Surgical results of dynamic nonfusion stabilization with the Segmental Spinal Correction System for degenerative lumbar spinal diseases with instability: Minimum 2-year follow-up

PubMed Central

Ohta, Hideki; Matsumoto, Yoshiyuki; Morishita, Yuichirou; Sakai, Tsubasa; Huang, George; Kida, Hirotaka; Takemitsu, Yoshiharu

2011-01-01

Background When spinal fusion is applied to degenerative lumbar spinal disease with instability, adjacent segment disorder will be an issue in the future. However, decompression alone could cause recurrence of spinal canal stenosis because of increased instability on operated segments and lead to revision surgery. Covering the disadvantages of both procedures, we applied nonfusion stabilization with the Segmental Spinal Correction System (Ulrich Medical, Ulm, Germany) and decompression. Methods The surgical results of 52 patients (35 men and 17 women) with a minimum 2-year follow-up were analyzed: 10 patients with lumbar spinal canal stenosis, 15 with lumbar canal stenosis with disc herniation, 20 with degenerative spondylolisthesis, 6 with disc herniation, and 1 with lumbar discopathy. Results The Japanese Orthopaedic Association score was improved, from 14.4 ± 5.3 to 25.5 ± 2.8. The improvement rate was 76%. Range of motion of the operated segments was significantly decreased, from 9.6° ± 4.2° to 2.0° ± 1.8°. Only 1 patient had adjacent segment disease that required revision surgery. There was only 1 screw breakage, but the patient was asymptomatic. Conclusions Over a minimum 2-year follow-up, the results of nonfusion stabilization with the Segmental Spinal Correction System for unstable degenerative lumbar disease were good. It is necessary to follow up the cases with a focus on adjacent segment disorders in the future. PMID:25802671

Final Scientific/Technical Report for Low Cost, High Capacity Non- Intercalation Chemistry Automotive Cells

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

Berdichevsky, Gene

Commercial Li-ion batteries typically use Ni- and Co-based intercalation cathodes. As the demand for improved performance from batteries increases, these cathode materials will no longer be able to provide the desired energy storage characteristics since they are currently approaching their theoretical limits. Conversion cathode materials are prime candidates for improvement of Li-ion batteries. On both a volumetric and gravimetric basis they have higher theoretical capacity than intercalation cathode materials. Metal fluoride (MFx) cathodes offer higher specific energy density and dramatically higher volumetric energy density. Challenges associated with metal fluoride cathodes were addressed through nanostructured material design and synthesis. A majormore » goal of this project was to develop and demonstrate Li-ion cells based on Si-comprising anodes and metal fluoride (MFx) comprising cathodes. Pairing the high-capacity MFx cathode with a high-capacity anode, such as an alloying Si anode, allows for the highest possible energy density on a cell level. After facing and overcoming multiple material synthesis and electrochemical instability challenges, we succeeded in fabrication of MFx half cells with cycle stability in excess of 500 cycles (to 20% or smaller degradation) and full cells with MFx-based cathodes and Si-based anodes with cycle stability in excess of 200 cycles (to 20% or smaller degradation).« less

Resistance to hypertension mediated by intercalated cells of the collecting duct

PubMed Central

Chen, Daian; Herrera, Marcela; Sparks, Matthew A.; Gurley, Susan B.

2017-01-01

The renal collecting duct (CD), as the terminal segment of the nephron, is responsible for the final adjustments to the amount of sodium excreted in urine. While angiotensin II modulates reabsorptive functions of the CD, the contribution of these actions to physiological homeostasis is not clear. To examine this question, we generated mice with cell-specific deletion of AT1A receptors from the CD. Elimination of AT1A receptors from both principal and intercalated cells (CDKO mice) had no effect on blood pressures at baseline or during successive feeding of low- or high-salt diets. In contrast, the severity of hypertension caused by chronic infusion of angiotensin II was paradoxically exaggerated in CDKO mice compared with controls. In wild-type mice, angiotensin II induced robust expression of cyclooxygenase-2 (COX-2) in renal medulla, primarily localized to intercalated cells. Upregulation of COX-2 was diminished in CDKO mice, resulting in reduced generation of vasodilator prostanoids. This impaired expression of COX-2 has physiological consequences, since administration of a specific COX-2 inhibitor to CDKO and control mice during angiotensin II infusion equalized their blood pressures. Stimulation of COX-2 was also triggered by exposure of isolated preparations of medullary CDs to angiotensin II. Deletion of AT1A receptors from principal cells alone did not affect angiotensin II–dependent COX2 stimulation, implicating intercalated cells as the main source of COX2 in this setting. These findings suggest a novel paracrine role for the intercalated cell to attenuate the severity of hypertension. Strategies for preserving or augmenting this pathway may have value for improving the management of hypertension. PMID:28405625

The Segmented Aperture Interferometric Nulling Testbed (SAINT) I: Overview and Air-side System Description

NASA Technical Reports Server (NTRS)

Hicks, Brian A.; Lyon, Richard G.; Petrone, Peter, III; Bolcar, Matthew R.; Bolognese, Jeff; Clampin, Mark; Dogoda, Peter; Dworzanski, Daniel; Helmbrecht, Michael A.; Koca, Corina;

Proflavine sensitivity of RNA processing in isolated nuclei.

PubMed Central

Yannarell, A; Niemann, M; Schumm, D E; Webb, T E

1977-01-01

The intercalating agent proflavine inhibits the processing and subsequent release of preformed messenger RNA and ribosomal RNA from isolated liver nuclei to surrogate cytoplasm. The direct effect of proflavine on these processes, as monitored in a reconstituted cell-free system, supports the theory that base-paired segments (i.e. hairpin loops) in the precursor RNA's are involved as recognition sites in nuclear RNA processing. PMID:866181

Effect of kinesiotaping, non-elastic taping and bracing on segmental foot kinematics during drop landing in healthy subjects and subjects with chronic ankle instability.

PubMed

Kuni, B; Mussler, J; Kalkum, E; Schmitt, H; Wolf, S I

2016-09-01

To evaluate the effects of kinesiotape, non-elastic tape, and soft brace on segmental foot kinematics during drop landing in subjects with chronic ankle instability and healthy subjects. Controlled study with repeated measurements. Three-dimensional motion analysis laboratory. Twenty participants with chronic ankle instability and 20 healthy subjects. The subjects performed drop landings with 17 retroreflective markers on the foot and lower leg in four conditions: barefoot, with kinesiotape, with non-elastic tape and with a soft brace. Ranges of motion of foot segments using a foot measurement method. In participants with chronic ankle instability, midfoot movement in the frontal plane (inclination of the medial arch) was reduced significantly by non-elastic taping, but kinesiotaping and bracing had no effect. In healthy subjects, both non-elastic taping and bracing reduced that movement. In both groups, non-elastic taping and bracing reduced rearfoot excursion in inversion/eversion significantly, which indicates a stabilisation effect. No such effect was found with kinesiotaping. All three methods reduced maximum plantar flexion significantly. Non-elastic taping stabilised the midfoot best in patients with chronic ankle instability, while kinesiotaping did not influence foot kinematics other than to stabilise the rearfoot in the sagittal plane. ClinicalTrials.gov NCT01810471. Copyright © 2015 Chartered Society of Physiotherapy. Published by Elsevier Ltd. All rights reserved.

Superconductivity at 7.4 K in few layer graphene by Li-intercalation.

PubMed

Tiwari, Anand P; Shin, Soohyeon; Hwang, Eunhee; Jung, Soon-Gil; Park, Tuson; Lee, Hyoyoung

2017-11-08

Superconductivity in graphene has been highly sought after for its promise in various device applications and for general scientific interest. Ironically, the simple electronic structure of graphene, which is responsible for novel quantum phenomena, hinders the emergence of superconductivity. Theory predicts that doping the surface of the graphene effectively alters the electronic structure, thus promoting propensity towards Cooper pair instability (Profeta et al (2012) Nat. Phys. 8 131-4; Nandkishore et al (2012) Nat. Phys. 8 158-63) [1, 2]. Here we report the emergence of superconductivity at 7.4 K in Li-intercalated few-layer-graphene (FLG). The absence of superconductivity in 3D Li-doped graphite underlines that superconductivity in Li-FLG arises from the novel electronic properties of the 2D graphene layer. These results are expected to guide future research on graphene-based superconductivity, both in theory and experiments. In addition, easy control of the Li-doping process holds promise for various device applications.

Dynamics of Hyperbranched Polymers under Confinement

NASA Astrophysics Data System (ADS)

Androulaki, Krystallenia; Chrissopoulou, Kiriaki; Anastasiadis, Spiros H.; Prevosto, Daniele; Labardi, Massimiliano

2015-03-01

The effect of severe confinement on the dynamics of three different generations of hyperbranched polyesters (Boltorns) is investigated by Dielectric Spectroscopy. The polymers are intercalated within the galleries of natural Na+-MMT, thus, forming 1nm polymer films confined between solid walls. The Tg's of the polymers determined by DSC show a clear dependence on the generation whereas the transition is completely suppressed when all the polymer chains are intercalated. The dynamic investigation of the bulk polymers reveals two sub-Tg processes, with similar behavior for the three polymers with the segmental relaxation observed above the Tg of each. For the nanocomposites, where all polymers are severely confined, the dynamics show significant differences compared to that of the bulk polymers. The sub-Tg processes are similar for the three generations but significantly faster and with weaker temperature dependence than those in the bulk. The segmental process appears at temperatures below the bulk polymer Tg, it exhibits an Arrhenius temperature dependence and shows differences for the three generations. A slow process that appears at higher temperatures is due to interfacial polarization. Co-financed by the EU and Greek funds through the Operational Program ``Education and Lifelong Learning'' of the NSRF-Research Funding Program: THALES-Investing in knowledge society through the Eur. Social Fund (MIS 377278) and COST Action MP0902-COINAPO.

Investigation of a subsonic-arc-attachment thruster using segmented anodes

NASA Technical Reports Server (NTRS)

Berns, Darren H.; Sankovic, John M.; Sarmiento, Charles J.

1993-01-01

To investigate high frequency arc instabilities observed in subsonic-arc-attachment thrusters, a 3 kW, segmented-anode arc jet was designed and tested using hydrogen as the propellant. The thruster nozzle geometry was scaled from a 30 kW design previously tested in the 1960's. By observing the current to each segment and the arc voltage, it was determined that the 75-200 kHz instabilities were results of axial movements of the arc anode attachment point. The arc attachment point was fully contained in the subsonic portion of the nozzle for nearly all flow rates. The effects of isolating selected segments were investigated. In some cases, forcing the arc downstream caused the restrike to cease. Finally, decreasing the background pressure from 18 to 0.05 Pa affected the pressure distribution in the nozzle including the pressure in the subsonic arc chamber.

Investigation of a subsonic-arc-attachment thruster using segmented anodes

NASA Technical Reports Server (NTRS)

Berns, Darren H.; Sankovic, John M.; Sarmiento, Charles J.

1993-01-01

To investigate high frequency arc instabilities observed in subsonic-arc-attachment thrusters, a 3 kW, segmented-anode arcjet was designed and tested using hydrogen as the propellant. The thruster nozzle geometry was scaled from a 30 kW design previously tested in the 1960's. By observing the current to each segment and the arc voltage, it was determined that the 75-200 kHz instabilities were results of axial movements of the arc anode attachment point. The arc attachment point was fully contained in the subsonic portion of the nozzle for nearly all flow rates. The effects of isolating selected segments were investigated. In some cases, forcing the arc downstream caused the restrike to cease. Finally, decreasing the background pressure from 18 Pa to 0.05 Pa affected the pressure distribution in the nozzle, including the pressure in the subsonic arc chamber.

Preparation and properties of poly HTBN-based urethane-urea/organo reactive montmorillonite nanocomposites

NASA Astrophysics Data System (ADS)

Li, Zai-Feng; Wu, Yuan; Zhang, Fu-Tao; Cao, Yu-Yang; Wu, Shou-Peng; Wang, Ting

2012-12-01

With ultrasonic assistant mixing way, an intercalated mixture of polyol/organo reactive montmorillonite (ORMMT) was pretreated. The prepolymer composed MMT clay was prepared by reaction of polyol/ORMMT mixture with toluene diisocyanate (TDI). The resultant prepolymer reacted with extender (DMTDA) and then the polyurethane-urea/organo reactive montmorillonite (PUU/ORMMT) nanocomposites were obtained. The structure, morphology and properties of PUU/ORMMT nanocomposites were characterized by FT-IR, TEM, AFM, strain-stress machine, TGA, and dynamic mechanical analysis (DMA). The results showed that when the OMMT content is 3%, the PUU/ORMMT nanocomposities performed super mechanical properties. Because of the presence of ORMMT, both T g of the soft segment and tan δ of the PUU increased, and the decomposition temperature for the first step and the second step increased respectively. TEM images showed that the organophilic MMT particles in the PUU composite exhibit a high degree of intercalation and exfoliation.

Histochemical carbonic anhydrase in rat inner medullary collecting duct

NASA Technical Reports Server (NTRS)

Kleinman, J. G.; Bain, J. L.; Fritsche, C.; Riley, D. A.

1992-01-01

Rat inner medullary collecting duct (IMCD) secretes substantial amounts of H+. However, carbonic anhydrase (CA), a concomitant of H+ secretion, has been generally reported absent in this segment. To reexamine this problem, we investigated CA and the morphological phenotypes of cells comprising the IMCD by CA histochemistry, using a modified Hansson technique with light and electron microscopy. Throughout the medulla, tubule cells exhibit histochemical CA activity. In the initial third of the inner medulla, a small proportion have features of intercalated cells and demonstrate some degree of CA activity. However, the majority population in the early portions of the IMCD appears to consist of principal cells. These also show CA staining of widely variable intensity, both among and within cells. A third cell type, previously called "IMCD cells", appears in the middle portion of the IMCD and is the only cell type present near the papilla tip. In contrast to previous reports, these "IMCD cells" have histochemical CA staining, also of highly variable intensity. These results demonstrate that stainable carbonic anhydrase to support acidification is present throughout the rat IMCD, both in intercalated cells and in some cells clearly not of this type. Therefore, the presence of CA is not specific for the intercalated cell type and suggests that other cell types may participate in acid secretion in IMCD.

On estimating the effects of clock instability with flicker noise characteristics

NASA Technical Reports Server (NTRS)

Wu, S. C.

1981-01-01

A scheme for flicker noise generation is given. The second approach is that of successive segmentation: A clock fluctuation is represented by 2N piecewise linear segments and then converted into a summation of N+1 triangular pulse train functions. The statistics of the clock instability are then formulated in terms of two sample variances at N+1 specified averaging times. The summation converges very rapidly that a value of N 6 is seldom necessary. An application to radio interferometric geodesy shows excellent agreement between the two approaches. Limitations to and the relative merits of the two approaches are discussed.

Engine Hydraulic Stability. [injector model for analyzing combustion instability

NASA Technical Reports Server (NTRS)

Kesselring, R. C.; Sprouse, K. M.

1977-01-01

An analytical injector model was developed specifically to analyze combustion instability coupling between the injector hydraulics and the combustion process. This digital computer dynamic injector model will, for any imposed chamber of inlet pressure profile with a frequency ranging from 100 to 3000 Hz (minimum) accurately predict/calculate the instantaneous injector flowrates. The injector system is described in terms of which flow segments enter and leave each pressure node. For each flow segment, a resistance, line lengths, and areas are required as inputs (the line lengths and areas are used in determining inertance). For each pressure node, volume and acoustic velocity are required as inputs (volume and acoustic velocity determine capacitance). The geometric criteria for determining inertances of flow segments and capacitance of pressure nodes was set. Also, a technique was developed for analytically determining time averaged steady-state pressure drops and flowrates for every flow segment in an injector when such data is not known. These pressure drops and flowrates are then used in determining the linearized flow resistance for each line segment of flow.

Sympathetic preganglionic efferent and afferent neurons mediated by the greater splanchnic nerve in rabbit

NASA Technical Reports Server (NTRS)

Torigoe, Yasuhiro; Cernucan, Roxana D.; Nishimoto, Jo Ann S.; Blanks, Robert H. I.

