony forming units counts from intrasulcular microbial samples at implants with G1n-Ag coated abutment remained close to the basal inoculum; G3 and ZnO35 coatings showed similar low counts; and anaerobic bacterias counts at control abutments exhibited a logarithmic increase by more than 2. Bone loss during passive breakdown period was no statistically significant. Additional bone loss occurred during ligature-induce breakdown: 0.71 (SD 0.48) at G3 coating, 0.57 (SD 0.36) at ZnO35 coating, 0.74 (SD 0.47) at G1n-Ag coating, and 1.29 (SD 0.45) at control abutments; and statistically significant differences (p<0.001) were found. The lowest bone loss at the end of the experiment was exhibited by implants dressing G3 coated abutments (mean 2.1; SD 0.42). Antimicrobial glassy coatings could be a useful tool to ward off, diminish or delay peri-implantitis progression.

Proteins at the air-water interface in a lattice model

NASA Astrophysics Data System (ADS)

Zhao, Yani; Cieplak, Marek

2018-03-01

We construct a lattice protein version of the hydrophobic-polar model to study the effects of the air-water interface on the protein and on an interfacial layer formed through aggregation of many proteins. The basic unit of the model is a 14-mer that is known to have a unique ground state in three dimensions. The equilibrium and kinetic properties of the systems with and without the interface are studied through a Monte Carlo process. We find that the proteins at high dilution can be pinned and depinned many times from the air-water interface. When pinned, the proteins undergo deformation. The staying time depends on the strength of the coupling to the interface. For dense protein systems, we observe glassy effects. Thus, the lattice model yields results which are similar to those obtained through molecular dynamics in off-lattice models. In addition, we study dynamical effects induced by local temperature gradients in protein films.

Non-enzymatic detection of glucose using poly(azure A)-nickel modified glassy carbon electrode.

PubMed

Liu, Tong; Luo, Yiqun; Zhu, Jiaming; Kong, Liyan; Wang, Wen; Tan, Liang

2016-08-15

A simple, sensitive and selective non-enzymatic glucose sensor was constructed in this paper. The poly(azure A)-nickel modified glassy carbon electrode was successfully fabricated by the electropolymerization of azure A and the adsorption of Ni(2+). The Ni modified electrode, which was characterized by scanning electron microscope, cyclic voltammetry, electrochemical impedance spectra and X-ray photoelectron spectroscopy measurements, respectively, displayed well-defined current responses of the Ni(III)/Ni(II) couple and showed a good activity for electrocatalytic oxidation of glucose in alkaline medium. Under the optimized conditions, the developed sensor exhibited a broad linear calibration range of 5 μM-12mM for quantification of glucose and a low detection limit of 0.64μM (3σ). The excellent analytical performance including simple structure, fast response time, good anti-interference ability, satisfying stability and reliable reproducibility were also found from the proposed amperometric sensor. The results were satisfactory for the determination of glucose in human serum samples as comparison to those from a local hospital. Copyright © 2016 Elsevier B.V. All rights reserved.

Characterization of cell lines developed from the glassy-winged sharpshooter, Homalodisca coagulata (Hemiptera: Cicadellidae).

PubMed

Kamita, Shizuo G; Do, Zung N; Samra, Aman I; Hagler, James R; Hammock, Bruce D

2005-01-01

Four continuous cell lines were established from the embryos of the glassy-winged sharpshooter, Homalodisca coagulata (Say), an economically important insect vector of bacterial pathogens of grape, almond, citrus, oleander, and other agricultural and ornamental plantings. The cell lines were designated GWSS-Z10, GWSS-Z15, GWSS-G3, and GWSS-LH. The GWSS-Z10, GWSS-Z15, and GWSS-G3 lines were cultured in Ex-Cell 401 medium supplemented with 10% fetal bovine serum (FBS), whereas the GWSS-LH line was cultured in LH medium supplemented with 20% FBS. The cell lines were characterized in terms of their morphology, growth, protein composition, and polymerase chain reaction- amplification patterns of their chromosomal deoxyribonucleic acid. The population doubling times of GWSS-Z10, GWSS-Z15, GWSS-G3, and GWSS-LH were 46.2, 90.9, 100.3, and 60.2 h, respectively. These lines should be useful for the study of insect-pathogenic viruses of leafhoppers, aphids, treehoppers, and other related insects as well as plant-pathogenic viruses that are transmitted by these insects.

New design strategy for reversible plasticity shape memory polymers with deformable glassy aggregates.

PubMed

Lin, Tengfei; Tang, Zhenghai; Guo, Baochun

2014-12-10

Reversible plasticity shape memory (RPSM) is a new concept in the study of shape memory performance behavior and describes a phenomenon in which shape memory polymers (SMPs) can undergo a large plastic deformation at room temperature and subsequently recover their original shape upon heating. To date, RPSM behavior has been demonstrated in only a few polymers. In the present study, we implement a new design strategy, in which deformable glassy hindered phenol (AO-80) aggregates are incorporated into an amorphous network of epoxidized natural rubber (ENR) cured with zinc diacrylate (ZDA), in order to achieve RPSM properties. We propose that AO-80 continuously tunes the glass transition temperature (Tg) and improves the chain mobility of the SMP, providing traction and anchoring the ENR chains by intermolecular hydrogen bonding interactions. The RPSM behavior of the amorphous SMPs is characterized, and the results demonstrate good fixity at large deformations (up to 300%) and excellent recovery upon heating. Large energy storage capacities at Td in these RPSM materials are demonstrated compared with those achieved at elevated temperature in traditional SMPs. Interestingly, the further revealed self-healing properties of these materials are closely related to their RPSM behavior.

Highly selective determination of dopamine in the presence of ascorbic acid and serotonin at glassy carbon electrodes modified with carbon nanotubes dispersed in polyethylenimine.

PubMed

Rodríguez, Marcela C; Rubianes, María D; Rivas, Gustavo A

2008-11-01

We report the highly selective and sensitive voltammetric dopamine quantification in the presence of ascorbic acid and serotonin by using glassy carbon electrodes modified with a dispersion of multi-wall carbon nanotubes (MWCNT) in polyethylenimine, PEI (GCE/MWCNT-PEI). The electrocatalytic activity of the MWCNT deposited on the glassy carbon electrode has allowed an important decrease in the overvoltages for the oxidation of ascorbic acid and dopamine, making possible a clear definition of dopamine, serotonin and ascorbic acid oxidation processes. The sensitivities for dopamine in the presence and absence of 1.0 mM ascorbic acid and serotonin were (2.18 +/- 0.03) x 10(5) microAM(-1) (r = 0.9998); and (2.10 +/- 0.07) x 10(5) miroAM(-1) (r=0.9985), respectively, demonstrating the excellent performance of the GCE/MWCNT-PEI. The detection limit for dopamine in the mixture was 9.2 x 10(-7) M. The R. S. D. for the determination of 50 microM dopamine using four different electrodes was 3.9% when modified with the same MWCNT/PEI dispersion, and 4.6% when using four different dispersions. The modified electrode has been successfully applied for recovery assays of dopamine in human blood serum. Therefore, the new sensor represents an interesting and promising alternative for the electrochemical quantification of neurotransmitters and other analytes of clinical interest.

Glasslike dynamical behavior of the plastocyanin hydration water

NASA Astrophysics Data System (ADS)

Bizzarri, Anna Rita; Paciaroni, Alessandro; Cannistraro, Salvatore

2000-09-01

The dynamical behavior of water around plastocyanin has been investigated in a wide temperature range by molecular dynamics simulation. The mean square displacements of water oxygen atoms show, at long times, a tα trend for all temperatures. Below 150 K, α is constant and equal to 1; at higher temperatures it drops to a value significantly smaller than 1, and thereafter decreases with increasing temperature. The occurrence of such an anomalous diffusion matches the onset of the dynamical transition observed in the protein. The intermediate scattering function of water is characterized, at high temperature, by a stretched exponential decay evolving, at low temperature, toward a two step relaxation behavior, which becomes more evident on increasing the exchanged wave vector q. Both the mean square displacements and the intermediate scattering functions show, beyond the ballistic regime, a plateau, which progressively extends for longer times as long as the temperature is lowered, such behavior reflecting trapping of water molecules within a cage formed by the nearest neighbors. At low temperature, a low frequency broad inelastic peak is observed in the dynamical structure factor of hydration water; such an excess of vibrational modes being reminiscent of the boson peak, characteristic of disordered, amorphous systems. All these features, which are typical of complex systems, can be traced back to the glassy character of the hydration water and suggest a dynamical coupling occurring at the macromolecule-solvent interface.

Numerical modeling of perched water under Yucca Mountain, Nevada

USGS Publications Warehouse

Hinds, J.J.; Ge, S.; Fridrich, C.J.

1999-01-01

The presence of perched water near the potential high-level nuclear waste repository area at Yucca Mountain, Nevada, has important implications for waste isolation. Perched water occurs because of sharp contrasts in rock properties, in particular between the strongly fractured repository host rock (the Topopah Spring welded tuff) and the immediately underlying vitrophyric (glassy) subunit, in which fractures are sealed by clays that were formed by alteration of the volcanic glass. The vitrophyre acts as a vertical barrier to unsaturated flow throughout much of the potential repository area. Geochemical analyses (Yang et al. 1996) indicate that perched water is relatively young, perhaps younger than 10,000 years. Given the low permeability of the rock matrix, fractures and perhaps fault zones must play a crucial role in unsaturated flow. The geologic setting of the major perched water bodies under Yucca Mountain suggests that faults commonly form barriers to lateral flow at the level of the repository horizon, but may also form important pathways for vertical infiltration from the repository horizon down to the water table. Using the numerical code UNSAT2, two factors believed to influence the perched water system at Yucca Mountain, climate and fault-zone permeability, are explored. The two-dimensional model predicts that the volume of water held within the perched water system may greatly increase under wetter climatic conditions, and that perched water bodies may drain to the water table along fault zones. Modeling results also show fault flow to be significantly attenuated in the Paintbrush Tuff non-welded hydrogeologic unit.

Photogeneration of singlet oxygen by the phenothiazine derivatives covalently bound to the surface-modified glassy carbon

NASA Astrophysics Data System (ADS)

Blacha-Grzechnik, Agata; Piwowar, Katarzyna; Krukiewicz, Katarzyna; Koscielniak, Piotr; Szuber, Jacek; Zak, Jerzy K.

2016-05-01

The selected group of four amine-derivatives of phenothiazine was covalently grafted to the glassy carbon surface in the four-step procedure consisting of the electrochemical reduction of the diazonium salt followed by the electrochemical and chemical post-modification steps. The proposed strategy involves the bonding of linker molecule to which the photosensitizer is attached. The synthesized organic layers were characterized by means of cyclic voltammetry, XPS and Raman Spectroscopy. It was shown that the phenothiazines immobilized via proposed strategy retain their photochemical properties and are able to generate 1O2 when activated by the laser radiation. The effectiveness of in situ singlet oxygen generation by those new solid photoactive materials was determined by means of UVVis spectroscopy. The reported, covalently modified solid surfaces may find their application as the singlet oxygen photogenerators in the fine chemicals' synthesis or in the wastewater treatment.

Glassy formation ability, magnetic properties and magnetocaloric effect in Al27Cu18Er55 amorphous ribbon

NASA Astrophysics Data System (ADS)

Li, Lingwei; Xu, Chi; Yuan, Ye; Zhou, Shengqiang

2018-05-01

In this work, we have fabricated the Al27Cu18Er55 amorphous ribbon with good glassy formation ability by melt-spinning technology. A broad paramagnetic (PM) to ferromagnetic (FM) transition (second ordered) together with a large reversible magnetocaloric effect (MCE) in Al27Cu18Er55 amorphous ribbon was observed around the Curie temperature TC ∼ 11 K. Under the magnetic field change (ΔH of 0-7 T, the values of MCE parameter of the maximum magnetic entropy change (-ΔSMmax) and refrigerant capacity (RC) for Al27Cu18Er55 amorphous ribbon reach 21.4 J/kg K and 599 J/kg, respectively. The outstanding glass forming ability as well as the excellent magneto-caloric properties indicate that Al27Cu18Er55 amorphous could be a good candidate for low temperature magnetic refrigeration.

Disruption of Hydrogen-Bonding Network Eliminates Water Anomalies Normally Observed on Cooling to Its Calorimetric Glass Transition

DOE PAGES

Borreguero, Jose M.; Mamontov, Eugene

2017-04-11

Here, the calorimetric glass-transition temperature of water is 136 K, but extrapolation of thermodynamic and relaxation properties of water from ambient temperature to below its homogeneous nucleation temperature T H = 235 K predicts divergence at T S = 228 K. The “no-man’s land” between the T H and glassy water crystallization temperature of 150 K, which is encountered on warming up from the vitrified state, precludes a straightforward reconciliation of the two incompatible temperature dependences of water properties, above 235 K and below 150 K. The addition of lithium chloride to water allows bypassing both T H and Tmore » S on cooling, resulting in the dynamics with no features except the calorimetric glass transition, still at 136 K. We show that lithium chloride prevents hydrogen-bonding network completion in water on cooling, as manifested, in particular, in changing microscopic diffusion mechanism of the water molecules. Thus thermodynamic and relaxation peculiarities exhibited by pure water on cooling to its glass transition, such as the existence of the T H and T S, must be associated specifically with the hydrogen-bonding network.« less

Shrinking water's no man's land by lifting its low-temperature boundary

NASA Astrophysics Data System (ADS)

Seidl, Markus; Fayter, Alice; Stern, Josef N.; Zifferer, Gerhard; Loerting, Thomas

2015-04-01

Investigation of the properties and phase behavior of noncrystalline water is hampered by rapid crystallization in the so-called "no man's land." We here show that it is possible to shrink the no man's land by lifting its low-temperature boundary, i.e., the pressure-dependent crystallization temperature Tx(p ) . In particular, we investigate two types of high-density amorphous ice (HDA) in the pressure range of 0.10 -0.50 GPa and show that the commonly studied unannealed state, uHDA, is up to 11 K less stable against crystallization than a pressure-annealed state called eHDA. We interpret this finding based on our previously established microscopic picture of uHDA and eHDA, respectively [M. Seidl et al., Phys. Rev. B 88, 174105 (2013), 10.1103/PhysRevB.88.174105]. In this picture the glassy uHDA matrix contains ice Ih-like nanocrystals, which simply grow upon heating uHDA at pressures ≤0.20 GPa . By contrast, they experience a polymorphic phase transition followed by subsequent crystal growth at higher pressures. In comparison, upon heating purely glassy eHDA, ice nuclei of a critical size have to form in the first step of crystallization, resulting in a lifted Tx(p ) . Accordingly, utilizing eHDA enables the study of amorphous ice at significantly higher temperatures at which we regard it to be in the ultraviscous liquid state. This will boost experiments aiming at investigating the proposed liquid-liquid phase transition.

The application of statistical mechanics on the study of glassy behaviors in transportation networks and dynamics in models of financial markets

NASA Astrophysics Data System (ADS)

Yeung, Chi Ho

In this thesis, we study two interdisciplinary problems in the framework of statistical physics, which show the broad applicability of physics on problems with various origins. The first problem corresponds to an optimization problem in allocating resources on random regular networks. Frustrations arise from competition for resources. When the initial resources are uniform, different regimes with discrete fractions of satisfied nodes are observed, resembling the Devil's staircase. We apply the spin glass theory in analyses and demonstrate how functional recursions are converted to simple recursions of probabilities. Equilibrium properties such as the average energy and the fraction of free nodes are derived. When the initial resources are bimodally distributed, increases in the fraction of rich nodes induce a glassy transition, entering a glassy phase described by the existence of multiple metastable states, in which we employ the replica symmetry breaking ansatz for analysis. The second problem corresponds to the study of multi-agent systems modeling financial markets. Agents in the system trade among themselves, and self-organize to produce macroscopic trading behaviors resembling the real financial markets. These behaviors include the arbitraging activities, the setting up and the following of price trends. A phase diagram of these behaviors is obtained, as a function of the sensitivity of price and the market impact factor. We finally test the applicability of the models with real financial data including the Hang Seng Index, the Nasdaq Composite and the Dow Jones Industrial Average. A substantial fraction of agents gains faster than the inflation rate of the indices, suggesting the possibility of using multi-agent systems as a tool for real trading.

Physicochemical characterization and water vapor sorption of organic solution advanced spray-dried inhalable trehalose microparticles and nanoparticles for targeted dry powder pulmonary inhalation delivery.

PubMed

Li, Xiaojian; Mansour, Heidi M

2011-12-01

Novel advanced spray-dried inhalable trehalose microparticulate/nanoparticulate powders with low water content were successfully produced by organic solution advanced spray drying from dilute solution under various spray-drying conditions. Laser diffraction was used to determine the volumetric particle size and size distribution. Particle morphology and surface morphology was imaged and examined by scanning electron microscopy. Hot-stage microscopy was used to visualize the presence/absence of birefringency before and following particle engineering design pharmaceutical processing, as well as phase transition behavior upon heating. Water content in the solid state was quantified by Karl Fisher (KF) coulometric titration. Solid-state phase transitions and degree of molecular order were examined by differential scanning calorimetry (DSC) and powder X-ray diffraction, respectively. Scanning electron microscopy showed a correlation between particle morphology, surface morphology, and spray drying pump rate. All advanced spray-dried microparticulate/nanoparticulate trehalose powders were in the respirable size range and exhibited a unimodal distribution. All spray-dried powders had very low water content, as quantified by KF. The absence of crystallinity in spray-dried particles was reflected in the powder X-ray diffractograms and confirmed by thermal analysis. DSC thermal analysis indicated that the novel advanced spray-dried inhalable trehalose microparticles and nanoparticles exhibited a clear glass transition (T(g)). This is consistent with the formation of the amorphous glassy state. Spray-dried amorphous glassy trehalose inhalable microparticles and nanoparticles exhibited vapor-induced (lyotropic) phase transitions with varying levels of relative humidity as measured by gravimetric vapor sorption at 25°C and 37°C.

Electrochemistry of raloxifene on glassy carbon electrode and its determination in pharmaceutical formulations and human plasma.

PubMed

Bagheri, Akbar; Hosseini, Hadi

2012-12-01

The electrochemical behavior of raloxifene (RLX) on the surface of a glassy carbon electrode (GCE) has been studied by cyclic voltammetry (CV). The CV studies were performed in various supporting electrolytes, wide range of potential scan rates, and pHs. The results showed an adsorption-controlled and quasi-reversible process for the electrochemical reaction of RLX, and a probable redox mechanism was suggested. Under the optimum conditions, differential pulse voltammetry (DPV) was applied for quantitative determination of the RLX in pharmaceutical formulations. The DPV measurements showed that the anodic peak current of the RLX was linear to its concentration in the range of 0.2-50.0μM with a detection limit of 0.0750μM, relative standard deviation (RSD %) below 3.0%, and a good sensitivity. The proposed method was successfully applied for determination of the RLX in pharmaceutical and human plasma samples with a good selectivity and suitable recovery. Copyright © 2012 Elsevier B.V. All rights reserved.

Controls on ground-water chemistry in the Horse Heaven Hills, south-central Washington

USGS Publications Warehouse

Steinkampf, W.C.; Bortleson, Gilbert C.; Packard, F.A.

1985-01-01

Miocene basaltic aquifers are the source of domestic and municipal water, and about 20,000 acre-feet of irrigation water annually, in the Horse Heaven Hills in south-central Washington State. Groundwater chemical variations derive from the hydraulic characteristics is of the geohydrologic system, from groundwater basalt reactions, and from irrigation. Some dissolved species concentrations increase with residence time; others decrease. Recharge area groundwaters are calcium magnesium sodium bicarbonate waters with sodium-adsorption ratios (SAR's) less than 1.0. They evolve to sodium potassium bicarbonate waters with SAR 's as high as 17. Glassy and cryptocrystalline phases of the basalt are the main sources of dissolved sodium. They dissolve by silicate hydrolysis in carbon dioxide charged waters that recharge the aquifer system. Dissolved silicon, iron, and aluminum concentrations are controlled by the solubilities of amorphous secondary alteration products, which order to silica phases, oxyhydroxides, and smectite. Carbonate mineral precipitation is induced by increasing pH from the hydrolysis reaction. Sodium and potassium concentrations increase until clinoptilolite saturation is reached and precipitation begins. Deviations from the general variation patterns are due to localized geologic structures which distort the groundwater flow system, and to the irrigation use of Columbia River water. (USGS)

The Enhanced Photo-Electrochemical Detection of Uric Acid on Au Nanoparticles Modified Glassy Carbon Electrode

NASA Astrophysics Data System (ADS)

Shi, Yuting; Wang, Jin; Li, Shumin; Yan, Bo; Xu, Hui; Zhang, Ke; Du, Yukou

2017-07-01

In this work, a sensitive and novel method for determining uric acid (UA) has been developed, in which the glassy carbon electrode (GCE) was modified with electrodeposition Au nanoparticles and used to monitor the concentration of UA with the assistant of visible light illumination. The morphology of the Au nanoparticles deposited on GCE surface were characterized by scanning electron microscope (SEM) and the nanoparticles were found to be well-dispersed spheres with the average diameter approaching 26.1 nm. A series of cyclic voltammetry (CV) and differential pulse voltammetry (DPV) measurements have revealed that the introduction of visible light can greatly enhance both the strength and stability of response current due to the surface plasmon resonance (SPR). Specifically, the DPV showed a linear relationship between peak current and UA concentration in the range of 2.8 to 57.5 μM with the equation of I pa (μA) = 0.0121 c UA (μM) + 0.3122 ( R 2 = 0.9987). Herein, the visible light illuminated Au/GCE possesses a potential to be a sensitive electrochemical sensor in the future.

Study of the overall behavior of thin films of the 7,7,8,8-tetracyanoquinodimethane neutral/anion couple on glassy carbon electrodes in the presence of cesium ion.

PubMed

Gómez, L; Rodríguez-Amaro, R

2008-10-07

The overall electrochemistry of 7,7,8,8-tetracyanoquinodimethane thin films on glassy carbon electrodes in media containing Cs+ ions is explained in light of a layer-by-layer nucleation and growth model, and kinetic data for the processes involved are reported. Using in situ UV-vis spectroelectrochemistry allowed available mechanistic knowledge on such processes to be expanded and the presence of various intermediates in the redox reactions confirmed.

Stable, fast and high-energy-density LiCoO2 cathode at high operation voltage enabled by glassy B2O3 modification

NASA Astrophysics Data System (ADS)

Zhou, Aijun; Wang, Weihang; Liu, Qin; Wang, Yi; Yao, Xu; Qing, Fangzhu; Li, Enzhu; Yang, Tingting; Zhang, Long; Li, Jingze

2017-09-01

In this work, commercial LiCoO2 is modified with a glassy B2O3 by solution mixing with H3BO3 followed by post-calcination in order to enhance its high-voltage electrochemical performance. The glassy B2O3 coating/additive is believed to serve as an effective physiochemical buffer and protection between LiCoO2 and liquid electrolyte, which can suppress the high-voltage induced electrolyte decomposition and active material dissolution. During the early cycling and due to the electrochemical force, the as-coated B2O3 glasses which have 3D open frameworks tend to accommodate some mobile Li+ and form a more chemically-resistant and ion-conductive lithium boron oxide (LBO) interphase as a major component of the solid electrolyte interphase (SEI), which consequently enables much easier Li+ diffusion/transfer at the solid-liquid interfaces upon further cycling. Due to the synergetic effects of B2O3 coating/modification, the high-voltage capacity and energy density of the B2O3-modified LiCoO2 cathode are promisingly improved by 35% and 30% after 100 cycles at 1 C within 3.0-4.5 V vs. Li/Li+. Meanwhile, the high-rate performance of the B2O3-modified electrode is even more greatly improved, showing a capacity of 105 mAh g-1 at 10 C while the bare electrode has dropped to no more than 30 mAh g-1 under this rate condition.

Adsorptive Behavior and Voltammetric Determination of Hydralazine Hydrochloride at A Glassy Carbon Electrode Modified with Multiwalled Carbon Nanotubes

PubMed Central

Khodadadian, Mehdi; Jalili, Ronak; Bahrami, Mohammad Taher; Bahrami, Gholamreza

2017-01-01

An electroanalytical method has been introduced for highly sensitive determination of hydralazine hydrochloride (Hy-HCl) based on its oxidation at a glassy carbon electrode modified with multiwalled carbon nanotubes (MWCNT/GCE). Studies showed that the electrochemical oxidation of Hy-HCl was accompanied by adsorption and highly sensitive responses could be achieved by adsorptive stripping voltammetry. The electrooxidation of Hy-HCl at MWCNT/GCE occurred at ~32 mV which was lower than that observed at bare GCE (~52 mV). The optimum working conditions for determination of the drug using differential-pulse adsorptive stripping voltammetry (DPAdSV) were established. The method exhibited linear responses to Hy-HCl in the concentration range 10-220 nM with a detection limit of 2.7 nM. The proposed method was successfully applied to the determination of this compound in pharmaceutical dosage forms. PMID:29552043

Electrocatalytic oxidation of 2-mercaptoethanol using modified glassy carbon electrode by MWCNT in combination with unsymmetrical manganese (II) Schiff base complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohebbi, Sajjad, E-mail: smohebbi@uok.ac.ir; Eslami, Saadat

2015-06-15

Highlights: • High electocatalytic efficiency and stability of modified hybrid electrode GC/MWCNTs/MnSaloph. • Direct reflection of catalytic activity of manganese complexes on electrocatalytic oxidation of 2-ME. • Decreasing overpotential and increasing catalytic peak current toward oxidation of 2-ME. • Deposition of range of novel substituted N{sub 2}O{sub 2} Saloph complexes of manganese(II) on GCE/MWCNT. • Enhancement of electrocatalytic oxidation activity upon electron donating substitutions on the Saloph. - Abstract: The performance of modified hybrid glassy carbon electrode with composite of carbon nanotubes and manganese complexes for the electrocatalytic oxidation of 2-mercaptoethanol is developed. GC electrode was modified using MWCNT andmore » new N{sub 2}O{sub 2} unsymmetrical tetradentate Schiff base complexes of manganese namely Manganese Saloph complexes 1-5, with general formula Mn[(5-x-4-y-Sal)(5-x′-4-y′-Sal) Ph], where x, x′ = H, Br, NO{sub 2} and y, y′ = H, MeO. Direct immobilization of CNT on the surface of GCE is performed by abrasive immobilization, and then modified by manganese(II) complexes via direct deposition method. These novel modified electrodes clearly demonstrate the necessity of modifying bare carbon electrodes to endow them with the desired behavior and were identified by HRTEM. Also complexes were characterized by elemental analyses, MS, UV–vis and IR spectroscopy. Modified hybrid GC/MWCNT/MnSaloph electrode exhibits strong and stable electrocatalytic activity towards the electrooxidation of 2-mercaptoethanol molecules in comparison with bare glassy carbon electrode with advantages of very low over potential and high catalytic current. Such ability promotes the thiol’s electron transfer reaction. Also, electron withdrawing substituent on the Saloph was enhanced electrocatalytic oxidation activity.« less

Short-Time Glassy Dynamics in Viscous Protein Solutions with Competing Interactions

DOE PAGES

Godfrin, P. Douglas; Hudson, Steven; Hong, Kunlun; ...

2015-11-24

Although there have been numerous investigations of the glass transition for colloidal dispersions with only a short-ranged attraction, less is understood for systems interacting with a long-ranged repulsion in addition to this attraction, which is ubiquitous in aqueous protein solutions at low ionic strength. Highly puri ed concentrated lysozyme solutions are used as a model system and investigated over a large range of protein concentrations at very low ionic strength. Newtonian liquid behavior is observed at all concentrations, even up to 480 mg/mL, where the zero shear viscosity increases by more than three orders of magnitude with increasing concentration. Remarkably,more » despite this macroscopic liquid-like behavior, the measurements of the dynamics in the short-time limit shows features typical of glassy colloidal systems. Investigation of the inter-protein structure indicates that the reduced short-time mobility of the protein is caused by localized regions of high density within a heterogeneous density distribution. This structural heterogeneity occurs on intermediate range length scale, driven by the competing potential features, and is distinct from commonly studied colloidal gel systems in which a heterogeneous density distribution tends to extend to the whole system. The presence of long-ranged repulsion also allows for more mobility over large length and long time scales resulting in the macroscopic relaxation of the structure. The experimental results provide evidence for the need to explicitly include intermediate range order in theories for the macroscopic properties of protein solutions interacting via competing potential features.« less

Raman non-coincidence effect of boroxol ring: The interplay between repulsion and attraction forces in the glassy, supercooled and liquid state

NASA Astrophysics Data System (ADS)

Kalampounias, Angelos G.; Papatheodorou, George N.

2018-06-01

Temperature dependent Raman spectra of boric oxide have been measured in a temperature range covering the glassy, supercooled and liquid state. The shift of the isotropic band assigned to boroxol rings relative to the anisotropic component upon heating the glass is measured and attributed to the Raman non-coincidence effect. The measured shift is associated with the competition between attraction and repulsion forces with increasing temperature. The relation of dephasing and orientational relaxation times to the non-coincidence effect of the condensed phases has been examined. We discuss our results in the framework of the current phenomenological status of the field in an attempt to separate the attraction and repulsion contributions corresponding to the observed non-coincidence effect.

On the nature of a glassy state of matter in a hydrated protein: Relation to protein function.

PubMed

Teeter, M M; Yamano, A; Stec, B; Mohanty, U

2001-09-25

Diverse biochemical and biophysical experiments indicate that all proteins, regardless of size or origin, undergo a dynamic transition near 200 K. The cause of this shift in dynamic behavior, termed a "glass transition," and its relation to protein function are important open questions. One explanation postulated for the transition is solidification of correlated motions in proteins below the transition. We verified this conjecture by showing that crambin's radius of gyration (Rg) remains constant below approximately 180 K. We show that both atom position and dynamics of protein and solvent are physically coupled, leading to a novel cooperative state. This glassy state is identified by negative slopes of the Debye-Waller (B) factor vs. temperature. It is composed of multisubstate side chains and solvent. Based on generalization of Adam-Gibbs' notion of a cooperatively rearranging region and decrease of the total entropy with temperature, we calculate the slope of the Debye-Waller factor. The results are in accord with experiment.

Interfacial electron transfer of glucose oxidase on poly(glutamic acid)-modified glassy carbon electrode and glucose sensing.

PubMed

Zhou, Xuechou; Tan, Bingcan; Zheng, Xinyu; Kong, Dexian; Li, Qinglu

2015-11-15

The interfacial electron transfer of glucose oxidase (GOx) on a poly(glutamic acid)-modified glassy carbon electrode (PGA/GCE) was investigated. The redox peaks measured for GOx and flavin adenine dinucleotide (FAD) are similar, and the anodic peak of GOx does not increase in the presence of glucose in a mediator-free solution. These indicate that the electroactivity of GOx is not the direct electron transfer (DET) between GOx and PGA/GCE and that the observed electroactivity of GOx is ascribed to free FAD that is released from GOx. However, efficient electron transfer occurred if an appropriate mediator was placed in solution, suggesting that GOx is active. The PGA/GCE-based biosensor showed wide linear response in the range of 0.5-5.5 mM with a low detection limit of 0.12 mM and high sensitivity and selectivity for measuring glucose. Copyright © 2015 Elsevier Inc. All rights reserved.