1985-01-01

As a part of the study of the vestibular-autonomic pathways involved in motion sickness, the location and the morphology of preganglionic sympathetic neurons (PSNs) projecting via the greater splanchnic nerve were examined. Retrograde labeling of neurons was obtained by application of horseradish peroxidase to the cut end of the greater splanchnic nerve. Labeled PSNs were found, ipsilaterally, within the T1 to T11 spinal cord segments, with the highest density of neurons in T6. Most PSNs were located within the intermediolateral column, but a significant portion also occurred within the lateral funiculus, the intercalated region, and the central autonomic area; the proportion of labeling between the four regions depended on the spinal cord segment.

Athlete shoulder injuries: CT arthrographic findings.

PubMed

Rafii, M; Firooznia, H; Bonamo, J J; Minkoff, J; Golimbu, C

1987-02-01

Forty-three professional and amateur athletes with persistent shoulder pain that interfered with their sports activities were evaluated by computed tomographic (CT) arthrography. In 19 patients, glenohumeral instability (14 anterior, two posterior, three multidirectional) was diagnosed with CT arthrography based on the simultaneous presence of labral and capsular lesions. The findings were crucial in establishing the diagnosis of instability in six patients in whom the condition was not suggested or could not be confirmed clinically. Another significant injury consisted of labral lesions not associated with glenohumeral instability. These tears often involved the anterior and parasuperior segments of this structure. Other, less frequently detected lesions included segmental labral enlargement and several labra with abnormal orientation (everted labrum). Early onset of degenerative disease was present in many athletes, especially those with a long history of sports activity. CT arthrographic findings were correlated with arthroscopic or surgical results in 19 patients.

The Segmented Aperture Interferometric Nulling Testbed (SAINT) I: overview and air-side system description

NASA Astrophysics Data System (ADS)

Hicks, Brian A.; Lyon, Richard G.; Petrone, Peter; Ballard, Marlin; Bolcar, Matthew R.; Bolognese, Jeff; Clampin, Mark; Dogoda, Peter; Dworzanski, Daniel; Helmbrecht, Michael A.; Koca, Corina; Shiri, Ron

2016-07-01

This work presents an overview of the Segmented Aperture Interferometric Nulling Testbed (SAINT), a project that will pair an actively-controlled macro-scale segmented mirror with the Visible Nulling Coronagraph (VNC). SAINT will incorporate the VNC's demonstrated wavefront sensing and control system to refine and quantify end-to-end high-contrast starlight suppression performance. This pathfinder testbed will be used as a tool to study and refine approaches to mitigating instabilities and complex diffraction expected from future large segmented aperture telescopes.

Unusually large earthquakes inferred from tsunami deposits along the Kuril trench

USGS Publications Warehouse

Nanayama, F.; Satake, K.; Furukawa, R.; Shimokawa, K.; Atwater, B.F.; Shigeno, K.; Yamaki, S.

2003-01-01

The Pacific plate converges with northeastern Eurasia at a rate of 8-9 m per century along the Kamchatka, Kuril and Japan trenches. Along the southern Kuril trench, which faces the Japanese island of Hokkaido, this fast subduction has recurrently generated earthquakes with magnitudes of up to ???8 over the past two centuries. These historical events, on rupture segments 100-200 km long, have been considered characteristic of Hokkaido's plate-boundary earthquakes. But here we use deposits of prehistoric tsunamis to infer the infrequent occurrence of larger earthquakes generated from longer ruptures. Many of these tsunami deposits form sheets of sand that extend kilometres inland from the deposits of historical tsunamis. Stratigraphic series of extensive sand sheets, intercalated with dated volcanic-ash layers, show that such unusually large tsunamis occurred about every 500 years on average over the past 2,000-7,000 years, most recently ???350 years ago. Numerical simulations of these tsunamis are best explained by earthquakes that individually rupture multiple segments along the southern Kuril trench. We infer that such multi-segment earthquakes persistently recur among a larger number of single-segment events.

End Point of the Ultraspinning Instability and Violation of Cosmic Censorship.

PubMed

Figueras, Pau; Kunesch, Markus; Lehner, Luis; Tunyasuvunakool, Saran

2017-04-14

We determine the end point of the axisymmetric ultraspinning instability of asymptotically flat Myers-Perry black holes in D=6 spacetime dimensions. In the nonlinear regime, this instability gives rise to a sequence of concentric rings connected by segments of black membrane on the rotation plane. The latter become thinner over time, resulting in the formation of a naked singularity in finite asymptotic time and hence a violation of the weak cosmic censorship conjecture in asymptotically flat higher-dimensional spaces.

End Point of the Ultraspinning Instability and Violation of Cosmic Censorship

NASA Astrophysics Data System (ADS)

Figueras, Pau; Kunesch, Markus; Lehner, Luis; Tunyasuvunakool, Saran

2017-04-01

We determine the end point of the axisymmetric ultraspinning instability of asymptotically flat Myers-Perry black holes in D =6 spacetime dimensions. In the nonlinear regime, this instability gives rise to a sequence of concentric rings connected by segments of black membrane on the rotation plane. The latter become thinner over time, resulting in the formation of a naked singularity in finite asymptotic time and hence a violation of the weak cosmic censorship conjecture in asymptotically flat higher-dimensional spaces.

Thermodynamical study of boron doped CeX{sub 3} (X=Pd, Rh)

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

Sharma, Ramesh; Dwivedi, Shalini; Sharma, Yamini, E-mail: sharma.yamini62@gmail.com

2016-05-06

The structural, electronic, thermal, and optical properties of cubic non magnetic CeX{sub 3}(X=Pd, Rh) compounds which crystallize in the Au{sub 3}Cu structure have been studied using the projected augmented wave (PAW) method within the density functional theory (DFT) with generalized gradient approximation (GGA) for exchange correlation potential. In this paper we have calculated the band structure which are interpreted using the density of states. The optical properties such as extinction coefficients clearly illustrate the changes in CeX{sub 3} due to intercalation of boron. Lattice instability is observed in CePd{sub 3}B from the calculated dynamical properties.

The pelvic kidney of male Ambystoma maculatum (Amphibia, urodela, ambystomatidae) with special reference to the sexual collecting ducts.

PubMed

Siegel, Dustin S; Sever, David M; Aldridge, Robert D

2010-12-01

This study details the gross and microscopic anatomy of the pelvic kidney in male Ambystoma maculatum. The nephron of male Ambystoma maculatum is divided into six distinct regions leading sequentially away from a renal corpuscle: (1) neck segment, which communicates with the coelomic cavity via a ventrally positioned pleuroperitoneal funnel, (2) proximal tubule, (3) intermediate segment, (4) distal tubule, (5) collecting tubule, and (6) collecting duct. The proximal tubule is divided into a vacuolated proximal region and a distal lysosomic region. The basal plasma membrane is modified into intertwining microvillus lamellae. The epithelium of the distal tubule varies little along its length and is demarcated by columns of mitochondria with their long axes oriented perpendicular to the basal lamina. The distal tubule possesses highly interdigitating microvillus lamellae from the lateral membranes and pronounced foot processes of the basal membrane that are not intertwined, but perpendicular to the basal lamina. The collecting tubule is lined by an epithelium with dark and light cells. Light cells are similar to those observed in the distal tuble except with less mitochondria and microvillus lamellae of the lateral and basal plasma membrane. Dark cells possess dark euchromatic nuclei and are filled with numerous small mitochondria. The epithelium of the neck segment, pleuroperitoneal funnel, and intermediate segment is composed entirely of ciliated cells with cilia protruding from only the central portion of the apical plasma membrane. The collecting duct is lined by a highly secretory epithelium that produces numerous membrane bound granules that stain positively for neutral carbohydrates and proteins. Apically positioned ciliated cells are intercalated between secretory cells. The collecting ducts anastomose caudally and unite with the Wolffian duct via a common collecting duct. The Wolffian duct is secretory, but not to the extent of the collecting duct, synthesizes neutral carbohydrates and proteins, and is also lined by apical ciliated cells intercalated between secretory cells. Although functional aspects associated with the morphological variation along the length of the proximal portions of the nephron have been investigated, the role of a highly secretory collecting duct has not. Historical data that implicated secretory activity concordant with mating activity, and similarity of structure and chemistry to sexual segments of the kidneys in other vertebrates, lead us to believe that the collecting duct functions as a secondary sexual organ in Ambystoma maculatum. © 2010 Wiley-Liss, Inc.

Improved photostability of hydrophobic natural dye incorporated in organo-modified hydrotalcite

NASA Astrophysics Data System (ADS)

Kohno, Yoshiumi; Asai, Saeko; Shibata, Masashi; Fukuhara, Choji; Maeda, Yasuhisa; Tomita, Yasumasa; Kobayashi, Kenkichiro

2014-08-01

β-carotene and annatto extract are typical carotenoids used as safe colorants for foods. However, the instability against irradiation limits their wide use. The improvement of stability was investigated by the intercalation of dye into the interlayer space of the anion-exchangeable clay, hydrotalcite. A hydrophobic environment was constructed in the interlayer space of the hydrotalcite by its modification with anionic surfactants (dodecyl sulfate and dodecylbenzene sulfonate). The lipophilic β-carotene and annatto dye were successfully incorporated into the organo-modified hydrotalcite, and the incorporated dyes exhibited improved photostability under visible irradiation from a 100 W halogen lamp (190 klux) in the air. The effect of the stabilization on the anionic annatto dye was higher by the incorporation in the modified hydrotalcite than that in the modified cation exchangeable clay, suggesting that the polarity of the clay sheet had some influence on the stabilization of the incorporated dye. The stabilization effect of β-carotene was not so significant as that of the annatto dye, because sufficient intercalation of non-polar β-carotene might require stronger hydrophobic environment. The π-π interaction between the β-carotene and the benzene ring of dodecylbenzene sulfonate was found to contribute to the stability enhancement.

Dynamic stability of electrodynamic maglev systems

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

Cai, Y.; Chen, S.S.; Mulcahy, T.M.

1997-01-01

Because dynamic instabilities are not acceptable in any commercial maglev system, it is important to consider dynamic instability in the development of all maglev systems. This study considers the stability of maglev systems based on mathematical models and experimental data. Divergence and flutter are obtained for coupled vibration of a three-degree-of-freedom maglev vehicle on a guideway consisting of double L-shaped aluminum segments. The theory and analysis for motion-dependent magnetic-force-induced instability developed in this study provides basic stability characteristics and identifies future research needs for maglev systems.

Flutter instability of freely hanging articulated pipes conveying fluid

NASA Astrophysics Data System (ADS)

Schouveiler, Lionel; Chermette, Félix

2018-03-01

We experimentally investigate the stability of freely hanging articulated pipes made of rigid segments connected by flexible joints and with their displacements constrained in a vertical plane. When the velocity of the fluid conveyed by the pipe is increased, flutter-type instability occurs above a critical value. The critical velocity and the characteristics of the flutter modes (frequency, amplitude, and shape) are determined as a function of the number n of segments into the pipe which is varied from 2 to 5. Experimental results are compared to predictions from linear stability analysis extending previous studies by taking into account damping due to the dissipation in the joints. Qualitative agreement is found and the limits of the analysis are discussed.

Electrolyte additives for lithium metal anodes and rechargeable lithium metal batteries: progresses and perspectives.

PubMed

Zhang, Heng; Eshetu, Gebrekidan Gebresilassie; Judez, Xabier; Li, Chunmei; Rodriguez-Martínez, Lide M; Armand, Michel

2018-02-14

Lithium metal (Li°) - based rechargeable batteries (LMBs), such as Li° anode vs. intercalation and/or conversion type cathode batteries, lithium-sulphur (Li-S), and lithium-oxygen (O2)/air (Li-O2/air) are becoming increasingly important for electrifying the modern transportation system, enabling sustainable mobility in the near future. Though some rechargeable LMBs batteries (e.g., Li°/LiFePO4 batteries from Bolloré Bluecar®, Li-S batteries from OXIS Energy and Sion Power) are already commercially viable in niche applications, their large-scale deployment is still hampered due to the existence of a number of formidable challenges, including lithium dendrite growth, electrolyte instability towards high voltage intercalation type cathode, poor electronic and ionic conductivities of sulphur (S8) and O2, as well as their corresponding reduction products (e.g., Li2S and Li2O), dissolution and shuttling of polysulphide (PS) intermediates etc. This ultimately results in short cycle life, low coulombic/energy efficiency, poor safety, and a high self-discharge rate. Among other mitigating strategies, the use of electrolyte additives is considered as one of the most economical, and effective approach for circumventing these dilemmas. Set out to offer an in-depth insight into the rapidly growing research on the account of electrolyte additives for rechargeable LMBs, this review presents an overview of the various functional additives, that are being applied in Li-anode/intercalation cathode-based, Li-S and Li-O2 batteries. This review is believed to assess the status quo of the research and thereby arouse new thoughts and opportunities, opening new avenues for the practical realization of these appealing devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Family Instability and Exposure to Violence in the Early Life Course.

PubMed

Cavanagh, Shannon E; Stritzel, Haley; Smith, Chelsea; Crosnoe, Robert

2017-10-11

Family instability has been linked with a host of outcomes across the early life course. This study extends this literature by connecting instability with violence in the community by examining the associations among family structure, family structure change, and secondary exposure to violence during adolescence across diverse segments of the population. Using longitudinal data from the Project on Human Development in Chicago Neighborhoods study, we found that living with a single parent and experiencing family structure changes were associated with secondary exposure to violence. Multiple group models suggest that partner change translated into more exposure for boys than girls. Findings also suggest that family instability may lead to more secondary exposure to violence for African American youth. © 2017 Society for Research on Adolescence.

On the importance of reduced scale Ariane 5 P230 solid rocket motor models in the comprehension and prevention of thrust oscillations

NASA Astrophysics Data System (ADS)

Hijlkema, J.; Prévost, M.; Casalis, G.

2011-09-01

Down-scaled solid propellant motors are a valuable tool in the study of thrust oscillations and the underlying, vortex-shedding-induced, pressure instabilities. These fluctuations, observed in large segmented solid rocket motors such as the Ariane 5 P230, impose a serious constraint on both structure and payload. This paper contains a survey of the numerous configurations tested at ONERA over the last 20 years. Presented are the phenomena searched to reproduce and the successes and failures of the different approaches tried. The results of over 130 experiments have contributed to numerous studies aimed at understanding the complicated physics behind this thorny problem, in order to pave the way to pressure instability reduction measures. Slowly but surely our understanding of what makes large segmented solid boosters exhibit this type of instabilities will lead to realistic modifications that will allow for a reduction of pressure oscillations. A "quieter" launcher will be an important advantage in an ever more competitive market, giving a easier ride to payload and designers alike.

Open-Structured V 2 O 5 · n H 2 O Nanoflakes as Highly Reversible Cathode Material for Monovalent and Multivalent Intercalation Batteries

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

Wang, Huali; Bi, Xuanxuan; Bai, Ying

The high-capacity cathode material V2O5·nH2O has attracted considerable attention for metal ion batteries due to the multielectron redox reaction during electrochemical processes. It has an expanded layer structure, which can host large ions or multivalent ions. However, structural instability and poor electronic and ionic conductivities greatly handicap its application. Here, in cell tests, self-assembly V2O5·nH2O nanoflakes shows excellent electrochemical performance with either monovalent or multivalent cation intercalation. They are directly grown on a 3D conductive stainless steel mesh substrate via a simple and green hydrothermal method. Well-layered nanoflakes are obtained after heat treatment at 300 °C (V2O5·0.3H2O). Nanoflakes with ultrathinmore » flower petals deliver a stable capacity of 250 mA h g-1 in a Li-ion cell, 110 mA h g-1 in a Na-ion cell, and 80 mA h g-1 in an Al-ion cell in their respective potential ranges (2.0–4.0 V for Li and Na-ion batteries and 0.1–2.5 V for Al-ion battery) after 100 cycles.« less

Graphite fiber intercalation: Dynamics of the bromine intercalation process

NASA Technical Reports Server (NTRS)

Jaworske, D. A.; Zinolabedini, R.