Thermal Barrier Coatings Resistant to Glassy Deposits

NASA Astrophysics Data System (ADS)

Drexler, Julie Marie

Engineering of alloys has for years allowed aircraft turbine engines to become more efficient and operate at higher temperatures. As advancements in these alloy systems have become more difficult, ceramic thermal barrier coatings (TBCs), often yttria (7 wt %) stabilized zirconia (7YSZ), have been utilized for thermal protection. TBCs have allowed for higher engine operating temperatures and better fuel efficiency but have also created new engineering problems. Specifically, silica based particles such as sand and volcanic ash that enter the engine during operation form glassy deposits on the TBCs. These deposits can cause the current industrial 7YSZ thermal barrier coatings to fail since the glass formed penetrates and chemically interacts with the TBC. When this occurs, coating failure may occur due to a loss of strain tolerance, which can lead to fracture, and phase changes of the TBC material. There have been several approaches used to stop calcium-magnesium aluminio-silcate (CMAS) glasses (molten sand) from destroying the entire TBC, but overall there is still limited knowledge. In this thesis, 7YSZ and new TBC materials will be examined for thermochemical and thermomechanical performance in the presence of molten CMAS and volcanic ash. Two air plasma sprayed TBCs will be shown to be resistant to volcanic ash and CMAS. The first type of coating is a modified 7YSZ coating with 20 mol% Al2O3 and 5 mol% TiO2 in solid solution (YSZ+20Al+5Ti). The second TBC is made of gadolinium zirconate. These novel TBCs impede CMAS and ash penetration by interacting with the molten CMAS or ash and drastically changing the chemistry. The chemically modified CMAS or ash will crystallize into an apatite or anorthite phase, blocking the CMAS or ash from further destroying the coating. A presented mechanism study will show these coatings are effective due to the large amount of solute (Gd, Al) in the zirconia structure, which is the key to creating the crystalline apatite or

Apollo 11 stereo view showing lump of surface powder with glassy material

NASA Image and Video Library

1969-07-20

AS11-45-6704 (20 July 1969) --- An Apollo stereo view showing a close-up of a small lump of lunar surface powder about a half inch across, with a splash of a glassy material over it. It seems that a drop of molten material fell on it, splashed and froze. The exposure was made by the Apollo 11 35mm stereo close-up camera. The camera was specially developed to get the highest possible resolution of a small area. A three-inch square area is photographed with a flash illumination and at a fixed distance. The camera is mounted on a walking stick, and the astronauts use it by holding it up against the object to be photographed and pulling the trigger. The pictures are in color and give a stereo view, enabling the fine detail to be seen very clearly. The project is under the direction of Professor T. Gold of Cornell University and Dr. F. Pearce of NASA. The camera was designed and built by Eastman Kodak. Professor E. Purcell of Harvard University and Dr. E. Land of the Polaroid Corporation have contributed to the project. The pictures brought back from the moon by the Apollo 11 crew are of excellent quality and allow fine detail of the undisturbed lunar surface to be seen. Scientists hope to be able to deduce from them some of the processes that have taken place that have shaped and modified the surface.

A Raman Microspectroscopy Study of Water and Trehalose in Spin-Dried Cells

PubMed Central

Abazari, Alireza; Chakraborty, Nilay; Hand, Steven; Aksan, Alptekin; Toner, Mehmet

2014-01-01

Long-term storage of desiccated nucleated mammalian cells at ambient temperature may be accomplished in a stable glassy state, which can be achieved by removal of water from the biological sample in the presence of glass-forming agents including trehalose. The stability of the glass may be compromised due to a nonuniform distribution of residual water and trehalose within and around the desiccated cells. Thus, quantification of water and trehalose contents at the single-cell level is critical for predicting the glass formation and stability for dry storage. Using Raman microspectroscopy, we estimated the trehalose and residual water contents in the microenvironment of spin-dried cells. Individual cells with or without intracellular trehalose were embedded in a solid thin layer of extracellular trehalose after spin-drying. We found strong evidence suggesting that the residual water was bound at a 2:1 water/trehalose molar ratio in both the extracellular and intracellular milieus. Other than the water associated with trehalose, we did not find any more residual water in the spin-dried sample, intra- or extracellularly. The extracellular trehalose film exhibited characteristics of an amorphous state with a glass transition temperature of ∼22°C. The intracellular milieu also dried to levels suitable for glass formation at room temperature. These findings demonstrate a method for quantification of water and trehalose in desiccated specimens using confocal Raman microspectroscopy. This approach has broad use in desiccation studies to carefully investigate the relationship of water and trehalose content and distribution with the tolerance to drying in mammalian cells. PMID:25418294

Outstanding resistance and passivation behaviour of new Fe-Co metal-metal glassy alloys in alkaline media

PubMed Central

Al-Harbi, Albandaree K.

2018-01-01

The electrochemical behavior of the oxide layers on two metal-metal glassy alloys, Fe78Co9Cr10Mo2Al1 (VX9)and Fe49Co49V2 (VX50) (at.%), were studied using electrochemical techniques including electrochemical frequency modulation (EFM), electrochemical impedance spectroscopy (EIS) and cyclic polarization (CP) measurements. The morphology and composition of the alloy surfaces were investigated using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion rate and surface roughness of both alloys increased as the concentration of NaOH in aqueous solution was raised. The presence of some protective elements in the composition of the alloys led to the formation of a spontaneous passive layer on the alloy surface. The higher resistance values of both alloys were associated with the magnitude of the dielectric properties of the passive films formed on their surfaces. Both alloys are classified as having outstanding resistance to corrosion, which results from the formation of a passive film that acts as an efficient barrier to corrosion in alkaline solution. PMID:29337992

Outstanding resistance and passivation behaviour of new Fe-Co metal-metal glassy alloys in alkaline media.

PubMed

Emran, Khadijah M; Al-Harbi, Albandaree K

2018-01-01

The electrochemical behavior of the oxide layers on two metal-metal glassy alloys, Fe78Co9Cr10Mo2Al1 (VX9)and Fe49Co49V2 (VX50) (at.%), were studied using electrochemical techniques including electrochemical frequency modulation (EFM), electrochemical impedance spectroscopy (EIS) and cyclic polarization (CP) measurements. The morphology and composition of the alloy surfaces were investigated using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion rate and surface roughness of both alloys increased as the concentration of NaOH in aqueous solution was raised. The presence of some protective elements in the composition of the alloys led to the formation of a spontaneous passive layer on the alloy surface. The higher resistance values of both alloys were associated with the magnitude of the dielectric properties of the passive films formed on their surfaces. Both alloys are classified as having outstanding resistance to corrosion, which results from the formation of a passive film that acts as an efficient barrier to corrosion in alkaline solution.

Ultrasensitive Determination of Piroxicam at Diflunisal-Derived Gold Nanoparticle-Modified Glassy Carbon Electrode

NASA Astrophysics Data System (ADS)

Shaikh, Tayyaba; uddin, SiraJ; Talpur, Farah N.; Khaskeli, Abdul R.; Agheem, Muhammad H.; Shah, Muhammad R.; Sherazi, Tufail H.; Siddiqui, Samia

2017-10-01

We present a simple and green approach for synthesis of gold nanoparticles (AuNps) using analgesic drug diflunisal (DF) as capping and stabilizing agent in aqueous solution. Characterization of the synthesized diflunisal-derived gold nanoparticles (DF-AuNps) was performed by ultraviolet-visible (UV-Vis) spectroscopy, revealing the surface plasmon absorption band at 520 nm under optimized experimental conditions. Fourier-transform infrared (FTIR) spectroscopy established the effective interaction of the capping agent with the AuNps. Topographical features of the synthesized DF-AuNps were assessed by atomic force microscopy (AFM), revealing average particle height of 29 nm to 32 nm. X-ray diffractometry was used to study the crystalline nature, revealing that the synthesized DF-AuNps possessed excellent crystalline properties. The synthesized DF-AuNps were employed to modify the surface of glassy carbon electrode (GCE) for selective determination of piroxicam (PX) using differential pulse voltammetry technique. The fabricated Nafion/DF-AuNps/GCE sensor exhibited high sensitivity compared with bare GCE. The current response of the fabricated sensor was found to be linear in the PX concentration range of 0.5 μM to 50 μM, with limit of detection (LOD) and limit of quantification (LOQ) of 50 nM and 150 nM, respectively. The proposed sensor was successfully utilized for sensitive and rapid determination of PX in human serum, urine, and pharmaceutical samples.

Detection of the Bacterium, Xylella fastidiosa, in Saliva of Glassy-Winged Sharpshooter, Homalodisca vitripennis

PubMed Central

Ramirez, Jose L.; Lacava, Paulo T.; Miller, Thomas A.

2008-01-01

Homalodisca vitripennis (Germar) (Hemiptera: Cicadellidae), the glassy-winged sharpshooter, is one of the most important vectors of the bacterium, Xylella fastidiosa subsp. piercei (Xanthomonadales: Xanthomonadaceae) that causes Pierce's Disease in grapevines in California. In the present study we report a new method for studying pathogen transmission or probing behavior of H. vitripennis. When confined, H. vitripennis attempt to probe the surface of sterile containers 48 hours post-acquisition of X. f. piercei. The saliva deposited during attempted feeding probes was found to contain X. f. piercei. We observed no correlation between X. f. piercei titers in the foregut of H. vitripennis that fed on Xylella-infected grapevines and the presence of this bacterium in the deposited saliva. The infection rate after a 48 h post-acquisition feeding on healthy citrus and grapevines was observed to be 77% for H. vitripennis that fed on grapevines and 81% for H. vitripennis that fed on citrus, with no difference in the number of positive probing sites from H. vitripennis that fed on either grapevine or citrus. This method is amenable for individual assessment of X. f. piercei-infecuvity, with samples less likely to be affected by tissue contamination that is usually present in whole body extracts. PMID:20233080

On the Fluctuations that Order and Frustrate Liquid Water

NASA Astrophysics Data System (ADS)

Limmer, David Tyler

At ambient conditions, water sits close to phase coexistence with its crystal. More so than in many other materials, this fact is manifested in the fluctuations that maintain a large degree of local order in the liquid. These fluctuations and how they result in long-ranged order, or its absence, are emergent features of many interacting molecules. Their study therefore requires using the tools of statistical mechanics for their their systematic understanding. In this dissertation we develop such an understanding. In particular, we focus on collective behavior that emerges in liquid and solid water. At room temperatures, the thermophysical properties of water are quantified and rationalized with simple molecular models. A key feature of these models is the correct characterization of the competition between entropic forces of packing and the energetic preference for tetrahedral order. At cold temperatures, the properties of ice surfaces are studied with statistical field theory. The theory we develop for the long wavelength features of ice interfaces allows us to explain the existence of a premelting layer on the surface of ice and the stability of ice in confinement. In between these extremes, the dynamics of supercooled water are considered. A detailed theory for the early stages of coarsening is developed and used to explain the peculiar observation of a transient second liquid state of water. When coarsening dynamics are arrested, the result is the formation of a glassy states of water. We show that out-of-equilibrium the phase diagram for supercooled water exhibits a rich amount of structure, including a triple point between two glass phases of water and the liquid. At the end, we explore possible technological implications for the interplay between ordering and frustration in studies of water at metal interfaces.

Exchange bias effect and glassy-like behavior of EuCrO{sub 3} and CeCrO{sub 3} nano-powders

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taheri, M., E-mail: maryam.taheri@brocku.ca; Razavi, F. S.; Kremer, R. K.

2015-09-28

The magnetic properties of nano-sized EuCrO{sub 3} and CeCrO{sub 3} powders, synthesized by a solution combustion method, were investigated using DC/AC magnetization measurements. An exchange bias effect, magnetization irreversibility and AC susceptibility dispersion in these samples provided evidence for the presence of the spin disorder magnetic phase. The exchange bias phenomenon, which is assigned to the exchange coupling between the glassy-like shell and canted antiferromagnetic core, showed the opposite sign in EuCrO{sub 3} and CeCrO{sub 3} at low temperatures, suggesting different exchange interactions at the interfaces in these compounds. We also observed a sign reversal of exchange bias in CeCrO{submore » 3} at different temperatures.« less

Breakdown of water super-permeation in electrically insulating graphene oxide films: role of dual interlayer spacing.

PubMed

Kavitha, Maheshwari Kavirajan; Sakorikar, Tushar; Vayalamkuzhi, Pramitha; Jaiswal, Manu

2018-08-10

Conventional graphene oxide (GO) is characterized by low sp 2 content in a sp 3 rich matrix, which is responsible both for electrical insulation and water super-permeation. Upon reduction, electrical conduction is achieved at the expense of water permeation ability. Here, we demonstrate that charge conduction and water permeation can be simultaneously restricted in a functionalized form of GO. Gravimetric studies reveal that diffusion of water vapor through a glassy polymer membrane is arrested by loading a hydrophobic form of GO (H-GO) in the polymer matrix, even as such, water inhibition cannot be realized by substantially increasing the thickness of the bare polymer. As an application, the ability of the coating to impede the degradation of methyl ammonium lead iodide films under high humidity conditions is demonstrated. At the same time the H-GO film has a resistance over 10 7 times higher when compared to thermally reduced GO of similar sp 2 fraction. We attribute this unique behavior to the presence of a sub-micron matrix of GO with simultaneous presence of large (∼9.5 Å) and small (∼4.7 Å) interlayer spacing. This leads to disruption of the spatially distributed percolation pathways for electrical charge, and it also serves to block the nanocapillary networks for water molecules.

Direct Measurement of Water States in Cryopreserved Cells Reveals Tolerance toward Ice Crystallization

PubMed Central

Huebinger, Jan; Han, Hong-Mei; Hofnagel, Oliver; Vetter, Ingrid R.; Bastiaens, Philippe I.H.; Grabenbauer, Markus

2016-01-01

Complex living systems such as mammalian cells can be arrested in a solid phase by ultrarapid cooling. This allows for precise observation of cellular structures as well as cryopreservation of cells. The state of water, the main constituent of biological samples, is crucial for the success of cryogenic applications. Water exhibits many different solid states. If it is cooled extremely rapidly, liquid water turns into amorphous ice, also called vitreous water, a glassy and amorphous solid. For cryo-preservation, the vitrification of cells is believed to be mandatory for cell survival after freezing. Intracellular ice crystallization is assumed to be lethal, but experimental data on the state of water during cryopreservation are lacking. To better understand the water conditions in cells subjected to freezing protocols, we chose to directly analyze their subcellular water states by cryo-electron microscopy and tomography, cryoelectron diffraction, and x-ray diffraction both in the cryofixed state and after warming to different temperatures. By correlating the survival rates of cells with their respective water states during cryopreservation, we found that survival is less dependent on ice-crystal formation than expected. Using high-resolution cryo-imaging, we were able to directly show that cells tolerate crystallization of extra- and intracellular water. However, if warming is too slow, many small ice crystals will recrystallize into fewer but bigger crystals, which is lethal. The applied cryoprotective agents determine which crystal size is tolerable. This suggests that cryoprotectants can act by inhibiting crystallization or recrystallization, but they also increase the tolerance toward ice-crystal growth. PMID:26541066

Temporal disconnectivity of the energy landscape in glassy systems

NASA Astrophysics Data System (ADS)

Lempesis, Nikolaos; Boulougouris, Georgios C.; Theodorou, Doros N.

2013-03-01

An alternative graphical representation of the potential energy landscape (PEL) has been developed and applied to a binary Lennard-Jones glassy system, providing insight into the unique topology of the system's potential energy hypersurface. With the help of this representation one is able to monitor the different explored basins of the PEL, as well as how - and mainly when - subsets of basins communicate with each other via transitions in such a way that details of the prior temporal history have been erased, i.e., local equilibration between the basins in each subset has been achieved. In this way, apart from detailed information about the structure of the PEL, the system's temporal evolution on the PEL is described. In order to gather all necessary information about the identities of two or more basins that are connected with each other, we consider two different approaches. The first one is based on consideration of the time needed for two basins to mutually equilibrate their populations according to the transition rate between them, in the absence of any effect induced by the rest of the landscape. The second approach is based on an analytical solution of the master equation that explicitly takes into account the entire explored landscape. It is shown that both approaches lead to the same result concerning the topology of the PEL and dynamical evolution on it. Moreover, a "temporal disconnectivity graph" is introduced to represent a lumped system stemming from the initial one. The lumped system is obtained via a specially designed algorithm [N. Lempesis, D. G. Tsalikis, G. C. Boulougouris, and D. N. Theodorou, J. Chem. Phys. 135, 204507 (2011), 10.1063/1.3663207]. The temporal disconnectivity graph provides useful information about both the lumped and the initial systems, including the definition of "metabasins" as collections of basins that communicate with each other via transitions that are fast relative to the observation time. Finally, the two examined

Biosensor based on tyrosinase immobilized on a single-walled carbon nanotube-modified glassy carbon electrode for detection of epinephrine

PubMed Central

Apetrei, Irina Mirela; Apetrei, Constantin

2013-01-01

A biosensor comprising tyrosinase immobilized on a single-walled carbon nanotube-modified glassy carbon electrode has been developed. The sensitive element, ie, tyrosinase, was immobilized using a drop-and-dry method followed by cross-linking. Tyrosinase maintained high bioactivity on this nanomaterial, catalyzing the oxidation of epinephrine to epinephrine-quinone, which was electrochemically reduced (−0.07 V versus Ag/AgCl) on the biosensor surface. Under optimum conditions, the biosensor showed a linear response in the range of 10–110 μM. The limit of detection was calculated to be 2.54 μM with a correlation coefficient of 0.977. The repeatability, expressed as the relative standard deviation for five consecutive determinations of 10−5 M epinephrine solution was 3.4%. A good correlation was obtained between results obtained by the biosensor and those obtained by ultraviolet spectrophotometric methods. PMID:24348034

Steady-State Diffusion of Water through Soft-Contact LensMaterials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fornasiero, Francesco; Krull, Florian; Radke, Clayton J.

2005-01-31

Water transport through soft contact lenses (SCL) is important for acceptable performance on the human eye. Chemical-potential gradient-driven diffusion rates of water through soft-contact-lens materials are measured with an evaporation-cell technique. Water is evaporated from the bottom surface of a lens membrane by impinging air at controlled flow rate and humidity. The resulting weight loss of a water reservoir covering the top surface of the contact-lens material is recorded as a function of time. New results are reported for a conventional hydrogel material (SofLens{trademark} One Day, hilafilcon A, water content at saturation W{sub 10} = 70 weight %) and amore » silicone hydrogel material (PureVision{trademark}, balafilcon A, W{sub 10} = 36 %), with and without surface oxygen plasma treatment. Also, previously reported data for a conventional HEMA-SCL (W{sub 10} = 38 %) hydrogel are reexamined and compared with those for SofLens{trademark} One Day and PureVision{trademark} hydrogels. Measured steady-state water fluxes are largest for SofLens{trademark} One Day, followed by PureVision{trademark} and HEMA. In some cases, the measured steady-state water fluxes increase with rising relative air humidity. This increase, due to an apparent mass-transfer resistance at the surface (trapping skinning), is associated with formation of a glassy skin at the air/membrane interface when the relative humidity is below 55-75%. Steady-state water-fluxes are interpreted through an extended Maxwell-Stefan diffusion model for a mixture of species starkly different in size. Thermodynamic nonideality is considered through Flory-Rehner polymer-solution theory. Shrinking/swelling is self-consistently modeled by conservation of the total polymer mass. Fitted Maxwell-Stefan diffusivities increase significantly with water concentration in the contact lens.« less

Enzymatic biosensor based on entrapment of d-amino acid oxidase on gold nanofilm/MWCNTs nanocomposite modified glassy carbon electrode by sol-gel network: Analytical applications for d-alanine in human serum.

PubMed

Shoja, Yalda; Rafati, Amir Abbas; Ghodsi, Javad

2017-05-01

Sensing and determination of d-alanine is studied by using an enzymatic biosensor which was constructed on the basis of d-amino acid oxidase (DAAO) immobilization by sol-gel film onto glassy carbon electrode surface modified with nanocomposite of gold nanofilm (Au-NF) and multiwalled carbon nanotubes (MWCNTs). The Au-NF/MWCNT nanocomposite was prepared by applying the potentiostatic technique for electrodeposition of Au-NF on the MWCNT immobilized on glassy carbon electrode surface. The modified electrode is investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), linear sweep voltammetry (LSV) and cyclic voltammetry(CV) techniques. The linear sweep voltammetry was used for determination of d-alanine and the results showed an excellent linear relationship between biosensor response and d-alanine concentration ranging from 0.25μM to 4.5μM with correction coefficient of 0.999 (n=20). Detection limit for the fabricated sensor was calculated about 20nM (for S/N=3) and sensitivity was about 56.1μAμM -1 cm -2 . The developed biosensor exhibited rapid and accurate response to d-alanine, a good stability (4 weeks) and an average recovery of 98.9% in human serum samples. Copyright © 2017 Elsevier Inc. All rights reserved.

Brillouin-scattering study of liquid-glass transitions in ternary mixtures of water, trehalose, and an ionic liquid

NASA Astrophysics Data System (ADS)

Takayama, Haruki; Shibata, Tomohiko; Ishii, Takahiro; Kojima, Seiji

2013-04-01

Ternary mixtures of water, sugar, and ionic liquid have been studied as new candidates for bioprotectants. To clarify the elastic properties and relaxation dynamics of the supercooled liquid and glassy states at low temperatures, the liquid-glass transitions were investigated by using a micro-Brillouin-scattering technique. The refractive index was measured accurately as a function of content and temperature to determine the sound velocity and the attenuation from Brillouin frequency shift and peak width. The relaxation times of structural relaxations related to liquidglass transitions were determined as functions of temperature. The Meyer-Neldel rule was found to hold for the activation energy and the prefactor of the Arrhenius law for the relaxation time.

Characterization of the glass transition of water predicted by molecular dynamics simulations using nonpolarizable intermolecular potentials.

PubMed

Kreck, Cara A; Mancera, Ricardo L

2014-02-20

Molecular dynamics simulations allow detailed study of the experimentally inaccessible liquid state of supercooled water below its homogeneous nucleation temperature and the characterization of the glass transition. Simple, nonpolarizable intermolecular potentials are commonly used in classical molecular dynamics simulations of water and aqueous systems due to their lower computational cost and their ability to reproduce a wide range of properties. Because the quality of these predictions varies between the potentials, the predicted glass transition of water is likely to be influenced by the choice of potential. We have thus conducted an extensive comparative investigation of various three-, four-, five-, and six-point water potentials in both the NPT and NVT ensembles. The T(g) predicted from NPT simulations is strongly correlated with the temperature of minimum density, whereas the maximum in the heat capacity plot corresponds to the minimum in the thermal expansion coefficient. In the NVT ensemble, these points are instead related to the maximum in the internal pressure and the minimum of its derivative, respectively. A detailed analysis of the hydrogen-bonding properties at the glass transition reveals that the extent of hydrogen-bonds lost upon the melting of the glassy state is related to the height of the heat capacity peak and varies between water potentials.

Volcanic Rocks As Targets For Astrobiology Missions

NASA Astrophysics Data System (ADS)

Banerjee, N.

2010-12-01

Almost two decades of study highlight the importance of terrestrial subaqueous volcanic rocks as microbial habitats, particularly in glass produced by the quenching of basaltic lava upon contact with water. On Earth, microbes rapidly begin colonizing glassy surfaces along fractures and cracks exposed to water. Microbial colonization of basaltic glass leads to enhanced alteration through production of characteristic granular and/or tubular bioalteration textures. Infilling of formerly hollow alteration textures by minerals enable their preservation through geologic time. Basaltic rocks are a major component of the Martian crust and are widespread on other solar system bodies. A variety of lines of evidence strongly suggest the long-term existence of abundant liquid water on ancient Mars. Recent orbiter, lander and rover missions have found evidence for the presence of transient liquid water on Mars, perhaps persisting to the present day. Many other solar system bodies, notably Europa, Enceladus and other icy satellites, may contain (or have once hosted) subaqueous basaltic glasses. The record of terrestrial glass bioalteration has been interpreted to extend back ~3.5 billion years and is widespread in modern oceanic crust and its ancient metamorphic equivalents. The terrestrial record of glass bioalteration strongly suggests that glassy or formerly glassy basaltic rocks on extraterrestrial bodies that have interacted with liquid water are high-value targets for astrobiological exploration.

Pt/glassy carbon model catalysts prepared from PS-b-P2VP micellar templates.

PubMed

Gu, Yunlong; St-Pierre, Jean; Ploehn, Harry J

2008-11-04

Poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer was used as a micellar template to fabricate arrays of Pt nanoparticles on mica and glassy carbon (GC) supports. Polymer micellar deposition yields Pt nanoparticles with tunable particle size and surface number density on both mica and GC. After deposition of precursor-loaded micelles onto GC, oxygen plasma etching removes the polymer shell, followed by thermal treatment with H2 gas to reduce the Pt. Etching conditions were optimized to maximize removal of the polymer while minimizing damage to the GC. Arrays of Pt nanoparticles with controlled size and surface number density can be prepared on mica (for particle size characterization) and GC to make Pt/GC model catalysts. These model catalysts were characterized by tapping mode atomic force microscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry to measure activity for oxidation of carbon monoxide or methanol. Cyclic voltammetry results demonstrate the existence of a correlation between Pt particle size and electrocatalytic properties including onset potential, tolerance of carbonaceous adsorbates, and intrinsic activity (based on active Pt area from CO stripping voltammetry). Results obtained with Pt/GC model catalysts duplicate prior results obtained with Pt/porous carbon catalysts therefore validating the synthesis approach and offering a new, tunable platform to study catalyst structure and other effects such as aging on proton exchange membrane fuel cell (PEMFC) reactions.

Mechanisms of devitrification of grain boundary glassy phases in Si3N4 materials

NASA Technical Reports Server (NTRS)

Hench, L. L.

1982-01-01

Changes in the grain boundary (g.b.) phases of Si3N4 are analyzed, the effects of composition and thermal history on devitrification of the g.b. phases are determined, devitrification of the g.b. phases of Si3N are related to mechanical behavior and oxidation sensitivity of the material. The phase relationships that occur within the grain boundaries of Si3N4 containing various densification aids are reviewed. Comparisons of the effects of MgO, Y2O3, CeO2, and Y2O3 + AL2O3 are made in terms of the phase equilibria of the Si3N4 + SiO2 + additive compositional system. Two new equilibrium phase diagrams for the Si3N4-SiO2 and Y2O3 and Si3N4-SiO2-Ce2O3 systems are preented. The effects of Y2O3 vs CeO2 densification aids on the fracture surfaces of Si3N4 are compared. Auger electron spectroscopy shows that both oxides are concentrated within the fracture surface. Scanning electron microscopy shows evidence that Si3N4 with CeO2 formed an intergranular structure of fine grained oxynitride reaction products, as predicted by phase quilibria, whereas the Y2O3 containing sample shows evidence of an intergranular glassy phase.

Acoustic excitations in glassy sorbitol and their relation with the fragility and the boson peak

NASA Astrophysics Data System (ADS)

Ruta, B.; Baldi, G.; Scarponi, F.; Fioretto, D.; Giordano, V. M.; Monaco, G.

2012-12-01

We report a detailed analysis of the dynamic structure factor of glassy sorbitol by using inelastic X-ray scattering and previously measured light scattering data [B. Ruta, G. Monaco, F. Scarponi, and D. Fioretto, Philos. Mag. 88, 3939 (2008), 10.1080/14786430802317586]. The thus obtained knowledge on the density-density fluctuations at both the mesoscopic and macroscopic length scale has been used to address two debated topics concerning the vibrational properties of glasses. The relation between the acoustic modes and the universal boson peak (BP) appearing in the vibrational density of states of glasses has been investigated, also in relation with some recent theoretical models. Moreover, the connection between the elastic properties of glasses and the slowing down of the structural relaxation process in supercooled liquids has been scrutinized. For what concerns the first issue, it is here shown that the wave vector dependence of the acoustic excitations can be used, in sorbitol, to quantitatively reproduce the shape of the boson peak, supporting the relation between BP and acoustic modes. For what concerns the second issue, a proper study of elasticity over a wide spatial range is shown to be fundamental in order to investigate the relation between elastic properties and the slowing down of the dynamics in the corresponding supercooled liquid phase.

Catalytic carbide formation at aluminium-carbon interfaces

NASA Technical Reports Server (NTRS)

Maruyama, B.; Rabenberg, L.; Ohuchi, F. S.

1990-01-01

X-ray photoelectron spectroscopy investigations of the reaction of several monolayer-thick films of aluminum with glassy carbon substrates are presented. The influence of molecular oxygen and water vapor on the rate of reaction is examined. It is concluded that water vapor catalyzed the formation of aluminum carbide from aluminum and carbon by forming active sites which weakened carbon-carbon bonds at the glassy carbon surface, thus assisting their cleavage. The rate of carbide formation for undosed and molecular oxygen-dosed examples was less as neither metallic aluminum nor oxygen-formed alumina could bond to the carbon atom with sufficient strength to dissociate it quickly.

A voltammetric determination of caffeic acid in red wines based on the nitrogen doped carbon modified glassy carbon electrode.

PubMed

Karikalan, Natarajan; Karthik, Raj; Chen, Shen-Ming; Chen, Hsi-An

2017-04-05

We reported an electrochemical determination of caffeic acid (CA) based on the nitrogen doped carbon (NDC). The described sensor material was prepared by the flame synthesis method, which gave an excellent platform for the synthesis of carbon nanomaterials with the hetero atom dopant. The synthesized material was confirmed by various physical characterizations and it was further characterized by different electrochemical experiments. The NDC modified glassy carbon electrode (NDC/GCE) shows the superior electrocatalytic performance towards the determination of CA with the wide linear concentration range from 0.01 to 350 μM. It achieves the lowest detection limit of 0.0024 μM and the limit of quantification of 0.004 μM. The NDC/GCE-CA sensor reveals the good selectivity, stability, sensitivity and reproducibility which endorsed that the NDC is promising electrode for the determination of CA. In addition, NDC modified electrode is applied to the determination of CA in red wines and acquired good results.

Enhanced amperometric detection of metronidazole in drug formulations and urine samples based on chitosan protected tetrasulfonated copper phthalocyanine thin-film modified glassy carbon electrode.

PubMed

Meenakshi, S; Pandian, K; Jayakumari, L S; Inbasekaran, S

2016-02-01

An enhanced electrocatalytic reduction of metronidazole antibiotic drug molecule using chitosan protected tetrasulfonated copper phthalocyanine (Chit/CuTsPc) thin-film modified glassy carbon electrode (GCE) has been developed. An irreversible reduction occurs at -0.47V (vs. Ag/AgCl) using Chit/CuTsPc modified GCE. A maximum peak current value is obtained at pH1 and the electrochemical reduction reaction is a diffusion controlled one. The detection limit is found to be 0.41nM from differential pulse voltammetry (DPV) method. This present investigation method is adopted for electrochemical detection of metronidazole in drug formulation and urine samples by using DPV method. Copyright © 2015 Elsevier B.V. All rights reserved.

Predict the glass transition temperature and plasticization of β-cyclodextrin/water binary system by molecular dynamics simulation.

PubMed

Zhou, Guohui; Zhao, Tianhai; Wan, Jie; Liu, Chengmei; Liu, Wei; Wang, Risi

2015-01-12

The glass transition temperature, diffusion behavior and plasticization of β-cyclodextrin (β-CD), and three amorphous β-CD/water mixtures (3%, 5% and 10% [w/w] water, respectively) were investigated by molecular dynamics simulation, which were performed using Condensed-phase Optimized Molecular Potentials for Atomistic Simulation Studies (COMPASS) force field and isothermal-isobaric ensembles. The specific volumes of four amorphous cells were obtained as a function of temperature. The glass transition temperatures (T(g)) were estimated to be 334.25 K, 325.12 K, 317.32 K, and 305.41 K for amorphous β-CD containing 0%, 3%, 5% and 10% w/w water, respectively, which compares well with the values observed in published literature. The radial distribution function was computed to elucidate the intermolecular interactions between amorphous β-CD and water, which acts as a plasticizer. These results indicate that the hydrogen bond interactions of oxygen in hydroxyl ions was higher than oxygen in acetal groups in β-CD amorphous mixtures with that in water, due to less accessibility of ring oxygens to the surrounding water molecules. The mobility of water molecules was investigated over various temperature ranges, including the rubbery and glassy phases of the β-CD/water mixtures, by calculating the diffusion coefficients and the fractional free volume. In β-CD amorphous models, the higher mobility of water molecules was observed at temperatures above Tg, and almost no change was observed at temperatures below T(g). Copyright © 2014 Elsevier Ltd. All rights reserved.

Opal-A in Glassy Pumice, Acid Alteration, and the 1817 Phreatomagmatic Eruption at Kawah Ijen (Java), Indonesia

NASA Astrophysics Data System (ADS)

Lowenstern, Jacob B.; van Hinsberg, Vincent; Berlo, Kim; Liesegang, Moritz; Iacovino, Kayla; Bindeman, Ilya N.; Wright, Heather M.

2018-02-01

At Kawah Ijen (Indonesia), vigorous SO2 and HCl degassing sustains a hyperacid lake (pH 0) and intensely alters the subsurface, producing widespread residual silica and advanced argillic alteration products. In 1817, a VEI 2 phreatomagmatic eruption evacuated the lake, depositing a widespread layer of muddy ash fall, and sending lahars down river drainages. We discovered multiple types of opaline silica in juvenile low-silica dacite pumice and in particles within co-erupted laharic sediments. Most spectacular are opal-replaced phenocrysts of plagioclase and pyroxene adjacent to pristine matrix glass and melt inclusions. Opal-bearing pumice has been found at numerous sites, including where post-eruption infiltration of acid water is unlikely. Through detailed analyses of an initial sampling of 1817 eruption products, we find evidence for multiple origins of opaline materials in pumice and laharic sediments. Evidently, magma encountered acid-altered materials in the subsurface and triggered phreatomagmatic eruptions. Syn-eruptive incorporation of opal-alunite clasts, layered opal, and fragment-filled vesicles of opal and glass, all suggest magma-rock interactions in concert with vesiculation, followed by cooling within minutes. Our experiments at magmatic temperature confirm that the opaline materials would show noticeable degradation in time periods longer than a few tens of minutes. Some glassy laharic sedimentary grains are more andesitic than the main pumice type and may represent older volcanic materials that were altered beneath the lake bottom and were forcefully ejected during the 1817 eruption. A post-eruptive origin remains likely for most of the opal-replaced phenocrysts in pumice. Experiments at 25°C and 100°C reveal that when fresh pumice is bathed in Kawah Ijen hyperacid fluid for six weeks, plagioclase is replaced without altering either matrix glass or melt inclusions. Moreover, lack of evidence for high-temperature annealing of the opal suggests

Opal-A in glassy pumice, acid alteration, and the 1817 phreatomagmatic eruption at Kawah Ijen (Java), Indonesia

USGS Publications Warehouse

Lowenstern, Jacob B.; van Hinsberg, Vincent; Berlo, Kim; Liesegang, Moritz; Iacovino, Kayla D.; Bindeman, Ilya N.; Wright, Heather M.