1985-01-01

The resistance of pitch-based graphite fibers was monitored, in situ, during a series of bromine intercalation experiments. The threshold pressure for the bromine intercalation of pitch-based fibers was estimated to be 102 torr. When the bromine atmosphere was removed from the reaction chamber, the resistivity of the intercalated graphite fibers increased consistently. This increase was attributed to loss of bromine from the perimeter of the fiber. The loss was confirmed by mapping the bromine concentration across the diameter of single intercalated fibers with either energy dispersive spectroscopy or scanning Auger microscopy. A statistical study comparing fibers intercalated in bromine vapor with fibers intercalated in bromine liquid showed that similar products were obtained with both methods of intercalation.

Evaluation of lumbar segmental instability in degenerative diseases by using a new intraoperative measurement system.

PubMed

Hasegawa, Kazuhiro; Kitahara, Ko; Hara, Toshiaki; Takano, Ko; Shimoda, Haruka; Homma, Takao

2008-03-01

In vivo quantitative measurement of lumbar segmental stability has not been established. The authors developed a new measurement system to determine intraoperative lumbar stability. The objective of this study was to clarify the biomechanical properties of degenerative lumbar segments by using the new method. Twenty-two patients with a degenerative symptomatic segment were studied and their measurements compared with those obtained in normal or asymptomatic degenerative segments (Normal group). The measurement system produces cyclic flexion-extension through spinous process holders by using a computer-controlled motion generator with all ligamentous structures intact. The following biomechanical parameters were determined: stiffness, absorption energy (AE), and neutral zone (NZ). Discs with degeneration were divided into 2 groups based on magnetic resonance imaging grading: degeneration without collapse (Collapse[-]) and degeneration with collapse (Collapse[+]). Biomechanical parameters were compared among the groups. Relationships among the biomechanical parameters and age, diagnosis, or radiographic parameters were analyzed. The mean stiffness value in the Normal group was significantly greater than that in Collapse(-) or Collapse(+) group. There was no significant difference in the average AE value among the Normal, Collapse(-), and Collapse(+) groups. The NZ in the Collapse(-) was significantly higher than in the Normal or Collapse(+) groups. Stiffness was negatively and NZ was positively correlated with age. Stiffness demonstrated a significant negative and NZ a significant positive relationship with disc height, however. There were no significant differences in stiffness between spines in the Collapse(-) and Collapse(+) groups. The values of a more sensitive parameter, NZ, were higher in Collapse(-) than in Collapse(+) groups, demonstrating that degenerative segments with preserved disc height have a latent instability compared to segments with collapsed discs.

Genetic instability of an oligomycin resistance mutation in yeast is associated with an amplification of a mitochondrial DNA segment.

PubMed Central

Ragnini, A; Fukuhara, H

1989-01-01

In the yeast Kluyveromyces lactis, mutations affecting mitochondrial functions are often highly unstable. In order to understand the basis of this genetic instability, we examined the case of an oligomycin resistant mutant. When the mutant was grown in the absence of the drug, the resistance was rapidly lost. This character showed a typical cytoplasmic inheritance. The unstable resistance was found to be associated with the presence of a repetitive DNA in which the repeating unit was a specific segment of the mitochondrial DNA. The amplified molecules were co-replicating with the wild type genome in the mutant cells. The spontaneous loss of the drug resistance was accompanied by the disappearance of the amplified DNA. The repetitive sequence came from a 405 base-pair segment immediately downstream of a cluster of two transfer RNA genes (threonyl 2 and glutamyl). Modified processing of these tRNAs was detected in the mutant. A possible mechanism by which these events could lead to drug resistance is discussed. Images PMID:2780315

Rescue of mutant rhodopsin traffic by metformin-induced AMPK activation accelerates photoreceptor degeneration

PubMed Central

Athanasiou, Dimitra; Aguila, Monica; Opefi, Chikwado A.; South, Kieron; Bellingham, James; Bevilacqua, Dalila; Munro, Peter M.; Kanuga, Naheed; Mackenzie, Francesca E.; Dubis, Adam M.; Georgiadis, Anastasios; Graca, Anna B.; Pearson, Rachael A.; Ali, Robin R.; Sakami, Sanae; Palczewski, Krzysztof; Sherman, Michael Y.; Reeves, Philip J.

2017-01-01

Abstract Protein misfolding caused by inherited mutations leads to loss of protein function and potentially toxic ‘gain of function’, such as the dominant P23H rhodopsin mutation that causes retinitis pigmentosa (RP). Here, we tested whether the AMPK activator metformin could affect the P23H rhodopsin synthesis and folding. In cell models, metformin treatment improved P23H rhodopsin folding and traffic. In animal models of P23H RP, metformin treatment successfully enhanced P23H traffic to the rod outer segment, but this led to reduced photoreceptor function and increased photoreceptor cell death. The metformin-rescued P23H rhodopsin was still intrinsically unstable and led to increased structural instability of the rod outer segments. These data suggest that improving the traffic of misfolding rhodopsin mutants is unlikely to be a practical therapy, because of their intrinsic instability and long half-life in the outer segment, but also highlights the potential of altering translation through AMPK to improve protein function in other protein misfolding diseases. PMID:28065882

Dynamics of graphite fiber intercalation: In situ resistivity measurements with a four point probe

NASA Technical Reports Server (NTRS)

Jaworske, D. A.

1984-01-01

The dynamics of ferric chloride intercalation of single graphite fibers were studied, in situ, using a four point dc bridge. Measurements before, during and after the intercalation showed that the intercalation occurred within minutes at 200 C. Changes in fiber resistivity after exposure to air suggested hydration of the graphite intercalation compound. Deintercalation of the ferric chloride was initiated at temperatures in excess of 400 C. cycling the intercalant into and out of the graphite fiber gave no improvements in fiber resistivity. The activation energy of the ferric chloride intercalation reaction was found to be 17 + or - 4 kcal/mol 1 consistent with the concept of a preliminary nucleation step in the intercalation reaction.

Formation of intercalation compound of kaolinite-glycine via displacing guest water by glycine.

PubMed

Zheng, Wan; Zhou, Jing; Zhang, Zhenqian; Chen, Likun; Zhang, Zhongfei; Li, Yong; Ma, Ning; Du, Piyi

2014-10-15

The kaolinite-glycine intercalation compound was successfully formed by displacing intercalated guest water molecules in kaolinite hydrate as a precursor. The microstructure of the compound was characterized by X-ray diffraction, Fourier Transform Infrared Spectroscopy and Scanning Electron Microscope. Results show that glycine can only be intercalated into hydrated kaolinite to form glycine-kaolinite by utilizing water molecules as a transition phase. The intercalated glycine molecules were squeezed partially into the ditrigonal holes in the silicate layer, resulting in the interlayer distance of kaolinite reaching 1.03nm. The proper intercalation temperature range was between 20°C and 80°C. An intercalation time of 24h or above was necessary to ensure the complete formation of kaolinite-glycine. The highest intercalation degree of about 84% appeared when the system was reacted at the temperature of 80°C for 48h. There were two activation energies for the intercalation of glycine into kaolinite, one being 21kJ/mol within the temperature range of 20-65°C and the other 5.8kJ/mol between 65°C and 80°C. The intercalation degree (N) and intercalation velocity (v) of as a function of intercalation time (t) can be empirically expressed as N=-79.35e(-)(t)(/14.8)+80.1 and v=5.37e(-)(t)(/14.8), respectively. Copyright © 2014 Elsevier Inc. All rights reserved.

Biomechanical effect of interspinous process distraction height after lumbar fixation surgery: An in vitro model.

PubMed

Fu, Lin; Ma, Jianxiong; Lu, Bin; Jia, Haobo; Zhao, Jie; Kuang, Mingjie; Feng, Rui; Xu, Liyan; Bai, Haohao; Sun, Lei; Wang, Ying; Ma, Xinlong

2017-07-01

Pedicle screw fixation may induce abnormal activity at adjacent segment and accelerate the degeneration of lumbar vertebrae. Dynamic stabilizers could provide an intermediate solution between conservative treatment and fusion surgery. Lumbar vertebral segment cephalad to instrumented fixation was the most common localization of adjacent segment degeneration. The aim of this study is to explore the use of interspinous process devices in the lumbar vertebral segment cephalad to fixation segment in changing the mechanical distribution and limiting abnormal activity of the spine. Eight specimens were tested in the following groups: intact group, instability group (bilateral facetectomy at L3-L4), fixation group (bilateral facetectomy and pedicle screw fixation at L3-L4), and hybrid fixation group (fixation at L3-L4 and simulating interspinous device implantation of 6, 8, 10, 12, 14, 16, and 18 mm at L2-L3). Range of motion, motion of vertebral body, and strain distribution change were recorded. The range of motion in extension with 16- and 18-mm hybrid constructs was significantly lower than intact, instability, and fixation groups. In flexion and lateral bending, the strain values of L4 inferior articular process with 18-mm hybrid construct have a significant difference compared with other groups. In axial rotation, under the condition of a contralateral state, the strain values of L2 superior articular process with 18-mm hybrid construct have a significant difference compared with intact and fixation groups. The strain value of the L4 inferior articular process had negative correlation with height distraction in three dimensions, except extension. A negative correlation between the strain value of the L2 superior articular process and distraction height was found in contralateral bending and contralateral axial rotation. Interspinous process devices above the fixation segment can change the mechanical distribution of the spine and limit activity in some of the segments of the spine, which may delay the degeneration of the adjacent segment.

Dynamic stability of maglev systems

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

Cai, Y.; Chen, S.S.; Mulcahy, T.M.

1994-05-01

Because dynamic instabilities are not acceptable in any commercial maglev system, it is important to consider dynamic instability in the development of all maglev systems. This study considers the stability of maglev systems based on experimental data, scoping calculations, and simple mathematical models. Divergence and flutter are obtained for coupled vibration of a three-degree-of-freedom maglev vehicle on a guideway consisting of double L-shaped aluminum segments. The theory and analysis developed in this study provides basic stability characteristics and identifies future research needs for maglev systems.

The intercalation chemistry of layered iron chalcogenide superconductors

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

Vivanco, Hector K.; Rodriguez, Efrain E., E-mail: efrain@umd.edu

The iron chalcogenides FeSe and FeS are superconductors composed of two-dimensional sheets held together by van der Waals interactions, which makes them prime candidates for the intercalation of various guest species. We review the intercalation chemistry of FeSe and FeS superconductors and discuss their synthesis, structure, and physical properties. Before we review the latest work in this area, we provide a brief background on the intercalation chemistry of other inorganic materials that exhibit enhanced superconducting properties upon intercalation, which include the transition metal dichalcogenides, fullerenes, and layered cobalt oxides. From past studies of these intercalated superconductors, we discuss the rolemore » of the intercalates in terms of charge doping, structural distortions, and Fermi surface reconstruction. We also briefly review the physical and chemical properties of the host materials—mackinawite-type FeS and β-FeSe. The three types of intercalates for the iron chalcogenides can be placed in three categories: 1.) alkali and alkaline earth cations intercalated through the liquid ammonia technique; 2.) cations intercalated with organic amines such as ethylenediamine; and 3.) layered hydroxides intercalated during hydrothermal conditions. A recurring theme in these studies is the role of the intercalated guest in electron doping the chalcogenide host and in enhancing the two-dimensionality of the electronic structure by spacing the FeSe layers apart. We end this review discussing possible new avenues in the intercalation chemistry of transition metal monochalcogenides, and the promise of these materials as a unique set of new inorganic two-dimensional systems.« less

Synthesis and electrical characterization of magnetic bilayer graphene intercalate.

PubMed

Kim, Namdong; Kim, Kwang S; Jung, Naeyoung; Brus, Louis; Kim, Philip

2011-02-09

We report synthesis and transport properties of the minimal graphite intercalation compound, a ferric chloride (FeCl(3))(n) island monolayer inside bilayer graphene. Chemical doping by the intercalant is simultaneously probed by micro-Raman spectroscopy and Hall measurements. Quantum oscillations of conductivity originate from microscopic domains of intercalated and unintercalated regions. A slight upturn in resistance related to magnetic transition is observed. Two-dimensional intercalation in bilayer graphene opens new possibilities to engineer two-dimensional properties of intercalates.

Orthorhombic fulleride (CH3NH2)K3C60 close to Mott-Hubbard instability: Ab initio study

NASA Astrophysics Data System (ADS)

Potočnik, Anton; Manini, Nicola; Komelj, Matej; Tosatti, Erio; Arčon, Denis

2012-08-01

We study the electronic structure and magnetic interactions in methylamine-intercalated orthorhombic alkali-doped fullerene (CH3NH2)K3C60 within the density functional theory. As in the simpler ammonia intercalated compound (NH3)K3C60, the orthorhombic crystal-field anisotropy Δ lifts the t1u triple degeneracy at the Γ point and drives the system deep into the Mott-insulating phase. However, the computed Δ and conduction electron bandwidth W cannot alone account for the abnormally low experimental Néel temperature, TN=11 K, of the methylamine compound, compared to the much higher value TN=40 K of the ammonia one. Significant interactions between CH3NH2 and C603- are responsible for the stabilization of particular fullerene-cage distortions and the ensuing low-spin S=1/2 state. These interactions also seem to affect the magnetic properties, as interfullerene exchange interactions depend on the relative orientation of deformations of neighboring C603- molecules. For the ferro-orientational order of CH3NH2-K+ groups we find an apparent reduced dimensionality in magnetic exchange interactions, which may explain the suppressed Néel temperature. The disorder in exchange interactions caused by orientational disorder of CH3NH2-K+ groups could further contribute to this suppression.

C1-C2 instability with severe occipital headache in the setting of vertebral artery facet complex erosion.

PubMed

Taher, Fadi; Bokums, Kristaps; Aichmair, Alexander; Hughes, Alexander P

2014-05-01

An exact understanding of patient vertebral artery anatomy is essential to safely place screws at the atlanto-axial level in posterior arthrodesis. We aim to report a case of erosion of the left vertebral artery into the C1-C2 facet complex with resultant rotatory and lateral listhesis presenting with severe occipital headache. This represents a novel etiology for this diagnosis and our report illustrates technical considerations when instrumenting the C1-C2 segment. We report a case of severe occipital headache due to C1-C2 instability with resultant left C2 nerve compression in the setting of erosion of the vertebral artery into the C1-C2 facet complex. A 68-year-old woman presented with a 12-month history of progressively debilitating headache and neck pain with atlanto-axial instability. Computed tomography (CT) angiography demonstrated erosion of the left vertebral artery into the left C1-C2 facet complex. In addition, the tortuous vertebral arteries had eroded into the C2 pedicles, eliminating the possibility for posterior pedicle screw placement. The patient underwent posterior arthrodesis of C1-C2 utilizing bilateral lateral mass fixation into C1 and bilateral trans-laminar fixation into C2 with resolution of all preoperative complaints. This study constitutes the first report of a tortuous vertebral artery causing the partial destruction of a C1-C2 facet complex, as well as instability, with the clinical presentation of severe occipital headache. It hereby presents a novel etiology for both the development of C1-C2 segment instability as well as the development of occipital headache. Careful evaluation of such lesions utilizing CT angiography is important when formulating a surgical plan.

Tuning the electronic structure of graphene through alkali metal and halogen atom intercalation

NASA Astrophysics Data System (ADS)

Ahmad, Sohail; Miró, Pere; Audiffred, Martha; Heine, Thomas

2018-04-01

The deposition, intercalation and co-intercalation of heavy alkali metals and light halogens atoms in graphene mono- and bilayers have been studied using first principles density-functional calculations. Both the deposition and the intercalation of alkali metals gives rise to n-type doping due to the formation of M+-C- pairs. The co-intercalation of a 1:1 ratio of alkali metals and halogens derives into the formation of ionic pairs among the intercalated species, unaltering the electronic structure of the layered material.

The Statistical Segment Length of DNA: Opportunities for Biomechanical Modeling in Polymer Physics and Next-Generation Genomics.