2018-01-01

At Kawah Ijen (Indonesia), vigorous SO2 and HCl degassing sustains a hyperacid lake (pH ~0) and intensely alters the subsurface, producing widespread residual silica and advanced argillic alteration products. In 1817, a VEI 2 phreatomagmatic eruption evacuated the lake, depositing a widespread layer of muddy ash fall, and sending lahars down river drainages. We discovered multiple types of opaline silica in juvenile low-silica dacite pumice and in particles within co-erupted laharic sediments. Most spectacular are opal-replaced phenocrysts of plagioclase and pyroxene adjacent to pristine matrix glass and melt inclusions. Opal-bearing pumice has been found at numerous sites, including where post-eruption infiltration of acid water is unlikely. Through detailed analyses of an initial sampling of 1817 eruption products, we find evidence for multiple origins of opaline materials in pumice and laharic sediments. Evidently, magma encountered acid-altered materials in the subsurface and triggered phreatomagmatic eruptions. Syn-eruptive incorporation of opal-alunite clasts, layered opal, and fragment-filled vesicles of opal and glass, all suggest magma-rock interactions in concert with vesiculation, followed by cooling within minutes. Our experiments at magmatic temperature confirm that the opaline materials would show noticeable degradation in time periods longer than a few tens of minutes. Some glassy laharic sedimentary grains are more andesitic than the main pumice type and may represent older volcanic materials that were altered beneath the lake bottom and were forcefully ejected during the 1817 eruption. A post-eruptive origin remains likely for most of the opal-replaced phenocrysts in pumice. Experiments at 25°C and 100°C reveal that when fresh pumice is bathed in Kawah Ijen hyperacid fluid for 6 weeks, plagioclase is replaced without altering either matrix glass or melt inclusions. Moreover, lack of evidence for high-temperature annealing of the opal suggests

Development and validation of a real-time PCR assay for the glassy-winged sharpshooter Homalodisca vitripennis (Hemiptera: Cicadellidae).

PubMed

Waite, D W; Li, D; D'Souza, M; Gunawardana, D

2017-06-01

The glassy-winged sharpshooter (Homalodisca vitripennis) is an invasive pest organism, which is found throughout Central America and has recently invaded a few countries in the Pacific Islands. As a carrier of the highly virulent plant pathogenic bacterium Xylella fastidiosa, it is of great economic significance to horticulture and is estimated to cost Californian vineyards over US$100 million per year in control and losses. New Zealand is currently free from this pest, but its recent spread through the Pacific has raised concerns of it establishing in New Zealand, potentially as a result of introduction through human travel. We report here a real-time polymerase chain reaction assay for the rapid identification of H. vitripennis. The assay was extensively validated in silico then optimized and tested against a range of Cicadellidae species, both internationally collected and local to New Zealand. This assay was able to correctly identify H. vitripennis samples, and distinguish between H. vitripennis and close relatives, such as the smoke-tree sharpshooter (Homalodisca liturata) and will be of great benefit to New Zealand biosecurity.

Direct Electrodeposition of Gold Nanoparticles on Glassy Carbon Electrode for Selective Determination Catechol in the Presence of Hydroquinone.

PubMed

Jayakumar, C; Magdalane, C Maria; Kaviyarasu, K; Kulandainathan, M Anbu; Jeyaraj, Boniface; Maaza, M

2018-07-01

A simple and reliable voltammetric sensor for simultaneous determination of Catechol (CT) and Hydroquinone (HQ) was developed by electrodepositing the gold nanoparticles on the surface of the Glassy Carbon Electrode (GCE). The cyclic voltammograms in a mixed solution of CT and HQ have shown that the oxidation peaks become well resolved and were separated by 110 mV, although the bare GCE gave a single broad oxidation peak. Moreover, the oxidation peak currents of both CT and HQ were remarkably increased three times in comparison with the bare GCE. This makes gold nanoparticles deposited GCE a suitable candidate for the determination of these isomers. In the presence of 1 mM HQ isomer, the oxidation peak currents of differential pulse voltammograms are proportional to the concentration of CT in the range of 21 μM to 323 μM with limit of detection 3.0 μM (S/N = 3). The proposed sensor has some important advantages such as low cost, ease of preparation, good stability and high reproducibility.

Waterlike glass polyamorphism in a monoatomic isotropic Jagla model.

PubMed

Xu, Limei; Giovambattista, Nicolas; Buldyrev, Sergey V; Debenedetti, Pablo G; Stanley, H Eugene

2011-02-14

We perform discrete-event molecular dynamics simulations of a system of particles interacting with a spherically-symmetric (isotropic) two-scale Jagla pair potential characterized by a hard inner core, a linear repulsion at intermediate separations, and a weak attractive interaction at larger separations. This model system has been extensively studied due to its ability to reproduce many thermodynamic, dynamic, and structural anomalies of liquid water. The model is also interesting because: (i) it is very simple, being composed of isotropically interacting particles, (ii) it exhibits polyamorphism in the liquid phase, and (iii) its slow crystallization kinetics facilitate the study of glassy states. There is interest in the degree to which the known polyamorphism in glassy water may have parallels in liquid water. Motivated by parallels between the properties of the Jagla potential and those of water in the liquid state, we study the metastable phase diagram in the glass state. Specifically, we perform the computational analog of the protocols followed in the experimental studies of glassy water. We find that the Jagla potential calculations reproduce three key experimental features of glassy water: (i) the crystal-to-high-density amorphous solid (HDA) transformation upon isothermal compression, (ii) the low-density amorphous solid (LDA)-to-HDA transformation upon isothermal compression, and (iii) the HDA-to-very-high-density amorphous solid (VHDA) transformation upon isobaric annealing at high pressure. In addition, the HDA-to-LDA transformation upon isobaric heating, observed in water experiments, can only be reproduced in the Jagla model if a free surface is introduced in the simulation box. The HDA configurations obtained in cases (i) and (ii) are structurally indistinguishable, suggesting that both processes result in the same glass. With the present parametrization, the evolution of density with pressure or temperature is remarkably similar to the

Effect of salts on the properties of aqueous sugar systems, in relation to biomaterial stabilization. 1. Water sorption behavior and ice crystallization/melting.

PubMed

Mazzobre, M F; Longinotti, M P; Corti, H R; Buera, M P

2001-11-01

Trehalose and sucrose, two sugars that are involved in the protection of living organisms under extreme conditions, and their mixtures with salts were employed to prepare supercooled or freeze-dried glassy systems. The objective of the present work was to explore the effects of different salts on water sorption, glass transition temperature (T(g)), and formation and melting of ice in aqueous sugar systems. In the sugar-salt mixtures, water adsorption was higher than expected on the basis of the water uptake by each pure component. In systems with a reduced mass fraction of water (w less-than-or-equal 0.4), salts delayed water crystallization, probably due to ion-water interactions. In systems where > 0.6, water crystallization could be explained by the known colligative properties of the solutes. The glass transition temperature of the maximally concentrated matrix (T(g)') was decreased by the presence of salts. However, the actual T(g) values of the systems were not modified. Thus, the effect of salts on sorption behavior and formation of ice may reflect dynamic water-salt-sugar interactions which take place at a molecular level and are related to the charge/mass ratio of the cation present without affecting supramolecular or macroscopic properties. Copyright 2001 Elsevier Science (USA).

Ruthenium Nanoparticles Mediated Electrocatalytic Reduction of UO22+ Ions for Its Rapid and Sensitive Detection in Natural Waters.

PubMed

Gupta, Ruma; Sundararajan, Mahesh; Gamare, Jayashree S

2017-08-01

Reduction of UO 2 2+ ions to U 4+ ions is difficult due to involvement of two axially bonded oxygen atoms, and often requires a catalyst to lower the activation barrier. The noble metal nanoparticles (NPs) exhibit high electrocatalytic activity, and could be employed for the sensitive and rapid quantifications of U0 2 2+ ions in the aqueous matrix. Therefore, the Pd, Ru, and Rh NPs decorated glassy carbon electrode were examined for their efficacy toward electrocatalytic reduction of UO 2 2+ ions and observed that Ru NPs mediate efficiently the electro-reduction of UO 2 2+ ions. The mechanism of the electroreduction of UO 2 2+ by the RuNPs/GC was studied using density functional theory calculations which pointed different approach of 5f metal ions electroreduction unlike 4p metal ions such as As(III). RuNP decorated on the glassy carbon would be hydrated, which in turn assist to adsorb the uranyl sulfates through hydrogen bonding thus facilitated electro-reduction. Differential pulse voltammetric (DPV) technique, was used for rapid and sensitive quantification of UO 2 2+ ions. The RuNPs/GC based DPV technique could be used to determine the concentration of uranyl in a few minutes with a detection limit of 1.95 ppb. The RuNPs/GC based DPV was evaluated for its analytical performance using seawater as well lake water and groundwater spiked with known amounts of UO 2 2+ .

Quasi-elastic neutron scattering studies of the slow dynamics of supercooled and glassy aspirin

NASA Astrophysics Data System (ADS)

Zhang, Yang; Tyagi, Madhusudan; Mamontov, Eugene; Chen, Sow-Hsin

2012-02-01

Aspirin, also known as acetylsalicylic acid (ASA), is not only a wonderful drug, but also a good glass former. Therefore, it serves as an important molecular system to study the near-arrest and arrested phenomena. In this paper, a high-resolution quasi-elastic neutron scattering (QENS) technique is used to investigate the slow dynamics of supercooled liquid and glassy aspirin from 410 down to 350 K. The measured QENS spectra can be analyzed with a stretched exponential model. We find that (i) the stretched exponent β(Q) is independent of the wavevector transfer Q in the measured Q range and (ii) the structural relaxation time τ(Q) follows a power-law dependence on Q. Consequently, the Q-independent structural relaxation time τ0 can be extracted for each temperature to characterize the slow dynamics of aspirin. The temperature dependence of τ0 can be fitted with the mode-coupling power law, the Vogel-Fulcher-Tammann equation and a universal equation for fragile glass forming liquids recently proposed by Tokuyama in the measured temperature range. The calculated dynamic response function χT(Q, t) using the experimentally determined self-intermediate scattering function of the hydrogen atoms of aspirin shows direct evidence of the enhanced dynamic fluctuations as the aspirin is increasingly supercooled, in agreement with the fixed-time mean squared displacement langx2rang and the non-Gaussian parameter α2 extracted from the elastic scattering.

Quasi-Elastic Neutron Scattering Studies of the Slow Dynamics of Supercooled and Glassy Aspirin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yang; Tyagi, M.; Mamontov, Eugene

Aspirin, also known as acetylsalicylic acid (ASA), is not only a wonderful drug, but also a good glass former. Therefore, it serves as an important molecular system to study the near-arrest and arrested phenomena. In this paper, a high-resolution quasi-elastic neutron scattering (QENS) technique is used to investigate the slow dynamics of supercooled liquid and glassy aspirin from 410 K down to 350 K. The measured QENS spectra can be analyzed with a stretched exponential model. We find that (i) the stretched exponent (Q) is independent of the wave vector transfer Q in the measured Q-range, and (ii) the structuralmore » relaxation time (Q) follows a power law dependence on Q. Consequently, the Q-independent structural relaxation time 0 can be extracted for each temperature to characterize the slow dynamics of aspirin. The temperature dependence of 0 can be fitted with the mode coupling power law, the Vogel-Fulcher-Tammann equation and a universal equation for fragile glass forming liquids recently proposed by M. Tokuyama in the measured temperature range. The calculated dynamic response function T(Q,t) using the experimentally determined self-intermediate scattering function of the hydrogen atoms of aspirin shows a direct evidence of the enhanced dynamic fluctuations as the aspirin is increasingly supercooled, in agreement with the fixed-time mean squared displacement x2 and non-Gaussian parameter 2 extracted from the elastic scattering.« less

Comparison of impedimetric detection of DNA hybridization on the various biosensors based on modified glassy carbon electrodes with PANHS and nanomaterials of RGO and MWCNTs.

PubMed

Benvidi, Ali; Tezerjani, Marzieh Dehghan; Jahanbani, Shahriar; Mazloum Ardakani, Mohammad; Moshtaghioun, Seyed Mohammad

2016-01-15

In this research, we have developed lable free DNA biosensors based on modified glassy carbon electrodes (GCE) with reduced graphene oxide (RGO) and carbon nanotubes (MWCNTs) for detection of DNA sequences. This paper compares the detection of BRCA1 5382insC mutation using independent glassy carbon electrodes (GCE) modified with RGO and MWCNTs. A probe (BRCA1 5382insC mutation detection (ssDNA)) was then immobilized on the modified electrodes for a specific time. The immobilization of the probe and its hybridization with the target DNA (Complementary DNA) were performed under optimum conditions using different electrochemical techniques such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The proposed biosensors were used for determination of complementary DNA sequences. The non-modified DNA biosensor (1-pyrenebutyric acid-N- hydroxysuccinimide ester (PANHS)/GCE), revealed a linear relationship between ∆Rct and logarithm of the complementary target DNA concentration ranging from 1.0×10(-16)molL(-1) to 1.0×10(-10)mol L(-1) with a correlation coefficient of 0.992, for DNA biosensors modified with multi-wall carbon nanotubes (MWCNTs) and reduced graphene oxide (RGO) wider linear range and lower detection limit were obtained. For ssDNA/PANHS/MWCNTs/GCE a linear range 1.0×10(-17)mol L(-1)-1.0×10(-10)mol L(-1) with a correlation coefficient of 0.993 and for ssDNA/PANHS/RGO/GCE a linear range from 1.0×10(-18)mol L(-1) to 1.0×10(-10)mol L(-1) with a correlation coefficient of 0.985 were obtained. In addition, the mentioned biosensors were satisfactorily applied for discriminating of complementary sequences from noncomplementary sequences, so the mentioned biosensors can be used for the detection of BRCA1-associated breast cancer. Copyright © 2015. Published by Elsevier B.V.

Potential of Glassy Carbon and Silicon Carbide Photonic Structures as Electromagnetic Radiation Shields for Atmospheric Re-entry

NASA Technical Reports Server (NTRS)

Komarevskiy,Nikolay; Shklover, Valery; Braginsky, Leonid; Hafner, Christian; Lawson, John W.

2012-01-01

During high-velocity atmospheric entries, space vehicles can be exposed to strong electromagnetic radiation from ionized gas in the shock layer. Glassy carbon (GC) and silicon carbide (SiC) are candidate thermal protection materials due to their high melting point and also their good thermal and mechanical properties. Based on data from shock tube experiments, a significant fraction of radiation at hypersonic entry conditions is in the frequency range from 215 to 415 THz. We propose and analyze SiC and GC photonic structures to increase the reflection of radiation in that range. For this purpose, we performed numerical optimizations of various structures using an evolutionary strategy. Among the considered structures are layered, porous, woodpile, inverse opal and guided-mode resonance structures. In order to estimate the impact of fabrication inaccuracies, the sensitivity of the reflectivity to structural imperfections is analyzed. We estimate that the reflectivity of GC photonic structures is limited to 38% in the aforementioned range, due to material absorption. However, GC material can be effective for photonic reflection of individual, strong spectral line. SiC on the other hand can be used to design a good reflector for the entire frequency range.

Potential of glassy carbon and silicon carbide photonic structures as electromagnetic radiation shields for atmospheric re-entry.

PubMed

Komarevskiy, Nikolay; Shklover, Valery; Braginsky, Leonid; Hafner, Christian; Lawson, John

2012-06-18

During high-velocity atmospheric entries, space vehicles can be exposed to strong electromagnetic radiation from ionized gas in the shock layer. Glassy carbon (GC) and silicon carbide (SiC) are candidate thermal protection materials due to their high melting point and also their good thermal and mechanical properties. Based on data from shock tube experiments, a significant fraction of radiation at hypersonic entry conditions is in the frequency range from 215 to 415 THz. We propose and analyze SiC and GC photonic structures to increase the reflection of radiation in that range. For this purpose, we performed numerical optimizations of various structures using an evolutionary strategy. Among the considered structures are layered, porous, woodpile, inverse opal and guided-mode resonance structures. In order to estimate the impact of fabrication inaccuracies, the sensitivity of the reflectivity to structural imperfections is analyzed. We estimate that the reflectivity of GC photonic structures is limited to 38% in the aforementioned range, due to material absorption. However, GC material can be effective for photonic reflection of individual, strong spectral line. SiC on the other hand can be used to design a good reflector for the entire frequency range.

Basaltic glass as a habitat for microbial life: Implications for astrobiology and planetary exploration

NASA Astrophysics Data System (ADS)

Izawa, M. R. M.; Banerjee, N. R.; Flemming, R. L.; Bridge, N. J.; Schultz, C.

2010-03-01

Recent studies have demonstrated that terrestrial subaqueous basalts and hyaloclastites are suitable microbial habitats. During subaqueous basaltic volcanism, glass is produced by the quenching of basaltic magma upon contact with water. On Earth, microbes rapidly begin colonizing the glassy surfaces along fractures and cracks that have been exposed to water. Microbial colonization of basaltic glass leads to the alteration and modification of the rocks and produces characteristic granular and/or tubular bioalteration textures. Infilling of the alteration textures by minerals such as phyllosilicates, zeolites and titanite may enable their preservation through geologic time. Basaltic rocks are a major component of the Martian crust and are widespread on other solar system bodies. A variety of lines of evidence strongly suggests the long-term existence of abundant liquid water on ancient Mars. Recent orbiter, lander and rover missions have found evidence for the presence of transient liquid water on Mars, perhaps persisting to the present day. Many other solar system bodies, notably Europa, Enceladus and other icy satellites, may contain (or have once hosted) subaqueous basaltic glasses. The record of terrestrial glass bioalteration has been interpreted to extend as far back as ˜3.5 billion years ago and is widespread in oceanic crust and its metamorphic equivalents. The terrestrial record of glass bioalteration strongly suggests that glassy or formerly glassy basaltic rocks on extraterrestrial bodies that have interacted with liquid water are high-value targets for astrobiological exploration.

MIPs-graphene nanoplatelets-MWCNTs modified glassy carbon electrode for the determination of cardiac troponin I.

PubMed

Ma, Ya; Shen, Xiao-Lei; Wang, Hai-Shui; Tao, Jia; Huang, Jian-Zhi; Zeng, Qiang; Wang, Li-Shi

2017-03-01

An electrochemical sensor with high selectivity in addition to sensitivity was developed for the determination of cardiac troponin I (cTnI), based on the modification of cTnI imprinted polymer film on a glassy carbon electrode (GCE). The sensor was fabricated by layer-by-layer assembled graphene nanoplatelets (GS), multiwalled carbon nanotubes (MWCNTs), chitosan (CS), glutaraldehyde (GA) composites, which can increase the electronic transfer rate and the active surface area to capture a larger number of antigenic proteins. MWCNTs/GS based imprinted polymers (MIPs/MWCNTs/GS) were synthesized by means of methacrylic acid (MAA) as the monomer, ethylene glycol dimethacrylate (EGDMA) as the cross linker α,α'-azobisisobutyronitrile (AIBN) as the initiator and cTnI as the template. In comparison with conventional methods, the proposed electrochemical sensor is highly sensitive for cTnI, providing a better linear response range from 0.005 to 60 ng cm -3 and a lower limit of detection (LOD) of 0.0008 ng cm -3 under optimal experimental conditions. In addition, the electrochemical sensor exhibited good specificity, acceptable reproducibility and stability. Moreover, satisfactory results were obtained in real human serum samples, indicating that the developed method has the potential to find application in clinical detection of cTnI as an alternative approach. Copyright © 2016 Elsevier Inc. All rights reserved.

Stability of α-tocopherol in freeze-dried sugar-protein-oil emulsion solids as affected by water plasticization and sugar crystallization.

PubMed

Zhou, Yankun; Roos, Yrjö H

2012-08-01

Water plasticization of sugar-protein encapsulants may cause structural changes and decrease the stability of encapsulated compounds during storage. The retention of α-tocopherol in freeze-dried lactose-milk protein-oil, lactose-soy protein-oil, trehalose-milk protein-oil, and trehalose-soy protein-oil systems at various water activities (a(w)) and in the presence of sugar crystallization was studied. Water sorption was determined gravimetrically. Glass transition and sugar crystallization were studied using differential scanning calorimetry and the retention of α-tocopherol spectrophotometrically. The loss of α-tocopherol followed lipid oxidation, but the greatest stability was found at 0 a(w) presumably because of α-tocopherol immobilization at interfaces and consequent reduction in antioxidant activity. A considerable loss of α-tocopherol coincided with sugar crystallization. The results showed that glassy matrices may protect encapsulated α-tocopherol; however, its role as an antioxidant at increasing aw accelerated its loss. Sugar crystallization excluded the oil-containing α-tocopherol from the protecting matrices and exposed it to surroundings, which decreased the stability of α-tocopherol.

Direct electrochemistry of glucose oxidase and glucose biosensing on a hydroxyl fullerenes modified glassy carbon electrode.

PubMed

Gao, Yun-Fei; Yang, Tian; Yang, Xiao-Lu; Zhang, Yu-Shuai; Xiao, Bao-Lin; Hong, Jun; Sheibani, Nader; Ghourchian, Hedayatollah; Hong, Tao; Moosavi-Movahedi, Ali Akbar

2014-10-15

Direct electrochemistry of glucose oxidase (GOD) was achieved when GOD-hydroxyl fullerenes (HFs) nano-complex was immobilized on a glassy carbon (GC) electrode and protected with a chitosan (Chit) membrane. The ultraviolet-visible absorption spectrometry (UV-vis), transmission electron microscopy (TEM), and circular dichroism spectropolarimeter (CD) methods were utilized for additional characterization of the GOD, GOD-HFs and Chit/GOD-HFs. Chit/HFs may preserve the secondary structure and catalytic properties of GOD. The cyclic voltammograms (CVs) of the modified GC electrode showed a pair of well-defined quasi-reversible redox peaks with the formal potential (E°') of 353 ± 2 mV versus Ag/AgCl at a scan rate of 0.05 V/s. The heterogeneous electron transfer constant (ks) was calculated to be 2.7 ± 0.2s(-1). The modified electrode response to glucose was linear in the concentrations ranging from 0.05 to 1.0mM, with a detection limit of 5 ± 1 μM. The apparent Michaelis-Menten constant (Km(app)) was 694 ± 8 μM. Thus, the modified electrode could be applied as a third generation biosensor for glucose with high sensitivity, selectivity and low detection limit. Copyright © 2014 Elsevier B.V. All rights reserved.

Electrocatalytic Oxidation of Ascorbic Acid Using a Poly(aniline-co-m-ferrocenylaniline) Modified Glassy Carbon Electrode

PubMed Central

Chairam, Sanoe; Sriraksa, Worawit; Amatatongchai, Maliwan; Somsook, Ekasith

2011-01-01

A poly(aniline-co-m-ferrocenylaniline) was successfully synthesized on a glassy carbon electrode (GCE) by electrochemical copolymerization using a scan potential range from −0.3 to +0.9 V (vs. Ag/AgCl) in 0.5 M H2SO4 containing 30% acetonitrile (ACN), 0.1 M aniline (Ani) and 0.005 M m-ferrocenyaniline (m-FcAni). The field emission scanning electron microscope (FESEM) and electrochemical methods were used to characterize the poly(Ani-co-m-FcAni) modified electrode. The poly(Ani-co-m-FcAni)/GCE exhibited excellent electrocatalytic oxidation of ascorbic acid (AA) in citrate buffer solution (CBS, pH 5.0). The anodic peak potential of AA was shifted from +0.55 V at the bare GCE to +0.25 V at the poly(Ani-co-m-FcAni)/GCE with higher current responses than those seen on the bare GCE. The scan number at the 10th cycle was selected as the maximum scan cycle in electrochemical polymerization. The limit of detection (LOD) was estimated to be 2.0 μM based on the signal-to-noise ratio (S/N = 3). The amperometric responses demonstrated an excellent selectivity for AA determination over glucose (Glu) and dopamine (DA). PMID:22346636

SiC nanoparticles-modified glassy carbon electrodes for simultaneous determination of purine and pyrimidine DNA bases.

PubMed

Ghavami, Raouf; Salimi, Abdollah; Navaee, Aso

2011-05-15

For the first time a novel and simple electrochemical method was used for simultaneous detection of DNA bases (guanine, adenine, thymine and cytosine) without any pretreatment or separation process. Glassy carbon electrode modified with silicon carbide nanoparticles (SiCNP/GC), have been used for electrocatalytic oxidation of purine (guanine and adenine) and pyrimidine bases (thymine and cytosine) nucleotides. Field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) techniques were used to examine the structure of the SiCNP/GC modified electrode. The modified electrode shows excellent electrocatalytic activity toward guanine, adenine, thymine and cytosine. Differential pulse voltammetry (DPV) was proposed for simultaneous determination of four DNA bases. The effects of different parameters such as the thickness of SiC layer, pulse amplitude, scan rate, supporting electrolyte composition and pH were optimized to obtain the best peak potential separation and higher sensitivity. Detection limit, sensitivity and linear concentration range of the modified electrode toward proposed analytes were calculated for, guanine, adenine, thymine and cytosine, respectively. As shown this sensor can be used for nanomolar or micromolar detection of different DNA bases simultaneously or individually. This sensor also exhibits good stability, reproducibility and long lifetime. Copyright © 2011 Elsevier B.V. All rights reserved.

[Electrochemically reductive dechlorination of chloroform in aqueous medium by codeposited palladium-nickel glassy carbon as cathode].

PubMed

Sun, Zhi-Rong; Li, Bao-Hua; Hu, Xiang; Shi, Min; Peng, Yong-Zhen

2008-05-01

The electrochemical deposition behaviors of Pd-Ni bimetal on glassy carbon (GC) electrode were studied by means of cyclic voltammetry (CV) based on orthogonal experiments. CV results reveal that Pd-Ni bimetal shows larger hydrogen adsorption peak than that of single Pd or Ni. The mixture of Ni2+ and Pd2+ can get hydrogen adsorption peak of -24.83 mA at - 500 mV (vs Hg/Hg2SO4). Scanning Electron Microscope (SEM) images reveal that nickel addition changes the distributing configuration of Pd microparticles on GC. And the appearance of Pd-Ni bimetal microparticles is distinctly different from that of single Pd and single Ni microparticles. Diameter of Pd-Ni microparticle is bigger than that of Pd microparticle and smaller than that of Ni microparticle. Effects of dechlorination current and time on removal efficiency of chloroform were also studied. The removal efficiency of chloroform increases at higher dechlorination current and longer dechlorination time. It reaches 42.53% when the dechlorination current and time are 0.5 mA and 180 min respectively on Pd-Ni/GC electrode prepared at optimum conditions. It can be envisioned that the removal efficiency of chloroform would increase further at longer dechlorination time.

Chemical order in the glassy As/sub x/S/sub 1-//sub x/ system: An x-ray-absorption spectroscopy study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, C.Y.; Paesler, M.A.; Sayers, D.E.

1989-05-15

We have examined chemical ordering in the glassy As/sub x/S/sub 1-//sub x/ system by determining the effect of composition on the local structure of these chalcogenide glasses using x-ray-absorption spectroscopy. Structural changes associated with composition indicate that with increasing S content, the S-rich glasses on the As site have a similar local structure to crystalline As/sub 2/S/sub 3/ (orpiment), but the As-S-As linkages are replaced by As-S-S linkages at higher S concentration. In As-rich glasses a breakdown of the local AsS/sub 3/ configuration is evident and the formation of As-As bonds is observed. Further comparison between As-rich alloys and crystallinemore » As/sub 4/S/sub 4/ (realgar) suggests that a significant fraction of disordered As/sub 4/S/sub 4/ molecular fragments is contained in the As-rich region.« less

A Highly Sensitive Oligonucleotide Hybridization Assay for Klebsiella pneumoniae Carbapenemase with the Probes on a Gold Nanoparticles Modified Glassy Carbon Electrode.

PubMed

Pan, Hong-zhi; Yu, Hong- Wei; Wang, Na; Zhang, Ze; Wan, Guang-Cai; Liu, Hao; Guan, Xue; Chang, Dong

2015-01-01

To develop a new electrochemical DNA biosensor for determination of Klebsiella pneumoniae carbapenemase, a highly sensitive and selective electrochemical biosensor for DNA detection was constructed based on a glassy carbon electrode (GCE) modified with gold nanoparticles (Au-nano). The Au-nano/GCE was characterized by scanning electromicroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The hybridization detection was measured by differential pulse voltammetry using methylene blue as the hybridization indicator. The dynamic range of detection of the sensor for the target DNA sequences was from 1 × 10(-11) to 1 × 10(-8) M, with an LOD of 1 × 10(-12) M. The DNA biosensor had excellent specificity for distinguishing complementary DNA sequence in the presence of non-complementary and mismatched DNA sequence. The Au-nano/GCE showed significant improvement in electrochemical characteristics, and this biosensor was successfully applied for determination of K. pneumoniae.

Occurrence and problems of high fluoride waters in Turkey: an overview.

PubMed

Oruc, Nazmi

2008-08-01

Endemic dental fluorosis was first observed in Turkey in Isparta Province, located in the SW of Anatolia, with mottled enamel related to the high levels of fluoride (1.5-4.0 ppm) in drinking waters, about 55 years ago. The origin of fluoride was attributed to the contents of minerals in volcanic rocks, consisting of pyroxene, hornblende, biotite, fluorapatite and glassy groundmass minerals. It was also reported about 35 years ago that severe dental and skeletal fluorosis has been observed in human beings and livestock in Dogubeyazit and Caldiran areas, located around Tendurek Volcano in eastern Turkey, where natural waters contained fluoride levels between 2.5 and 12.5 ppm. It was hypothesised that fluoride, which might be transported by fumaroles or escaped from devitrified lavas, could be held on the surface of some minerals and then exchanged with OH(-) in ground waters with high pH at the foothills of the young Tendurek Volcano. Endemic dental and skeletal fluorosis was also observed in the inhabitants in Kizilcaoren Village of Beylikova Town in Eskişehir Province situated in the midwest of Turkey, where the fluoride content of the drinking waters ranged from 3.9 to 4.8 ppm. The origin of high fluoride in the natural waters was related to the fluorspar deposits, occurring in the catchment area near the village. During the survey in the Güllü Village of Esme-Usak, located in south-midwest of Turkey, it was observed that most of the inhabitants born and raised in the village and aged between 10 and 30 years, showed mild to moderate levels of mottled enamel. The fluoride contents of the deep well waters used for drinking in the village, varied from 0.7 to 2.0 ppm. Amorphous microscopic fluorite existing in the Pliocene lake limestones was considered as a possible origin of fluoride in the waters.

Diffusive mass transport in agglomerated glassy fallout from a near-surface nuclear test

NASA Astrophysics Data System (ADS)

Weisz, David G.; Jacobsen, Benjamin; Marks, Naomi E.; Knight, Kim B.; Isselhardt, Brett H.; Matzel, Jennifer E.

2018-02-01

Aerodynamically-shaped glassy fallout is formed when vapor phase constituents from the nuclear device are incorporated into molten carriers (i.e. fallout precursor materials derived from soil or other near-field environmental debris). The effects of speciation and diffusive transport of condensing constituents are not well defined in models of fallout formation. Previously we reported observations of diffuse micrometer scale layers enriched in Na, Fe, Ca, and 235U, and depleted in Al and Ti, at the interfaces of agglomerated fallout objects. Here, we derive the timescales of uranium mass transport in such fallout as it cools from 2500 K to 1500 K by applying a 1-dimensional planar diffusion model to the observed 235U/30Si variation at the interfaces. By modeling the thermal transport between the fireball and the carrier materials, the time of mass transport is calculated to be <0.6 s, <1 s, <2 s, and <3.5 s for fireball yields of 0.1 kt, 1 kt, 10 kt, and 100 kt respectively. Based on the calculated times of mass transport, a maximum temperature of deposition of uranium onto the carrier material of ∼2200 K is inferred (1σ uncertainty of ∼200 K). We also determine that the occurrence of micrometer scale layers of material enriched in relatively volatile Na-species as well as more refractory Ca-species provides evidence for an oxygen-rich fireball based on the vapor pressure of the two species under oxidizing conditions. These results represent the first application of diffusion-based modeling to derive material transport, thermal environments, and oxidation-speciation in near-surface nuclear detonation environments.