PubMed

Dorfman, Kevin D

2018-02-01

The development of bright bisintercalating dyes for deoxyribonucleic acid (DNA) in the 1990s, most notably YOYO-1, revolutionized the field of polymer physics in the ensuing years. These dyes, in conjunction with modern molecular biology techniques, permit the facile observation of polymer dynamics via fluorescence microscopy and thus direct tests of different theories of polymer dynamics. At the same time, they have played a key role in advancing an emerging next-generation method known as genome mapping in nanochannels. The effect of intercalation on the bending energy of DNA as embodied by a change in its statistical segment length (or, alternatively, its persistence length) has been the subject of significant controversy. The precise value of the statistical segment length is critical for the proper interpretation of polymer physics experiments and controls the phenomena underlying the aforementioned genomics technology. In this perspective, we briefly review the model of DNA as a wormlike chain and a trio of methods (light scattering, optical or magnetic tweezers, and atomic force microscopy (AFM)) that have been used to determine the statistical segment length of DNA. We then outline the disagreement in the literature over the role of bisintercalation on the bending energy of DNA, and how a multiscale biomechanical approach could provide an important model for this scientifically and technologically relevant problem.

Simulated Cytoskeletal Collapse via Tau Degradation

PubMed Central

Sendek, Austin; Fuller, Henry R.; Hayre, N. Robert; Singh, Rajiv R. P.; Cox, Daniel L.

2014-01-01

We present a coarse-grained two dimensional mechanical model for the microtubule-tau bundles in neuronal axons in which we remove taus, as can happen in various neurodegenerative conditions such as Alzheimers disease, tauopathies, and chronic traumatic encephalopathy. Our simplified model includes (i) taus modeled as entropic springs between microtubules, (ii) removal of taus from the bundles due to phosphorylation, and (iii) a possible depletion force between microtubules due to these dissociated phosphorylated taus. We equilibrate upon tau removal using steepest descent relaxation. In the absence of the depletion force, the transverse rigidity to radial compression of the bundles falls to zero at about 60% tau occupancy, in agreement with standard percolation theory results. However, with the attractive depletion force, spring removal leads to a first order collapse of the bundles over a wide range of tau occupancies for physiologically realizable conditions. While our simplest calculations assume a constant concentration of microtubule intercalants to mediate the depletion force, including a dependence that is linear in the detached taus yields the same collapse. Applying percolation theory to removal of taus at microtubule tips, which are likely to be the protective sites against dynamic instability, we argue that the microtubule instability can only obtain at low tau occupancy, from 0.06–0.30 depending upon the tau coordination at the microtubule tips. Hence, the collapse we discover is likely to be more robust over a wide range of tau occupancies than the dynamic instability. We suggest in vitro tests of our predicted collapse. PMID:25162587

Formation and Elimination of Transform Faults on the Reykjanes Ridge

NASA Astrophysics Data System (ADS)

Martinez, Fernando; Hey, Richard

2017-04-01

The Reykjanes Ridge is a type-setting for examining processes that form and eliminate transform faults because it has undergone these events systematically within the Iceland gradient in hot-spot influence. A Paleogene change in plate motion led to the abrupt segmentation of the originally linear axis into a stair-step ridge-transform configuration. Its subsequent evolution diachronously and systematically eliminated the just-formed offsets re-establishing the original linear geometry of the ridge over the mantle, although now spreading obliquely. During segmented stages accreted crust was thinner and during unsegmented stages southward pointing V-shaped crustal ridges formed. Although mantle plume effects have been invoked to explain the changes in segmentation and crustal features, we propose that plate boundary processes can account for these changes [Martinez & Hey, EPSL, 2017]. Fragmentation of the axis was a mechanical effect of an abrupt change in plate opening direction, as observed in other areas, and did not require mantle plume temperature changes. Reassembly of the fragmented axis to its original linear configuration was controlled by a deep damp melting regime that persisted in a linear configuration following the abrupt change in opening direction. Whereas the shallow and stronger mantle of the dry melting regime broke up into a segmented plate boundary, the persistent deep linear damp melting regime guided reassembly of the ridge axis back to its original configuration by inducing asymmetric spreading of individual ridge segments. Effects of segmentation on mantle upwelling explain crustal thickness changes between segmented and unsegmented phases of spreading without mantle temperature changes. Buoyant upwelling instabilities propagate along the long linear deep melting regime driven by regional gradients in mantle properties away from Iceland. Once segmentation is eliminated, these propagating upwelling instabilities lead to crustal thickness variations forming the V-shaped ridges on the Reykjanes Ridge flanks, without requiring actual rapid radial mantle plume flow or temperature variations. Our study indicates that the Reykjanes Ridge can be used to study how plate boundary processes within a regional gradient in mantle properties lead to a range of effects on lithospheric segmentation, melt production and crustal accretion.

A method to remove intercalates from bromine and iodine intercalated carbon fibers

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh

1993-01-01

Upon exposure to room-temperature fluorine, intercalated carbon fibers (containing either bromine alone or iodine and bromine together) become heavier and less stable. For Amoco P-100 graphitized carbon fibers which were intercalated with 18 percent bromine by weight, 1 hr of fluorine exposure results in a large weight increase, but causes only a small decrease in thermal stability. More than l hr of fluorine exposure time results in small additional increases in fiber weight, but significant further decreases in fiber thermal stability. Such phenomena do not occur if the fluorine exposure is at 250 C. These observations suggest the mechanism that at room temperature, fluorine is absorbed quickly by the intercalated fibers and intercalated slowly into the fibers. Most of the original intercalates are replaced by fluorine in the process of fluorine intercalation. Under an inert environment, the bromine intercalated fibers are much more thermally stable. After 800 C vacuum heating for two weeks, the brominated fibers lost about 45 percent of their bromine, and their resistivity increased from 64 omega-cm to a range of 95 to 170 micro omega-cm. This is still much lower than the 300 micro omega-cm value for pristine P-100. For practical purposes, in order to preserve their thermal stability, brominated fibers need to be protected from exposure to fluorine at room temperature, or to any intercalate at a temperature where, upon direct contact to graphite, an intercalation compound can easily be formed.

Room-Temperature Fluorine-Induced Decrease in the Stability of Bromine and Iodine Intercalated Carbon Fibers

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh

1995-01-01

Upon exposure to room-temperature fluorine, intercalated carbon fibers (containing either bromine alone or iodine and bromine together) become heavier and less stable. For Amoco P-100 graphitized carbon fibers, which were intercalated with 18 wt percent bromine, 1 hour of fluorine exposure resulted in a large weight increase but caused only a small decrease in thermal stability. An additional 89 hours of fluorine exposure time resulted in small additional increases in fiber weight, but significant further decreases in fiber thermal stability. Such phenomena of weight increase and stability decrease do not occur if the intercalated fibers are exposed to 250 C fluorine. These observations suggest that, at room temperature, fluorine is absorbed quickly by the intercalated fibers and is intercalated slowly into the fibers. Most of the original intercalates are replaced by fluorine in the process of fluorine intercalation. In an inert environment, the bromine intercalated fibers are much more thermally stable. After 800 C vacuum heating for 2 weeks, the brominated fibers lost about 45% of their bromine, and their resistivity increased from 64 mu(Omega)-cm to a range of 95-170 mu(Omega)-cm. This is still much lower than the value of 300 mu(Omega)-cm for pristine P-100. For practical purposes, to preserve their thermal stability, brominated fibers need to be protected from exposure to fluorine at room temperature or to any intercalate at a temperature where, upon direct contact with graphite, an intercalation compound can easily be formed.

Dissecting the Dynamic Pathways of Stereoselective DNA Threading Intercalation

PubMed Central

Almaqwashi, Ali A.; Andersson, Johanna; Lincoln, Per; Rouzina, Ioulia; Westerlund, Fredrik; Williams, Mark C.

2016-01-01

DNA intercalators that have high affinity and slow kinetics are developed for potential DNA-targeted therapeutics. Although many natural intercalators contain multiple chiral subunits, only intercalators with a single chiral unit have been quantitatively probed. Dumbbell-shaped DNA threading intercalators represent the next order of structural complexity relative to simple intercalators, and can provide significant insights into the stereoselectivity of DNA-ligand intercalation. We investigated DNA threading intercalation by binuclear ruthenium complex [μ-dppzip(phen)4Ru2]4+ (Piz). Four Piz stereoisomers are defined by the chirality of the intercalating subunit (Ru(phen)2dppz) and the distal subunit (Ru(phen)2ip), respectively, each of which can be either right-handed (Δ) or left-handed (Λ). We used optical tweezers to measure single DNA molecule elongation due to threading intercalation, revealing force-dependent DNA intercalation rates and equilibrium dissociation constants. The force spectroscopy analysis provided the zero-force DNA binding affinity, the equilibrium DNA-ligand elongation Δxeq, and the dynamic DNA structural deformations during ligand association xon and dissociation xoff. We found that Piz stereoisomers exhibit over 20-fold differences in DNA binding affinity, from a Kd of 27 ± 3 nM for (Δ,Λ)-Piz to a Kd of 622 ± 55 nM for (Λ,Δ)-Piz. The striking affinity decrease is correlated with increasing Δxeq from 0.30 ± 0.02 to 0.48 ± 0.02 nm and xon from 0.25 ± 0.01 to 0.46 ± 0.02 nm, but limited xoff changes. Notably, the affinity and threading kinetics is 10-fold enhanced for right-handed intercalating subunits, and 2- to 5-fold enhanced for left-handed distal subunits. These findings demonstrate sterically dispersed transition pathways and robust DNA structural recognition of chiral intercalators, which are critical for optimizing DNA binding affinity and kinetics. PMID:27028636

Is it intelligent to intercalate? A two centre cross-sectional study exploring the value of intercalated degrees, and the possible effects of the recent tuition fee rise in England.

PubMed

Stubbs, Timothy Alan; Lightman, Elewys G; Mathieson, Peter

2013-01-24

To explore the value of intercalated degrees, including student perceptions and academic sequelae. To gauge the likely effect of the recent tuition fee rise and to identify any differences in intercalated degrees between Bristol and Sheffield universities. Cross-sectional study using questionnaires. Bristol and Sheffield Medical Schools, UK. 1484 medical students in their clinical years were e-mailed the questionnaire. 578 students responded: 291 from Bristol and 287 from Sheffield (n=578; mean age=22.41; SD 1.944; 38.9% male; 61.1% female). The response rate from previous intercalators was 52.5% from Bristol and 58.7% from Sheffield, while for non-intercalators it was 27.7% and 34.6%, respectively. (1) Student preconceptions, opinions, results and academic sequelae from intercalated degrees at both centres. (2) Students' attitudes concerning the effect of the increase in tuition fees. Those with clinical academic supervisors gained significantly more posters (p=0.0002) and publications (p<0.0001), and also showed a trend to gain more first class honours (p=0.055). Students at Sheffield had a significantly greater proportion of clinical academic supervisors than students at Bristol (p<0.0001). 89.2% said that an intercalated degree was the right decision for them; however, only 27.4% stated they would have intercalated if fees had been £9000 per annum. Students clearly value intercalated degrees, feel they gained a substantial advantage over their peers as well as skills helpful for their future careers. The rise in tuition fees is likely to reduce the number of medical students opting to undertake an intercalated degree, and could result in a further reduction in numbers following an academic path. Sheffield University have more intercalating students supervised by clinical academics. Clinical academics appear more effective as supervisors for medical students undertaking an intercalated degree in terms of results and additional academic sequelae.

Layered Compounds and Intercalation Chemistry: An Example of Chemistry and Diffusion in Solids.

ERIC Educational Resources Information Center

Whittingham, M. Stanley; Chianelli, Russell R.

1980-01-01

Considers a few areas of oxide/sulfide and intercalation-type chemistry. Discusses synthesis of the disulfides of the metals of group IVB, VB, and VIB; the intercalation reaction between lithium and titanium disulfide; other intercalates; and sulfide catalysts. (CS)

Comparison of fluoride intercalation/de-intercalation processes on graphite electrodes in aqueous and aqueous methanolic HF media

NASA Astrophysics Data System (ADS)

Noel, M.; Santhanam, R.; Francisca Flora, M.

The solvent can play a major role in the intercalation/de-intercalation process and the stability of graphite substrates towards this process. This fact is established in the present work that involves fluoride intercalation/de-intercatlation on graphite electrodes in aqueous and aqueous methanolic HF solutions where the HF concentration is varied between 1.0 and 18.0 M. In addition to cyclic voltammetry and potentiostatic polarization, open-circuit potential decay measurements, scanning electron microscopy and X-ray diffraction measurements have been employed. In general, addition of methanol and increasing concentration of HF raise the overall intercalation/de-intercalation efficiency. Methanol is adsorbed preferentially on the graphite lattice and, hence, suppresses both oxygen evolution and the formation of passive graphite oxides. In 15.0 M HF, the optimum methanol concentration is 5 vol.%. This suggests that, in addition to the adsorption effect, there is some weakening of the structured water molecules that facilitates the solvated fluoride ions for efficient intercalation.

Resolving DNA-ligand intercalation in the entropic stretching regime

NASA Astrophysics Data System (ADS)

Almaqwashi, Ali A.

Single molecule studies of DNA intercalation are typically conducted by applying stretching forces to obtain force-dependent DNA elongation measurements. The zero-force properties of DNA intercalation are determined by equilibrium and kinetic force-analysis. However, the applied stretching forces that are above the entropic regime (>5 pN) prevent DNA-DNA contact which may eliminate competitive DNA-ligand interactions. In particular, it is noted that cationic mono-intercalators investigated by single molecule force spectroscopy are mostly found to intercalate DNA with single rate, while bulk studies reported additional slower rates. Here, a proposed framework quantifies DNA intercalation by cationic ligands in competition with relatively rapid kinetic DNA-ligand aggregation. At a constant applied force in the entropic stretching regime, the analysis illustrates that DNA intercalation would be measurably optimized only within a narrow range of low ligand concentrations. As DNA intercalators are considered for potential DNA-targeted therapeutics, this analysis provides insights in tuning ligand concertation to maximize therapeutics efficiency.

Onset of superconductivity in sodium and potassium intercalated molybdenum disulphide

NASA Technical Reports Server (NTRS)

Somoano, R. B.; Rembaum, A.

1971-01-01

Molybdenum disulfide in the form of natural crystals or powder has been intercalated at -65 to -70 C with sodium and potassium using the liquid ammonia technique. All intercalated samples were found to show a superconducting transition. A plot of the percent of diamagnetic throw versus temperature indicates the possible existence of two phases in the potassium intercalated molybdenum disulfide. The onset of superconductivity in potassium and sodium intercalated molybdenite powder was found to be approximately 6.2 and approximately 4.5 K, respectively. The observed superconductivity is believed to be due to an increase in electron density as a result of intercalation.

Environmental stability of intercalated graphite fibers

NASA Technical Reports Server (NTRS)

Gaier, J. R.; Jaworske, D. A.

1985-01-01

Graphite fibers intercalated with bromine, iodine monochloride, ferric chloride, and cupric chloride were subjected to stability tests under four environments which are encountered by engineering materials in the aerospace industry: ambient laboratory conditions, as would be experienced during handling operations and terrestrial applications; high vacuum, as would be experienced in space applications; high humidity, as would be experienced in marine applications; and high temperature, as would be experienced in some processing steps and applications. Monitoring the resistance of the fibers at ambient laboratory conditions revealed that only the ferric chloride intercalated fibers were unstable, due to absorption of water from the air. All four types of intercalated fibers were unstable, due to absorption of water from the air. All four types of intercalated fibers were stable for long periods under high vacuum. Ferric chloride, cupric chloride, and iodine monochloride intercalated fibers were sensitive to high humidity conditions. All intercalated fibers began to degrade above 250 C. The order of their thermal stability, from lowest to highest, was cupric chloride, iodine monochloride, bromine, and ferric chloride. Of the four types of intercalated fibers tested, the bromine intercalated fibers appear to have the most potential for application, based on environmental stability.

Solution structure and thermodynamics of 2',5' RNA intercalation.