Diffusive mass transport in agglomerated glassy fallout from a near-surface nuclear test

DOE PAGES

Weisz, David G.; Jacobsen, Benjamin; Marks, Naomi E.; ...

2017-12-15

Aerodynamically-shaped glassy fallout is formed when vapor phase constituents from the nuclear device are incorporated into molten carriers (i.e. fallout precursor materials derived from soil or other near-field environmental debris). The effects of speciation and diffusive transport of condensing constituents are not well defined in models of fallout formation. Previously we reported observations of diffuse micrometer scale layers enriched in Na, Fe, Ca, and 235U, and depleted in Al and Ti, at the interfaces of agglomerated fallout objects. Here in this paper, we derive the timescales of uranium mass transport in such fallout as it cools from 2500 K tomore » 1500 K by applying a 1-dimensional planar diffusion model to the observed 235U/ 30Si variation at the interfaces. By modeling the thermal transport between the fireball and the carrier materials, the time of mass transport is calculated to be <0.6 s, <1 s, <2 s, and <3.5 s for fireball yields of 0.1 kt, 1 kt, 10 kt, and 100 kt respectively. Based on the calculated times of mass transport, a maximum temperature of deposition of uranium onto the carrier material of ~2200 K is inferred (1σ uncertainty of ~200 K). We also determine that the occurrence of micrometer scale layers of material enriched in relatively volatile Na-species as well as more refractory Ca-species provides evidence for an oxygen-rich fireball based on the vapor pressure of the two species under oxidizing conditions. These results represent the first application of diffusion-based modeling to derive material transport, thermal environments, and oxidation-speciation in near-surface nuclear detonation environments.« less

Diffusive mass transport in agglomerated glassy fallout from a near-surface nuclear test

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weisz, David G.; Jacobsen, Benjamin; Marks, Naomi E.

Aerodynamically-shaped glassy fallout is formed when vapor phase constituents from the nuclear device are incorporated into molten carriers (i.e. fallout precursor materials derived from soil or other near-field environmental debris). The effects of speciation and diffusive transport of condensing constituents are not well defined in models of fallout formation. Previously we reported observations of diffuse micrometer scale layers enriched in Na, Fe, Ca, and 235U, and depleted in Al and Ti, at the interfaces of agglomerated fallout objects. Here in this paper, we derive the timescales of uranium mass transport in such fallout as it cools from 2500 K tomore » 1500 K by applying a 1-dimensional planar diffusion model to the observed 235U/ 30Si variation at the interfaces. By modeling the thermal transport between the fireball and the carrier materials, the time of mass transport is calculated to be <0.6 s, <1 s, <2 s, and <3.5 s for fireball yields of 0.1 kt, 1 kt, 10 kt, and 100 kt respectively. Based on the calculated times of mass transport, a maximum temperature of deposition of uranium onto the carrier material of ~2200 K is inferred (1σ uncertainty of ~200 K). We also determine that the occurrence of micrometer scale layers of material enriched in relatively volatile Na-species as well as more refractory Ca-species provides evidence for an oxygen-rich fireball based on the vapor pressure of the two species under oxidizing conditions. These results represent the first application of diffusion-based modeling to derive material transport, thermal environments, and oxidation-speciation in near-surface nuclear detonation environments.« less

Apatite layer growth on glassy Zr48Cu36Al8Ag8 sputtered titanium for potential biomedical applications

NASA Astrophysics Data System (ADS)

Thanka Rajan, S.; Karthika, M.; Bendavid, Avi; Subramanian, B.

2016-04-01

The bioactivity of magnetron sputtered thin film metallic glasses (TFMGs) of Zr48Cu36Al8Ag8 (at.%) on titanium substrates was tested for bio implant applications. The structural and elemental compositions of TFMGs were analyzed by XRD, XPS and EDAX. X-ray diffraction analysis displayed a broad hump around the incident angle of 30-50°, suggesting that the coatings possess a glassy structure. An in situ crystal growth of hydroxyapatite was observed by soaking the sputtered specimen in simulated body fluid (SBF). The nucleation and growth of a calcium phosphate (Ca-P) bone-like hydroxyapatite on Zr48Cu36Al8Ag8 (at.%) TFMG from SBF was investigated by using XRD, AFM and SEM. The presence of calcium and phosphorus elements was confirmed by EDAX and XPS. In vitro electrochemical corrosion studies indicated that the Zr-based TFMG coating sustain in the stimulated body-fluid (SBF), exhibiting superior corrosion resistance with a lower corrosion penetration rate and electrochemical stability than the bare crystalline titanium substrate.

Benchmarking nanoparticulate metal oxide electrocatalysts for the alkaline water oxidation reaction

DOE PAGES

Jung, Suho; McCrory, Charles C. L.; Ferrer, Ivonne M.; ...

2016-11-27

Nanoparticulate metal-oxide catalysts are among the most prevalent systems for alkaline water oxidation. However, comparisons of the electrochemical performance of these materials have been challenging due to the different methods of attachment, catalyst loadings, and electrochemical test conditions reported in the literature. Here in this paper, we have leveraged a conventional drop-casting method that allows for the successful adhesion of a wide range of nanoparticulate catalysts to glassy-carbon electrode surfaces. We have applied this adhesion method to prepare catalyst films from 16 crystalline metal-oxide nanoparticles with a constant loading of 0.8 mg cm -2, and evaluated the resulting nanoparticulate filmsmore » for the oxygen evolution reaction under conditions relevant to an integrated solar fuels device. In general, the activities of the adhered nanoparticulate films are similar to those of thin-film catalysts prepared by electrodeposition or sputtering, achieving 10 mA cm -2 current densities per geometric area at overpotentials of ~0.35–0.5 V.« less

Glucose Biosensor Based on a Glassy Carbon Electrode Modified with Polythionine and Multiwalled Carbon Nanotubes

PubMed Central

Tang, Wenwei; Li, Lei; Wu, Lujun; Gong, Jiemin; Zeng, Xinping

2014-01-01

A novel glucose biosensor was fabricated. The first layer of the biosensor was polythionine, which was formed by the electrochemical polymerisation of the thionine monomer on a glassy carbon electrode. The remaining layers were coated with chitosan-MWCNTs, GOx, and the chitosan-PTFE film in sequence. The MWCNTs embedded in FAD were like “conductive wires” connecting FAD with electrode, reduced the distance between them and were propitious to fast direct electron transfer. Combining with good electrical conductivity of PTH and MWCNTs, the current response was enlarged. The sensor was a parallel multi-component reaction system (PMRS) and excellent electrocatalytic performance for glucose could be obtained without a mediator. The glucose sensor had a working voltage of −0.42 V, an optimum working temperature of 25°C, an optimum working pH of 7.0, and the best percentage of polytetrafluoroethylene emulsion (PTFE) in the outer composite film was 2%. Under the optimised conditions, the biosensor displayed a high sensitivity of 2.80 µA mM−1 cm−2 and a low detection limit of 5 µM (S/N = 3), with a response time of less than 15 s and a linear range of 0.04 mM to 2.5 mM. Furthermore, the fabricated biosensor had a good selectivity, reproducibility, and long-term stability, indicating that the novel CTS+PTFE/GOx/MWCNTs/PTH composite is a promising material for immobilization of biomolecules and fabrication of third generation biosensors. PMID:24816121

Glucose biosensor based on a glassy carbon electrode modified with polythionine and multiwalled carbon nanotubes.

PubMed

Tang, Wenwei; Li, Lei; Wu, Lujun; Gong, Jiemin; Zeng, Xinping

2014-01-01

A novel glucose biosensor was fabricated. The first layer of the biosensor was polythionine, which was formed by the electrochemical polymerisation of the thionine monomer on a glassy carbon electrode. The remaining layers were coated with chitosan-MWCNTs, GOx, and the chitosan-PTFE film in sequence. The MWCNTs embedded in FAD were like "conductive wires" connecting FAD with electrode, reduced the distance between them and were propitious to fast direct electron transfer. Combining with good electrical conductivity of PTH and MWCNTs, the current response was enlarged. The sensor was a parallel multi-component reaction system (PMRS) and excellent electrocatalytic performance for glucose could be obtained without a mediator. The glucose sensor had a working voltage of -0.42 V, an optimum working temperature of 25°C, an optimum working pH of 7.0, and the best percentage of polytetrafluoroethylene emulsion (PTFE) in the outer composite film was 2%. Under the optimised conditions, the biosensor displayed a high sensitivity of 2.80 µA mM(-1) cm(-2) and a low detection limit of 5 µM (S/N = 3), with a response time of less than 15 s and a linear range of 0.04 mM to 2.5 mM. Furthermore, the fabricated biosensor had a good selectivity, reproducibility, and long-term stability, indicating that the novel CTS+PTFE/GOx/MWCNTs/PTH composite is a promising material for immobilization of biomolecules and fabrication of third generation biosensors.

Highly efficient electrocatalytic vapor generation of methylmercury based on the gold particles deposited glassy carbon electrode: A typical application for sensitive mercury speciation analysis in fish samples.

PubMed

Shi, Meng-Ting; Yang, Xin-An; Qin, Li-Ming; Zhang, Wang-Bing

2018-09-26

A gold particle deposited glassy carbon electrode (Au/GCE) was first used in electrochemical vapor generation (ECVG) technology and demonstrated to have excellent catalytic property for the electrochemical conversion process of aqueous mercury, especially for methylmercury (CH 3 Hg + ), to gaseous mercury. Systematical research has shown that the highly consistent or distinct difference between the atomic fluorescence spectroscopy signals of CH 3 Hg + and Hg 2+ can be achieved by controlling the electrolytic parameters of ECVG. Hereby, a new green and accurate method for mercury speciation analysis based on the distinguishing electrochemical reaction behavior of Hg 2+ and CH 3 Hg +  on the modified electrode was firstly established. Furthermore, electrochemical impedance spectra and the square wave voltammetry displayed that the ECVG reaction of CH 3 Hg +  may belong to the electrocatalytic mechanism. Under the selected conditions, the limits of detection of Hg 2+ and CH 3 Hg +  are 5.3 ng L -1 and 4.4 ng L -1 for liquid samples and 0.53 pg mg -1 and 0.44 pg mg -1 for solid samples, respectively. The precision of the 5 measurements is less than 6% within the concentration of Hg 2+ and CH 3 Hg +  ranging from 0.2 to 15.0 μg L -1 . The accuracy and practicability of the proposed method was verified by analyzing the mercury content in the certified reference material and several fish as well as water samples. Copyright © 2018 Elsevier B.V. All rights reserved.

Fluorescence quenching studies of potential-dependent DNA reorientation dynamics at glassy carbon electrode surfaces.

PubMed

Li, Qin; Cui, Chenchen; Higgins, Daniel A; Li, Jun

2012-09-05

The potential-dependent reorientation dynamics of double-stranded DNA (ds-DNA) attached to planar glassy carbon electrode (GCE) surfaces were investigated. The orientation state of surface-bound ds-DNA was followed by monitoring the fluorescence from a 6-carboxyfluorescein (FAM6) fluorophore covalently linked to the distal end of the DNA. Positive potentials (i.e., +0.2 V vs open circuit potential, OCP) caused the ds-DNA to align parallel to the electrode surface, resulting in strong dipole-electrode quenching of FAM6 fluorescence. Switching of the GCE potential to negative values (i.e., -0.2 V vs OCP) caused the ds-DNA to reorient perpendicular to the electrode surface, with a concomitant increase in FAM6 fluorescence. In addition to the very fast (submilliseconds) dynamics of the initial reorientation process, slow (0.1-0.9 s) relaxation of FAM6 fluorescence to intermediate levels was also observed after potential switching. These dynamics have not been previously described in the literature. They are too slow to be explained by double layer charging, and chronoamperometry data showed no evidence of such effects. Both the amplitude and rate of the dynamics were found to depend upon buffer concentration, and ds-DNA length, demonstrating a dependence on the double layer field. The dynamics are concluded to arise from previously undetected complexities in the mechanism of potential-dependent ds-DNA reorientation. The possible origins of these dynamics are discussed. A better understanding of these dynamics will lead to improved models for potential-dependent ds-DNA reorientation at electrode surfaces and will facilitate the development of advanced electrochemical devices for detection of target DNAs.

Flower-Like Nanoparticles of Pt-BiIII Assembled on Agmatine Sulfate Modified Glassy Carbon Electrode and Their Electrocatalysis of H2O2

NASA Astrophysics Data System (ADS)

Xiao, Mingshu; Yan, Yuhua; Feng, Kai; Tian, Yanping; Miao, Yuqing

2015-04-01

A new electrochemical technique to detect hydrogen peroxide (H2O2) was developed. The Pt nanoparticles and BiIII were subsequently assembled on agmatine sulfate (AS) modified glassy carbon electrode (GCE) and the prepared GCE-AS-Pt-BiIII was characterized by scanning electron microscopy (SEM) with result showing that the flower-like nanostructure of Pt-BiIII was yielded. Compared with Pt nanoparticles, the flower-like nanostructure of Pt-BiIII greatly enhanced the electrocatalysis of GCE-AS-Pt-BiIII towards H2O2, which is ascribed to more Pt-OH obtained on GCE-AS-Pt-BiIII surface for the presence of BiIII. Based on its high electrocatalysis, GCE-AS-Pt-BiIII was used to determine the content of H2O2 in the sample of sheet bean curd with standard addition method. Meantime, its electrocatalytic activity also was studied.

Determination of trace levels of diosmin in a pharmaceutical preparation by adsorptive stripping voltammetry at a glassy carbon electrode.

PubMed

El-Shahawi, M S; Bashammakh, A S; El-Mogy, T

2006-10-01

A systematic study on the electrochemical behavior of diosmin in Britton-Robinson buffer (pH 2.0-10.0) at a glassy carbon electrode (GCE) was made. The oxidation process of the drug was found to be quasi-reversible with an adsorption-controlled step. The adsorption stripping response was evaluated with respect to various experimental conditions, such as the pH of the supporting electrolyte, the accumulation potential and the accumulation time. The observed anodic peak current at +0.73 V vs. Ag/AgCl reference electrode increased linearly over two orders of magnitude from 5.0x10(-8) M to 9.0x10(-6) M. A limit of detection down to 3.5x10(-8) M of diosmin at the GCE was achieved with a mean recovery of 97+/-2.1%. Based on the electrochemical data, an open-circuit accumulation step in a stirred sample solution of BR at pH 3.0 was developed. The proposed method was successfully applied to the determination of the drug in pharmaceutical formulations. The results compared favorably with the data obtained via spectrophotometric and HPLC methods.

Glassy-State Stabilization of a Dominant Negative Inhibitor Anthrax Vaccine Containing Aluminum Hydroxide and Glycopyranoside Lipid A Adjuvants

PubMed Central

Hassett, Kimberly J.; Vance, David J.; Jain, Nishant K.; Sahni, Neha; Rabia, Lilia A.; Cousins, Megan C.; Joshi, Sangeeta; Volkin, David B.; Middaugh, Russell; Mantis, Nicholas J.; Carpenter, John F.; Randolph, Theodore W.

2014-01-01

During transport and storage, vaccines may be exposed to temperatures outside of the range recommended for storage, potentially causing efficacy losses. To better understand and prevent such losses, Dominant Negative Inhibitor (DNI), a recombinant protein antigen for a candidate vaccine against anthrax, was formulated as a liquid and as a glassy lyophilized powder with the adjuvants aluminum hydroxide and glycopyranoside lipid A (GLA). Freeze-thawing of the liquid vaccine caused the adjuvants to aggregate and decreased its immunogenicity in mice. Immunogenicity of liquid vaccines also decreased when stored at 40 °C for 8 weeks, as measured by decreases in neutralizing antibody titers in vaccinated mice. Concomitant with efficacy losses at elevated temperatures, changes in DNI structure were detected by fluorescence spectroscopy and increased deamidation was observed by capillary isoelectric focusing (cIEF) after only 1 week of storage of the liquid formulation at 40 °C. In contrast, upon lyophilization, no additional deamidation after 4 weeks at 40 °C and no detectable changes in DNI structure or reduction in immunogenicity after 16 weeks at 40 °C was observed. Vaccines containing aluminum hydroxide and GLA elicited higher immune responses than vaccines adjuvanted with only aluminum hydroxide, with more mice responding to a single dose. PMID:25581103

Voltammetric behavior of Mammeisin (MA) at a glassy carbon electrode and its interaction with Bovine Serum Albumin (BSA).

PubMed

Leuna, Jules-Blaise Mabou; Sop, Sergeot Kungo; Makota, Suzanne; Njanja, Evangeline; Ebelle, Thiery Christophe; Azebaze, Anatole Guy; Ngameni, Emmanuel; Nassi, Achille

2018-02-01

The electrochemical oxidation of Mammeisin (MA) was studied in a solution containing acetone and 0.1M phosphate buffer +0.1M KCl (pH=5.3) at a glassy carbon electrode (GCE), using cyclic (CV) and square wave voltammetry (SWV). MA showed a quasi-reversible process, which is pH dependent and that involves the exchange of two electrons and two protons. The oxidation product was adsorbed by the electrode surface to form a film that blocks active sites over repetitive cyclic. Moreover, the interaction of MA and bovine serum albumin (BSA) was studied by CV and SWV at different pHs (5.4, 7.2, 9.5). As a result of the affinity binding with BSA, electrochemically inactive complex was formed. In addition, the oxidation potential of MA in the presence of BSA depends on the pH. The diffusion coefficients of both free and bound MA were estimated from the cyclic voltammetry data using the method developed by Randles-Sevich (D f =9.85×10 -5 cm 2 s -1 and D b =1.27×10 -9 cm 2 s -1 ) and the binding constant of MA-BSA complex, K=3.47×10 2 Lmol -1 , was obtained. Copyright © 2017. Published by Elsevier B.V.

Hierarchical Co(OH)2 nanostructures/glassy carbon electrode derived from Co(BTC) metal-organic frameworks for glucose sensing

NASA Astrophysics Data System (ADS)

He, Juan; Lu, Xingping; Yu, Jie; Wang, Li; Song, Yonghai

2016-07-01

A novel Co(OH)2/glassy carbon electrode (GCE) has been fabricated via metal-organic framework (MOF)-directed method. In the strategy, the Co(BTC, 1,3,5-benzentricarboxylic acid) MOFs/GCE was firstly prepared by alternately immersing GCE in Co2+ and BTC solution based on a layer-by-layer method. And then, the Co(OH)2 with hierarchical flake nanostructure/GCE was constructed by immersing Co(BTC) MOFs/GCE into 0.1 M NaOH solution at room temperature. Such strategy improves the distribution of hierarchical Co(OH)2 nanostructures on electrode surface greatly, enhances the stability of nanomaterials on the electrode surface, and increases the use efficiency of the Co(OH)2 nanostructures. Scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray powder diffraction, energy dispersive spectroscopy, Fourier transform infrared spectroscopy, and Raman spectra were used to characterize the Co(BTC) MOFs/GCE and Co(OH)2/GCE. Based on the hierarchical Co(OH)2 nanostructures/GCE, a novel and sensitive nonenzymatic glucose sensor was developed. The good performance of the resulted sensor toward the detection of glucose was ascribed to hierarchical flake nanostructures, good mechanical stability, excellent distribution, and large specific surface area of Co(OH)2 nanostructures. The proposed preparation method is simple, efficient, and cheap .

Probing the chemistry, structure, and dynamics of the water-silica interface

NASA Astrophysics Data System (ADS)

Lockwood, Glenn K.

Despite its natural abundance and wide-ranging technological relevance, much remains unknown or unclear about water-silica interfaces. Computer simulation stands to bridge the gaps of knowledge left by experiment, and a recently developed Dissociative Water Potential has enabled the simulation of large amorphous silica surfaces in contact with water without having to impose a model of surface chemistry a priori. Earlier work with this model has revealed the existence of several protonated surface sites such as SiOH2 + and Si-(OH+)-Si that have yet to be extensively characterized. However, both experiment and quantum mechanical simulation have provided an increasing body of evidence that suggests these sites exist, and these sites may play key roles in some of the unexplained phenomena observed in water-silica systems. To this end, this Dissociative Water Potential has been applied to develop a comprehensive picture of the chemistry, structure, and dynamics of the water-silica interface that is unbiased by any expectation of what sites should form. The bridging OH site, Si-(OH+)-Si, does form and is characterized as a highly acidic site that occurs predominantly on strained Si-O-Si bridges near the interface. Similarly, the transient formation of SiOH2 + is observed, and this site is found to be more acidic than Si-(OH +)-Si. In addition to H3O+ that forms near the interface, all of these sites readily deprotonate and are expected to play a role in the enhanced proton conductivity experimentally observed in hydrated mesoporous silica. The reactions between water and silica are particularly relevant to the engineering of nuclear waste forms, and the role of water-silica interactions are also explored within the context of the degradation of silica-based waste forms exposed to radiation. Despite the significant simulation effort employed in glassy waste form research, no molecular models of radiation damage in silica include the effects of moisture. This deficiency is

Electrochemical Determination of Chlorpyrifos on a Nano-TiO₂Cellulose Acetate Composite Modified Glassy Carbon Electrode.

PubMed

Kumaravel, Ammasai; Chandrasekaran, Maruthai

2015-07-15

A rapid and simple method of determination of chlorpyrifos is important in environmental monitoring and quality control. Electrochemical methods for the determination of pesticides are fast, sensitive, reproducible, and cost-effective. The key factor in electrochemical methods is the choice of suitable electrode materials. The electrode materials should have good stability, reproducibility, more sensitivity, and easy method of preparation. Mercury-based electrodes have been widely used for the determination of chlorpyrifos. From an environmental point of view mercury cannot be used. In this study a biocompatible nano-TiO2/cellulose acetate modified glassy carbon electrode was prepared by a simple method and used for the electrochemical sensing of chlorpyrifos in aqueous methanolic solution. Electroanalytical techniques such as cyclic voltammetry, differential pulse voltammetry, and amperometry were used in this work. This electrode showed very good stability, reproducibility, and sensitivity. A well-defined peak was obtained for the reduction of chlorpyrifos in cyclic voltammetry and differential pulse voltammetry. A smooth noise-free current response was obtained in amperometric analysis. The peak current obtained was proportional to the concentration of chlorpyrifos and was used to determine the unknown concentration of chlorpyrifos in the samples. Analytical parameters such as LOD, LOQ, and linear range were estimated. Analysis of real samples was also carried out. The results were validated through HPLC. This composite electrode can be used as an alternative to mercury electrodes reported in the literature.

A novel enzymatic glucose sensor based on Pt nanoparticles-decorated hollow carbon spheres-modified glassy carbon electrode

NASA Astrophysics Data System (ADS)

Luhana, Charles; Bo, Xiang-Jie; Ju, Jian; Guo, Li-Ping

2012-10-01

A new glucose biosensor was developed based on hollow carbon spheres decorated with platinum nanoparticles (Pt/HCSs)-modified glassy carbon electrode immobilized with glucose oxidase (GOx) with the help of Nafion. The Pt nanoparticles were well dispersed on the HCSs with an average size of 2.29 nm. The detection of glucose was achieved via electrochemical detection of the enzymatically liberated H2O2 at +0.5 V versus Ag/AgCl at physiologic pH of 7.4. The Pt/HCSs-modified electrode exhibited excellent electrocatalytic activities toward both the oxidation and reduction of H2O2. The glucose biosensor showed good electrocatalytic performance in terms of high sensitivity (4.1 μA mM-1), low detection limit (1.8 μM), fast response time <3 s, and wide linear range (0.04-8.62 mM). The apparent Michaelis-Menten constant ( K m) and the maximum current density ( i max) values for the biosensor were 10.94 mM and 887 μA cm-2 respectively. Furthermore, this biosensor showed an acceptable reproducibility and high stability. The interfering signals from ascorbic acid and uric acid at concentration levels normally found in human blood were not much compared with the response to glucose. Blood serum samples were also tested with this biosensor and a good recovery was achieved for the two spiked serum samples.

Several routes to the glassy states in the one component soft core system: revisited by molecular dynamics.

PubMed

Habasaki, Junko; Ueda, Akira

2011-02-28

Molecular dynamics simulations have been performed to study the glass transition for the soft core system with a pair potential φ(n)(r) = ε(σ∕r)(n) of n = 12. Using the compressibility factor, PV/Nk(B)T=P̃(ρ*), its phase diagram can be represented as a function of a reduced density, ρ∗ = ρ(ε∕k(B)T)(3∕n), where ρ = Nσ(3)∕V. In the present work, NVE relaxations to the glassy or crystalline states starting from the unstable states in the phase diagram have been revisited in details and compared with other processes. Relaxation processes can be characterized by the time dependence of the dynamical compressibility factor (PV/Nk(B)T)(t) (≡g(ρ(t)*)) on the phase diagram. In some cases, g(ρ(t)*) reached a crystal branch in the phase diagram; however, metastable states are found in many cases. With connecting points for the metastable states in the phase diagram, we can define a glass branch where the dynamics of particles are almost frozen. The structures observed there have common properties characterized as glasses. Although overlaps of glass forming process and nanocrystallization process are observed in some cases, these behaviors are distinguishable to each other by the characteristics of structures. There are several routes to the glass branch and we suggest that all of them are the glass transition.

Heating- and pressure-induced transformations in amorphous and hexagonal ice: A computer simulation study using the TIP4P/2005 model

NASA Astrophysics Data System (ADS)

Engstler, Justin; Giovambattista, Nicolas

2017-08-01

We characterize the phase behavior of glassy water by performing extensive out-of-equilibrium molecular dynamics simulations using the TIP4P/2005 water model. Specifically, we study (i) the pressure-induced transformations between low-density (LDA) and high-density amorphous ice (HDA), (ii) the pressure-induced amorphization (PIA) of hexagonal ice (Ih), (iii) the heating-induced LDA-to-HDA transformation at high pressures, (iv) the heating-induced HDA-to-LDA transformation at low and negative pressures, (v) the glass transition temperatures of LDA and HDA as a function of pressure, and (vi) the limit of stability of LDA upon isobaric heating and isothermal decompression (at negative pressures). These transformations are studied systematically, over a wide range of temperatures and pressures, allowing us to construct a P-T phase diagram for glassy TIP4P/2005 water. Our results are in qualitative agreement with experimental observations and with the P-T phase diagram obtained for glassy ST2 water that exhibits a liquid-liquid phase transition and critical point. We also discuss the mechanism for PIA of ice Ih and show that this is a two-step process where first, the hydrogen-bond network (HBN) is distorted and then the HBN abruptly collapses. Remarkably, the collapse of the HB in ice Ih occurs when the average molecular orientations order, a measure of the tetrahedrality of the HBN, is of the same order as in LDA, suggesting a common mechanism for the LDA-to-HDA and Ih-to-HDA transformations.

Heating- and pressure-induced transformations in amorphous and hexagonal ice: A computer simulation study using the TIP4P/2005 model.

PubMed

Engstler, Justin; Giovambattista, Nicolas

2017-08-21

We characterize the phase behavior of glassy water by performing extensive out-of-equilibrium molecular dynamics simulations using the TIP4P/2005 water model. Specifically, we study (i) the pressure-induced transformations between low-density (LDA) and high-density amorphous ice (HDA), (ii) the pressure-induced amorphization (PIA) of hexagonal ice (I h ), (iii) the heating-induced LDA-to-HDA transformation at high pressures, (iv) the heating-induced HDA-to-LDA transformation at low and negative pressures, (v) the glass transition temperatures of LDA and HDA as a function of pressure, and (vi) the limit of stability of LDA upon isobaric heating and isothermal decompression (at negative pressures). These transformations are studied systematically, over a wide range of temperatures and pressures, allowing us to construct a P-T phase diagram for glassy TIP4P/2005 water. Our results are in qualitative agreement with experimental observations and with the P-T phase diagram obtained for glassy ST2 water that exhibits a liquid-liquid phase transition and critical point. We also discuss the mechanism for PIA of ice I h and show that this is a two-step process where first, the hydrogen-bond network (HBN) is distorted and then the HBN abruptly collapses. Remarkably, the collapse of the HB in ice I h occurs when the average molecular orientations order, a measure of the tetrahedrality of the HBN, is of the same order as in LDA, suggesting a common mechanism for the LDA-to-HDA and I h -to-HDA transformations.

Electrochemical determination of estrogenic compound bisphenol F in food packaging using carboxyl functionalized multi-walled carbon nanotubes modified glassy carbon electrode.

PubMed

Wang, Xin; Yang, Lijun; Jin, Xudong; Zhang, Lei

2014-08-15

A simple and highly sensitive electroanalytical method for the determination of bisphenol F (BPF) was developed, which was carried out on multi-walled carbon nanotubes-COOH (MWCNT-COOH) modified glassy carbon electrode (GCE) using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The results showed that MWCNT-COOH remarkably enhanced the oxidation of BPF, which improved the anodic peak current of BPF significantly. The mechanism was oxidation of BPF lose electrons on the electrode surface via adsorption-controlled process, electrode reaction is the two electrons/two protons process. Under the optimised conditions, the oxidation peak current was proportional to BPF concentration the range from 0.12 to 6.01 μg mL(-1). The detection limit was 0.11 μg mL(-1) (S/N=3), and the relative standard deviation (R.S.D.) was 3.5% (n=9). Moreover, the MWCNT-COOH/GCE electrode showed good reproducibility, stability and anti-interference. Therefore, the proposed method was successfully applied to determine BPF in food packing and the results were satisfactory. Copyright © 2014 Elsevier Ltd. All rights reserved.

Molecular Packing, Hydrogen Bonding, and Fast Dynamics in Lysozyme/Trehalose/Glycerol and Trehalose/Glycerol Glasses at Low Hydration.

PubMed

Lerbret, Adrien; Affouard, Frédéric

2017-10-12

Water and glycerol are well-known to facilitate the structural relaxation of amorphous protein matrices. However, several studies evidenced that they may also limit fast (∼picosecond-nanosecond, ps-ns) and small-amplitude (∼Å) motions of proteins, which govern their stability in freeze-dried sugar mixtures. To determine how they interact with proteins and sugars in glassy matrices and, thereby, modulate their fast dynamics, we performed molecular dynamics (MD) simulations of lysozyme/trehalose/glycerol (LTG) and trehalose/glycerol (TG) mixtures at low glycerol and water concentrations. Upon addition of glycerol and/or water, the glass transition temperature, T g , of LTG and TG mixtures decreases, the molecular packing of glasses is improved, and the mean-square displacements (MSDs) of lysozyme and trehalose either decrease or increase, depending on the time scale and on the temperature considered. A detailed analysis of the hydrogen bonds (HBs) formed between species reveals that water and glycerol may antiplasticize the fast dynamics of lysozyme and trehalose by increasing the total number and/or the strength of the HBs they form in glassy matrices.

A very low potential electrochemical detection of L-cysteine based on a glassy carbon electrode modified with multi-walled carbon nanotubes/gold nanorods.

PubMed

Silva, Francisco de Assis dos Santos; da Silva, Monique Gabriella Angelo; Lima, Phabyanno Rodrigues; Meneghetti, Mario Roberto; Kubota, Lauro Tatsuo; Goulart, Marilia Oliveira Fonseca

2013-12-15

A nanohybrid platform built with multi-walled carbon nanotubes and gold nanorods, prepared via a cationic surfactant-containing seed-mediated sequential growth process, in aqueous solution, on a glassy carbon substrate has been successfully developed to be used in the electrocatalytic oxidation of L-cysteine (Cys). The nanohybrid was characterized by transmission electron microscopy, Raman spectroscopy and electrochemical measurements. Cyclic voltammetry results had shown that the modified electrode allows the oxidation of Cys at a very low anodic potential (0.00 V vs. Ag/AgCl). The kinetic constant kcat for the catalytic oxidation of Cys was evaluated by chronoamperometry and provided a value of 5.6×10(4) L mol(-1) s(-1). The sensor presents a linear response range from 5.0 up to 200.0 µmol L(-1), detection limit of 8.25 nmol L(-1) and a sensitivity of 120 nA L µmol(-1). Copyright © 2013 Elsevier B.V. All rights reserved.

Development of vinylic and acetylenic functionalized structures based on high permeable glassy polymers as membrane materials for gas mixtures separation

NASA Astrophysics Data System (ADS)

Roizard, D.; Kiryukhina, Y.; Masalev, A.; Khotimskiy, V.; Teplyakov, V.; Barth, D.