PubMed

Horowitz, Eric D; Lilavivat, Seth; Holladay, Benjamin W; Germann, Markus W; Hud, Nicholas V

2009-04-29

As a means to explore the influence of the nucleic acid backbone on the intercalative binding of ligands to DNA and RNA, we have determined the solution structure of a proflavine-bound 2',5'-linked octamer duplex with the sequence GCCGCGGC. This structure represents the first NMR structure of an intercalated RNA duplex, of either backbone structural isomer. By comparison with X-ray crystal structures, we have identified similarities and differences between intercalated 3',5' and 2',5'-linked RNA duplexes. First, the two forms of RNA have different sugar pucker geometries at the intercalated nucleotide steps, yet have the same interphosphate distances. Second, as in intercalated 3',5' RNA, the phosphate backbone angle zeta at the 2',5' RNA intercalation site prefers to be in the trans conformation, whereas unintercalated 2',5' and 3',5' RNA prefer the -gauche conformation. These observations provide new insights regarding the transitions required for intercalation of a phosphodiester-ribose backbone and suggest a possible contribution of the backbone to the origin of the nearest-neighbor exclusion principle. Thermodynamic studies presented for intercalation of both structural RNA isomers also reveal a surprising sensitivity of intercalator binding enthalpy and entropy to the details of RNA backbone structure.

Highly Conductive and Transparent Large-Area Bilayer Graphene Realized by MoCl5 Intercalation.

PubMed

Kinoshita, Hiroki; Jeon, Il; Maruyama, Mina; Kawahara, Kenji; Terao, Yuri; Ding, Dong; Matsumoto, Rika; Matsuo, Yutaka; Okada, Susumu; Ago, Hiroki

2017-11-01

Bilayer graphene (BLG) comprises a 2D nanospace sandwiched by two parallel graphene sheets that can be used to intercalate molecules or ions for attaining novel functionalities. However, intercalation is mostly demonstrated with small, exfoliated graphene flakes. This study demonstrates intercalation of molybdenum chloride (MoCl 5 ) into a large-area, uniform BLG sheet, which is grown by chemical vapor deposition (CVD). This study reveals that the degree of MoCl 5 intercalation strongly depends on the stacking order of the graphene; twist-stacked graphene shows a much higher degree of intercalation than AB-stacked. Density functional theory calculations suggest that weak interlayer coupling in the twist-stacked graphene contributes to the effective intercalation. By selectively synthesizing twist-rich BLG films through control of the CVD conditions, low sheet resistance (83 Ω ▫ -1 ) is realized after MoCl 5 intercalation, while maintaining high optical transmittance (≈95%). The low sheet resistance state is relatively stable in air for more than three months. Furthermore, the intercalated BLG film is applied to organic solar cells, realizing a high power conversion efficiency. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intercalation and de-intercalation pathway of proflavine through the minor and major grooves of DNA: roles of water and entropy.

PubMed

Sasikala, Wilbee D; Mukherjee, Arnab

2013-05-07

DNA intercalation is a clinically relevant biophysical process due to its potential to inhibit the growth and survival of tumor cells and microbes through the arrest of the transcription and replication processes. Extensive kinetic and thermodynamic studies have followed since the discovery of the intercalative binding mode. However, the molecular mechanism and the origin of the thermodynamic and kinetic profile of the process are still not clear. Here we have constructed the free energy landscape of intercalation, de-intercalation and dissociation from both the major and minor grooves of DNA using extensive all-atom metadynamics simulations, capturing both the free energy barriers and stability in close agreement with fluorescence kinetic experiments. In the intercalated state, an alternate orientation of proflavine is found with an almost equal stability compared to the crystal orientation, however, separated by a 5.0 kcal mol(-1) barrier that decreases as the drug approaches the groove edges. This study provides a comprehensive picture in comparison with experiments, which indicates that the intercalation and de-intercalation of proflavine happen through the major groove side, although the effective intercalation barrier increases because the path of intercalation goes through the stable (abortive) minor groove bound state, making the process a millisecond long one in excellent agreement with the experiments. The molecular origin of the higher barrier for the intercalation from the minor groove side is attributed to the desolvation energy of DNA and the loss of entropy, while the barrier from the major groove, in the absence of desolvation energy, is primarily entropic.

Reshaping the Energy Landscape Transforms the Mechanism and Binding Kinetics of DNA Threading Intercalation.

PubMed

Clark, Andrew G; Naufer, M Nabuan; Westerlund, Fredrik; Lincoln, Per; Rouzina, Ioulia; Paramanathan, Thayaparan; Williams, Mark C

2018-02-06

Molecules that bind DNA via threading intercalation show high binding affinity as well as slow dissociation kinetics, properties ideal for the development of anticancer drugs. To this end, it is critical to identify the specific molecular characteristics of threading intercalators that result in optimal DNA interactions. Using single-molecule techniques, we quantify the binding of a small metal-organic ruthenium threading intercalator (Δ,Δ-B) and compare its binding characteristics to a similar molecule with significantly larger threading moieties (Δ,Δ-P). The binding affinities of the two molecules are the same, while comparison of the binding kinetics reveals significantly faster kinetics for Δ,Δ-B. However, the kinetics is still much slower than that observed for conventional intercalators. Comparison of the two threading intercalators shows that the binding affinity is modulated independently by the intercalating section and the binding kinetics is modulated by the threading moiety. In order to thread DNA, Δ,Δ-P requires a "lock mechanism", in which a large length increase of the DNA duplex is required for both association and dissociation. In contrast, measurements of the force-dependent binding kinetics show that Δ,Δ-B requires a large DNA length increase for association but no length increase for dissociation from DNA. This contrasts strongly with conventional intercalators, for which almost no DNA length change is required for association but a large DNA length change must occur for dissociation. This result illustrates the fundamentally different mechanism of threading intercalation compared with conventional intercalation and will pave the way for the rational design of therapeutic drugs based on DNA threading intercalation.

Effectiveness of Co intercalation between Graphene and Ir(1 1 1)

NASA Astrophysics Data System (ADS)

Carlomagno, I.; Drnec, J.; Scaparro, A. M.; Cicia, S.; Mobilio, S.; Felici, R.; Meneghini, C.

2018-04-01

Graphene can be used to avoid the oxidation of metallic films. This work explores the effectiveness of such stabilizing effect on Cobalt (Co) films intercalated between Graphene and Ir(1 1 1). After intercalation at 300 °C, two Co films are exposed to ambient pressure and investigated using Co-K edge X-ray Absorption Near Edge Spectroscopy. The formation of a disordered oxide phase is observed, and associated to the presence of some non-intercalated Co. Further annealing at 500 °C causes the oxide reduction to metallic Co which further intercalates below the Graphene. Once the intercalation is completed, Graphene prevents the Co from oxidation under ambient pressure conditions.

Crack Front Segmentation and Facet Coarsening in Mixed-Mode Fracture

NASA Astrophysics Data System (ADS)

Chen, Chih-Hung; Cambonie, Tristan; Lazarus, Veronique; Nicoli, Matteo; Pons, Antonio J.; Karma, Alain

2015-12-01

A planar crack generically segments into an array of "daughter cracks" shaped as tilted facets when loaded with both a tensile stress normal to the crack plane (mode I) and a shear stress parallel to the crack front (mode III). We investigate facet propagation and coarsening using in situ microscopy observations of fracture surfaces at different stages of quasistatic mixed-mode crack propagation and phase-field simulations. The results demonstrate that the bifurcation from propagating a planar to segmented crack front is strongly subcritical, reconciling previous theoretical predictions of linear stability analysis with experimental observations. They further show that facet coarsening is a self-similar process driven by a spatial period-doubling instability of facet arrays.

Nano-scaled top-down of bismuth chalcogenides based on electrochemical lithium intercalation

NASA Astrophysics Data System (ADS)

Chen, Jikun; Zhu, Yingjie; Chen, Nuofu; Liu, Xinling; Sun, Zhengliang; Huang, Zhenghong; Kang, Feiyu; Gao, Qiuming; Jiang, Jun; Chen, Lidong

2011-12-01

A two-step method has been used to fabricate nano-particles of layer-structured bismuth chalcogenide compounds, including Bi2Te3, Bi2Se3, and Bi2Se0.3Te2.7, through a nano-scaled top-down route. In the first step, lithium (Li) atoms are intercalated between the van der Waals bonded quintuple layers of bismuth chalcogenide compounds by controllable electrochemical process inside self-designed lithium ion batteries. And in the second step, the Li intercalated bismuth chalcogenides are subsequently exposed to ethanol, in which process the intercalated Li atoms would explode like atom-scaled bombs to exfoliate original microscaled powder into nano-scaled particles with size around 10 nm. The influence of lithium intercalation speed and amount to three types of bismuth chalcogenide compounds are compared and the optimized intercalation conditions are explored. As to maintain the phase purity of the final nano-particle product, the intercalation lithium amount should be well controlled in Se contained bismuth chalcogenide compounds. Besides, compared with binary bismuth chalcogenide compound, lower lithium intercalation speed should be applied in ternary bismuth chalcogenide compound.

Housing instability and alcohol problems during the 2007-2009 US recession: the moderating role of perceived family support.

PubMed

Murphy, Ryan D; Zemore, Sarah E; Mulia, Nina

2014-02-01

The 2007-2009 US economic recession was marked by unprecedented rates of housing instability and relatively little is known about how this instability impacted alcohol problems. While previous studies have linked homelessness to increased rates of alcohol use and abuse, housing instability during a recession impacts a much larger segment of the population and usually does not result in homelessness. Using a nationally representative sample of US adults, this study examines the association between housing instability during the recession and alcohol outcomes. Additionally, we assess whether this association is moderated by perceived family support. In multivariate negative binomial regressions, both trouble paying the rent/mortgage (vs. stable housing) and lost (vs. stable) housing were associated with experiencing more negative drinking consequences and alcohol dependence symptoms. However, these associations were moderated by perceived family support. In contrast to those with low perceived family support, participants with high perceived family support reported relatively few alcohol problems, irrespective of housing instability. Furthermore, while job loss was strongly associated with alcohol problems in univariate models, no significant associations between job loss and alcohol outcomes were observed in multivariate models that included indicators of housing instability. Findings point to the importance of the informal safety net and suggest that alcohol screening and abuse prevention efforts should be intensified during periods of recession, particularly among those who experience housing instability.

Mechanisms of small molecule–DNA interactions probed by single-molecule force spectroscopy

PubMed Central

Almaqwashi, Ali A.; Paramanathan, Thayaparan; Rouzina, Ioulia; Williams, Mark C.

2016-01-01

There is a wide range of applications for non-covalent DNA binding ligands, and optimization of such interactions requires detailed understanding of the binding mechanisms. One important class of these ligands is that of intercalators, which bind DNA by inserting aromatic moieties between adjacent DNA base pairs. Characterizing the dynamic and equilibrium aspects of DNA-intercalator complex assembly may allow optimization of DNA binding for specific functions. Single-molecule force spectroscopy studies have recently revealed new details about the molecular mechanisms governing DNA intercalation. These studies can provide the binding kinetics and affinity as well as determining the magnitude of the double helix structural deformations during the dynamic assembly of DNA–ligand complexes. These results may in turn guide the rational design of intercalators synthesized for DNA-targeted drugs, optical probes, or integrated biological self-assembly processes. Herein, we survey the progress in experimental methods as well as the corresponding analysis framework for understanding single molecule DNA binding mechanisms. We discuss briefly minor and major groove binding ligands, and then focus on intercalators, which have been probed extensively with these methods. Conventional mono-intercalators and bis-intercalators are discussed, followed by unconventional DNA intercalation. We then consider the prospects for using these methods in optimizing conventional and unconventional DNA-intercalating small molecules. PMID:27085806

Is it intelligent to intercalate? A two centre cross-sectional study exploring the value of intercalated degrees, and the possible effects of the recent tuition fee rise in England

PubMed Central

Stubbs, Timothy Alan; Lightman, Elewys G; Mathieson, Peter

2013-01-01

Aims and objectives To explore the value of intercalated degrees, including student perceptions and academic sequelae. To gauge the likely effect of the recent tuition fee rise and to identify any differences in intercalated degrees between Bristol and Sheffield universities. Design Cross-sectional study using questionnaires. Setting Bristol and Sheffield Medical Schools, UK. Participants 1484 medical students in their clinical years were e-mailed the questionnaire. 578 students responded: 291 from Bristol and 287 from Sheffield (n=578; mean age=22.41; SD 1.944; 38.9% male; 61.1% female). The response rate from previous intercalators was 52.5% from Bristol and 58.7% from Sheffield, while for non-intercalators it was 27.7% and 34.6%, respectively. Main outcome measures (1) Student preconceptions, opinions, results and academic sequelae from intercalated degrees at both centres. (2) Students’ attitudes concerning the effect of the increase in tuition fees. Results Those with clinical academic supervisors gained significantly more posters (p=0.0002) and publications (p<0.0001), and also showed a trend to gain more first class honours (p=0.055). Students at Sheffield had a significantly greater proportion of clinical academic supervisors than students at Bristol (p<0.0001). 89.2% said that an intercalated degree was the right decision for them; however, only 27.4% stated they would have intercalated if fees had been £9000 per annum. Conclusions Students clearly value intercalated degrees, feel they gained a substantial advantage over their peers as well as skills helpful for their future careers. The rise in tuition fees is likely to reduce the number of medical students opting to undertake an intercalated degree, and could result in a further reduction in numbers following an academic path. Sheffield University have more intercalating students supervised by clinical academics. Clinical academics appear more effective as supervisors for medical students undertaking an intercalated degree in terms of results and additional academic sequelae. PMID:23355672

Dynamics of DNA/intercalator complexes

NASA Astrophysics Data System (ADS)

Schurr, J. M.; Wu, Pengguang; Fujimoto, Bryant S.

1990-05-01

Complexes of linear and supercoiled DNAs with different intercalating dyes are studied by time-resolved fluorescence polarization anisotropy using intercalated ethidium as the probe. Existing theory is generalized to take account of excitation transfer between intercalated ethidiums, and Forster theory is shown to be valid in this context. The effects of intercalated ethidium, 9-aminoacridine, and proflavine on the torsional rigidity of linear and supercoiled DNAs are studied up to rather high binding ratios. Evidence is presented that metastable secondary structure persists in dye-relaxed supercoiled DNAs, which contradicts the standard model of supercoiled DNAs.

A Novel Battery Cathode Material Based on intercalation Chemistry: Redox Reactions of the 2,5-Dimercapto-1,3,4-Thiadiazole/V2O5 Xerogel System

DTIC Science & Technology

1998-06-29

of some interstitial water during intercalation of the disulfide polymer of DMcT. Elemental analysis gives a composition for the intercalation...the disulfide polymer of DMcT. Elemental analysis gives a composition for the intercalation material of [(polyDMcT)o25*V205𔃻.4H20]. The cyclic...13.5 A). This change is consistent with loss of some interstitial water during intercalation of the disulfide polymer of DMcT. Elemental analysis

Structure and thermal decomposition of sulfated β-cyclodextrin intercalated in a layered double hydroxide

NASA Astrophysics Data System (ADS)

Wang, Ji; Wei, Min; Rao, Guoying; Evans, David G.; Duan, Xue

2004-01-01

The sodium salt of hexasulfated β-cyclodextrin has been synthesized and intercalated into a magnesium-aluminum layered double hydroxide by ion exchange. The structure, composition and thermal decomposition behavior of the intercalated material have been studied by variable temperature X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma emission spectroscopy (ICP), and thermal analysis (TG-DTA) and a model for the structure has been proposed. The thermal stability of the intercalated sulfated β-cyclodextrin is significantly enhanced compared with the pure form before intercalation.