2013-03-01

There are several challenging separation problems in industries which can be solved with the help of membrane technologies. It is the case for instance of the purification of gas energy carriers (i.e. H2, CH4) from CO2 as well as the CO2 recovery from flue gas. Glassy polymers containing trimethylsilyl residues like poly(1-trimethylsilyl-1-propyne) [PTMSP] and polyvinyltrimethylsilane [PVTMS] are known to exhibit good membrane properties for gas separation. This paper reports two ways of improving their performances based on the controlled introduction of selective groups - alkyl imidazomium salts (C4I) and polyethyleneglycol (M-PEG)- able to enhance CO2 selectivity. CO2 Isotherm sorption data and permeability measurements have shown that the membrane performances could be significantly improved when C4I and M-PEG were introduced as residues covalently bounded to the main polymer chain. Moreover the introduced bromine reactive centres could also be used to induce chemical crosslinking giving rise to more resistant and stable membranes to organic vapours. With the C4I groups, the CO2 sorption could be enhanced by a factor 4.4.

Fuel blends: Enhanced electro-oxidation of formic acid in its blend with methanol at platinum nanoparticles modified glassy carbon electrodes

NASA Astrophysics Data System (ADS)

El-Deab, Mohamed S.; El-Nagar, Gumaa A.; Mohammad, Ahmad M.; El-Anadouli, Bahgat E.

2015-07-01

The current study addresses, for the first time, the enhanced direct electro-oxidation of formic acid (FA) at platinum-nanoparticles modified glassy carbon (nano-Pt/GC) electrode in the presence of methanol (MeOH) as a blending fuel. This enhancement is probed by: (i) the increase of the direct oxidation current of FA to CO2 (Ipd, dehydrogenation pathway), (ii) suppressing the dehydration pathway (Ipind, producing the poisoning intermediate CO) and (iii) a favorable negative shift of the onset potential of Ipd with increasing the mole fraction of MeOH in the blend. Furthermore, the charge of the direct FA oxidation in 0.3 M FA + 0.3 M MeOH blend is by 14 and 21times higher than that observed for 0.3 M FA and 0.3 M MeOH, respectively. MeOH is believed to adsorb at the Pt surface sites and thus disfavor the "non-faradaic" dissociation of FA (which produces the poisoning CO intermediate), i.e., MeOH induces a high CO tolerance of the Pt catalyst. The enhanced oxidation activity indicates that FA/MeOH blend is a promising fuel system.

An amperometric hydrogen peroxide biosensor based on Co3O4 nanoparticles and multiwalled carbon nanotube modified glassy carbon electrode

NASA Astrophysics Data System (ADS)

Kaçar, Ceren; Dalkiran, Berna; Erden, Pınar Esra; Kiliç, Esma

2014-08-01

In this work a new type of hydrogen peroxide biosensor was fabricated based on the immobilization of horseradish peroxidase (HRP) by cross-linking on a glassy carbon electrode (GCE) modified with Co3O4 nanoparticles, multiwall carbon nanotubes (MWCNTs) and gelatin. The introduction of MWCNTs and Co3O4 nanoparticles not only enhanced the surface area of the modified electrode for enzyme immobilization but also facilitated the electron transfer rate, resulting in a high sensitivity of the biosensor. The fabrication process of the sensing surface was characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Amperometric detection of hydrogen peroxide was investigated by holding the modified electrode at -0.30 V (vs. Ag/AgCl). The biosensor showed optimum response within 5 s at pH 7.0. The optimized biosensor showed linear response range of 7.4 × 10-7-1.9 × 10-5 M with a detection limit of 7.4 × 10-7. The applicability of the purposed biosensor was tested by detecting hydrogen peroxide in disinfector samples. The average recovery was calculated as 100.78 ± 0.89.

Molecular Dynamics, Recrystallization Behavior, and Water Solubility of the Amorphous Anticancer Agent Bicalutamide and Its Polyvinylpyrrolidone Mixtures.

PubMed

Szczurek, Justyna; Rams-Baron, Marzena; Knapik-Kowalczuk, Justyna; Antosik, Agata; Szafraniec, Joanna; Jamróz, Witold; Dulski, Mateusz; Jachowicz, Renata; Paluch, Marian

2017-04-03

In this paper, we investigated the molecular mobility and physical stability of amorphous bicalutamide, a poorly water-soluble drug widely used in prostate cancer treatment. Our broadband dielectric spectroscopy measurements and differential scanning calorimetry studies revealed that amorphous BIC is a moderately fragile material with a strong tendency to recrystallize from the amorphous state. However, mixing the drug with polymer polyvinylpyrrolidone results in a substantial improvement of physical stability attributed to the antiplasticizing effect governed by the polymer additive. Furthermore, IR study demonstrated the existence of specific interactions between the drug and excipient. We found out that preparation of bicalutamide-polyvinylpyrrolidone mixture in a 2-1 weight ratio completely hinder material recrystallization. Moreover, we determined the time-scale of structural relaxation in the glassy state for investigated materials. Because molecular mobility is considered an important factor governing crystallization behavior, such information was used to approximate the long-term physical stability of an amorphous drug and drug-polymer systems upon their storage at room temperature. Moreover, we found that such systems have distinctly higher water solubility and dissolution rate in comparison to the pure amorphous form, indicating the genuine formulation potential of the proposed approach.

Deposition of vaporized species onto glassy fallout from a near-surface nuclear test

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weisz, David G.; Jacobsen, Benjamin; Marks, Naomi E.

In a near-surface nuclear explosion where the resultant fireball can interact with the surface, vaporized materials from the nuclear device can be incorporated into molten soil and other carrier materials from that surface. This mixed material becomes a source of glassy fallout upon quenching and is locally deposited. Fallout formation models have been proposed; however, the specific mechanisms and physical conditions by which soil and other carrier materials interact in the fireball, as well as the subsequent incorporation of device materials with carrier materials, are not well constrained. We observe a surface deposition layer preserved at interfaces where two aerodynamicmore » fallout glasses agglomerated and fused, and characterized 11 such boundaries using spatial analyses to better understand the vaporization and condensation behavior of species in the fireball. Using nanoscale secondary ion mass spectrometry (NanoSIMS), we identify higher enrichments of uranium from the device ( 235U/ 238U ratio >7.5) in 8 of the interface layers. Major element analysis of the interfaces reveals the deposition layer to be enriched in Fe, Ca, Mg, Mn, and Na-bearing species and depleted in Ti and Al-bearing species. Most notably, the Fe and Ca-bearing species are enriched approximately 50% at the interface layer relative to the average concentrations measured within the fallout glasses, while Ti and Al-bearing species are depleted by approximately 20%. SiO 2 is found to be relatively invariable across the samples and interfaces (~3% standard deviation). The notable depletion of Al, a refractory oxide abundant in the soil, together with the enrichment of 235U and Fe, suggests an anthropogenic source of the enriched species or an unexpected vaporization/condensation behavior. The presence of both refractory (e.g., Ca and U) and volatile (e.g., Na) species approximately co-located in most of the observed layers (within 1.5 μm) suggests a continuous condensation process may

Deposition of vaporized species onto glassy fallout from a near-surface nuclear test

NASA Astrophysics Data System (ADS)

Weisz, David G.; Jacobsen, Benjamin; Marks, Naomi E.; Knight, Kim B.; Isselhardt, Brett H.; Matzel, Jennifer E.; Weber, Peter K.; Prussin, Stan G.; Hutcheon, Ian D.

2017-03-01

In a near-surface nuclear explosion where the resultant fireball can interact with the surface, vaporized materials from the nuclear device can be incorporated into molten soil and other carrier materials from that surface. This mixed material becomes a source of glassy fallout upon quenching and is locally deposited. Fallout formation models have been proposed; however, the specific mechanisms and physical conditions by which soil and other carrier materials interact in the fireball, as well as the subsequent incorporation of device materials with carrier materials, are not well constrained. We observe a surface deposition layer preserved at interfaces where two aerodynamic fallout glasses agglomerated and fused, and characterized 11 such boundaries using spatial analyses to better understand the vaporization and condensation behavior of species in the fireball. Using nanoscale secondary ion mass spectrometry (NanoSIMS), we identify higher enrichments of uranium from the device (235U/238U ratio >7.5) in 8 of the interface layers. Major element analysis of the interfaces reveals the deposition layer to be enriched in Fe, Ca, Mg, Mn, and Na-bearing species and depleted in Ti and Al-bearing species. Most notably, the Fe and Ca-bearing species are enriched approximately 50% at the interface layer relative to the average concentrations measured within the fallout glasses, while Ti and Al-bearing species are depleted by approximately 20%. SiO2 is found to be relatively invariable across the samples and interfaces (∼3% standard deviation). The notable depletion of Al, a refractory oxide abundant in the soil, together with the enrichment of 235U and Fe, suggests an anthropogenic source of the enriched species or an unexpected vaporization/condensation behavior. The presence of both refractory (e.g., Ca and U) and volatile (e.g., Na) species approximately co-located in most of the observed layers (within 1.5 μm) suggests a continuous condensation process may also be

Deposition of vaporized species onto glassy fallout from a near-surface nuclear test

DOE PAGES

Weisz, David G.; Jacobsen, Benjamin; Marks, Naomi E.; ...

2016-10-29

In a near-surface nuclear explosion where the resultant fireball can interact with the surface, vaporized materials from the nuclear device can be incorporated into molten soil and other carrier materials from that surface. This mixed material becomes a source of glassy fallout upon quenching and is locally deposited. Fallout formation models have been proposed; however, the specific mechanisms and physical conditions by which soil and other carrier materials interact in the fireball, as well as the subsequent incorporation of device materials with carrier materials, are not well constrained. We observe a surface deposition layer preserved at interfaces where two aerodynamicmore » fallout glasses agglomerated and fused, and characterized 11 such boundaries using spatial analyses to better understand the vaporization and condensation behavior of species in the fireball. Using nanoscale secondary ion mass spectrometry (NanoSIMS), we identify higher enrichments of uranium from the device ( 235U/ 238U ratio >7.5) in 8 of the interface layers. Major element analysis of the interfaces reveals the deposition layer to be enriched in Fe, Ca, Mg, Mn, and Na-bearing species and depleted in Ti and Al-bearing species. Most notably, the Fe and Ca-bearing species are enriched approximately 50% at the interface layer relative to the average concentrations measured within the fallout glasses, while Ti and Al-bearing species are depleted by approximately 20%. SiO 2 is found to be relatively invariable across the samples and interfaces (~3% standard deviation). The notable depletion of Al, a refractory oxide abundant in the soil, together with the enrichment of 235U and Fe, suggests an anthropogenic source of the enriched species or an unexpected vaporization/condensation behavior. The presence of both refractory (e.g., Ca and U) and volatile (e.g., Na) species approximately co-located in most of the observed layers (within 1.5 μm) suggests a continuous condensation process may

Nanocrystallization of Zr-Cu-Ni-Al-Au glassy alloys during severe plastic deformation

NASA Astrophysics Data System (ADS)

Yamada, Masahiro; Kamisato, Ryo; Yamasaki, Tohru; Adachi, Hiroki; Tsuchiya, Koichi; Yokoyama, Yoshihiko

2014-08-01

A study has been carried out into the formation of nanocrystalline grains during high-pressure torsion (HPT) deformation of Zr65Cu17Ni5Al10Au3 bulk alloys prepared using tilt casting. As a preliminary to this, X-ray diffraction (XRD) and differential scanning calorimetry (DSC) analyses were carried out on as-cast Zr65+xCu17-xNi5Al10Au3 (x=0~5 at.%) and Zr65Cu20Ni5Al10Au3 alloys, in order to determine the effect on the microstructure of the excess Zr content x and the presence of Au. From the XRD patterns, it was determined that all of the alloys had a metallic glassy nature. For Zr65Cu17Ni5Al10Au3, the DSC results indicated the presence of a wide supercooled liquid region between the glass transition temperature (Tg) of 644 K and the crystallization temperature of 763 K, where the stable body-centered tetragonal Zr2Cu phase was formed. In contrast, for the Zr65+xCu17-xNi5Al10Au3 alloys, precipitation of an icosahedral quasicrystalline phase (I-phase) was observed in the supercooled liquid region at about 715 K. HPT deformation of the Zr65Cu17Ni5Al10Au3 alloys was carried out under a high pressure of 5 GPa. Both as-cast specimens and those annealed at Tg-50 K for 90 min were used. Following a single HPT rotation (N=1), transmission electron microscopy identified the presence of face- centered cubic Zr2Ni precipitates in the as-cast alloy, with a size of about 50 nm. For the annealed alloy, a high density of I-phase precipitates with sizes of less than 10 nm was observed following HPT with N=10, indicating that the combination of severe plastic deformation and annealing is effective at producing extremely small grains.

Pronounced microheterogeneity in a sorbitol-water mixture observed through variable temperature neutron scattering.

PubMed

Chou, Shin G; Soper, Alan K; Khodadadi, Sheila; Curtis, Joseph E; Krueger, Susan; Cicerone, Marcus T; Fitch, Andrew N; Shalaev, Evgenyi Y

2012-04-19

In this study, the structure of concentrated d-sorbitol-water mixtures is studied by wide- and small-angle neutron scattering (WANS and SANS) as a function of temperature. The mixtures are prepared using both deuterated and regular sorbitol and water at a molar fraction of sorbitol of 0.19 (equivalent to 70% by weight of regular sorbitol in water). Retention of an amorphous structure (i.e., absence of crystallinity) is confirmed for this system over the entire temperature range, 100-298 K. The glass transition temperature, Tg, is found from differential scanning calorimetry to be approximately 200 K. WANS data are analyzed using empirical potential structure refinement, to obtain the site-site radial distribution functions (RDFs) and coordination numbers. This analysis reveals the presence of nanoscaled water clusters surrounded by (and interacting with) sorbitol molecules. The water clusters appear more structured compared to bulk water and, especially at the lowest temperatures, resemble the structure of low-density amorphous ice (LDA). Upon cooling to 100 K the peaks in the water RDFs become markedly sharper, with increased coordination number, indicating enhanced local (nanometer-scale) ordering, with changes taking place both above and well below the Tg. On the mesoscopic (submicrometer) scale, although there are no changes between 298 and 213 K, cooling the sample to 100 K results in a significant increase in the SANS signal, which is indicative of pronounced inhomogeneities. This increase in the scattering is partly reversed during heating, although some hysteresis is observed. Furthermore, a power law analysis of the SANS data indicates the existence of domains with well-defined interfaces on the submicrometer length scale, probably as a result of the appearance and growth of microscopic voids in the glassy matrix. Because of the unusual combination of small and wide scattering data used here, the present results provide new physical insight into the

Preface: Proceedings of the ESF Exploratory Workshop on Glassy Liquids under Pressure: Fundamentals and Applications (Ustroń, Poland, 10-12 October 2007) Proceedings of the ESF Exploratory Workshop on Glassy Liquids under Pressure: Fundamentals and Applications (Ustroń, Poland, 10-12 October 2007)

NASA Astrophysics Data System (ADS)

Drozd-Rzoska, Aleksandra; Rzoska, Sylwester J.; Tamarit, Josep Ll

2008-06-01

This preface focuses on the importance of pressure studies for explaining the glass transitions puzzle. Subsequently, some issues related to the European Science Foundation Exploratory Workshop (ESF EW) Glassy Liquids under Pressure: Fundamentals and Applications (Ustroń, Poland, 10-12 October 2007) are recalled. Most liquids crystallize on 'normal' cooling at the melting temperature Tm. However, some liquids can skip crystallization and undergo supercooling down to glass temperature Tg. Turnbull 1 proposed an empirical link between these temperatures indicating good glass forming ability (GFA) for Tg/Tm « 2/3. Values of the GFA factor Tg/Tm → 1/2 were suggested for 'poor' glass formers, where crystallization is difficult to avoid. Recently, the significance of the pressure dependence of the GFA factor was also noted 2. Reaching the glass transition is associated with a series of phenomena, namely 3: (i) the thermal expansion coefficient at constant pressure changes smoothly from values common for a liquid to those of a crystal, showing anomalous behaviour near Tg, (ii) viscosity reaches a value of η = 1013 P and the structural relaxation time τ ≈ 100 s, (iii) the specific heat drop occurs, giving rise to the famous Kauzmann paradox. On cooling towards glass transition, the 'pretransitional' behaviour can be observed for dynamic properties even well above Tg + 100 K 3. This includes the non-Arrhenius evolution of such magnitudes as viscosity, primary (structural-, α-) relaxation time, electric conductivity or diffusion coefficient associated with increasingly non-Debye distribution of relaxation times 3. Such behaviour is associated with short-time scale relaxation processes. The most characteristic is the secondary (β-) relaxation 4, 5 which merges with the 'structural' dynamics near τ(TB) = 10-7+/-1s, the hypothetically universal (magic) time-scale 6. Below TB the split in the evolution of the translation and orientation related properties occurs 4, 5

Simultaneous determination of caffeine and paracetamol by square wave voltammetry at poly(4-amino-3-hydroxynaphthalene sulfonic acid)-modified glassy carbon electrode.

PubMed

Tefera, Molla; Geto, Alemnew; Tessema, Merid; Admassie, Shimelis

2016-11-01

Poly(4-amino-3-hydroxynaphthalene sulfonic acid)-modified glassy carbon electrode (poly(AHNSA)/GCE) was prepared for simultaneous determination of caffeine and paracetamol using square-wave voltammetry. The method was used to study the effects of pH and scan rate on the voltammetric response of caffeine and paracetamol. Linear calibration curves in the range of 10-125μM were obtained for both caffeine and paracetamol in acetate buffer solution of pH 4.5 with a correlation coefficient of 0.9989 and 0.9986, respectively. The calculated detection limits (S/N=3) were 0.79μM for caffeine and 0.45μM for paracetamol. The effects of some interfering substances in the determination of caffeine and paracetamol were also studied and their interferences were found to be negligible which proved the selectivity of the modified electrode. The method was successfully applied for the quantitative determination of caffeine and paracetamol in Coca-Cola, Pepsi-Cola and tea samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

Glassy carbon electrode modified with carbon black for sensitive estradiol determination by means of voltammetry and flow injection analysis with amperometric detection.

PubMed

Smajdor, Joanna; Piech, Robert; Ławrywianiec, Martyna; Paczosa-Bator, Beata

2018-03-01

A voltammetric method for fast and sensitive estradiol determination using carbon black modified glassy carbon electrode (CBGC) is proposed. The use of carbon black as a modifying layer led to obtain low detection limit (9.2·10 -8  mol L -1 for a preconcentration time of 60 s) and stability of registered signals (measured as RSD is 1.3%, n = 7, estradiol concentration 0.5·10 -6  mol L -1 ). Cyclic voltammetry study revealed that in phosphate media estradiol suffers irreversible one-proton and one-electron oxidation process. Under the optimum conditions, estradiol calibration curve was linear in the concentration range from 0.15·10 -6 to 3.5·10 -6  mol L -1 . The proposed method enable to determine estradiol content in different pharmaceutical formulation with good recovery. Amperometric measurements of estradiol were performed as well to indicate the possibility of its fast and accurate determination under the flow conditions. Copyright © 2017 Elsevier Inc. All rights reserved.

Electrochemical DNA biosensor based on a glassy carbon electrode modified with gold nanoparticles and graphene for sensitive determination of Klebsiella pneumoniae carbapenemase.

PubMed

Pan, Hong-zhi; Yu, Hong-wei; Wang, Na; Zhang, Ze; Wan, Guang-cai; Liu, Hao; Guan, Xue; Chang, Dong

2015-11-20

We describe the fabrication of a sensitive electrochemical DNA biosensor for determination of Klebsiella pneumoniae carbapenemase (KPC). The highly sensitive and selective electrochemical biosensor for DNA detection was constructed based on a glassy carbon electrode (GCE) modified with gold nanoparticles (Au-NPs) and graphene (Gr). Then Au-NPs/Gr/GCE was characterized by scanning electro microscope (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The hybridization detection was measured by diffierential pulse voltammetry (DPV) using methylene blue (MB) as the hybridization indicator. The dynamic range of detection of the sensor for the target DNA sequences was from 1 × 10(-12) to 1 × 10(-7)mol/L, with a detection limit of 2 × 10(-13)mol/L. The DNA biosensor had excellent specificity for distinguishing complementary DNA sequence in the presence of non-complementary and mismatched DNA sequence. The results demonstrated that the Au-NPs/Gr nanocomposite was a promising substrate for the development of high-performance electrocatalysts for determination of KPC. Copyright © 2015 Elsevier B.V. All rights reserved.

Glassy-state stabilization of a dominant negative inhibitor anthrax vaccine containing aluminum hydroxide and glycopyranoside lipid A adjuvants.

PubMed

Hassett, Kimberly J; Vance, David J; Jain, Nishant K; Sahni, Neha; Rabia, Lilia A; Cousins, Megan C; Joshi, Sangeeta; Volkin, David B; Middaugh, C Russell; Mantis, Nicholas J; Carpenter, John F; Randolph, Theodore W

2015-02-01

During transport and storage, vaccines may be exposed to temperatures outside of the range recommended for storage, potentially causing efficacy losses. To better understand and prevent such losses, dominant negative inhibitor (DNI), a recombinant protein antigen for a candidate vaccine against anthrax, was formulated as a liquid and as a glassy lyophilized powder with the adjuvants aluminum hydroxide and glycopyranoside lipid A (GLA). Freeze-thawing of the liquid vaccine caused the adjuvants to aggregate and decreased its immunogenicity in mice. Immunogenicity of liquid vaccines also decreased when stored at 40°C for 8 weeks, as measured by decreases in neutralizing antibody titers in vaccinated mice. Concomitant with efficacy losses at elevated temperatures, changes in DNI structure were detected by fluorescence spectroscopy and increased deamidation was observed by capillary isoelectric focusing (cIEF) after only 1 week of storage of the liquid formulation at 40°C. In contrast, upon lyophilization, no additional deamidation after 4 weeks at 40°C and no detectable changes in DNI structure or reduction in immunogenicity after 16 weeks at 40°C were observed. Vaccines containing aluminum hydroxide and GLA elicited higher immune responses than vaccines adjuvanted with only aluminum hydroxide, with more mice responding to a single dose. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Hysteresis of Low-Temperature Thermal Conductivity and Boson Peak in Glassy (g) As2S3: Nanocluster Contribution.

PubMed

Mitsa, V; Feher, A; Petretskyi, S; Holomb, R; Tkac, V; Ihnatolia, P; Laver, A

2017-12-01

Experimental results of the thermal conductivity (k(T)) of nanostructured g-As 2 S 3 during cooling and heating processes within the temperature range from 2.5 to 100 K have been analysed. The paper has considered thermal conductivity is weakly temperature k(T) dependent from 2.5 to 100 K showing a plateau in region from 3.6 to 10.7 K during both cooling and heating regimes. This paper is the first attempt to consider the k(T) hysteresis above plateau while heating in the range of temperature from 11 to 60 K. The results obtained have not been reported yet in the scientific literature. Differential curve Δk(T) of k(T) (heating k(T) curve minus cooling k(T) curve) possesses a complex asymmetric peak in the energy range from 1 to 10 meV. Δk(T) reproduces the density of states in a g(ω)/ω 2 representation estimated from a boson peak experimentally obtained by Raman measurement within the range of low and room temperatures. Theoretical and experimental spectroscopic studies have confirmed a glassy structure of g-As 2 S 3 in cluster approximation. The origin of the low-frequency excitations resulted from a rich variety of vibrational properties. The nanocluster vibrations can be created by disorder on atomic scale.

Periodic structure formation and surface morphology evolution of glassy carbon surfaces applying 35-fs-200-ps laser pulses

NASA Astrophysics Data System (ADS)

Csontos, J.; Toth, Z.; Pápa, Z.; Budai, J.; Kiss, B.; Börzsönyi, A.; Füle, M.

2016-06-01

In this work laser-induced periodic structures with lateral dimensions smaller than the central wavelength of the laser were studied on glassy carbon as a function of laser pulse duration. To generate diverse pulse durations titanium-sapphire (Ti:S) laser (center wavelength 800 nm, pulse durations: 35 fs-200 ps) and a dye-KrF excimer laser system (248 nm, pulse durations: 280 fs, 2.1 ps) were used. In the case of Ti:S laser treatment comparing the central part of the laser-treated areas a striking difference is observed between the femtoseconds and picoseconds treatments. Ripple structure generated with short pulse durations can be characterized with periodic length significantly smaller than the laser wavelength (between 120 and 165 nm). At higher pulse durations the structure has a higher periodic length (between 780 and 800 nm), which is comparable to the wavelength. In case of the excimer laser treatment the different pulse durations produced similar surface structures with different periodic length and different orientation. One of the structures was parallel with the polarization of the laser light and has a higher periodic length (~335 nm), and the other was perpendicular with smaller periodic length (~78-80 nm). The possible mechanisms of structure formation will be outlined and discussed in the frame of our experimental results.

Two Glass Transitions Associated to Different Dynamic Disorders in the Nematic Glassy State of a Non-Symmetric Liquid Crystal Dimer Dopped with γ-Alumina Nanoparticles

PubMed Central

Diez-Berart, Sergio; López, David O.; Salud, Josep; Diego, José Antonio; Sellarès, Jordi; Robles-Hernández, Beatriz; de la Fuente, María Rosario; Ros, María Blanca

2015-01-01

In the present work, the nematic glassy state of the non-symmetric LC dimer α-(4-cyanobiphenyl-4′-yloxy)-ω-(1-pyrenimine-benzylidene-4′-oxy) undecane is studied by means of calorimetric and dielectric measurements. The most striking result of the work is the presence of two different glass transition temperatures: one due to the freezing of the flip-flop motions of the bulkier unit of the dimer and the other, at a lower temperature, related to the freezing of the flip-flop and precessional motions of the cyanobiphenyl unit. This result shows the fact that glass transition is the consequence of the freezing of one or more coupled dynamic disorders and not of the disordered phase itself. In order to avoid crystallization when the bulk sample is cooled down, the LC dimer has been confined via the dispersion of γ-alumina nanoparticles, in several concentrations.

What Controls the Low Ice Number Concentration in the Upper Tropical Troposphere?

NASA Astrophysics Data System (ADS)

Penner, J.; Zhou, C.; Lin, G.; Liu, X.; Wang, M.

2015-12-01

Cirrus clouds in the tropical tropopause play a key role in regulating the moisture entering the stratosphere through their dehydrating effect. Low ice number concentrations and high supersaturations were frequently were observed in these clouds. However, low ice number concentrations are inconsistent with cirrus cloud formation based on homogeneous freezing. Different mechanisms have been proposed to explain this discrepancy, including the inhibition of homogeneous freezing by pre-existing ice crystals and/or glassy organic aerosol heterogeneous ice nuclei (IN) and limiting the formation of ice number from high frequency gravity waves. In this study, we examined the effect from three different parameterizations of in-cloud updraft velocities, the effect from pre-existing ice crystals, the effect from different water vapor deposition coefficients (α=0.1 or 1), and the effect from 0.1% of secondary organic aerosol (SOA) acting as glassy heterogeneous ice nuclei (IN) in CAM5. Model simulated ice crystal numbers are compared against an aircraft observational dataset. Using grid resolved large-scale updraft velocity in the ice nucleation parameterization generates ice number concentrations in better agreement with observations for temperatures below 205K while using updraft velocities based on the model-generated turbulence kinetic energy generates ice number concentrations in better agreement with observations for temperatures above 205K. A larger water vapor deposition coefficient (α=1) can efficiently reduce the ice number at temperatures below 205K but less so at higher temperatures. Glassy SOA IN are most effective at reducing the ice number concentrations when the effective in-cloud updraft velocities are moderate (~0.05-0.2 m s-1). Including the removal of water vapor on pre-existing ice can also effectively reduce the ice number and diminish the effects from the additional glassy SOA heterogeneous IN. We also re-evaluate whether IN seeding in cirrus cloud is

In Situ Determination of Bisphenol A in Beverage Using a Molybdenum Selenide/Reduced Graphene Oxide Nanoparticle Composite Modified Glassy Carbon Electrode.

PubMed

Shi, Rongguang; Liang, Jing; Zhao, Zongshan; Liu, Yi; Liu, Aifeng

2018-05-22

Due to the endocrine disturbing effects of bisphenol A (BPA) on organisms, rapid detection has become one of the most important techniques for monitoring its levels in the aqueous solutions associated with plastics and human beings. In this paper, a glassy carbon electrode (GCE) modified with molybdenum selenide/reduced graphene oxide (MoSe₂/rGO) was fabricated for in situ determination of bisphenol A in several beverages. The surface area of the electrode dramatically increases due to the existence of ultra-thin nanosheets in a flower-like structure of MoSe₂. Adding phosphotungstic acid in the electrolyte can significantly enhance the repeatability (RSD = 0.4%) and reproducibility (RSD = 2.2%) of the electrode. Under the optimized condition (pH = 6.5), the linear range of BPA was from 0.1 μM⁻100 μM and the detection limit was 0.015 μM (S/ N = 3). When using the as-prepared electrode for analyzing BPA in beverage samples without any pretreatments, the recoveries ranged from 98⁻107%, and the concentrations were from below the detection limit to 1.7 μM, indicating its potential prospect for routine analysis of BPA.

Dopamine and uric acid electrochemical sensor based on a glassy carbon electrode modified with cubic Pd and reduced graphene oxide nanocomposite.

PubMed

Wang, Jin; Yang, Beibei; Zhong, Jiatai; Yan, Bo; Zhang, Ke; Zhai, Chunyang; Shiraishi, Yukihide; Du, Yukou; Yang, Ping

2017-07-01

A cubic Pd and reduced graphene oxide modified glassy carbon electrode (Pd/RGO/GCE) was fabricated to simultaneously detect dopamine (DA) and uric acid (UA) by cyclic voltammetry (CV) and different pulse voltammetry (DPV) methods. Compared with Pd/GCE and RGO/GCE, the Pd/RGO/GCE exhibited excellent electrochemical activity in electrocatalytic behaviors. Performing the Pd/RGO/GCE in CV measurement, the well-defined oxidation peak potentials separation between DA and UA reached to 145mV. By using the differential pulse voltammetry (DPV) technique, the calibration curves for DA and UA were found linear with the concentration range of 0.45-421μM and 6-469.5μM and the detection limit (S/N =3) were calculated to be 0.18μM and 1.6μM, respectively. Furthermore, the Pd/RGO/GCE displayed high selectivity when it was applied into the determination of DA and UA even though in presence of high concentration of interferents. Additionally, the prepared electrochemical sensor of Pd/RGO/GCE demonstrated a practical feasibility in rat urine and serum samples determination. Copyright © 2017 Elsevier Inc. All rights reserved.

Simple flow injection for determination of sulfite by amperometric detection using glassy carbon electrode modified with carbon nanotubes-PDDA-gold nanoparticles.

PubMed

Amatatongchai, Maliwan; Sroysee, Wongduan; Chairam, Sanoe; Nacapricha, Duangjai

2015-02-01

A new approach is presented for sensitive and selective measurement of sulfite (SO3(2-)) in beverages based on a simple flow injection system with amperometric detection. In this work, the sulfite sensor was a glassy carbon electrode modified with multiwall carbon nanotubes-poly(diallyldimethylammonium chloride)-gold nanoparticles composites (CNTs-PDDA-AuNPs/GC). Electrochemical oxidation of sulfite with this electrode was first studied in 0.1M phosphate buffer (pH 7.0) using cyclic voltammetry. The results indicated that the CNTs-PDDA-AuNPs/GC electrode possesses electrocatalytic activity for the oxidation of sulfite with high sensitivity and selectivity. Sulfite was quantified using amperometric measurement with the new sensor at +0.4V vs Ag/AgCl in conjunction with flow injection. The linear working range for the quantitation of sulfite was 2-200 mg L(-1) (r(2)=0.998) with a detection limit of 0.03 mg L(-1) (3σ of blank) and an estimated precision of 1.5%.The proposed method was successfully applied to the determination of sulfite in fruit juices and wines with a sample throughput of 23 samples per hour. Copyright © 2014 Elsevier B.V. All rights reserved.

Functionalization of carbon nanotubes with water-insoluble porphyrin in ionic liquid: direct electrochemistry and highly sensitive amperometric biosensing for trichloroacetic acid.

PubMed

Tu, Wenwen; Lei, Jianping; Ju, Huangxian

2009-01-01

A functional composite of single-walled carbon nanotubes (SWNTs) with hematin, a water-insoluble porphyrin, was first prepared in 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]) ionic liquid. The novel composite in ionic liquid was characterized by scanning electron microscopy, ultraviolet absorption spectroscopy, and electrochemical impedance spectroscopy, and showed a pair of direct redox peaks of the Fe(III)/Fe(II) couple. The composite-[BMIM][PF(6)]-modified glassy carbon electrode showed excellent electrocatalytic activity toward the reduction of trichloroacetic acid (TCA) in neutral media due to the synergic effect among SWNTs, [BMIM][PF(6)], and porphyrin, which led to a highly sensitive and stable amperometric biosensor for TCA with a linear range from 9.0x10(-7) to 1.4x10(-4) M. The detection limit was 3.8x10(-7) M at a signal-to-noise ratio of 3. The TCA biosensor had good analytical performance, such as rapid response, good reproducibility, and acceptable accuracy, and could be successfully used for the detection of residual TCA in polluted water. The functional composite in ionic liquid provides a facile way to not only obtain the direct electrochemistry of water-insoluble porphyrin, but also construct novel biosensors for monitoring analytes in real environmental samples.

Molecularly imprinted poly(4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid) modified glassy carbon electrode as an electrochemical theophylline sensor.

PubMed

Aswini, K K; Vinu Mohan, A M; Biju, V M

2016-08-01

Theophylline is an inexpensive drug employed in asthma and chronic obstructive pulmonary disorder medications and is toxic at higher concentration. The development of a molecularly imprinted polymer based theophylline electrochemical sensor on glassy carbon electrode by the electropolymerization of 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid is being discussed in this work. The MIP modification enhances the theophylline recognition ability and the electron transfer kinetics of the bare electrode. The parameters, controlling the performance of the imprinted polymer based sensor, like number of electropolymerization cycles, composition of the pre-polymerization mixture, pH and immersion time were investigated and optimized. The interaction energy and the most stable conformation of the template-monomer complex in the pre-polymerization mixture were determined computationally using ab initio calculations based on density functional theory. The amperometric measurements showed that the developed sensor has a method detection limit of 0.32μM for the dynamic range of 0.4 to 17μM, at optimized conditions. The transducer possesses appreciable selectivity in the presence of structurally similar interferents such as theobromine, caffeine and doxofylline. The developed sensor showed remarkable stability and reproducibility and was also successfully employed in theophylline detection from commercially available tablets. Copyright © 2016 Elsevier B.V. All rights reserved.

A novel lable-free electrochemical immunosensor for carcinoembryonic antigen based on gold nanoparticles-thionine-reduced graphene oxide nanocomposite film modified glassy carbon electrode.

PubMed

Kong, Fen-Ying; Xu, Mao-Tian; Xu, Jing-Juan; Chen, Hong-Yuan

2011-10-15

In this paper, gold nanoparticle-thionine-reduced graphene oxide (GNP-THi-GR) nanocomposites were prepared to design a label-free immunosensor for the sensitive detection of carcinoembryonic antigen (CEA). The nanocomposites with good biocompatibility, excellent redox electrochemical activity and large surface area were coated onto the glassy carbon electrode (GCE) surface and then CEA antibody (anti-CEA) was immobilized on the electrode to construct the immunosensor. The morphologies and electrochemistry of the formed nanocomposites were investigated by using scanning electron microscopy (SEM), ultraviolet-visible (UV-vis) spectrometry, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). CV and differential pulse voltammetry (DPV) studies demonstrated that the formation of antibody-antigen complexes decreased the peak current of THi in the GNP-THi-GR nanocomposites. The decreased currents were proportional to the CEA concentration in the range of 10-500 pg/mL with a detection limit of 4 pg/mL. The proposed method was simple, fast and inexpensive for the determination of CEA at very low levels. Copyright © 2011 Elsevier B.V. All rights reserved.

The submarine record of a large-scale explosive eruption in the Vanuatu Arc: ˜1 Ma Efaté Pumice Formation

NASA Astrophysics Data System (ADS)

Raos, Alison M.; McPhie, Jocelyn

The Efaté Pumice Formation (EPF) is the record of a major explosive eruption that occurred in the Vanuatu arc, southwestern Pacific, at about 1 Ma. The EPF is the oldest stratigraphic unit of the Efaté Island Group and consists of a succession of non-welded, trachydacitic pumice breccia and shard-rich sand and silt beds with a minimum thickness of ˜500 m and a minimum bulk volume of approximately 85 km3. The lower part (Efaté Pumice Breccias) of the EPF comprises very thick beds composed almost exclusively of glassy, trachydacitic, pumice fragments with ragged terminations. In contrast, the upper part (Rentabau Tuffs) consists of up to 70 m of well-bedded and well-sorted shard-rich sand and silt. The clast population of this upper part comprises >95% glassy or formerly glassy shards, but fossil foraminifera are a ubiquitous and important non-volcanic component. Some glass shards have blocky, equant shapes and arcuate fracture surfaces, features typically associated with the influence of external water during fragmentation, but most are cuspate and platy bubble-wall shards. Pyroclast morphologies indicate that the Efaté Pumice Breccias were largely generated by magmatic-volatile-driven ("dry"), explosive fragmentation processes, and lithofacies characteristics indicate deposition in below-storm-wave-base environments, from eruption-sourced, water-supported density currents of waterlogged pumice. The Rentabau Tuffs are interpreted to represent a change to hydromagmatic activity in response to waning discharge that allowed ingress of water (presumably seawater) to the vent(s).

Non-Gaussian effects, space-time decoupling, and mobility bifurcation in glassy hard-sphere fluids and suspensions.

PubMed

Saltzman, Erica J; Schweizer, Kenneth S

2006-12-01

Brownian trajectory simulation methods are employed to fully establish the non-Gaussian fluctuation effects predicted by our nonlinear Langevin equation theory of single particle activated dynamics in glassy hard-sphere fluids. The consequences of stochastic mobility fluctuations associated with the space-time complexities of the transient localization and barrier hopping processes have been determined. The incoherent dynamic structure factor was computed for a range of wave vectors and becomes of an increasingly non-Gaussian form for volume fractions beyond the (naive) ideal mode coupling theory (MCT) transition. The non-Gaussian parameter (NGP) amplitude increases markedly with volume fraction and is well described by a power law in the maximum restoring force of the nonequilibrium free energy profile. The time scale associated with the NGP peak becomes much smaller than the alpha relaxation time for systems characterized by significant entropic barriers. An alternate non-Gaussian parameter that probes the long time alpha relaxation process displays a different shape, peak intensity, and time scale of its maximum. However, a strong correspondence between the classic and alternate NGP amplitudes is predicted which suggests a deep connection between the early and final stages of cage escape. Strong space-time decoupling emerges at high volume fractions as indicated by a nondiffusive wave vector dependence of the relaxation time and growth of the translation-relaxation decoupling parameter. Displacement distributions exhibit non-Gaussian behavior at intermediate times, evolving into a strongly bimodal form with slow and fast subpopulations at high volume fractions. Qualitative and semiquantitative comparisons of the theoretical results with colloid experiments, ideal MCT, and multiple simulation studies are presented.

para-Sulfonatocalix[6]arene-modified silver nanoparticles electrodeposited on glassy carbon electrode: preparation and electrochemical sensing of methyl parathion.

PubMed

Bian, Yinghui; Li, Chunya; Li, Haibing

2010-05-15

In this paper, a new electrochemical sensor, based on modified silver nanoparticles, was fabricated using one-step electrodeposition approach. The para-sulfonatocalix[6]arene-modified silver nanoparticles coated on glassy carbon electrode (pSC(6)-Ag NPs/GCE) was characterized by attenuated total reflection IR spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), etc. The pSC(6) as the host are highly efficient to capture organophosphates (OPs), which dramatically facilitates the enrichment of nitroaromatic OPs onto the electrochemical sensor surface. The combination of the host-guest supramolecular structure and the excellent electrochemical catalytic activities of the pSC(6)-Ag NPs/GCE provides a fast, simple, and sensitive electrochemical method for detecting nitroaromatic OPs. In this work, methyl parathion (MP) was used as a nitroaromatic OP model for testing the proposed sensor. In comparison with Ag NPs-modified electrode, the cathodic peak current of MP was amplified significantly. Differential pulse voltammetry was used for the simultaneous determination of MP. Under optimum conditions, the current increased linearly with the increasing concentration of MP in the range of 0.01-80microM, with a detection limit of 4.0nM (S/N=3). The fabrication reproducibility and stability of the sensor is better than that of enzyme-based electrodes. The possible underlying mechanism is discussed.

Detection and analysis of the bacterium, Xylella fastidiosa, in glassy-winged sharpshooter, Homalodisca vitripennis, populations in Texas.

PubMed

Hail, Daymon; Mitchell, Forrest; Lauzière, Isabelle; Marshall, Patrick; Brady, Jeff; Bextine, Blake

2010-01-01

The glassy-winged sharpshooter, Homalodisca vitripeninis Germar (Hemiptera: Cicadellidae), is a xylophagous insect that is an endemic pest of several economically important plants in Texas. H. vitripennis is the main vector of Xylella fastidiosa Wells (Xanthomonadales: Xanthomonadaceae), the bacterium that causes Pierce's disease of grapevine and can travel long distances putting much of Texas grape production at risk. Understanding the movement of H. vitripennis populations capable of transmitting X. fastidiosa into Pierce's-disease-free areas is critical for developing a management program for Pierce's disease. To that end, the USDA-APHIS has developed a program to sample vineyards across Texas to monitor populations of H. vitripennis. From this sampling, H vitripennis collected during 2005 and 2006 over the months of May, June, and July from eight vineyards in different regions of Texas were recovered from yellow sticky traps and tested for the presence of X. fastidiosa. The foregut contents were vacuum extracted and analyzed using RT-PCR to determine the percentage of H. vitripennis within each population that harbor X. fastidiosa and have the potential to transmit this pathogen. H. vitripennis from vineyards known to have Pierce's disease routinely tested positive for the presence of X. fastidiosa. While almost all H. vitripennis collected from vineyards with no history of Pierce's disease tested negative for the presence of the pathogen, three individual insects tested positive. Furthermore, all three insects were determined, by DNA sequencing, to be carrying a strain of X. fastidiosa homologous to known Pierce's disease strains, signifying them as a risk factor for new X. fastidiosa infections.

Detection and Analysis of the Bacterium, Xylella fastidiosa, in Glassy-Winged Sharpshooter, Homalodisca vitripennis, Populations in Texas

PubMed Central

Hail, Daymon; Mitchell, Forrest; Lauzière, Isabelle; Marshall, Patrick; Brady, Jeff; Bextine, Blake

2010-01-01

The glassy-winged sharpshooter, Homalodisca vitripeninis Germar (Hemiptera: Cicadellidae), is a xylophagous insect that is an endemic pest of several economically important plants in Texas. H. vitripennis is the main vector of Xylella fastidiosa Wells (Xanthomonadales: Xanthomonadaceae), the bacterium that causes Pierce's disease of grapevine and can travel long distances putting much of Texas grape production at risk. Understanding the movement of H. vitripennis populations capable of transmitting X. fastidiosa into Pierce's-disease-free areas is critical for developing a management program for Pierce's disease. To that end, the USDA-APHIS has developed a program to sample vineyards across Texas to monitor populations of H. vitripennis. From this sampling, H vitripennis collected during 2005 and 2006 over the months of May, June, and July from eight vineyards in different regions of Texas were recovered from yellow sticky traps and tested for the presence of X. fastidiosa. The foregut contents were vacuum extracted and analyzed using RT-PCR to determine the percentage of H. vitripennis within each population that harbor X. fastidiosa and have the potential to transmit this pathogen. H. vitripennis from vineyards known to have Pierce's disease routinely tested positive for the presence of X. fastidiosa. While almost all H. vitripennis collected from vineyards with no history of Pierce's disease tested negative for the presence of the pathogen, three individual insects tested positive. Furthermore, all three insects were determined, by DNA sequencing, to be carrying a strain of X. fastidiosa homologous to known Pierce's disease strains, signifying them as a risk factor for new X. fastidiosa infections. PMID:21062210

Seasonal Population Dynamics of Homalodisca vitripennis (Germar) (Hemiptera: Cicadellidae) in Sweet Orange Trees Maintained under Continuous Deficit Irrigation

USDA-ARS?s Scientific Manuscript database

A two-year study was conducted in a citrus orchard [Citrus sinensis (L.) Osbeck cv. ‘Valencia’] to determine influence of plant water stress on population dynamics of glassy-winged sharpshooter (GWSS), Homalodisca vitripennis (Germar). Experimental treatments included irrigation at 100% of the crop...

Amperometric cholesterol biosensor based on the direct electrochemistry of cholesterol oxidase and catalase on a graphene/ionic liquid-modified glassy carbon electrode.

PubMed

Gholivand, Mohammad Bagher; Khodadadian, Mehdi

2014-03-15

Cholesterol oxidase (ChOx) and catalase (CAT) were co-immobilized on a graphene/ionic liquid-modified glassy carbon electrode (GR-IL/GCE) to develop a highly sensitive amperometric cholesterol biosensor. The H2O2 generated during the enzymatic reaction of ChOx with cholesterol could be reduced electrocatalytically by immobilized CAT to obtain a sensitive amperometric response to cholesterol. The direct electron transfer between enzymes and electrode surface was investigated by cyclic voltammetry. Both enzymes showed well-defined redox peaks with quasi-reversible behaviors. An excellent sensitivity of 4.163 mA mM(-1)cm(-2), a response time less than 6s, and a linear range of 0.25-215 μM (R(2)>0.99) have been observed for cholesterol determination using the proposed biosensor. The apparent Michaelis-Menten constant (KM(app)) was calculated to be 2.32 mM. The bienzymatic cholesterol biosensor showed good reproducibility (RSDs<5%) with minimal interference from the coexisting electroactive compounds such as ascorbic acid and uric acid. The CAT/ChOx/GR-IL/GCE showed excellent analytical performance for the determination of free cholesterol in human serum samples. © 2013 Elsevier B.V. All rights reserved.

Biogas desulfurization and biogas upgrading using a hybrid membrane system--modeling study.

PubMed

Makaruk, A; Miltner, M; Harasek, M

2013-01-01

Membrane gas permeation using glassy membranes proved to be a suitable method for biogas upgrading and natural gas substitute production on account of low energy consumption and high compactness. Glassy membranes are very effective in the separation of bulk carbon dioxide and water from a methane-containing stream. However, the content of hydrogen sulfide can be lowered only partially. This work employs process modeling based upon the finite difference method to evaluate a hybrid membrane system built of a combination of rubbery and glassy membranes. The former are responsible for the separation of hydrogen sulfide and the latter separate carbon dioxide to produce standard-conform natural gas substitute. The evaluation focuses on the most critical upgrading parameters like achievable gas purity, methane recovery and specific energy consumption. The obtained results indicate that the evaluated hybrid membrane configuration is a potentially efficient system for the biogas processing tasks that do not require high methane recoveries, and allows effective desulfurization for medium and high hydrogen sulfide concentrations without additional process steps.

An investigation of the well-water quality: immunosensor for pathogenic Pseudomonas aeruginosa detection based on antibody-modified poly(pyrrole-3 carboxylic acid) screen-printed carbon electrode.

PubMed

Bekir, Karima; Bousimma, Feriel; Barhoumi, Houcine; Fedhila, Kais; Maaref, Abderrazak; Bakhrouf, Amina; Ben Ouada, Hafedh; Namour, Philippe; Jaffrezic-Renault, Nicole; Ben Mansour, Hedi

2015-12-01

In this report, we describe a new immunosensor designed for the detection and the quantification of Pseudomonas aeruginosa bacteria in water. The developed biosensing system was based on the immobilization of purified polyclonal anti P. aeruginosa antibodies on electropolymerized poly(pyrrole-3-carboxylic acid)/glassy carbon electrode. The building of the immunosensor step by step was evaluated by electrochemical measurements such as cyclic voltammetry (CV) and impedance spectroscopy (EIS). The electrochemical signature of the immunosensor was established by the change of the charge transfer resistance when the bacteria suspended in solution became attached to the immobilized antibodies. As a result, stable and high sensitive impedimetric immunosensor was obtained with a sensitivity of 0.19 kΩ/decade defined in the linear range from 10(1) to 10(7) CFU/mL of cellular concentrations. A low detection limit was obtained for the P. aeruginosa bacteria and a high selectivity when other bacteria were occasioned as well as Escherichia coli. The developed immunosensor was applied in detecting pathogenic P. aeruginosa in well-water.

Electrochemical behavior and voltammetric determination of acetaminophen based on glassy carbon electrodes modified with poly(4-aminobenzoic acid)/electrochemically reduced graphene oxide composite films.

PubMed

Zhu, Wencai; Huang, Hui; Gao, Xiaochun; Ma, Houyi

2014-12-01

Poly(4-aminobenzoic acid)/electrochemically reduced graphene oxide composite film modified glassy carbon electrodes (4-ABA/ERGO/GCEs) were fabricated by a two-step electrochemical method. The electrochemical behavior of acetaminophen at the modified electrode was investigated by means of cyclic voltammetry. The results indicated that 4-ABA/ERGO composite films possessed excellent electrocatalytic activity towards the oxidation of acetaminophen. The electrochemical reaction of acetaminophen at 4-ABA/ERGO/GCE is proved to be a surface-controlled process involving the same number of protons and electrons. The voltammetric determination of acetaminophen performed with the 4-ABA/ERGO modified electrode presents a good linearity in the range of 0.1-65 μM with a low detection limit of 0.01 μM (S/N=3). In the case of using the 4-ABA/ERGO/GCE, acetaminophen and dopamine can be simultaneously determined without mutual interference. Furthermore, the 4-ABA/ERGO/GCE has good reproducibility and stability, and can be used to determine acetaminophen in tablets. Copyright © 2014 Elsevier B.V. All rights reserved.

Temperature-programed time-of-flight secondary ion mass spectrometry study of 1-butyl-3-methylimidazolium trifluoromethanesulfonate during glass-liquid transition, crystallization, melting, and solvation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Souda, Ryutaro; Guenster, Jens; CiC Ceramic Institute Clausthal GmbH, D-38678 Clausthal-Zellerfeld

2008-09-07

For this study, time-of-flight secondary ion mass spectrometry was used to analyze the molecular orientation of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim][OTf]) and its interaction with the adsorbed Na and LiI species at temperatures of 150-300 K. A glassy [bmim][OTf] film crystallizes at around 230 K, as observed from the increase in the [bmim]{sup +} yield. LiI and Na adsorbed on the glassy film are solvated, whereas they tend to form islands on a crystalline film. The crystalline surface inertness is ascribable to the termination with the CF{sub 3} and C{sub 4}H{sub 9} groups, whereas the exposure of polar SO{sub 3} and imidazolemore » groups at the glassy film results in the solvation. Surface layering occurs during solvation of LiI on the glassy film in such a way that the [bmim]{sup +} ([OTf]{sup -}) moiety is exposed to the vacuum (oriented to the bulk). The LiI adsorbed on the glassy film is incorporated into the bulk at temperatures higher than 200 K because of the glass-liquid transition. No further uptake of LiI is observed during crystallization, providing a contrast to the results of normal molecular solids such as water and ethanol. The surface layers of the crystal melt at temperatures below the bulk melting point, as confirmed from the dissolution of adsorbed LiI, but the melting layer retains a short-range order similar to the crystal. The [bmim][OTf] can be regarded as a strongly correlated liquid with the combined liquid property and crystal-type local structure. The origin of this behavior is discussed.« less

PdCo porous nanostructures decorated on polypyrrole @ MWCNTs conductive nanocomposite-Modified glassy carbon electrode as a powerful catalyst for ethanol electrooxidation

NASA Astrophysics Data System (ADS)

Fard, Leyla Abolghasemi; Ojani, Reza; Raoof, Jahan Bakhsh; Zare, Ehsan Nazarzadeh; Lakouraj, Moslem Mansour

2017-04-01

In the current study, well-defined PdCo porous nanostructure (PdCo PNS) is prepared by a simple one-pot wet-chemical method and polypyrrole@multi-walled carbon nanotubes (PPy@MWCNTs) nanocomposite is used as a catalyst support. The morphology and the structural properties of the prepared catalyst were studied by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The electrocatalytic performance of PdCo PNS/PPy@MWCNTs on glassy carbon electrode has been evaluated by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) techniques. The specific activity of PdCo PNS/PPy@MWCNTs for ethanol electrooxidation (1.65 mA cm-2) is higher than those of other compared electrocatalysts. Also, PdCo PNS/PPy@MWCNTs catalyst represented higher electrocatalytic activity, better long-term stability and high level of poisoning tolerance to the carbonaceous oxidative intermediates for ethanol electrooxidation reaction in alkaline media. Furthermore, the presence of PPY@MWCNTs on the surface of GCE produce a high activity to electrocatalyst, which might be due to the easier charge transfer at polymer/carbon nanotubes interfaces, higher electrochemically accessible surface areas and electronic conductivity. The superior catalytic activity of PdCo PNS/PPy@MWCNTs suggests it to be as a promising electrocatalyst for future direct ethanol fuel cells.

Sensitive voltammetric determination of chloramphenicol by using single-wall carbon nanotube-gold nanoparticle-ionic liquid composite film modified glassy carbon electrodes.

PubMed

Xiao, Fei; Zhao, Faqiong; Li, Jiangwen; Yan, Rui; Yu, Jingjing; Zeng, Baizhao

2007-07-16

A novel composite film modified glassy carbon electrode has been fabricated and characterized by scanning electron microscope (SEM) and voltammetry. The composite film comprises of single-wall carbon nanotube (SWNT), gold nanoparticle (GNP) and ionic liquid (i.e. 1-octyl-3-methylimidazolium hexafluorophosphate), thus has the characteristics of them. The resulting electrode shows good stability, high accumulation efficiency and strong promotion to electron transfer. On it, chloramphenicol can produce a sensitive cathodic peak at -0.66 V (versus SCE) in pH 7.0 phosphate buffer solutions. Parameters influencing the voltammetric response of chloramphenicol are optimized, which include the composition of the film and the operation conditions. Under the optimized conditions, the peak current is linear to chloramphenicol concentration in the range of 1.0x10(-8)-6.0x10(-6) M, and the detection limit is estimated to be 5.0x10(-9) M after an accumulation for 150 s on open circuit. The electrode is applied to the determination of chloramphenicol in milk samples, and the recoveries for the standards added are 97.0% and 100.3%. In addition, the electrochemical reaction of chloramphenicol and the effect of single-wall carbon nanotube, gold nanoparticle and ionic liquid are discussed.

Electrochemical DNA biosensor based on poly(2,6-pyridinedicarboxylic acid) modified glassy carbon electrode for the determination of anticancer drug gemcitabine.

PubMed

Tığ, Gözde Aydoğdu; Zeybek, Bülent; Pekyardımcı, Şule

2016-07-01

In this study, a simple methodology was used to develop a new electrochemical DNA biosensor based on poly(2,6-pyridinedicarboxylic acid) (P(PDCA)) modified glassy carbon electrode (GCE). This modified electrode was used to monitor for the electrochemical interaction between the dsDNA and gemcitabine (GEM) for the first time. A decrease in oxidation signals of guanine after the interaction of the dsDNA with the GEM was used as an indicator for the selective determination of the GEM via differential pulse voltammetry (DPV). The guanine oxidation peak currents were linearly proportional to the concentrations of the GEM in the range of 1-30mgL(‒1). Limit of detection (LOD) and limit of quantification (LOQ) were found to be 0.276mgL(‒1) and 0.922mgL(‒1), respectively. The reproducibility, repeatability, and applicability of the analysis to pharmaceutical dosage forms and human serum samples were also examined. In addition to DPV method, UV-vis and viscosity measurements were utilized to propose the interaction mechanism between the GEM and the dsDNA. The novel DNA biosensor could serve for sensitive, accurate and rapid determination of the GEM. Copyright © 2016 Elsevier B.V. All rights reserved.

Salivary enzymes are injected into xylem by the glassy-winged sharpshooter, a vector of Xylella fastidiosa.

PubMed

Backus, Elaine A; Andrews, Kim B; Shugart, Holly J; Carl Greve, L; Labavitch, John M; Alhaddad, Hasan

2012-07-01

A few phytophagous hemipteran species such as the glassy-winged sharpshooter, Homalodisca vitripennis, (Germar), subsist entirely on xylem fluid. Although poorly understood, aspects of the insect's salivary physiology may facilitate both xylem-feeding and transmission of plant pathogens. Xylella fastidiosa is a xylem-limited bacterium that causes Pierce's disease of grape and other scorch diseases in many important crops. X. fastidiosa colonizes the anterior foregut (precibarium and cibarium) of H. vitripennis and other xylem-feeding vectors. Bacteria form a dense biofilm anchored in part by an exopolysaccharide (EPS) matrix that is reported to have a β-1,4-glucan backbone. Recently published evidence supports the following, salivation-egestion hypothesis for the inoculation of X. fastidiosa during vector feeding. The insect secretes saliva into the plant and then rapidly takes up a mixture of saliva and plant constituents. During turbulent fluid movements in the precibarium, the bacteria may become mechanically and enzymatically dislodged; the mixture is then egested back out through the stylets into plant cells, possibly including xylem vessels. The present study found that proteins extracted from dissected H. vitripennis salivary glands contain several enzyme activities capable of hydrolyzing glycosidic linkages in polysaccharides such as those found in EPS and plant cell walls, based on current information about the structures of those polysaccharides. One of these enzymes, a β-1,4-endoglucanase (EGase) was enriched in the salivary gland protein extract by subjecting the extract to a few, simple purification steps. The EGase-enriched extract was then used to generate a polyclonal antiserum that was used for immunohistochemical imaging of enzymes in sharpshooter salivary sheaths in grape. Results showed that enzyme-containing gelling saliva is injected into xylem vessels during sharpshooter feeding, in one case being carried by the transpiration stream away

Water activity and mobility in solutions of glycerol and small molecular weight sugars: Implication for cryo- and lyopreservation

NASA Astrophysics Data System (ADS)

He, Xiaoming; Fowler, Alex; Toner, Mehmet

2006-10-01

In this study, the free volume models, originally developed for large molecular weight polymer-solvent systems, were used to study the water activity and mobility in solutions of four small molecular weight cryo-/lyoprotectants, viz., glycerol, a monosaccharide (fructose), and two disaccharides (sucrose and trehalose). The free volume model parameters were determined by fitting the models to available experimental data using a nonlinear optimization procedure. It was found that free volume models could accurately predict the available experimental data, which suggests that the free volume models might be generally applicable to aqueous solutions of small molecular weight cryo-/lyoprotectants. Furthermore, several models for estimating the mutual diffusion coefficient were tested using available experimental data for aqueous solutions of glycerol and a better method to estimate the mutual diffusion coefficient was proposed. Free volume models were used to predict and analyze the water activity and mobility in solutions of four cryo-/lyoprotectants under conditions frequently encountered in cryo-/lyopreservation applications. It was found that the water mobility in the glassy state of the above four solutions is essentially negligible in the case of cryopreservation with storage temperature lower than -110°C. However, the water mobility in a glass at higher temperature (>-80°C) may be significant. As a result, a subcooling of up to 50°C may be necessary for the long-term cryo-/lyopreservation of biomaterials depending on the water content and the type of cryo-/lyoprotectants. It was further shown that trehalose might be the best of the four protectants studied for lyopreservation (water mass fraction ⩽0.1) when the storage temperature is above the room temperature. The results from this study might be useful for the development of more effective protocols for both cryopreservation and lyopreservation of living cells and other biomaterials.

Simultaneous electrochemical detection of dopamine and ascorbic acid using an iron oxide/reduced graphene oxide modified glassy carbon electrode.

PubMed

Peik-See, Teo; Pandikumar, Alagarsamy; Nay-Ming, Huang; Hong-Ngee, Lim; Sulaiman, Yusran

2014-08-19

The fabrication of an electrochemical sensor based on an iron oxide/graphene modified glassy carbon electrode (Fe3O4/rGO/GCE) and its simultaneous detection of dopamine (DA) and ascorbic acid (AA) is described here. The Fe3O4/rGO nanocomposite was synthesized via a simple, one step in-situ wet chemical method and characterized by different techniques. The presence of Fe3O4 nanoparticles on the surface of rGO sheets was confirmed by FESEM and TEM images. The electrochemical behavior of Fe3O4/rGO/GCE towards electrocatalytic oxidation of DA was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) analysis. The electrochemical studies revealed that the Fe3O4/rGO/GCE dramatically increased the current response against the DA, due to the synergistic effect emerged between Fe3O4 and rGO. This implies that Fe3O4/rGO/GCE could exhibit excellent electrocatalytic activity and remarkable electron transfer kinetics towards the oxidation of DA. Moreover, the modified sensor electrode portrayed sensitivity and selectivity for simultaneous determination of AA and DA. The observed DPVs response linearly depends on AA and DA concentration in the range of 1-9 mM and 0.5-100 µM, with correlation coefficients of 0.995 and 0.996, respectively. The detection limit of (S/N = 3) was found to be 0.42 and 0.12 µM for AA and DA, respectively.

Metallic glassy Zr70Ni20Pd10 powders for improving the hydrogenation/dehydrogenation behavior of MgH2

PubMed Central

El-Eskandarany, M. Sherif

2016-01-01

Because of its low density, storage of hydrogen in the gaseous and liquids states possess technical and economic challenges. One practical solution for utilizing hydrogen in vehicles with proton-exchange fuel cells membranes is storing hydrogen in metal hydrides. Magnesium hydride (MgH2) remains the best hydrogen storage material due to its high hydrogen capacity and low cost of production. Due to its high activation energy and poor hydrogen sorption/desorption kinetics at moderate temperatures, the pure form of MgH2 is usually mechanically treated by high-energy ball mills and catalyzed with different types of catalysts. These steps are necessary for destabilizing MgH2 to enhance its kinetics behaviors. In the present work, we used a small mole fractions (5 wt.%) of metallic glassy of Zr70Ni20Pd10 powders as a new enhancement agent to improve its hydrogenation/dehydrogenation behaviors of MgH2. This short-range ordered material led to lower the decomposition temperature of MgH2 and its activation energy by about 121 °C and 51 kJ/mol, respectively. Complete hydrogenation/dehydrogenation processes were successfully achieved to charge/discharge about 6 wt.%H2 at 100 °C/200 °C within 1.18 min/3.8 min, respectively. In addition, this new nanocomposite system shows high performance of achieving continuous 100 hydrogen charging/discharging cycles without degradation. PMID:27220994

Electrochemical determination of Sudan I in food samples at graphene modified glassy carbon electrode based on the enhancement effect of sodium dodecyl sulphonate.

PubMed

Ma, Xinying; Chao, Mingyong; Wang, Zhaoxia

2013-06-01

This paper describes a novel electrochemical method for the determination of Sudan I in food samples based on the electrochemical catalytic activity of graphene modified glassy carbon electrode (GMGCE) and the enhancement effect of an anionic surfactant: sodium dodecyl sulphonate (SDS). Using pH 6.0 phosphate buffer solution (PBS) as supporting electrolyte and in the presence of 1.5 × 10(-4)mol L(-1) SDS, Sudan I yielded a well-defined and sensitive oxidation peak at a GMGCE. The oxidation peak current of Sudan I remarkably increased in the presence of SDS. The experimental parameters, such as supporting electrolyte, concentration of SDS, and accumulation time, were optimised for Sudan I determination. The oxidation peak current showed a linear relationship with the concentrations of Sudan I in the range of 7.50 × 10(-8)-7.50 × 10(-6)mol L(-1), with the detection limit of 4.0 × 10(-8)mol L(-1). This new voltammetric method was successfully used to determine Sudan I in food products such as ketchup and chili sauce with satisfactory results. Copyright © 2012 Elsevier Ltd. All rights reserved.

Voltammetric behavior of dopamine at a glassy carbon electrode modified with NiFe(2)O(4) magnetic nanoparticles decorated with multiwall carbon nanotubes.

PubMed

Ensafi, Ali A; Arashpour, B; Rezaei, B; Allafchian, Ali R

2014-06-01

Voltammetric behavior of dopamine was studied on a glassy carbon electrode (GCE) modified-NiFe(2)O(4) magnetic nanoparticles decorated with multiwall carbon nanotubes. Impedance spectroscopy and cyclic voltammetry were used to characterize the behavior of dopamine at the surface of modified-GCE. The modified electrode showed a synergic effect toward the oxidation of dopamine. The oxidation peak current is increased linearly with the dopamine concentration (at pH7.0) in wide dynamic ranges of 0.05-6.0 and 6.0-100μmolL(-1) with a detection limit of 0.02μmolL(-1), using differential pulse voltammetry. The selectivity of the method was studied and the results showed that the modified electrode is free from interference of organic compounds especially ascorbic acid, uric acid, cysteine and urea. Its applicability in the determination of dopamine in pharmaceutical, urine samples and human blood serum was also evaluated. The proposed electrochemical sensor has appropriate properties such as high selectivity, low detection limit and wide linear dynamic range when compared with that of the previous reported papers for dopamine detection. Copyright © 2014 Elsevier B.V. All rights reserved.