Controlled release formulation of an anti-depression drug based on a L-phenylalanate-zinc layered hydroxide intercalation compound

NASA Astrophysics Data System (ADS)

Hashim, Norhayati; Sharif, Sharifah Norain Mohd; Isa, Illyas Md; Hamid, Shahidah Abdul; Hussein, Mohd Zobir; Bakar, Suriani Abu; Mamat, Mazidah

2017-06-01

The intercalation of L-phenylalanate (LP) into the interlayer gallery of zinc layered hydroxide (ZLH) has been successfully executed using a simple direct reaction method. The synthesised intercalation compound, zinc layered hydroxide-L-phenylalanate (ZLH-LP), was characterised using PXRD, FTIR, CHNS, ICP-OES, TGA/DTG, FESEM and TEM. The PXRD patterns of the intercalation compound demonstrate an intense and symmetrical peak, indicating a well-ordered crystalline layered structure. The appearance of an intercalation peak at a low angle of 2θ with a basal spacing of 16.3 Å, signifies the successful intercalation of the L-phenylalanate anion into the interlayer gallery of the host. The intercalation is also validated by FTIR spectroscopy and CHNS elemental analysis. Thermogravimetric analysis confirms that the ZLH-LP intercalation compound has higher thermal stability than the pristine L-phenylalanine. The observed percentage of L-phenylalanate accumulated release varies in each release media, with 84.5%, 79.8%, 63.8% and 61.8% release in phosphate buffer saline (PBS) solution at pH 4.8, deionised water, PBS solution at pH 7.4 and NaCl solution, respectively. The release behaviour of LP from its intercalation compounds in deionised water and PBS solution at pH 4.8 follows pseudo second order, whereas in NaCl solution and PBS solution at pH 7.4, it follows the parabolic diffusion model. This study shows that the synthesised ZLH-LP intercalation compound can be used for the formation of a new generation of materials for targeted drug release with controlled release properties.

The staging mechanism of AlCl4 intercalation in a graphite electrode for an aluminium-ion battery.

PubMed

Bhauriyal, Preeti; Mahata, Arup; Pathak, Biswarup

2017-03-15

Identifying a suitable electrode material with desirable electrochemical properties remains a primary challenge for rechargeable Al-ion batteries. Recently an ultrafast rechargeable Al-ion battery was reported with high charge/discharge rate, (relatively) high discharge voltage and high capacity that uses a graphite-based cathode. Using calculations from first-principles, we have investigated the staging mechanism of AlCl 4 intercalation into bulk graphite and evaluated the stability, specific capacity and voltage profile of AlCl 4 intercalated compounds. Ab initio molecular dynamics is performed to investigate the thermal stability of AlCl 4 intercalated graphite structures. Our voltage profiles show that the first AlCl 4 intercalation step could be a more sluggish step than the successive intercalation steps. However, the diffusion of AlCl 4 is very fast in the expanded graphite host layers with a diffusion barrier of ∼0.01 eV, which justifies the ultrafast charging rate of a graphite based Al-ion battery. And such an AlCl 4 intercalated battery provides an average voltage of 2.01-2.3 V with a maximum specific capacity of 69.62 mA h g -1 , which is excellent for anion intercalated batteries. Our density of states and Bader charge analysis shows that the AlCl 4 intercalation into the bulk graphite is a charging process. Hence, we believe that our present study will be helpful in understanding the staging mechanism of AlCl 4 intercalation into graphite-like layered electrodes for Al-ion batteries, thus encouraging further experimental work.

Optical determination of the electronic coupling and intercalation geometry of thiazole orange homodimer in DNA

NASA Astrophysics Data System (ADS)

Cunningham, Paul D.; Bricker, William P.; Díaz, Sebastián A.; Medintz, Igor L.; Bathe, Mark; Melinger, Joseph S.

2017-08-01

Sequence-selective bis-intercalating dyes exhibit large increases in fluorescence in the presence of specific DNA sequences. This property makes this class of fluorophore of particular importance to biosensing and super-resolution imaging. Here we report ultrafast transient anisotropy measurements of resonance energy transfer (RET) between thiazole orange (TO) molecules in a complex formed between the homodimer TOTO and double-stranded (ds) DNA. Biexponential homo-RET dynamics suggest two subpopulations within the ensemble: 80% intercalated and 20% non-intercalated. Based on the application of the transition density cube method to describe the electronic coupling and Monte Carlo simulations of the TOTO/dsDNA geometry, the dihedral angle between intercalated TO molecules is estimated to be 81° ± 5°, corresponding to a coupling strength of 45 ± 22 cm-1. Dye intercalation with this geometry is found to occur independently of the underlying DNA sequence, despite the known preference of TOTO for the nucleobase sequence CTAG. The non-intercalated subpopulation is inferred to have a mean inter-dye separation distance of 19 Å, corresponding to coupling strengths between 0 and 25 cm-1. This information is important to enable the rational design of energy transfer systems that utilize TOTO as a relay dye. The approach used here is generally applicable to determining the electronic coupling strength and intercalation configuration of other dimeric bis-intercalators.

Evaluation and optimization of the conditions for an improved ferulic acid intercalation into a synthetic lamellar anionic clay.

PubMed

Schoubben, Aurélie; Blasi, Paolo; Giovagnoli, Stefano; Nocchetti, Morena; Ricci, Maurizio; Perioli, Luana; Rossi, Carlo

2006-03-01

The aim of the study is to optimize the intercalation conditions of ferulic acid (FERH), an antioxidant compound, into Mg-Al-hydrotalcite for a safe skin photoprotection. The intercalation products were prepared incubating hydrotalcite (HTlc) in aqueous solutions of FERH sodium salt at different temperatures over 4 and 8 days. Quantitative determination of intercalated FERH was performed by thermogravimetric analysis and morphology by scanning electron microscopy (SEM). FERH stability study was carried out at different pHs and temperatures. FERH was analyzed by reversed phase-high-performance liquid chromatography. Response surface methods (RSMs) were used to assess optimal intercalation conditions and FERH stability. In all intercalation products, FERH content was found to be about 48% w/w except when the intercalation process was carried out at 52 degrees C for 8 days and at 60 degrees C for both 4 and 8 days, which resulted to be 40.39, 39.99, and 34.99%, respectively. The RSM designs showed that intercalation improvement can be achieved by working at pH 6, at temperatures below 40 degrees C, and over 4 days of incubation. The optimal conditions for a proper FERH intercalation were assessed. The development of a new optimized protocol may improve HTlc-FER complex performances and safety by augmenting dosage and reducing the presence of harmful reactive species in the final formulation.

77 FR 73345 - Safety Standard for Bedside Sleepers

Federal Register 2010, 2011, 2012, 2013, 2014

2012-12-10

... product-related issues, such as non- levelness of the product (two reports), instability of leg extensions...) Segmented Mattress Flatness Requirement and Test Method; (2) Removable Bassinet Bed Stability; and (3) Stability Test Dummy. Because bedside sleepers are already required to be tested to the bassinet standard...

Discriminating Intercalative Effects of Threading Intercalator Nogalamycin, from Classical Intercalator Daunomycin, Using Single Molecule Atomic Force Spectroscopy.

PubMed

Banerjee, T; Banerjee, S; Sett, S; Ghosh, S; Rakshit, T; Mukhopadhyay, R

2016-01-01

DNA threading intercalators are a unique class of intercalating agents, albeit little biophysical information is available on their intercalative actions. Herein, the intercalative effects of nogalamycin, which is a naturally-occurring DNA threading intercalator, have been investigated by high-resolution atomic force microscopy (AFM) and spectroscopy (AFS). The results have been compared with those of the well-known chemotherapeutic drug daunomycin, which is a non-threading classical intercalator bearing structural similarity to nogalamycin. A comparative AFM assessment revealed a greater increase in DNA contour length over the entire incubation period of 48 h for nogalamycin treatment, whereas the contour length increase manifested faster in case of daunomycin. The elastic response of single DNA molecules to an externally applied force was investigated by the single molecule AFS approach. Characteristic mechanical fingerprints in the overstretching behaviour clearly distinguished the nogalamycin/daunomycin-treated dsDNA from untreated dsDNA-the former appearing less elastic than the latter, and the nogalamycin-treated DNA distinguished from the daunomycin-treated DNA-the classically intercalated dsDNA appearing the least elastic. A single molecule AFS-based discrimination of threading intercalation from the classical type is being reported for the first time.

Discriminating Intercalative Effects of Threading Intercalator Nogalamycin, from Classical Intercalator Daunomycin, Using Single Molecule Atomic Force Spectroscopy

PubMed Central

Sett, S.; Ghosh, S.; Rakshit, T.; Mukhopadhyay, R.

2016-01-01

DNA threading intercalators are a unique class of intercalating agents, albeit little biophysical information is available on their intercalative actions. Herein, the intercalative effects of nogalamycin, which is a naturally-occurring DNA threading intercalator, have been investigated by high-resolution atomic force microscopy (AFM) and spectroscopy (AFS). The results have been compared with those of the well-known chemotherapeutic drug daunomycin, which is a non-threading classical intercalator bearing structural similarity to nogalamycin. A comparative AFM assessment revealed a greater increase in DNA contour length over the entire incubation period of 48 h for nogalamycin treatment, whereas the contour length increase manifested faster in case of daunomycin. The elastic response of single DNA molecules to an externally applied force was investigated by the single molecule AFS approach. Characteristic mechanical fingerprints in the overstretching behaviour clearly distinguished the nogalamycin/daunomycin-treated dsDNA from untreated dsDNA—the former appearing less elastic than the latter, and the nogalamycin-treated DNA distinguished from the daunomycin-treated DNA—the classically intercalated dsDNA appearing the least elastic. A single molecule AFS-based discrimination of threading intercalation from the classical type is being reported for the first time. PMID:27183010

Carbon dioxide intercalation in Na-fluorohectorite clay at near-ambient conditions

NASA Astrophysics Data System (ADS)

Fossum, Jon Otto; Hemmen, Henrik; Rolseth, Erlend G.; Fonseca, Davi; Lindbo Hansen, Elisabeth; Plivelic, Tomas

2012-02-01

A molecular dynamics study by Cygan et al.[1] shows the possibility of intercalation and retention of CO2 in smectite clays at 37 ^oC and 200 bar, which suggests that clay minerals may prove suitable for carbon capture and carbon dioxide sequestration. In this work we show from x-ray diffraction measurements that gaseous CO2 intercalates into the interlayer space of the synthetic smectite clay Na-fluorohectorite. The mean interlayer distance of the clay when CO2 is intercalated is 12.5 å at -20 C and 15 bar. The magnitude of the expansion of the interlayer upon intercalation is indistinguishable from that of the dehydrated-monohydrated intercalation of H2O, but this possibility is ruled out by careful repeating the measurements exposing the clay to nitrogen gas. The dynamics of the CO2 intercalation process displays a higher intercalation rate at increased pressure, and the rate is several orders of magnitude slower than that of water or vapor at ambient pressure and temperature.[4pt] [1] Cygan, R. T.; Romanov, V. N.; Myshakin, E. M. Natural materials for carbon capture; Techincal report SAND2010-7217; Sandia National Laboratories: Albuquerque, New Mexico, November, 2010.

Electrochemical Control of Copper Intercalation into Nanoscale Bi 2Se 3

DOE PAGES

Zhang, Jinsong; Sun, Jie; Li, Yanbin; ...

2017-02-20

Intercalation of exotic atoms or molecules into the layered materials remains an extensively investigated subject in current physics and chemistry. However, traditionally melt-growth and chemical interaction strategies are either limited by insufficiency of intercalant concentrations or destitute of accurate controllability. Here, we have developed a general electrochemical intercalation method to efficaciously regulate the concentration of zerovalent copper atoms into layered Bi 2Se 3, followed by comprehensive experimental characterization and analyses. Up to 57% copper atoms (Cu 6.7Bi 2Se 3) can be intercalated with no disruption to the host lattice. Meanwhile the unconventional resistance dip accompanied by a hysteresis loop belowmore » 40 K, as well as the emergence of new Raman peak in Cu xBi 2Se 3, is a distinct manifestation of the interplay between intercalated Cu atoms with Bi 2Se 3 host. Furthermore, our work demonstrates a new methodology to study fundamentally new and unexpected physical behaviors in intercalated metastable materials.« less

Synthesis and Characterization of Highly Intercalated Graphite Bisulfate

NASA Astrophysics Data System (ADS)

Salvatore, Marcella; Carotenuto, Gianfranco; De Nicola, Sergio; Camerlingo, Carlo; Ambrogi, Veronica; Carfagna, Cosimo

2017-03-01

Different chemical formulations for the synthesis of highly intercalated graphite bisulfate have been tested. In particular, nitric acid, potassium nitrate, potassium dichromate, potassium permanganate, sodium periodate, sodium chlorate, and hydrogen peroxide have been used in this synthesis scheme as the auxiliary reagent (oxidizing agent). In order to evaluate the presence of delamination, and pre-expansion phenomena, and the achieved intercalation degree in the prepared samples, the obtained graphite intercalation compounds have been characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray powder diffraction (XRD), infrared spectroscopy (FT-IR), micro-Raman spectroscopy ( μ-RS), and thermal analysis (TGA). Delamination and pre-expansion phenomena were observed only for nitric acid, sodium chlorate, and hydrogen peroxide, while the presence of strong oxidizers (KMnO4, K2Cr2O7) led to stable graphite intercalation compounds. The largest content of intercalated bisulfate is achieved in the intercalated compounds obtained from NaIO4 and NaClO3.

Synthesis and Characterization of Highly Intercalated Graphite Bisulfate.

PubMed

Salvatore, Marcella; Carotenuto, Gianfranco; De Nicola, Sergio; Camerlingo, Carlo; Ambrogi, Veronica; Carfagna, Cosimo

2017-12-01

Different chemical formulations for the synthesis of highly intercalated graphite bisulfate have been tested. In particular, nitric acid, potassium nitrate, potassium dichromate, potassium permanganate, sodium periodate, sodium chlorate, and hydrogen peroxide have been used in this synthesis scheme as the auxiliary reagent (oxidizing agent). In order to evaluate the presence of delamination, and pre-expansion phenomena, and the achieved intercalation degree in the prepared samples, the obtained graphite intercalation compounds have been characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray powder diffraction (XRD), infrared spectroscopy (FT-IR), micro-Raman spectroscopy (μ-RS), and thermal analysis (TGA). Delamination and pre-expansion phenomena were observed only for nitric acid, sodium chlorate, and hydrogen peroxide, while the presence of strong oxidizers (KMnO 4 , K 2 Cr 2 O 7 ) led to stable graphite intercalation compounds. The largest content of intercalated bisulfate is achieved in the intercalated compounds obtained from NaIO 4 and NaClO 3 .

Dynamic stability of maglev systems

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

Cai, Y.; Chen, S.S.; Mulcahy, T.M.

1992-09-01

Since the occurrence of dynamic instabilities is not acceptable for any commercial maglev systems, it is important to consider the dynamic instability in the development of all maglev systems. This study is to consider the stability of maglev systems based on experimental data, scoping calculations and simple mathematical models. Divergence and flutter are obtained for coupled vibration of a three-degree-of-freedom maglev vehicle on the guideway which consists of double L-shaped aluminum segments attached to a rotating wheel. The theory and analysis developed in this study provides basic stability characteristics and identifies future research needs for maglev system.

Stacking interactions and DNA intercalation

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

Li, Dr. Shen; Cooper, Valentino R; Thonhauser, Prof. Timo

2009-01-01

The relationship between stacking interactions and the intercalation of proflavine and ellipticine within DNA is investigated using a nonempirical van der Waals density functional for the correlation energy. Our results, employing a binary stack model, highlight fundamental, qualitative differences between base-pair base-pair interactions and that of the stacked intercalator base pair system. Most notable result is the paucity of torque which so distinctively defines the Twist of DNA. Surprisingly, this model, when combined with a constraint on the twist of the surrounding base-pair steps to match the observed unwinding of the sugar-phosphate backbone, was sufficient for explaining the experimentally observedmore » proflavine intercalator configuration. Our extensive mapping of the potential energy surface of base-pair intercalator interactions can provide valuable information for future nonempirical studies of DNA intercalation dynamics.« less

Metal intercalation-induced selective adatom mass transport on graphene

DOE PAGES

Liu, Xiaojie; Wang, Cai -Zhuang; Hupalo, Myron; ...