Glassy carbon MEMS for novel origami-styled 3D integrated intracortical and epicortical neural probes

NASA Astrophysics Data System (ADS)

Goshi, Noah; Castagnola, Elisa; Vomero, Maria; Gueli, Calogero; Cea, Claudia; Zucchini, Elena; Bjanes, David; Maggiolini, Emma; Moritz, Chet; Kassegne, Sam; Ricci, Davide; Fadiga, Luciano

2018-06-01

We report on a novel technology for microfabricating 3D origami-styled micro electro-mechanical systems (MEMS) structures with glassy carbon (GC) features and a supporting polymer substrate. GC MEMS devices that open to form 3D microstructures are microfabricated from GC patterns that are made through pyrolysis of polymer precursors on high-temperature resisting substrates like silicon or quartz and then transferring the patterned devices to a flexible substrate like polyimide followed by deposition of an insulation layer. The devices on flexible substrate are then folded into 3D form in an origami-fashion. These 3D MEMS devices have tunable mechanical properties that are achieved by selectively varying the thickness of the polymeric substrate and insulation layers at any desired location. This technology opens new possibilities by enabling microfabrication of a variety of 3D GC MEMS structures suited to applications ranging from biochemical sensing to implantable microelectrode arrays. As a demonstration of the technology, a neural signal recording microelectrode array platform that integrates both surface (cortical) and depth (intracortical) GC microelectrodes onto a single flexible thin-film device is introduced. When the device is unfurled, a pre-shaped shank of polyimide automatically comes off the substrate and forms the penetrating part of the device in a 3D fashion. With the advantage of being highly reproducible and batch-fabricated, the device introduced here allows for simultaneous recording of electrophysiological signals from both the brain surface (electrocorticography—ECoG) and depth (single neuron). Our device, therefore, has the potential to elucidate the roles of underlying neurons on the different components of µECoG signals. For in vivo validation of the design capabilities, the recording sites are coated with a poly(3,4-ethylenedioxythiophene)—polystyrene sulfonate—carbon nanotube composite, to improve the electrical conductivity of the

Revealing Hidden Structural Order Controlling Both Fast and Slow Glassy Dynamics in Supercooled Liquids

NASA Astrophysics Data System (ADS)

Tong, Hua; Tanaka, Hajime

2018-01-01

The dynamics of a supercooled liquid near the glass transition is characterized by two-step relaxation, fast β and slow α relaxations. Because of the apparently disordered nature of glassy structures, there have been long debates over whether the origin of drastic slowing-down of the α relaxation accompanied by heterogeneous dynamics is thermodynamic or dynamic. Furthermore, it has been elusive whether there is any deep connection between fast β and slow α modes. To settle these issues, here we introduce a set of new structural order parameters characterizing sterically favored structures with high local packing capability, and then access structure-dynamics correlation by a novel nonlocal approach. We find that the particle mobility is under control of the static order parameter field. The fast β process is controlled by the instantaneous order parameter field locally, resulting in short-time particle-scale dynamics. Then the mobility field progressively develops with time t , following the initial order parameter field from disorder to more ordered regions. As is well known, the heterogeneity in the mobility field (dynamic heterogeneity) is maximized with a characteristic length ξ4, when t reaches the relaxation time τα. We discover that this mobility pattern can be predicted solely by a spatial coarse graining of the initial order parameter field at t =0 over a length ξ without any dynamical information. Furthermore, we find a relation ξ ˜ξ4, indicating that the static length ξ grows coherently with the dynamic one ξ4 upon cooling. This further suggests an intrinsic link between τα and ξ : the growth of the static length ξ is the origin of dynamical slowing-down. These we confirm for the first time in binary glass formers both in two and three spatial dimensions. Thus, a static structure has two intrinsic characteristic lengths, particle size and ξ , which control dynamics in local and nonlocal manners, resulting in the emergence of the two

Synthesis and characterization of manganese diselenide nanoparticles (MnSeNPs): Determination of capsaicin by using MnSeNP-modified glassy carbon electrode.

PubMed

Sukanya, Ramaraj; Sakthivel, Mani; Chen, Shen-Ming; Chen, Tse-Wei; Al-Hemaid, Fahad M A; Ajmal Ali, M; Elshikh, Mohamed Soliman

2018-06-02

A new type of manganese diselenide nanoparticles (MnSeNPs) was synthesized by using a hydrothermal method. Their surface morphology, crystallinity and elemental distribution were characterized by using transmission electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy which scrutinize the formation of the NPs. The NPs were coated on a glassy carbon electrode (GCE), and electrochemical impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry were applied to study the electroanalytical properties towards the oxidation of the food additive capsaicin. The modified GCE displays lower charge transfer resistance (R ct  = 29.52 Ω), a larger active surface area (0.089 cm 2 /g, and more efficient electrochemical oxidation of capsaicin compared to a MnS 2 /GCE and a bare GCE. The oxidation peak potential is 0.43 V (vs. Ag/AgCl) which is lower than that of previously reported GCEs. The sensor has a detection limit as low as 0.05 μM and an electrochemical sensitivity of 2.41 μA μM -1  cm -2 . The method was applied to the determination of capsaicin in pepper samples. Graphical abstract Electrochemical determination of capsaicin in pepper extract by using MnSeNPs modified electrode.

Square-wave adsorptive stripping voltammetric determination of nanomolar levels of bezafibrate using a glassy carbon electrode modified with multi-walled carbon nanotubes within a dihexadecyl hydrogen phosphate film.

PubMed

Ardila, Jorge Armando; Oliveira, Geiser Gabriel; Medeiros, Roberta Antigo; Fatibello-Filho, Orlando

2014-04-07

A highly sensitive method for bezafibrate determination using a glassy carbon electrode (GCE) modified with multi-walled carbon nanotubes within a dihexadecyl hydrogen phosphate film based on square-wave adsorptive stripping voltammetry (SWAdSV) is proposed. The electrochemical behaviour of bezafibrate has been studied by cyclic voltammetry, showing an irreversible anodic peak at a potential of 1.09 V in 0.1 mol L(-1) phosphate buffer solution (pH 2.0). A study of the scan rate showed that the oxidation of bezafibrate is an adsorptive-controlled process, involving the transfer of two electrons and two protons per molecule. The analytical curve was linear over a bezafibrate concentration range from 50 to 910 nmol L(-1), with a detection limit of 16 nmol L(-1). This analytical method was successfully applied for benzafibrate determination in pharmaceutical formulations, with results showing good agreement with those obtained using a comparative spectrophotometric method, and has the potential for field application.

Glassy carbon electrodes sequentially modified by cysteamine-capped gold nanoparticles and poly(amidoamine) dendrimers generation 4.5 for detecting uric acid in human serum without ascorbic acid interference.

PubMed

Ramírez-Segovia, A S; Banda-Alemán, J A; Gutiérrez-Granados, S; Rodríguez, A; Rodríguez, F J; Godínez, Luis A; Bustos, E; Manríquez, J

2014-02-17

Glassy carbon electrodes (GCE) were sequentially modified by cysteamine-capped gold nanoparticles (AuNp@cysteamine) and PAMAM dendrimers generation 4.5 bearing 128-COOH peripheral groups (GCE/AuNp@cysteamine/PAMAM), in order to explore their capabilities as electrochemical detectors of uric acid (UA) in human serum samples at pH 2. The results showed that concentrations of UA detected by cyclic voltammetry with GCE/AuNp@cysteamine/PAMAM were comparable (deviation <±10%; limits of detection (LOD) and quantification (LOQ) were 1.7×10(-4) and 5.8×10(-4) mg dL(-1), respectively) to those concentrations obtained using the uricase-based enzymatic-colorimetric method. It was also observed that the presence of dendrimers in the GCE/AuNp@cysteamine/PAMAM system minimizes ascorbic acid (AA) interference during UA oxidation, thus improving the electrocatalytic activity of the gold nanoparticles. Copyright © 2013 Elsevier B.V. All rights reserved.

Fabrication of Glassy and Crystalline Ferroelectric Oxide by Containerless Processing

NASA Astrophysics Data System (ADS)

Yoda, Shinichi

1. Instruction Much effort has been devoted to forming bulk glass from the melt of ferroelectric crystalline materials without adding any network-forming oxides such as SiO2 due to the potential for producing transparent glass ceramics with high dielectric constant and enhanced piezoelectric, pyroelectric and electro-optic effects. However, they require a higher cooling rate than glass formed by conventional techniques. Therefore, only amorphous thin-films have been formed, using rapid quenching with a cooling rate >105 K/s. The containerless processing is an attractive synthesis technique as it can prevent melt contamination, minimize heterogeneous nucleation, and allow melt to achieve deep undercooling for forming metastable phase and glassy material. Recently a new ferroelectric materiel, monoclinic BaTi2 O5 , with Currie temperature as 747 K was reported. In this study, we fabricated a bulk BaTi2 O5 glass from melt using containerless processing to study the phase relations and ferroelectric properties of BaTi2 O5 . To our knowledge, this was the first time that a bulk glass of ferroelectric material was fabricated from melt without adding any network-forming oxide. 2. Experiments BaTi2 O5 sphere glass with 2mm diameter was fabricated using containerless processing in an Aerodynamic Levitation Furnace (ALF). The containerless processing allowed the melt to achieve deep undercooling for glass forming. High purity commercial BaTiO3 and TiO2 powders were mixed with a mole ratio of 1:1 and compressed into rods and then sintered at 1427 K for 10 h. Bulk samples with a mass of about 20 mg were cut from the rod, levitated with the ALF, and then melted by a CO2 laser beam. After quenching with a cooling rate of about 1000 K/s, 2 mm diameter sphere glass could be obtained. To analyze the glass structure, a high-energy x-ray diffraction experiment was performed using an incident photon energy of 113.5 keV at the high-energy x-ray diffraction beamline BL04B2 of SPring-8

``Ideal glassformers'' vs ``ideal glasses'': Studies of crystal-free routes to the glassy state by ``potential tuning'' molecular dynamics, and laboratory calorimetry

NASA Astrophysics Data System (ADS)

Kapko, Vitaliy; Zhao, Zuofeng; Matyushov, Dmitry V.; Austen Angell, C.

2013-03-01

of "ideal glassformers" - single or multicomponent liquids that vitrify before ever becoming metastable with respect to crystals. We find evidence that "ideal glassformer" systems might also be highly fragile systems, approaching the "ideal glass" condition. We link this to the high "volume fragility" behavior observed in recent hard dumbbell studies at similar length/diameter ratios [R. Zhang and K. S. Schweitzer, J. Chem. Phys. 133, 104902 (2010), 10.1063/1.3483601]. The discussion suggests some unusual systems for laboratory study. Using differential scanning calorimetry detection of fusion points Tm, liquidus temperatures Tl, and glass transition temperatures Tg, we describe a system that would seem incapable of crystallizing before glass transition, i.e., an "ideal glassformer." The existence of crystal-free routes to the glassy state will eliminate precrystalline fluctuations as a source of the dynamic heterogeneities that are generally considered important in the discussion of the "glassy state problem [P. W. Anderson, Science 267, 1615 (1995), 10.1126/science.267.5204.1615-e]."

Inhomogeneities in particle composition of single, levitated aerosol particles observed by Mie resonance spectroscopy

NASA Astrophysics Data System (ADS)

Krieger, Ulrich; Lienhard, Daniel; Bastelberger, Sandra; Steimer, Sarah

2014-05-01

Recent observations have indicated that organic aerosol particles in the atmosphere may exist in an amorphous semi-solid or even solid (i.e. glassy) state, e.g. [1]. The influence of highly viscous and glassy states on the timescale of aerosol particle equilibration with respect to water vapor have been investigated for some model systems of atmospheric aerosol, e.g. [2,3]. In particular, it has been shown that the kinetics of the water absorption/desorption process is controlled entirely by liquid-phase diffusion of water molecules for a highly viscous aerosol particle. A liquid phase diffusion model based on numerically solving the non-linear diffusion equation predicts strong internal gradients in water concentration when condensed phase diffusion impedes the water uptake from the gas phase [2]. Here we observe and quantify the internal concentration gradients in single, levitated, micron size aerosol particles of aqueous shikimic acid using elastic Mie resonance spectroscopy. A single, aqueous particle is levitated in an electro-dynamic balance (for details see [2]), dried for several days at room temperature, cooled to the target temperature and exposed to a rapid change in relative humidity. In addition to measuring the elastically backscattered light of a "white light" LED source and recording the full spectrum with a spectrograph as in [2], we use a tunable diode laser (TDL) to scan high resolution TE- and TM spectra. This combination allows observing various Mie resonance mode orders simultaneously. Since we perform the experiment at low temperatures and low humidities the changes in the Mie-spectra due to water uptake are sufficiently slow to resolve the kinetics. Experimental Mie resonance spectra are inverted to concentration profiles of water within the particle by applying the numerical diffusion model [2] in conjunction with Mie calculations of multilayered spheres [4]. [1] A. Virtanen et al. (2010): An amorphous solid state of biogenic secondary

Simultaneous Electrochemical Detection of Dopamine and Ascorbic Acid Using an Iron Oxide/Reduced Graphene Oxide Modified Glassy Carbon Electrode

PubMed Central

Peik-See, Teo; Pandikumar, Alagarsamy; Nay-Ming, Huang; Hong-Ngee, Lim; Sulaiman, Yusran

2014-01-01

The fabrication of an electrochemical sensor based on an iron oxide/graphene modified glassy carbon electrode (Fe3O4/rGO/GCE) and its simultaneous detection of dopamine (DA) and ascorbic acid (AA) is described here. The Fe3O4/rGO nanocomposite was synthesized via a simple, one step in-situ wet chemical method and characterized by different techniques. The presence of Fe3O4 nanoparticles on the surface of rGO sheets was confirmed by FESEM and TEM images. The electrochemical behavior of Fe3O4/rGO/GCE towards electrocatalytic oxidation of DA was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) analysis. The electrochemical studies revealed that the Fe3O4/rGO/GCE dramatically increased the current response against the DA, due to the synergistic effect emerged between Fe3O4 and rGO. This implies that Fe3O4/rGO/GCE could exhibit excellent electrocatalytic activity and remarkable electron transfer kinetics towards the oxidation of DA. Moreover, the modified sensor electrode portrayed sensitivity and selectivity for simultaneous determination of AA and DA. The observed DPVs response linearly depends on AA and DA concentration in the range of 1–9 mM and 0.5–100 μM, with correlation coefficients of 0.995 and 0.996, respectively. The detection limit of (S/N = 3) was found to be 0.42 and 0.12 μM for AA and DA, respectively. PMID:25195850

A highly efficient nano-cluster artificial peroxidase and its direct electrochemistry on a nano complex modified glassy carbon electrode.

PubMed

Hong, Jun; Wang, Wei; Huang, Kun; Yang, Wei-Yun; Zhao, Ying-Xue; Xiao, Bao-Lin; Gao, Yun-Fei; Moosavi-Movahedi, Zainab; Ghourchian, Hedayatollah; Moosavi-Movahedi, Ali Akbar

2012-01-01

A nano-cluster with highly efficient peroxide activity was constructed based on nafion (NF) and cytochrome c (Cyt c). UV-Vis spectrometry and transmission electron microscopy (TEM) methods were utilized for characterization of the nano-structured enzyme or artificial peroxidase (AP). The nano-cluster was composed of a Chain-Ball structure, with an average ball size of about 40 nm. The Michaelis-Menten (K(m)) and catalytic rate (k(cat)) constants of the AP were determined to be 2.5 ± 0.4 µM and 0.069 ± 0.001 s(-1), respectively, in 50 mM PBS at pH 7.0. The catalytic efficiency of the AP was evaluated to be 0.028 ± 0.005 µM(-1) s(-1), which was 39 ± 5% as efficient as the native horseradish peroxidase (HRP). The AP was also immobilized on a functional multi-wall carbon nanotube (MWNCTs)-gold colloid nanoparticles (AuNPs) nano-complex modified glassy carbon (GC) electrode. The cyclic voltammetry of AP on the nano complex modified GC electrode showed a pair of well-defined redox peaks with a formal potential (E°') of -45 ± 2 mV (vs. Ag/AgCl) at a scan rate of 0.05 V/s. The heterogeneous electron transfer rate constant (k(s)) was evaluated to be 0.65 s(-1). The surface concentration of electroactive AP on GC electrode (Γ) was 7 × 10(-10) mol cm(-2). The apparent Michaelis-Menten constant (K(m)(app)) was 0.23 nM.

Electrochemical detection of a powerful estrogenic endocrine disruptor: ethinylestradiol in water samples through bioseparation procedure.

PubMed

Martínez, Noelia A; Pereira, Sirley V; Bertolino, Franco A; Schneider, Rudolf J; Messina, Germán A; Raba, Julio

2012-04-20

The synthetic estrogen ethinylestradiol (EE2) is an active component of oral contraceptives (OCs), considered as an endocrine disrupting compound (EDC). It is excreted from humans and released via sewage treatment plant effluents into aquatic environments. EDCs are any environmental pollutant chemical that, once incorporated into an organism, affects the hormonal balance of various species including humans. Its presence in the environment is becoming of great importance in water quality. This paper describes the development of an accurate, sensitive and selective method for capture, preconcentration and determination of EE2 present in water samples using: magnetic particles (MPs) as bioaffinity support for the capture and preconcentration of EE2 and a glassy carbon electrode modified with multi-walled carbon nanotubes (MWCNTs/GCE) as detection system. The capture procedure was based on the principle of immunoaffinity, the EE2 being extracted from the sample using the anti-EE2 antibodies (anti-EE2 Ab) which were previously immobilized on MPs. Subsequently the analyte desorption was done employing a sulfuric acid solution and the determination of the EE2 in the pre-concentrated solution was carried out by square wave voltammetry (SWV). This method can be used to determine EE2 in the range of 0.035-70 ng L(-1) with a detection limit (LOD) of 0.01 ng L(-1) and R.S.D.<4.20%. The proposed method has been successfully applied to the determination of EE2 in water samples and it has promising analytical applications for the direct determination of EE2 at trace levels. Copyright © 2012 Elsevier B.V. All rights reserved.

Study of the air-water interfacial properties of biodegradable polyesters and their block copolymers with poly(ethylene glycol).

PubMed

Park, Hae-Woong; Choi, Je; Ohn, Kimberly; Lee, Hyunsuk; Kim, Jin Woong; Won, You-Yeon

2012-08-07

It has been reported that the surface pressure-area isotherm of poly(D,L-lactic acid-ran-glycolic acid) (PLGA) at the air-water interface exhibits several interesting features: (1) a plateau at intermediate compression levels, (2) a sharp rise in surface pressure upon further compression, and (3) marked surface pressure-area hysteresis during compression-expansion cycles. To investigate the molecular origin of this behavior, we conducted an extensive set of surface pressure and AFM imaging measurements with PLGA materials having several different molecular weights and also a poly(D,L-lactic acid-ran-glycolic acid-ran-caprolactone) (PLGACL) material in which the caprolactone monomers were incorporated as a plasticizing component. The results suggest that (i) the plateau in the surface pressure-area isotherm of PLGA (or PLGACL) occurs because of the formation (and collapse) of a continuous monolayer of the polymer under continuous compression; (ii) the PLGA monolayer becomes significantly resistant to compression at high compression because under that condition the collapsed domains become large enough to become glassy (such behavior was not observed in the nonglassy PLGACL sample); and (iii) the isotherm hysteresis is due to a coarsening of the collapsed domains that occurs under high-compression conditions. We also investigated the monolayer properties of PEG-PLGA and PEG-PLGACL diblock copolymers. The results demonstrate that the tendency of PLGA (or PLGACL) to spread on water allows the polymer to be used as an anchoring block to form a smooth biodegradable monolayer of block copolymers at the air-water interface. These diblock copolymer monolayers exhibit protein resistance.

A label-free electrochemical impedance immunosensor based on AuNPs/PAMAM-MWCNT-Chi nanocomposite modified glassy carbon electrode for detection of Salmonella typhimurium in milk.

PubMed

Dong, Jing; Zhao, Han; Xu, Minrong; Ma, Qiang; Ai, Shiyun

2013-12-01

A sensitive and stable label-free electrochemical impedance immunosensor for the detection of Salmonella typhimurium was developed by immobilising anti-Salmonella antibodies onto the gold nanoparticles and poly(amidoamine)-multiwalled carbon nanotubes-chitosan nanocomposite film modified glassy carbon electrode (AuNPs/PAMAM-MWCNT-Chi/GCE). Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used to verify the stepwise assembly of the immunosensor. Co-addition of MWCNT, PAMAM and AuNPs greatly enhanced the sensitivity of the immunosensor. The immobilisation of antibodies and the binding of Salmonella cells to the modified electrode increased the electron-transfer resistance (Ret), which was directly measured with EIS using [Fe(CN)6](3-/4-) as a redox probe. A linear relationship of Ret and Salmonella concentration was obtained in the Salmonella concentration range of 1.0×10(3) to 1.0×10(7) CFU mL(-1) with a detection limit of 5.0×10(2) CFU mL(-1). Additionally, the proposed method was successfully applied to determine S. typhimurium content in milk samples with satisfactory results. Copyright © 2013 Elsevier Ltd. All rights reserved.

Plant water stress effects on stylet probing behaviors of Homalodisca vitripennis (Hemiptera: Cicadellidae) associated with acquisition and inoculation of the bacterium Xylella fastidiosa.

PubMed

Krugner, Rodrigo; Backus, Elaine A

2014-02-01

ABSTRACT The glassy-winged sharpshooter, Homalodisca vitripennis (Germar) (Hemiptera: Cicadellidae), is a xylem fluid-ingesting leafhopper that transmits Xylella fastidiosa Wells et al., a plant-infecting bacterium that causes several plant diseases in the Americas. Although the role of plant water stress on the population density and dispersal ofH. vitripennis has been studied, nothing is known about the effects of plant water stress on the transmission of X. fastidiosa by H. vitripennis. A laboratory study was conducted to determine the influence of plant water stress on the sharpshooter stylet probing behaviors associated with the acquisition and inoculation of X. fastidiosa. Electrical penetration graph was used to monitor H. vitripennis feeding behaviors for 20-h periods on citrus [Citrus sinensis (L.) Osbeck] and almond [Prunus dulcis (Miller) D.A. Webb] plants subjected to levels of water stress. Adult H. vitripennis successfully located xylem vessels, then performed behaviors related to the evaluation of the xylem cell and fluid, and finally ingested xylem fluid from citrus and almond plants under the tested fluid tensions ranging from -5.5 to -33.0 bars and -6.0 to -24.5 bars, respectively. In general, long and frequent feeding events associated with the acquisition and inoculation of X. fastidiosa were observed only in fully irrigated plants (i.e., >-10 bars), which suggests that even low levels of plant water stress may reduce the spread of X. fastidiosa. Results provided insights to disease epidemiology and support the hypothesis that application of regulated deficit irrigation has the potential to reduce the incidence of diseases caused by X.fastidiosa by reducing the number of vectors and by decreasing pathogen transmission efficiency.

Thermal insulation for high temperature microwave sintering operations and method thereof

DOEpatents

Holcombe, Cressie E.; Dykes, Norman L.; Morrow, Marvin S.

1995-01-01

Superior microwave transparent thermal insulations for high temperature microwave sintering operations were prepared. One embodiment of the thermal insulation comprises granules of boron nitride coated with a very thin layer of glassy carbon made by preparing a glassy carbon precursor and blending it with boron nitride powder to form a mixture. The blended mixture is granulated to form a grit which is dried and heated to form the granules of boron nitride coated with a glassy carbon. Alternatively, grains of glassy carbon are coated with boron nitride by blending a mixture of a slurry comprising boron nitride, boric acid binder, and methyl alcohol with glassy carbon grains to form a blended mixture. The blended mixture is dried to form grains of glassy carbon coated with boron nitride. In addition, a physical mixture of boron nitride powder and glassy carbon grains has also been shown to be an excellent thermal insulation material for microwave processing and sintering.

Method of preparing thermal insulation for high temperature microwave sintering operations

DOEpatents

Holcombe, Cressie E.; Dykes, Norman L.; Morrow, Marvin S.

1996-01-01

Superior microwave transparent thermal insulations for high temperature microwave sintering operations were prepared. One embodiment of the thermal insulation comprises granules of boron nitride coated with a very thin layer of glassy carbon made by preparing a glassy carbon precursor and blending it with boron nitride powder to form a mixture. The blended mixture is granulated to form a grit which is dried and heated to form the granules of boron nitride coated with a glassy carbon. Alternatively, grains of glassy carbon are coated with boron nitride by blending a mixture of a slurry comprising boron nitride, boric acid binder, and methyl alcohol with glassy carbon grains to form a blended mixture. The blended mixture is dried to form grains of glassy carbon coated with boron nitride. In addition, a physical mixture of boron nitride powder and glassy carbon grains has also been shown to be an excellent thermal insulation material for microwave processing and sintering.

Method of preparing thermal insulation for high temperature microwave sintering operations

DOEpatents

Holcombe, C.E.; Dykes, N.L.; Morrow, M.S.

1996-07-16

Superior microwave transparent thermal insulations for high temperature microwave sintering operations were prepared. One embodiment of the thermal insulation comprises granules of boron nitride coated with a very thin layer of glassy carbon made by preparing a glassy carbon precursor and blending it with boron nitride powder to form a mixture. The blended mixture is granulated to form a grit which is dried and heated to form the granules of boron nitride coated with a glassy carbon. Alternatively, grains of glassy carbon are coated with boron nitride by blending a mixture of a slurry comprising boron nitride, boric acid binder, and methyl alcohol with glassy carbon grains to form a blended mixture. The blended mixture is dried to form grains of glassy carbon coated with boron nitride. In addition, a physical mixture of boron nitride powder and glassy carbon grains has also been shown to be an excellent thermal insulation material for microwave processing and sintering. 1 fig.

Thermal insulation for high temperature microwave sintering operations and method thereof

DOEpatents

Holcombe, C.E.; Dykes, N.L.; Morrow, M.S.

1995-09-12

Superior microwave transparent thermal insulations for high temperature microwave sintering operations were prepared. One embodiment of the thermal insulation comprises granules of boron nitride coated with a very thin layer of glassy carbon made by preparing a glassy carbon precursor and blending it with boron nitride powder to form a mixture. The blended mixture is granulated to form a grit which is dried and heated to form the granules of boron nitride coated with a glassy carbon. Alternatively, grains of glassy carbon are coated with boron nitride by blending a mixture of a slurry comprising boron nitride, boric acid binder, and methyl alcohol with glassy carbon grains to form a blended mixture. The blended mixture is dried to form grains of glassy carbon coated with boron nitride. In addition, a physical mixture of boron nitride powder and glassy carbon grains has also been shown to be an excellent thermal insulation material for microwave processing and sintering. 1 fig.

Hydrogen peroxide biosensor based on hemoglobin immobilized at graphene, flower-like zinc oxide, and gold nanoparticles nanocomposite modified glassy carbon electrode.

PubMed

Xie, Lingling; Xu, Yuandong; Cao, Xiaoyu

2013-07-01

In this work, a highly sensitive hydrogen peroxide (H2O2) biosensor based on immobilization of hemoglobin (Hb) at Au nanoparticles (AuNPs)/flower-like zinc oxide/graphene (AuNPs/ZnO/Gr) composite modified glassy carbon electrode (GCE) was constructed, where ZnO and Au nanoparticles were modified through layer-by-layer onto Gr/GCE. Flower-like ZnO nanoparticles could be easily prepared by adding ethanol to the precursor solution having higher concentration of hydroxide ions. The Hb/AuNPs/ZnO/Gr composite film showed a pair of well-defined, quasi-reversible redox peaks with a formal potential (E(0)) of -0.367 V, characteristic features of heme redox couple of Hb. The electron transfer rate constant (k(s)) of immobilized Hb was 1.3 s(-1). The developed biosensor showed a very fast response (<2 s) toward H2O2 with good sensitivity, wide linear range, and low detection limit of 0.8 μM. The fabricated biosensor showed interesting features, including high selectivity, acceptable stability, good reproducibility, and repeatability along with excellent conductivity, facile electron mobility of Gr, and good biocompatibility of ZnO and AuNPs. The fabrication method of this biosensor was simple and effective for determination of H2O2 in real samples with quick response, good sensitivity, high selectivity, and acceptable recovery. Copyright © 2013 Elsevier B.V. All rights reserved.

Platinum nanoparticles decorated dendrite-like gold nanostructure on glassy carbon electrodes for enhancing electrocatalysis performance to glucose oxidation

NASA Astrophysics Data System (ADS)

Jia, Hongmei; Chang, Gang; Lei, Ming; He, Hanping; Liu, Xiong; Shu, Honghui; Xia, Tiantian; Su, Jie; He, Yunbin

2016-10-01

Platinum nanoparticles decorated dendrite-like gold nanostructure, bimetal composite materials on glassy carbon electrode (Pt/DGNs/GC) for enhancing electrocatalysis to glucose oxidation was designed and successfully fabricated by a facile two-step deposition method without any templates, surfactants, or stabilizers. Dendrite-like gold nanostructure was firstly deposited on the GC electrode via the potentiostatic method, and then platinum nanoparticles were decorated on the surface of gold substrate through chemical reduction deposition. X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), energy-dispersive X-ray spectroscopy (EDS) were applied to characterize the evolution of morphology and structure of the as-prepared Pt/DGNs/GC. Based on electrochemical measurements such as cyclic voltammetry, linear voltammetry and chronoamperometry, Pt/DGNs/GC exhibited significantly enhanced electrocatalytic performance to glucose oxidation compared those of pure dendrite-like Au nanoparticles in our previous report. Controlling chemical reduction deposition time, the amount of platinum nanoparticles on Au surface could be regulated, which further tuned electrocatalytic properties toward glucose oxidation. The dendrite-like gold surface partially covered by platinum nanoparticles dramatically enhanced the electrocatalytic performance for the oxidation of glucose because of excellent synergetic effects between gold and platinum species and the increased electrochemical active area from Pt nanoparticles loading. The non-enzymatic glucose biosensor based on Pt/DGNs/GC showed a rapid respond time (within 2 s), wide linear range (from 0.1 mM to 14 mM), low detection limit (0.01 mM), supernal sensitivity (275.44 μA cm-2 mM-1, R = 0.993), satisfactory reproducibility and good stability for glucose sensing. It was demonstrated that Pt/DGNs/GC could work as promising candidate for factual non-enzymatic glucose detection.

A novel third generation uric acid biosensor using uricase electro-activated with ferrocene on a Nafion coated glassy carbon electrode.

PubMed

Ghosh, Tanushree; Sarkar, Priyabrata; Turner, Anthony P F

2015-04-01

A new uric acid biosensor was constructed using ferrocene (Fc) induced electro-activated uricase (UOx) deposited within Nafion (Naf) on glassy carbon electrode (GCE). Electro-activation of UOx was successfully achieved by cyclic voltammetry through the electrostatic interaction of Fc with Trp residues within the hydrophobic pockets in UOx. The Naf/UOx/Fc composite was characterised by AFM, FTIR and EDX to ensure proper immobilisation. The interaction of Fc with the enzyme was analysed by Trp fluorescence spectroscopy and the α-helicity of the protein was measured by CD spectropolarimetry. The charge transfer resistance (Rct), calculated from electrochemical impedance spectroscopy, for the modified sensor was lowered (1.39 kΩ) and the enzyme efficiency was enhanced by more than two fold as a result of Fc incorporation. Cyclic voltammetry, differential pulse voltammetry and amperometry all demonstrated the excellent response of the Naf/UOx/Fc/GCE biosensor to uric acid. The sensor system generated a linear response over a range of 500 nM to 600 μM UA, with a sensitivity and limit of detection of 1.78 μA μM(-1) and 230 nM, respectively. The heterogeneous rate constant (ks) for UA oxidation was much higher for Naf/UOx/Fc/GCE (1.0 × 10(-4) cm s(-1)) than for Naf/UOx/GCE (8.2 × 10(-5) cm s(-1)). Real samples, i.e. human blood, were tested for serum UA and the sensor yielded accurate results at a 95% confidence limit. Copyright © 2014 Elsevier B.V. All rights reserved.