2016-03-29

Recent experiments indicate that metal intercalation is a very effective method to manipulate the graphene-adatom interaction and control metal nanostructure formation on graphene. A key question is mass transport, i.e., how atoms deposited uniformly on graphene populate different areas depending on the local intercalation. Using first-principles calculations, we show that partially intercalated graphene, with a mixture of intercalated and pristine areas, can induce an alternating electric field because of the spatial variations in electron doping, and thus, an oscillatory electrostatic potential. As a result, this alternating field can change normal stochastic adatom diffusion to biased diffusion, leading to selective massmore » transport and consequent nucleation, on either the intercalated or pristine areas, depending on the charge state of the adatoms.« less

Cobalt intercalation at the graphene/iridium(111) interface: Influence of rotational domains, wrinkles, and atomic steps

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

Vlaic, S.; Kimouche, A.; Coraux, J.

Using low-energy electron microscopy, we study Co intercalation under graphene grown on Ir(111). Depending on the rotational domain of graphene on which it is deposited, Co is found intercalated at different locations. While intercalated Co is observed preferentially at the substrate step edges below certain rotational domains, it is mostly found close to wrinkles below other domains. These results indicate that curved regions (near substrate atomic steps and wrinkles) of the graphene sheet facilitate Co intercalation and suggest that the strength of the graphene/Ir interaction determines which pathway is energetically more favorable.

Intercalated degrees, learning styles, and career preferences: prospective longitudinal study of UK medical students

PubMed Central

McManus, I C; Richards, P; Winder, B C

1999-01-01

Objectives To assess the effects of taking an intercalated degree (BSc) on the study habits and learning styles of medical students and on their interest in a career in medical research. Design Longitudinal questionnaire study of medical students at application to medical school and in their final year. Setting All UK medical schools. Participants 6901 medical school applicants for admission in 1991 were studied in the autumn of 1990. 3333 entered medical school in 1991 or 1992, and 2695 who were due to qualify in 1996 or 1997 were studied 3 months before the end of their clinical course. Response rates were 92% for applicants and 56% for final year students. Main outcome measures Study habits (surface, deep, and strategic learning style) and interest in different medical careers, including medical research. Identical questions were used at time of application and in final year. Results Students who had taken an intercalated degree had higher deep and strategic learning scores than at application to medical school. Those with highest degree classes had higher strategic and deep learning scores and lower surface learning scores. Students taking intercalated degrees showed greater interest in careers in medical research and laboratory medicine and less interest in general practice than their peers. The effects of the course on interest in medical research and learning styles were independent. The effect of the intercalated degree was greatest in schools where relatively few students took intercalated degrees. Conclusions Intercalated degrees result in a greater interest in research careers and higher deep and strategic learning scores. However, the effects are much reduced in schools where most students intercalate a degree. Introduction of intercalated degrees for all medical students without sufficient resources may not therefore achieve its expected effects. Key messagesAlthough intercalated degrees are well established, little is known about their effect on medical studentsIn this longitudinal study final year students who had taken intercalated degree were more interested in medical research, and had higher deep and strategic learning style scores than other studentsThe effects of the intercalated degree were dose dependent, being greatest in those gaining a first class degreeThe effects of the intercalated degree were greatest in medical schools where a relatively small proportion of medical students took the degree.Differences between medical schools are most easily explained by resource dilution PMID:10463892

78 FR 63019 - Safety Standard for Bassinets and Cradles

Federal Register 2010, 2011, 2012, 2013, 2014

2013-10-23

... directly attributable to product stability, the instability of the product, in many incidents, was to blame... stability test procedure, and (2) the addition of new provisions for a segmented mattress flatness test and a removable bed stability requirement. In this document, the Commission is issuing a safety standard...

Identification of neuroanatomic circuits from spinal cord to stomach in mouse: retrograde transneuronal viral tracing study.

PubMed

Ye, Da-Wei; Liu, Cheng; Tian, Xue-Bi; Xiang, Hong-Bing

2014-01-01

To determine the spinal innervation and neuronal connections is important for studying gastric carbohydrate metabolism and motor responses. Neurons involved in the efferent control of the stomach were identified following visualization of pseudorabies virus (PRV)-614 retrograde tracing. PRV-614 was injected into the ventral stomach wall in 13 adult C57BL/6J strain male mice. On the fifth day postinjection, animals were humanely sacrificed, and spinal cords were removed and sectioned, and processed for PRV visualization. The virus injected into the ventral stomach wall was specifically transported to the thoracic spinal cord. At 5 d after injection of the PRV-614, stomach enlargement and tissue edema were found, and PRV-614 positive cells were found in the intermediolateral cell column, the intercalates nucleus or the central autonomic nucleus of spinal cord segments T3 to L1, and major PRV-614 labeled cells were focused in the T6-10 segment. Our results revealed neuroanatomical circuits between stomach and the spinal intermediolateral cell column neurons.

Intercalation studies of zinc hydroxide chloride: Ammonia and amino acids

NASA Astrophysics Data System (ADS)

Arízaga, Gregorio Guadalupe Carbajal

2012-01-01

Zinc hydroxide chloride (ZHC) is a layered hydroxide salt with formula Zn5(OH)8Cl2·2H2O. It was tested as intercalation matrix for the first time and results were compared with intercalation products of the well-known zinc hydroxide nitrate and a Zn/Al layered double hydroxide. Ammonia was intercalated into ZHC, while no significant intercalation occurred in ZHN. Aspartic acid intercalation was only achieved by co-precipitation at pH=10 with ZHC and pH=8 with zinc hydroxide nitrate. Higher pH resistance in ZHC favored total deprotonation of both carboxylic groups of the Asp molecule. ZHC conferred more thermal protection against Asp combustion presenting exothermic peaks even at 452 °C while the exothermic event in ZHN was 366 °C and in the LDH at 276 °C.

Ethidium and proflavine binding to a 2',5'-linked RNA duplex.

PubMed

Horowitz, Eric D; Hud, Nicholas V

2006-12-06

Despite over 40 years of physical investigations, fundamental questions persist regarding the energetics of RNA and DNA intercalation. The dramatic unwinding of a nucleic acid duplex upon intercalation immediately suggests that the nucleic acid backbone should play a significant role in dictating the free energy of intercalation. However, the contribution of the backbone to intercalation free energy is difficult to appreciate given the intertwined energetics associated with intercalation (e.g., pi-pi stacking and solvent effects). Fluorescence titrations were used to determine the association constants of two known intercalators, proflavine and ethidium, for duplex 2',5'-linked RNA. Proflavine was found to bind 2',5' RNA with an association constant 25-fold greater than that measured for standard, 3',5'-linked RNA. In contrast, ethidium binds 2',5' RNA less favorably than standard RNA.

Failure of the human lumbar motion-segments resulting from anterior shear fatigue loading

PubMed Central

SKRZYPIEC, Daniel M.; NAGEL, Katrin; SELLENSCHLOH, Kay; KLEIN, Anke; PÜSCHEL, Klaus; MORLOCK, Michael M.; HUBER, Gerd

2016-01-01

An in-vitro experiment was designed to investigate the mode of failure following shear fatigue loading of lumbar motion-segments. Human male lumbar motion-segments (age 32–42 years, n=6) were immersed in Ringer solution at 37°C and repeatedly loaded, using a modified materials testing machine. Fatigue loading consisted of a sinusoidal shear load from 0 N to 1,500 N (750 N±750 N) applied to the upper vertebra of the motion-segment, at a frequency of 5 Hz. During fatigue experiments, several failure events were observed in the dynamic creep curves. Post-test x-ray, CT and dissection revealed that all specimens had delamination of the intervertebral disc. Anterior shear fatigue predominantly resulted in fracture of the apophyseal processes of the upper vertebrae (n=4). Exposure to the anterior shear fatigue loading caused motion-segment instability and resulted in vertebral slip corresponding to grade I and ‘mild’ grade II spondylolisthesis, as observed clinically. PMID:26829975

Segmentation in cohesive systems constrained by elastic environments

NASA Astrophysics Data System (ADS)

Novak, I.; Truskinovsky, L.

2017-04-01

The complexity of fracture-induced segmentation in elastically constrained cohesive (fragile) systems originates from the presence of competing interactions. The role of discreteness in such phenomena is of interest in a variety of fields, from hierarchical self-assembly to developmental morphogenesis. In this paper, we study the analytically solvable example of segmentation in a breakable mass-spring chain elastically linked to a deformable lattice structure. We explicitly construct the complete set of local minima of the energy in this prototypical problem and identify among them the states corresponding to the global energy minima. We show that, even in the continuum limit, the dependence of the segmentation topology on the stretching/pre-stress parameter in this problem takes the form of a devil's type staircase. The peculiar nature of this staircase, characterized by locking in rational microstructures, is of particular importance for biological applications, where its structure may serve as an explanation of the robustness of stress-driven segmentation. This article is part of the themed issue 'Patterning through instabilities in complex media: theory and applications.'

The alkaline earth intercalates of molybdenum disulfide

NASA Technical Reports Server (NTRS)

Somoano, R. B.; Hadek, V.; Rembaum, A.; Samson, S.; Woollam, J. A.

1975-01-01

Molybdenum disulfide has been intercalated with calcium and strontium by means of the liquid ammonia technique. Chemical, X-ray, and superconductivity data are presented. The X-ray data reveal a lowering of crystal symmetry and increase of complexity of the structure upon intercalation with the alkaline earth metals. The Ca and Sr intercalates start to superconduct at 4 and 5.6 K, respectively, and show considerable anisotropy regarding the critical magnetic field.

Observation of Image Potential State in Oxygen Intercalated Graphene on Iridium by Two-Photon-Photoemission Spectroscopy

NASA Astrophysics Data System (ADS)

Lin, Yi; Li, Yunzhe; Sadowski, Jerzy; Dadap, Jerry; Jin, Wencan; Osgood, Richard

In this talk, we report our experimental results on the first direct observation of image potential state (IPS) in oxygen-intercalated graphene on iridium by two-photo-photoemission spectroscopy. We demonstrate how oxygen intercalation influences the IPS in Gr/Ir and decouples the interlayer interaction. We present measurements of the electronic dispersion and work function in pristine Gr/Ir, oxygen-intercalated Gr/O/Ir, and deintercalated Gr/Ir. LEED patterns are measured during the pristine, oxygen-intercalated, and deintercalated phases of the Gr/Ir sample. Based on these measurements, relative to the pristine case, the work function and the energy location of n =1 IPS relative to the Fermi level increases by 0.39 eV and 0.3 eV, respectively, due to oxygen intercalation, whereas the effective mass of n =1 IPS is hardly influenced by the intercalation process. Moreover, we achieve the quenching and restoration of the resonance from Ir Rashba states to n =1 IPS in Gr/Ir by oxygen intercalation and deintercalation. This work was supported by the DOE, Office of Basic Energy Sciences, Division of MSE under Contract No. DE-FG 02-04-ER-46157. This research used resources of the CFN, which is the U.S. DOE Office of Science User Facility, under Contract No. DE-SC0012704.

The Geomagnetic Field as a Transient: Constraints From Paleomagnetic Intensity Data

NASA Astrophysics Data System (ADS)

Aldridge, K. D.; Baker, R.; McMillan, D. G.

2009-12-01

Measurement of Earth’s magnetic field intensity from sedimentary rocks confirms that the field is a transient on millennial time scales. In accounting for this observation, parameters from dynamo models need to be compared with those obtained from observations. Here we model temporal changes in intensity of the geomagnetic field as either growths or decays, sometimes separated by stationary states. In order to obtain temporal properties of the geomagnetic field, our model, developed as a Matlab algorithm, searches records of relative paleointensity to measure objectively the rates of growth and decay of the field. Here we report on the application of our algorithm to six records of relative paleointensity obtained from oceanic cores. Our model for the fluid velocity field in Earth’s core is based on parametric instability produced externally through gradients of the gravitational field. It is well known that these gradients can lead to instability of the core fluid through both elliptical and shear straining of fluid streamlines. Such an instability will exist as long as the externally produced strain rate exceeds the dissipation rate in Earth’s fluid core. As known from both theoretical models and experimental observations that a sequence of alternately growing and decaying velocities will develop in the fluid, our algorithm has searched the records of relative paleointensity for exponential growths and decays. Since a balance may exist between strain and decay rates described above, our algorithm includes the possibility for a segment of relative paleointensity that is stationary. Such segments do indeed occur in the relative paleointensity record and are expected by the model of parametric instability. Results of the application of our algorithm spanning two Ma with broad geographical coverage will be presented.

Torsional mechanics of DNA are regulated by small-molecule intercalation.

PubMed

Celedon, Alfredo; Wirtz, Denis; Sun, Sean

2010-12-23

Whether the bend and twist mechanics of DNA molecules are coupled is unclear. Here, we report the direct measurement of the resistive torque of single DNA molecules to study the effect of ethidium bromide (EtBr) intercalation and pulling force on DNA twist mechanics. DNA molecules were overwound and unwound using recently developed magnetic tweezers where the molecular resistive torque was obtained from Brownian angular fluctuations. The effect of EtBr intercalation on the twist stiffness was found to be significantly different from the effect on the bend persistence length. The twist stiffness of DNA was dramatically reduced at low intercalator concentration (<10 nM); however, it did not decrease further when the intercalator concentration was increased by 3 orders of magnitude. We also determined the dependence of EtBr intercalation on the torque applied to DNA. We propose a model for the elasticity of DNA base pairs with intercalated EtBr molecules to explain the abrupt decrease of twist stiffness at low EtBr concentration. These results indicate that the bend and twist stiffnesses of DNA are independent and can be differently affected by small-molecule binding.

Intercalation of acrylic acid and sodium acrylate into kaolinite and their in situ polymerization

NASA Astrophysics Data System (ADS)

Zhang, Bo; Li, Yanfeng; Pan, Xiaobing; Jia, Xin; Wang, Xiaolong

2007-02-01

Novel nano-composites of poly (acrylic acid)-kaolinite were prepared, and intercalation and in situ polymerization were used in this process. The nano-composites were obtained by in situ polymerization of acrylic acid (AA) and sodium acrylate (AANa) intercalated into organo-kaolinite, which was obtained by refining and chemically modifying with solution intercalation step in order to increase the basal plane distance of the original clay. The modification was completed by using dimethyl-sulfoxide (DMSO)/methanol and potassium acetate (KAc)/water systems step by step. The materials were characterized with the help of XRD, FT-IR and TEM; the results confirmed that poly(acrylic acid) (PAA) and poly(sodium acrylate) (PAANa) were intercalated into the interlamellar spaces of kaolinite, the resulting copolymer composites (CC0 : copolymer crude kaolinite composite, CC1 : copolymer DMSO kaolinite composite, CC2 : copolymer KAc kaolinite composite) of CC2 exhibited a lamellar nano-composite with a mixed nano-morphology, and partial exfoliation of the intercalating clay platelets should be the main morphology. Finally, the effect of neutralization degree on the intercalation behavior was also investigated.

Synthesis of (cinnamate-zinc layered hydroxide) intercalation compound for sunscreen application

PubMed Central

2013-01-01

Background Zinc layered hydroxide (ZLH) intercalated with cinnamate, an anionic form of cinnamic acid (CA), an efficient UVA and UVB absorber, have been synthesized by direct method using zinc oxide (ZnO) and cinnamic acid as the precursor. Results The resulting obtained intercalation compound, ZCA, showed a basal spacing of 23.9 Å as a result of cinnamate intercalated in a bilayer arrangement between the interlayer spaces of ZLH with estimated percentage loading of cinnamate of about 40.4 % w/w. The UV–vis absorption spectrum of the intercalation compound showed excellent UVA and UVB absorption ability. Retention of cinnamate in ZLH interlayers was tested against media usually came across with sunscreen usage to show low release over an extended period of time. MTT assay of the intercalation compound on human dermal fibroblast (HDF) cells showed cytotoxicity of ZCA to be concentration dependent and is overall less toxic than its precursor, ZnO. Conclusions (Cinnamate-zinc layered hydroxide) intercalation compound is suitable to be used as a safe and effective sunscreen with long UV protection effect. PMID:23383738

Manipulation of Dirac cones in intercalated epitaxial graphene

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

Kim, Minsung; Tringides, Michael C.; Hershberger, Matthew T.