Tracking Water Diffusion Fronts in a Highly Viscous Aerosol Particle

NASA Astrophysics Data System (ADS)

Bastelberger, Sandra; Krieger, Ulrich; Peter, Thomas

2016-04-01

Field measurements indicate that atmospheric secondary aerosol particles can be present in a highly viscous, glassy state [1]. In contrast to liquid state particles, the gas phase equilibration is kinetically limited and governed by condensed phase diffusion. In recent water diffusion experiments on highly viscous single aerosol particles levitated in an electrodynamic balance (EDB) we observed a characteristic shift behavior of the Mie whispering gallery modes (WGM) indicative of the changing radial structure of the particle, thus providing us with an experimental method to track the diffusion process inside the particle. When a highly viscous, homogeneous particle is exposed to an abrupt increase in relative humidity, the rapid gas phase diffusion and strong concentration dependence of the diffusion coefficient in the condensed phase lead to extremely steep water concentration gradients inside the particle, reminiscent of diffusion fronts. The resulting quasi step-like concentration profile motivates the introduction of a simple core-shell model describing the morphology of the non-equilibrium particle during humidification. The subsequent particle growth and reduction of the shell refractive index can be observed as red and blueshift behavior of the WGM, respectively. The shift pattern can be attributed to a core-shell radius ratio and particle radius derived from model calculations [2]. If supplemented with growth information obtained from the WGM redshift and thermodynamic equilibrium data, we can infer a comprehensive picture of the time evolution of the diffusion fronts in the framework of our core-shell model. The measured time dependent concentration profile is then compared with simulations solving the non-linear diffusion equation [3] [1] Virtanen, A., et al., Nature, 467, 824-827, 2010 [2] Kaiser, T., Schweiger, G., Computers in Physics, Vol. 7, No. 6, 682-686, Nov/Dec 1993 [3] Zobrist, B., Soonsin, V., Luo, B.P., Peter, T. et al., Phys. Chem. Chem

Synthesis of water soluble chitosan stabilized gold nanoparticles and determination of uric acid

NASA Astrophysics Data System (ADS)

Lanh Le, Thi; Khieu Dinh, Quang; Hoa Tran, Thai; Nguyen, Hai Phong; Le Hien Hoang, Thi; Hien Nguyen, Quoc

2014-06-01

Gold nanoparticles (Au-NPs) have been successfully synthesized by utilizing water soluble chitosan as reducing and stabilizing agent. The colloidal Au-NPs were characterized by UV-Vis spectroscopy and transmission electron microscopy (TEM). The results showed that the colloidal Au-NPs had a plasmon absorption band with maximum wavelength in the range of 520-526 nm and the diameters were about 8-15 nm. In addition, a new Au-NPs-modified electrode was fabricated by self-assembling Au-NPs to the surface of the L-cysteine-modified glassy carbon electrode (Au-NPs/L-Cys/GCE). The Au-NPs-modified electrode showed an excellent character for electro-catalytic oxidization of uric acid (UA) in 0.1 mol L-1 phosphate buffer solution (pH 3.2). Using differential pulse anodic stripping voltammetry (DP-ASV), a high selectivity for determination of UA has been explored for the Au-NPs-modified electrode. DP-ASV peak currents of UA increased linearly with their concentration at the range of 2.0 × 10-6 to 4.0 × 10-5 mol L-1 with the detection limit of 2.7 × 10-6 mol L-1 for UA. The proposed method was applied for the detection of UA in human urine and serum samples with satisfactory results.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lienhard, D. M.; Huisman, A. J.; Krieger, U. K.

New measurements of water diffusion in secondary organic aerosol (SOA) material produced by oxidation of α-pinene and in a number of organic/inorganic model mixtures (3-methylbutane-1,2,3-tricarboxylic acid (3-MBTCA), levoglucosan, levoglucosan/NH 4HSO 4, raffinose) are presented. These indicate that water diffusion coefficients are determined by several properties of the aerosol substance and cannot be inferred from the glass transition temperature or bouncing properties. Our results suggest that water diffusion in SOA particles is faster than often assumed and imposes no significant kinetic limitation on water uptake and release at temperatures above 220 K. The fast diffusion of water suggests that heterogeneous icemore » nucleation on a glassy core is very unlikely in these systems. At temperatures below 220 K, model simulations of SOA particles suggest that heterogeneous ice nucleation may occur in the immersion mode on glassy cores which remain embedded in a liquid shell when experiencing fast updraft velocities. The particles absorb significant quantities of water during these updrafts which plasticize their outer layers such that these layers equilibrate readily with the gas phase humidity before the homogeneous ice nucleation threshold is reached. Glass formation is thus unlikely to restrict homogeneous ice nucleation. Only under most extreme conditions near the very high tropical tropopause may the homogeneous ice nucleation rate coefficient be reduced as a consequence of slow condensed-phase water diffusion. Since the differences between the behavior limited or non limited by diffusion are small even at the very high tropical tropopause, condensed-phase water diffusivity is unlikely to have significant consequences on the direct climatic effects of SOA particles under tropospheric conditions.« less

Immobilization of Ni-Pd/core-shell nanoparticles through thermal polymerization of acrylamide on glassy carbon electrode for highly stable and sensitive glutamate detection.

PubMed

Yu, Huicheng; Ma, Zhenzhen; Wu, Zhaoyang

2015-10-08

The preparation of a persistently stable and sensitive biosensor is highly important for practical applications. To improve the stability and sensitivity of glutamate sensors, an electrode modified with glutamate dehydrogenase (GDH)/Ni-Pd/core-shell nanoparticles was developed using the thermal polymerization of acrylamide (AM) to immobilize the synthesized Ni-Pd/core-shell nanoparticles onto a glassy carbon electrode (GCE). The modified electrode was characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). Electrochemical data showed that the prepared biosensor had remarkably enhanced electrocatalytic activity toward glutamate. Moreover, superior reproducibility and excellent stability were observed (relative average deviation was 2.96% after continuous use of the same sensor for 60 times, and current responses remained at 94.85% of the initial value after 60 d). The sensor also demonstrated highly sensitive amperometric detection of glutamate with a low limit of detection (0.052 μM, S/N = 3), high sensitivity (4.768 μA μM(-1) cm(-2)), and a wide, useful linear range (0.1-500 μM). No interference from potential interfering species such as l-cysteine, ascorbic acid, and l-aspartate were noted. The determination of glutamate levels in actual samples achieved good recovery percentages. Copyright © 2015 Elsevier B.V. All rights reserved.

Influence of Ag, Cd or Pb Addition on Electrical and Dielectric Properties of Bulk Glassy Se-Ge

NASA Astrophysics Data System (ADS)

El-Metwally, E. G.; Shakra, A. M.

2018-05-01

Bulk glassy samples of Se0.7Ge0.3 and Se0.7Ge0.25 X 0.05 (X = Ag, Cd or Pb) chalcogenide glass have been prepared by melt-quenching method. The studied compositions were examined in powder form by x-ray diffraction analysis. The direct-current (dc) conductivity σ_{{dc}} was measured for bulk samples in the temperature range from 303 K to 433 K, revealing enhancement with temperature for all samples. The results indicate two values of activation energy ( Δ E_{{σ1 }} and Δ E_{{σ2 }} ) due to two conduction mechanisms. Measurements of the alternating-current (ac) conductivity σ_{{ac}} ( ω ) and dielectric properties for bulk samples were carried out in the temperature range from 303 K to 433 K and frequency range from 1 kHz to 1 MHz. The ac conductivity σ_{{ac}} ( ω ) was temperature dependent and proportional to ωS , where S is the frequency exponent, which reduced with rising temperature, and ω is the angular frequency. These results are discussed based on a correlated barrier hopping model. The calculated values of the maximum height of the barrier W_{{M}} for each composition are consistent with carrier hopping over a potential barrier. The density of localized states N( {E_{{F}} } ) at the Fermi level lay in the range from 1019 eV-1 cm-3 to 1020 eV-1 cm-3, and increased with temperature. The dielectric constant ɛ1 ( ω ) and loss ɛ2 ( ω ) increased with temperature but decreased with frequency. The values of σ_{{dc}} , σ_{{ac}} ( ω ) , ɛ1 ( ω ) , and ɛ2 ( ω ) increased with temperature and with addition of Ag, Cd or Pb. The observed increase was greater for Se0.7Ge0.25Pb0.05 than for Se0.7Ge0.25Cd0.05, which was greater than for Se0.7Ge0.25Ag0.05.

The behavior of biogenic silica-rich rocks and volcanic tuffs as pozzolanic additives in cement

NASA Astrophysics Data System (ADS)

Fragoulis, Dimitris; Stamatakis, Michael; Anastasatou, Marianthi

2015-04-01

Cements currently produced, include a variety of pozzolanic materials, aiming for lower clinker addition and utilization of vast deposits of certain raw materials and/or mining wastes and byproducts. The major naturally occurring pozzolanic materials include glassy tuffs, zeolitic tuffs, diatomites and volcanic lavas rich in glassy phase, such as perlites. Therefore, based on the available raw materials in different locations, the cement composition might vary according to the accessibility of efficient pozzolanic materials. In the present investigation, the behavior of pozzolanic cements produced with representative samples of the aforementioned materials was studied, following the characterization of the implemented pozzolanas with respect to their chemical and mineralogical characteristics. Laboratory cements were produced by co-grinding 75% clinker, 5% gypsum and 20% pozzolana, for the same period of time (45 min). Regarding pozzolanic materials, four different types of pozzolanas were utilized namely, diatomite, perlite, zeolite tuff and glassy tuff. More specifically, two diatomite samples originated from Australia and Greece, with high and low reactive silica content respectively, two perlite samples originated from Turkey and from Milos Island, Greece, with different reactive silica contents, a zeolite tuff sample originated from Turkey and a glassy tuff sample originated from Milos Island, Greece. The above pozzolana samples, which were ground in the laboratory ball mill for cement production performed differently during grinding and that was reflected upon the specific surface area (cm2/gr) values. The perlites and the glassy tuff were the hardest to grind, whereas, the zeolite tuff and the Australian diatomite were the easiest ones. However, the exceedingly high specific surface area of the Australian diatomite renders cement difficult to transport and tricky to use for concrete manufacturing, due to the high water demand of the cement mixture. Regarding

Mechanism of drug release from polymethacrylate-based extrudates and milled strands prepared by hot-melt extrusion.

PubMed

Albers, Jessica; Alles, Rainer; Matthée, Karin; Knop, Klaus; Nahrup, Julia Schulze; Kleinebudde, Peter

2009-02-01

The aim of the study was the formulation of solid dispersions of the poorly water-soluble drug celecoxib and a polymethacrylate carrier by hot-melt extrusion. The objectives were to elucidate the mechanism of drug release from obtained extrudates and milled strands addicted to the solid-state properties of the solid dispersions and to examine and eliminate stability problems occurring under storage, exposure of mechanical stress, and in vitro dissolution. Transparent extrudates containing up to 60% drug could be prepared with a temperature setting below the melting point of celecoxib. XRPD and DSC measurements indicated the formation of a glassy solid solution, where the drug is molecularly dispersed in the carrier. The amorphous state of the glassy solid solution could be maintained during the exposure of mechanical stress in a milling process, and was stable under storage for at least 6 months. Solid-state properties and SEM images of extrudates after dissolution indicated a carrier-controlled dissolution, whereby the drug is molecularly dispersed within the concentrated carrier layer. The glassy solid solution showed a 58-fold supersaturation in 0.1 N HCl within the first 10 min, which was followed by a recrystallization process. Recrystallization could be inhibited by an external addition of HPMC.

Radial inhomogeneities in particle composition of single, levitated aerosol particles observed by Mie resonance spectroscopy (Invited)

NASA Astrophysics Data System (ADS)

Krieger, U. K.; Steimer, S.; Lienhard, D.; Bastelberger, S.

2013-12-01

Recent observations have indicated that organic aerosol particles in the atmosphere may exist in an amorphous semi-solid or even solid (i.e. glassy) state, e.g. [1]. The influence of highly viscous and glassy states on the timescale of aerosol particle equilibration with respect to water vapor have been investigated for some model systems of atmospheric aerosol, e.g. [2,3]. In particular, it has been shown that the kinetics of the water absorption/desorption process is controlled entirely by liquid-phase diffusion of water molecules for a highly viscous aerosol particle. A liquid phase diffusion model based on numerically solving the non-linear diffusion equation predicts strong internal gradients in water concentration when condensed phase diffusion impedes the water uptake from the gas phase [2]. Here we observe and quantify the internal concentration gradients in single, levitated, micron size aerosol particles of aqueous MBTCA (3-methyl-1,2,3-Butanetricarboxylic acid) and shikimic acid using elastic Mie resonance spectroscopy. A single, aqueous particle is levitated in an electro-dynamic balance (for details see [2]), dried for several days at room temperature, cooled to the target temperature and exposed to a rapid change in relative humidity. In addition to measuring the elastically backscattered light of a 'white light ' LED source and recording the full spectrum with a spectrograph as in [2], we use a tunable diode laser (TDL) to scan high resolution TE- and TM spectra. This combination allows observing various Mie resonance mode orders simultaneously. Since we perform the experiment at low temperatures and low humidities the changes in the Mie-spectra due to water uptake are sufficiently slow to resolve the kinetics. Experimental Mie resonance spectra are inverted to concentration profiles of water within the particle by applying the numerical diffusion model [2] in conjunction with Mie calculations of multilayered spheres [4]. Potential implications for

Open Access Discovery of alunite in Cross crater, Terra Sirenum, Mars: Evidence for acidic, sulfurous waters

USGS Publications Warehouse

Ehlmann, Bethany L.; Swayze, Gregg A.; Milliken, Ralph E.; Mustard, John F.; Clark, Roger N.; Murchie, Scott L.; Breit, George N.; Wray, James J.; Gondet, Brigitte; Poulet, Francois; Carter, John; Calvin, Wendy M.; Benzel, William M.; Seelos, Kimberly D.

2016-01-01

steam or fluids through fracture zones. The unique, highly aluminous nature of the Cross crater deposits relative to other martian acid sulfate deposits indicates acid waters, high water throughput during alteration, atypically glassy and/or felsic materials, or a combination of these conditions.

The Electrode as Organolithium Reagent: Catalyst-Free Covalent Attachment of Electrochemically Active Species to an Azide-Terminated Glassy Carbon Electrode Surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Atanu K.; Engelhard, Mark H.; Liu, Fei

2013-12-02

Glassy carbon electrodes have been activated for modification with azide groups and subsequent coupling with ferrocenyl reagents by a catalyst-free route using lithium acetylide-ethylenediamine complex, and also by the more common Cu(I)-catalyzed alkyne-azide coupling (CuAAC) route, both affording high surface coverages. Electrodes were preconditioned at ambient temperature under nitrogen, and ferrocenyl surface coverages obtained by CuAAC were comparable to those reported with preconditioning at 1000 °C under hydrogen/nitrogen. The reaction of lithium acetylide-ethylenediamine with the azide-terminated electrode affords a 1,2,3-triazolyllithium-terminated surface that is active toward covalent C-C coupling reactions including displacement at an aliphatic halide and nucleophilic addition at anmore » aldehyde. For example, surface ferrocenyl groups were introduced by reaction with (6-iodohexyl)ferrocene; the voltammetry shows narrow, symmetric peaks indicating uniform attachment. Coverages are competitive with those obtained by the CuAAC route. X-ray photoelectron spectroscopic data, presented for each synthetic step, are consistent with the proposed reactions. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. A portion of the research was performed using EMSL, 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.« less

Feeding and Development of the Glassy-Winged Sharpshooter, Homalodisca vitripennis, on Australian Native Plant Species and Implications for Australian Biosecurity

PubMed Central

Rathé, Anna A.; Pilkington, Leigh J.; Hoddle, Mark S.; Spohr, Lorraine J.; Daugherty, Matthew P.; Gurr, Geoff M.

2014-01-01

In any insect invasion the presence or absence of suitable food and oviposition hosts in the invaded range is a key factor determining establishment success. The glassy-winged sharpshooter, Homalodisca vitripennis, is an important insect vector of the xylem-limited bacterial plant pathogen, Xylella fastidiosa, which causes disease in numerous host plants including food and feedstock crops, ornamentals and weeds. Both the pathogen and the vector are native to the Americas and are considered to be highly invasive. Neither has been detected in Australia. Twelve Australian native plant species present in the USA were observed over two years for suitability as H. vitripennis feeding, oviposition and nymph development hosts. Hosts providing evidence of adult or nymph presence were Leptospermum laevigatum, Acacia cowleana, Eremophila divaricata, Eucalyptus wandoo, Hakea laurina, Melaleuca laterita and Swainsona galegifolia. An oviposition-suitability field study was conducted with citrus, a favoured oviposition host, as a positive control. Citrus and L. laevigatum, A. cowleana, B. ericifolia×B. spinulosa, C. pulchella, E. divaricata, E. wandoo, H. laurina, and S. galegifolia were found to be oviposition hosts. Egg parasitism by the mymarid parasitoid Gonatocerus ashmeadi was observed on all Australian plants. A number of Australian plants that may facilitate H. vitripennis invasion have been identified and categorised as ‘high risk’ due to their ability to support all three life stages (egg, nymph and adult) of the insect in the field (L. laevigatum, A. cowleana, E. divaricata, H. laurina, and S. galegifolia). The implications of these host status and natural enemy research findings are discussed and placed in an Australian invasion context. PMID:24614821

Diffusivity Measurements of Volatile Organics in Levitated Viscous Aerosol Particles

NASA Astrophysics Data System (ADS)

Bastelberger, Sandra; Krieger, Ulrich; Luo, Beiping; Peter, Thomas

2017-04-01

Field measurements indicating that atmospheric secondary aerosol (SOA) particles can be present in a highly viscous, glassy state have spurred numerous studies addressing low water diffusivities in glassy aerosols, focusing on kinetic limitations to hygroscopic growth and the plasticizing effect of water. Less is known about diffusion limitations of organic molecules and oxidants in viscous matrices and how these might affect atmospheric chemistry and gas-particle phase partitioning of complex mixtures with constituents of different volatility. Often viscosity data has been used to infer diffusivity via the Stokes- Einstein relationship even though strong deviations from this relationship have been observed for matrices of high viscosity. In this study, we provide a quantitative estimate for the diffusivity of a volatile organic in a viscous matrix. Evaporation of single particles generated from an aqueous solution of sucrose and a small quantity of volatile tetraethylene glycol (PEG-4) is investigated in an electrodynamic balance at controlled relative humidity (RH) and temperature conditions, thereby varying the viscosity of the sucrose matrix. The evaporative loss of tetraethylene glycol as determined by Mie resonance spectroscopy is used in conjunction with a diffusion model to retrieve translational diffusion coefficients of tetraethylene glycol. The evaporation of PEG-4 shows a pronounced RH and temperature dependence and is severely depressed for RH 30% corresponding to diffusivities < 10-14 cm2/s at temperatures as high as 15 °C, implying that atmospheric volatile organic compounds (VOC) can be subject to severe diffusion limitations in glassy SOA. Comparison of the experimentally derived diffusivities with viscosity estimates for the ternary system reveals a breakdown of the Stokes-Einstein relationship.

Cloud Point Extraction for Electroanalysis: Anodic Stripping Voltammetry of Cadmium.

PubMed

Rusinek, Cory A; Bange, Adam; Papautsky, Ian; Heineman, William R

2015-06-16

Cloud point extraction (CPE) is a well-established technique for the preconcentration of hydrophobic species from water without the use of organic solvents. Subsequent analysis is then typically performed via atomic absorption spectroscopy (AAS), UV-vis spectroscopy, or high performance liquid chromatography (HPLC). However, the suitability of CPE for electroanalytical methods such as stripping voltammetry has not been reported. We demonstrate the use of CPE for electroanalysis using the determination of cadmium (Cd(2+)) by anodic stripping voltammetry (ASV). Rather than using the chelating agents which are commonly used in CPE to form a hydrophobic, extractable metal complex, we used iodide and sulfuric acid to neutralize the charge on Cd(2+) to form an extractable ion pair. This offers good selectivity for Cd(2+) as no interferences were observed from other heavy metal ions. Triton X-114 was chosen as the surfactant for the extraction because its cloud point temperature is near room temperature (22-25 °C). Bare glassy carbon (GC), bismuth-coated glassy carbon (Bi-GC), and mercury-coated glassy carbon (Hg-GC) electrodes were compared for the CPE-ASV. A detection limit for Cd(2+) of 1.7 nM (0.2 ppb) was obtained with the Hg-GC electrode. ASV with CPE gave a 20x decrease (4.0 ppb) in the detection limit compared to ASV without CPE. The suitability of this procedure for the analysis of tap and river water samples was demonstrated. This simple, versatile, environmentally friendly, and cost-effective extraction method is potentially applicable to a wide variety of transition metals and organic compounds that are amenable to detection by electroanalytical methods.

Cloud Point Extraction for Electroanalysis: Anodic Stripping Voltammetry of Cadmium

PubMed Central

Rusinek, Cory A.; Bange, Adam; Papautsky, Ian; Heineman, William R.

2016-01-01

Cloud point extraction (CPE) is a well-established technique for the pre-concentration of hydrophobic species from water without the use of organic solvents. Subsequent analysis is then typically performed via atomic absorption spectroscopy (AAS), UV-Vis spectroscopy, or high performance liquid chromatography (HPLC). However, the suitability of CPE for electroanalytical methods such as stripping voltammetry has not been reported. We demonstrate the use of CPE for electroanalysis using the determination of cadmium (Cd2+) by anodic stripping voltammetry (ASV) as a representative example. Rather than using the chelating agents which are commonly used in CPE to form a hydrophobic, extractable metal complex, we used iodide and sulfuric acid to neutralize the charge on Cd2+ to form an extractable ion pair. Triton X-114 was chosen as the surfactant for the extraction because its cloud point temperature is near room temperature (22–25° C). Bare glassy carbon (GC), bismuth-coated glassy carbon (Bi-GC), and mercury-coated glassy carbon (Hg-GC) electrodes were compared for the CPE-ASV. A detection limit for Cd2+ of 1.7 nM (0.2 ppb) was obtained with the Hg-GC electrode. Comparison of ASV analysis without CPE was also investigated and a 20x decrease (4.0 ppb) in the detection limit was observed. The suitability of this procedure for the analysis of tap and river water samples was also demonstrated. This simple, versatile, environmentally friendly and cost-effective extraction method is potentially applicable to a wide variety of transition metals and organic compounds that are amenable to detection by electroanalytical methods. PMID:25996561

Probing the electrochemical double layer of an ionic liquid using voltammetry and impedance spectroscopy: a comparative study of carbon nanotube and glassy carbon electrodes in [EMIM](+)[EtSO(4)](-).

PubMed

Zheng, J P; Goonetilleke, P C; Pettit, C M; Roy, D

2010-05-15

Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are compared as techniques for analyzing double layer capacitances of ionic liquids (ILs) at the surfaces of two carbon-based electrodes. These systems are relevant for energy storage supercapacitors and often are associated with unconventional electrochemical properties. Certain theoretical and experimental aspects of CV and EIS necessary for quantitative evaluation of the capacitance characteristics of such systems are explored. The experiments use 1-ethyl-3-methyl imidazolium ethylsulfate as a model IL electrolyte in combination with a porous electrode of carbon nanotubes (CNTs). The results are compared with those obtained with a nonporous glassy carbon (GC) electrode. The time is constant, and hence the power delivery characteristics of the experimental cell are affected by the electrolyte resistance and residual faradaic reactions of the IL, as well as by the spatially inhomogeneous electrode surfaces. It is shown that adequate characterization of these IL-electrode systems can be achieved by combining CV with EIS. A phenomenological framework for utilizing this combination is discussed.

Glass polymorphism in glycerol–water mixtures: II. Experimental studies

PubMed Central

Bachler, Johannes; Fuentes-Landete, Violeta; Jahn, David A.; Wong, Jessina; Giovambattista, Nicolas

2016-01-01

We report a detailed experimental study of (i) pressure-induced transformations in glycerol–water mixtures at T = 77 K and P = 0–1.8 GPa, and (ii) heating-induced transformations of glycerol–water mixtures recovered at 1 atm and T = 77 K. Our samples are prepared by cooling the solutions at ambient pressure at various cooling rates (100 K s–1–10 K h–1) and for the whole range of glycerol mole fractions, χ g. Depending on concentration and cooling rates, cooling leads to samples containing amorphous ice (χ g ≥ 0.20), ice (χ g ≤ 0.32), and/or “distorted ice” (0 < χ g ≤ 0.38). Upon compression, we find that (a) fully vitrified samples at χ g ≥ 0.20 do not show glass polymorphism, in agreement with previous works; (b) samples containing ice show pressure-induced amorphization (PIA) leading to the formation of high-density amorphous ice (HDA). PIA of ice domains within the glycerol–water mixtures is shown to be possible only up to χ g ≈ 0.32 (T = 77 K). This is rather surprising since it has been known that at χ g < 0.38, cooling leads to phase-separated samples with ice and maximally freeze-concentrated solution of χ g ≈ 0.38. Accordingly, in the range 0.32 < χ g < 0.38, we suggest that the water domains freeze into an interfacial ice, i.e., a highly-distorted form of layered ice, which is unable to transform to HDA upon compression. Upon heating samples recovered at 1 atm, we observe a rich phase behavior. Differential scanning calorimetry indicates that only at χ g ≤ 0.15, the water domains within the sample exhibit polyamorphism, i.e., the HDA-to-LDA (low-density amorphous ice) transformation. At 0.15 < χ g ≤ 0.38, samples contain ice, interfacial ice, and/or HDA domains. All samples (χ g ≤ 0.38) show: the crystallization of amorphous ice domains, followed by the glass transition of the vitrified glycerol–water domains and, finally, the melting of ice at high temperatures. Our work exemplifies the complex �

Glassy Carbons

DTIC Science & Technology

1975-02-01

size is polydisperse. A controlled variation of the dispersion would be useful in tailoring properties, particularly in chemical ab- sorption and...20 10.8 ,, V-10-42 14.8 ---- PFA -2000 13.1 13.0 H-54 12.2 of Our Sample # 311-19(750) 5.0-65 Polydisperse312-10(2000) 19.7-53 of 312-31(2000) 14.2-65

Ice Nucleation in the Tropical Tropopause Layer: Implications for Cirrus Occurrence, Cirrus Microphysical Properties, and Dehydration of Air Entering the Stratosphere

NASA Technical Reports Server (NTRS)

Jensen, Eric; Kaercher, Bernd; Ueyama, Rei; Pfister, Leonhard

2017-01-01

Recent laboratory experiments have advanced our understanding of the physical properties and ice nucleating abilities of aerosol particles atlow temperatures. In particular, aerosols containing organics will transition to a glassy state at low temperatures, and these glassy aerosols are moderately effective as ice nuclei. These results have implications for ice nucleation in the cold Tropical Tropopause Layer (TTL; 13-19 km). We have developed a detailed cloud microphysical model that includes heterogeneous nucleation on a variety of aerosol types and homogeneous freezing of aqueous aerosols. This model has been incorporated into one-dimensional simulations of cirrus and water vapor driven by meteorological analysis temperature and wind fields. The model includes scavenging of ice nuclei by sedimenting ice crystals. The model is evaluated by comparing the simulated cloud properties and water vapor concentrations with aircraft and satellite measurements. In this presentation, I will discuss the relative importance of homogeneous and heterogeneous ice nucleation, the impact of ice nuclei scavenging as air slowly ascends through the TTL, and the implications for the final dehydration of air parcels crossing the tropical cold-point tropopause and entering the tropical stratosphere.

Roles of intracellular ice formation, vitrification of cell water, and recrystallisation of intracellular ice on the survival of mouse embryos and oocytes.

PubMed

Mazur, Peter; Paredes, Estefania

2016-03-01

Mazur and collaborators began examining the validity of initial views regarding mouse oocyte and embryo vitrification and found that most are partially or fully wrong. First, the relative effects of warming and cooling rates on the survival of mouse oocytes subjected to a vitrification procedure were determined. The high sensitivity to warming rate strongly suggests that the lethality of slow warming is a consequence of either the crystallisation of intracellular glassy water during warming or the recrystallisation during slow warming of small intracellular crystals that had formed during cooling. Warming rates of 107°C min-1 were achieved in 0.1-µL drops of ethylene glycol-acetamide-Ficoll-sucrose (EAFS) solution plus a small amount of India ink on Cryotops warmed using an infrared laser pulse. Under these conditions, survival rates of 90% were obtained even when mouse oocytes were suspended in 0.3× EAFS, a concentration that falls in the range that many cells can tolerate. A second important finding was that the survival of oocytes is more dependent on the osmotic withdrawal of much of the intracellular water before vitrification than it is on the penetration of cryoprotective solutes into the cells. Herein we review the roles of internal ice formation, vitrification and recrystallisation. It remains to be seen how widely these findings will be applicable to other types of cells and tissues from other species.

Electrocatalytic simultaneous determination of ascorbic acid, uric acid and L-Cysteine in real samples using quercetin silver nanoparticles-graphene nanosheets modified glassy carbon electrode

NASA Astrophysics Data System (ADS)

Zare, Hamid R.; Jahangiri-Dehaghani, Fahime; Shekari, Zahra; Benvidi, Ali

2016-07-01

By immobilizing of quercetin at the surface of a glassy carbon electrode modified with silver nanoparticles and graphene nanosheets (Q-AgNPs-GNs-GCE) a new sensor has been fabricated. The cyclic voltammogram of Q-AgNPs-GNs-GCE shows a stable redox couple with surface confined characteristics. Q-AgNPs-GNs-GCE demonstrated a high catalytic activity for L-Cysteine (L-Cys) oxidation. Results indicated that L-Cys peak potential at Q-AgNPs-GNs-GCE shifted to less positive values compared to GNs-GCE or AgNPs-GCE. Also, the kinetic parameters such as the electron transfer coefficient,, and the heterogeneous electron transfer rate constant, k‧, for the oxidation of L-Cys at the Q-AgNPs-GNs-GCE surface were estimated. In differential pulse voltammetric determination, the detection limit of L-Cys was obtained 0.28 μM, and the calibration plots were linear within two ranges of 0.9-12.4 μM and 12.4-538.5 μM of L-Cys. Also, the proposed modified electrode is used for the simultaneous determinations of ascorbic acid (AA), uric acid (UA), and L-Cys. Finally, this study has demonstrated the practical analytical utility of the sensor for determination of AA in vitamin C tablet, L-Cys in a milk sample and UA in a human urine sample.

Selective electrochemical reduction of CO2 to CO with a cobalt chlorin complex adsorbed on multi-walled carbon nanotubes in water.

PubMed

Aoi, Shoko; Mase, Kentaro; Ohkubo, Kei; Fukuzumi, Shunichi

2015-06-25

Electrocatalytic reduction of CO2 occurred efficiently using a glassy carbon electrode modified with a cobalt(II) chlorin complex adsorbed on multi-walled carbon nanotubes at an applied potential of -1.1 V vs. NHE to yield CO with a Faradaic efficiency of 89% with hydrogen production accounting for the remaining 11% at pH 4.6.

Flexible continuous manufacturing platforms for solid dispersion formulations

NASA Astrophysics Data System (ADS)

Karry-Rivera, Krizia Marie

In 2013 16,000 people died in the US due to overdose from prescription drugs and synthetic narcotics. As of that same year, 90% of new molecular entities in the pharmaceutical drug pipeline are classified as poor water-soluble. The work in this dissertation aims to design, develop and validate platforms that solubilize weak acids and can potentially deter drug abuse. These platforms are based on processing solid dispersions via solvent-casting and hot-melt extrusion methods to produce oral transmucosal films and melt tablets. To develop these platforms, nanocrystalline suspensions and glassy solutions were solvent-casted in the form of films after physicochemical characterizations of drug-excipient interactions and design of experiment approaches. A second order model was fitted to the emulsion diffusion process to predict average nanoparticle size and for process optimization. To further validate the manufacturing flexibility of the formulations, glassy solutions were also extruded and molded into tablets. This process included a systematic quality-by-design (QbD) approach that served to identify the factors affecting the critical quality attributes (CQAs) of the melt tablets. These products, due to their novelty, lack discriminatory performance tests that serve as predictors to their compliance and stability. Consequently, Process Analytical Technology (PAT) tools were integrated into the continuous manufacturing platform for films. Near-infrared (NIR) spectroscopy, including chemical imaging, combined with deconvolution algorithms were utilized for a holistic assessment of the effect of formulation and process variables on the product's CQAs. Biorelevant dissolution protocols were then established to improve the in-vivo in-vitro correlation of the oral transmucosal films. In conclusion, the work in this dissertation supports the delivery of poor-water soluble drugs in products that may deter abuse. Drug nanocrystals ensured high bioavailability, while glassy

Glassy dynamics of sorbitol solutions at terahertz frequencies.

PubMed

Sibik, Juraj; Shalaev, Evgenyi Y; Zeitler, J Axel

2013-07-28

The absorption spectra of D-sorbitol and a range of its concentrated aqueous solutions were studied by terahertz spectroscopy over the temperature interval of 80 K < T < 310 K. It is shown that the slow-down of molecules at around the glass transition temperature, Tg, dramatically influences the thermal dependence of the absorption at terahertz frequencies. Furthermore, two different absorption regimes are revealed below Tg: at temperatures well below Tg, the absorption resembles the coupling of terahertz radiation to the vibrational density of states (VDOS); above these temperatures, between 160 K and Tg, in the sample of pure sorbitol and the sample of a solution of 70 wt% sorbitol in water, another type of absorption is observed at terahertz frequencies. Several possibilities of the physical origin of this absorption are discussed and based on the experimental data this process is tentatively assigned to the Johari-Goldstein β-relaxation processes shifting to lower frequencies at temperatures below Tg leaving behind a spectrum largely dominated by losses into the VDOS.