Graphene is an intriguing material in view of its unique Dirac quasi-particles, and the manipulation of its electronic structure is important in material design and applications. Here, we theoretically investigate the electronic band structure of epitaxial graphene on SiC with intercalation of rare earth metal ions (e.g., Yb and Dy) using first-principles calculations. We can use the intercalation to control the coupling of the constituent components (buffer layer, graphene, and substrate), resulting in strong modification of the graphene band structure. We also demonstrate that the metal-intercalated epitaxial graphene has tunable band structures by controlling the energies of Dirac cones asmore » well as the linear and quadratic band dispersion depending on the intercalation layer and density. Thus, the metal intercalation is a viable method to manipulate the electronic band structure of the epitaxial graphene, which can enhance the functional utility and controllability of the material.« less

Synthesis and Catalytic Performance of Gold Intercalated in the Walls of Mesoporous Silica.

PubMed

Ji, Yazhou; Caskey, Christopher; Richards, Ryan M

2015-07-09

As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties of the materials were investigated. We used a one pot sol-gel approach to intercalate gold nano particles in the walls of mesoporous silica. To start with the synthesis, P123 was used as template to form micelles. Then TESPTS was used as a surface modification agent to intercalate gold nano particles. Following this process, TEOS was added in as a silica source which underwent a polymerization process in acid environment. After hydrothermal processing and calcination, the final product was acquired. Several techniques were utilized to characterize the porosity, morphology and structure of the gold intercalated mesoporous silica. The results showed a stable structure of mesoporous silica after gold intercalation. Through the oxidation of benzyl alcohol as a benchmark reaction, the GMS materials showed high selectivity and recyclability.

Synthesis and Catalytic Performance of Gold Intercalated in the Walls of Mesoporous Silica

PubMed Central

Ji, Yazhou; Caskey, Christopher; Richards, Ryan M.

2015-01-01

As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties of the materials were investigated. We used a one pot sol-gel approach to intercalate gold nano particles in the walls of mesoporous silica. To start with the synthesis, P123 was used as template to form micelles. Then TESPTS was used as a surface modification agent to intercalate gold nano particles. Following this process, TEOS was added in as a silica source which underwent a polymerization process in acid environment. After hydrothermal processing and calcination, the final product was acquired. Several techniques were utilized to characterize the porosity, morphology and structure of the gold intercalated mesoporous silica. The results showed a stable structure of mesoporous silica after gold intercalation. Through the oxidation of benzyl alcohol as a benchmark reaction, the GMS materials showed high selectivity and recyclability. PMID:26274058

Ab initio density functional theory investigation of Li-intercalated silicon carbide nanotube bundles

NASA Astrophysics Data System (ADS)

Moradian, Rostam; Behzad, Somayeh; Chegel, Raad

2009-06-01

We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated ( 6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated ( 6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.

Synergetic effects of K + and Mg 2+ ion intercalation on the electrochemical and actuation properties of the two-dimensional Ti 3 C 2 MXene

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

Gao, Qiang; Come, Jeremy; Naguib, Michael

2017-01-01

Two-dimensional materials, such as MXenes, are attractive candidates for energy storage and electrochemical actuators due to their high volume changes upon ion intercalation. Of special interest for boosting energy storage is the intercalation of multivalent ions such as Mg 2+, which suffers from sluggish intercalation and transport kinetics due to its ion size. By combining traditional electrochemical characterization techniques with electrochemical dilatometry and contact resonance atomic force microscopy, the synergetic effects of the pre-intercalation of K +ions are demonstrated to improve the charge storage of multivalent ions, as well as tune the mechanical and actuation properties of the Ti 3Cmore » 2MXene. Our results have important implications for quantitatively understanding the charge storage processes in intercalation compounds and provide a new path for studying the mechanical evolution of energy storage materials.« less

Manipulation of Dirac cones in intercalated epitaxial graphene

DOE PAGES

Kim, Minsung; Tringides, Michael C.; Hershberger, Matthew T.; ...

2017-07-12

Graphene is an intriguing material in view of its unique Dirac quasi-particles, and the manipulation of its electronic structure is important in material design and applications. Here, we theoretically investigate the electronic band structure of epitaxial graphene on SiC with intercalation of rare earth metal ions (e.g., Yb and Dy) using first-principles calculations. We can use the intercalation to control the coupling of the constituent components (buffer layer, graphene, and substrate), resulting in strong modification of the graphene band structure. We also demonstrate that the metal-intercalated epitaxial graphene has tunable band structures by controlling the energies of Dirac cones asmore » well as the linear and quadratic band dispersion depending on the intercalation layer and density. Thus, the metal intercalation is a viable method to manipulate the electronic band structure of the epitaxial graphene, which can enhance the functional utility and controllability of the material.« less

Effects of electrostatic screening on the conformation of single DNA molecules confined in a nanochannel

NASA Astrophysics Data System (ADS)

Zhang, Ce; Zhang, Fang; van Kan, Jeroen A.; van der Maarel, Johan R. C.

2008-06-01

Single T4-DNA molecules were confined in rectangular-shaped channels with a depth of 300 nm and a width in the range of 150-300 nm casted in a poly(dimethylsiloxane) nanofluidic chip. The extensions of the DNA molecules were measured with fluorescence microscopy as a function of the ionic strength and composition of the buffer as well as the DNA intercalation level by the YOYO-1 dye. The data were interpreted with the scaling theory for a wormlike polymer in good solvent, including the effects of confinement, charge, and self-avoidance. It was found that the elongation of the DNA molecules with decreasing ionic strength can be interpreted in terms of an increase of the persistence length. Self-avoidance effects on the extension are moderate, due to the small correlation length imposed by the channel cross-sectional diameter. Intercalation of the dye results in an increase of the DNA contour length and a partial neutralization of the DNA charge, but besides effects of electrostatic origin it has no significant effect on the bare bending rigidity. In the presence of divalent cations, the DNA molecules were observed to contract, but they do not collapse into a condensed structure. It is proposed that this contraction results from a divalent counterion mediated attractive force between the segments of the DNA molecule.

Alkali metal intercalates of molybdenum disulfide.

NASA Technical Reports Server (NTRS)

Somoano, R. B.; Hadek, V.; Rembaum, A.

1973-01-01

Study of some of the physicochemical properties of compounds obtained by subjecting natural molybdenite and single crystals of molybdenum disulfide grown by chemical vapor transport to intercalation with the alkali group of metals (Li, Na, K, Rb, and Cs) by means of the liquid ammonia technique. Reported data and results include: (1) the intercalation of the entire alkali metal group, (2) stoichiometries and X-ray data on all of the compounds, and (3) superconductivity data for all the intercalation compounds.

Physics and chemistry of MoS2 intercalation compounds

NASA Technical Reports Server (NTRS)

Woollam, J. A.; Somoano, R. B.

1977-01-01

An investigation is made of the physics and chemistry of MoS2 intercalation compounds. These compounds may be separated into two groups according to their stoichiometry, structure and superconducting properties. The first group consists of Na, Ca, and Sr intercalates, and the second group consists of K, Rb, and Cs intercalates. Particular attention is given to the structure of the electronic energy band and to the normal state and superconducting properties of these compounds.

Synthesis and characterization of montmorillonite clay intercalated with molecular magnetic compounds

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

Martins, Marcel G.; Martins, Daniel O.T.A.; Carvalho, Beatriz L.C. de

2015-08-15

In this work montmorillonite (MMT) clay, whose matrix was modified with an ammonium salt (hexadecyltrimethylammonium bromide – CTAB), was employed as an inorganic host for the intercalation of three different molecular magnetic compounds through ion exchange: a nitronyl nitroxide derivative 2-[4-(N-ethyl)-pyridinium]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (p-EtRad{sup +}) and two binuclear coordination compounds, [Ni(valpn)Ln]{sup 3+}, where H{sub 2}valpn stands for 1,3-propanediyl-bis(2-iminomethylene-6-methoxy-phenol), and Ln=Gd{sup III}; Dy{sup III}. The pristine MMT and the intercalated materials were characterized by X-ray powder diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and magnetic measurements. The X-ray diffraction data analysis showed an increase of the interlamellar spacemore » of the intercalated MMT, indicating the intercalation of the magnetic compounds. Furthermore, the magnetic properties of the hybrid compounds were investigated, showing similar behavior as the pure magnetic guest species. - Graphical abstract: Montmorillonite clay was employed as inorganic host for the intercalation of three different molecular magnetic compounds through ion exchange - Highlights: • Montmorillonite was employed as a host material. • Three molecular magnetic compounds were intercalated through ion exchange. • The compounds were successful intercalated maintaining the layered structure. • The hybrid materials exhibited similar magnetic behavior as the pure magnetic guest.« less

Strong DNA deformation required for extremely slow DNA threading intercalation by a binuclear ruthenium complex

PubMed Central

Almaqwashi, Ali A.; Paramanathan, Thayaparan; Lincoln, Per; Rouzina, Ioulia; Westerlund, Fredrik; Williams, Mark C.

2014-01-01

DNA intercalation by threading is expected to yield high affinity and slow dissociation, properties desirable for DNA-targeted therapeutics. To measure these properties, we utilize single molecule DNA stretching to quantify both the binding affinity and the force-dependent threading intercalation kinetics of the binuclear ruthenium complex Δ,Δ-[μ‐bidppz‐(phen)4Ru2]4+ (Δ,Δ-P). We measure the DNA elongation at a range of constant stretching forces using optical tweezers, allowing direct characterization of the intercalation kinetics as well as the amount intercalated at equilibrium. Higher forces exponentially facilitate the intercalative binding, leading to a profound decrease in the binding site size that results in one ligand intercalated at almost every DNA base stack. The zero force Δ,Δ-P intercalation Kd is 44 nM, 25-fold stronger than the analogous mono-nuclear ligand (Δ-P). The force-dependent kinetics analysis reveals a mechanism that requires DNA elongation of 0.33 nm for association, relaxation to an equilibrium elongation of 0.19 nm, and an additional elongation of 0.14 nm from the equilibrium state for dissociation. In cells, a molecule with binding properties similar to Δ,Δ-P may rapidly bind DNA destabilized by enzymes during replication or transcription, but upon enzyme dissociation it is predicted to remain intercalated for several hours, thereby interfering with essential biological processes. PMID:25245944

The Invisible Homeless: A New Urban Ecology.

ERIC Educational Resources Information Center

Ropers, Richard H.

Contemporary homelessness is the result of increasing social and economic inequality faced by those in American society who are most vulnerable to individual, family, and economic instability. This case study of the homeless population of Los Angeles (California), based on two surveys conducted in 1984, views the homeless as a segment of the…

Alkali metal intercalated fullerene-like MS(2) (M = W, Mo) nanoparticles and their properties.

PubMed

Zak, Alla; Feldman, Yishay; Lyakhovitskaya, Vera; Leitus, Gregory; Popovitz-Biro, Ronit; Wachtel, Ellen; Cohen, Hagai; Reich, Shimon; Tenne, Reshef

2002-05-01

Layered metal disulfides-MS(2) (M = Mo, W) in the form of fullerene-like nanoparticles and in the form of platelets (crystallites of the 2H polytype) have been intercalated by exposure to alkali metal (potassium and sodium) vapor using a two-zone transport method. The composition of the intercalated systems was established using X-ray energy dispersive spectrometer and X-ray photoelectron spectroscopy (XPS). The alkali metal concentration in the host lattice was found to depend on the kind of sample and the experimental conditions. Furthermore, an inhomogeneity of the intercalated samples was observed. The product consisted of both nonintercalated and intercalated phases. X-ray diffraction analysis and transmission electron microscopy of the samples, which were not exposed to the ambient atmosphere, showed that they suffered little change in their lattice parameters. On the other hand, after exposure to ambient atmosphere, substantial increase in the interplanar spacing (3-5 A) was observed for the intercalated phases. Insertion of one to two water molecules per intercalated metal atom was suggested as a possible explanation for this large expansion along the c-axis. Deintercalation of the hydrated alkali atoms and restacking of the MS(2) layers was observed in all the samples after prolonged exposure to the atmosphere. Electric field induced deintercalation of the alkali metal atoms from the host lattice was also observed by means of the XPS technique. Magnetic moment measurements for all the samples indicate a diamagnetic to paramagnetic transition after intercalation. Measurements of the transport properties reveal a semiconductor to metal transition for the heavily K intercalated 2H-MoS(2). Other samples show several orders of magnitude decrease in resistivity and two- to five-fold decrease in activation energies upon intercalation. These modifications are believed to occur via charge transfer from the alkali metal to the conduction band of the host lattice. Recovery of the pristine compound properties (diamagnetism and semiconductivity) was observed as a result of deintercalation.

Real-time electrochemical LAMP: a rational comparative study of different DNA intercalating and non-intercalating redox probes.

PubMed

Martin, Alexandra; Bouffier, Laurent; Grant, Kathryn B; Limoges, Benoît; Marchal, Damien

2016-06-20

We present a comparative study of ten redox-active probes for use in real-time electrochemical loop-mediated isothermal amplification (LAMP). Our main objectives were to establish the criteria that need to be fulfilled for minimizing some of the current limitations of the technique and to provide future guidelines in the search for ideal redox reporters. To ensure a reliable comparative study, each redox probe was tested under similar conditions using the same LAMP reaction and the same entirely automatized custom-made real-time electrochemical device (designed for electrochemically monitoring in real-time and in parallel up to 48 LAMP samples). Electrochemical melt curve analyses were recorded immediately at the end of each LAMP reaction. Our results show that there are a number of intercalating and non-intercalating redox compounds suitable for real-time electrochemical LAMP and that the best candidates are those able to intercalate strongly into ds-DNA but not too much to avoid inhibition of the LAMP reaction. The strongest intercalating redox probes were finally shown to provide higher LAMP sensitivity, speed, greater signal amplitude, and cleaner-cut DNA melting curves than the non-intercalating molecules.

Simulation assisted characterization of kaolinite-methanol intercalation complexes synthesized using cost-efficient homogenization method

NASA Astrophysics Data System (ADS)

Makó, Éva; Kovács, András; Ható, Zoltán; Kristóf, Tamás

2015-12-01

Recent experimental and simulation findings with kaolinite-methanol intercalation complexes raised the question of the existence of more stable structures in wet and dry state, which has not been fully cleared up yet. Experimental and molecular simulation analyses were used to investigate different types of kaolinite-methanol complexes, revealing their real structures. Cost-efficient homogenization methods were applied to synthesize the kaolinite-dimethyl sulfoxide and kaolinite-urea pre-intercalation complexes of the kaolinite-methanol ones. The tested homogenization method required an order of magnitude lower amount of reagents than the generally applied solution method. The influence of the type of pre-intercalated molecules and of the wetting or drying (at room temperature and at 150 °C) procedure on the intercalation was characterized experimentally by X-ray diffraction and thermal analysis. Consistent with the suggestion from the present simulations, 1.12-nm and 0.83-nm stable kaolinite-methanol complexes were identified. For these complexes, our molecular simulations predict either single-layered structures of mobile methanol/water molecules or non-intercalated structures of methoxy-functionalized kaolinite. We found that the methoxy-modified kaolinite can easily be intercalated by liquid methanol.

Transition metal intercalated bilayer silicene

NASA Astrophysics Data System (ADS)

Pandey, Dhanshree; Kamal, C.; Chakrabarti, Aparna

2018-04-01

We investigate the electronic and magnetic properties of Mn, Fe and Co-intercalated silicene bilayer with AA and AB stacking by using spin polarized density functional theory. The intercalation of Mn increases the gap between the two layers of silicene due to the larger atomic radii of Mn as compared to Fe and Co. Bader charge analysis has been performed to understand the bonding between the TM and Si atoms. This also helps in explaining the magnetic moment possessed by the composite systems after intercalating TM in between the layers of bilayer silicene system. This study reveals that a significant net magnetic moment is observed in cases of Mn-intercalated silicene bilayers, whereas Fe has a very small moment of 0.78 µB in the case of AA stacking configuration only. Co intercalation leads to net zero magnetic moment. Further, we find that Fe and Co marginally favor the AB stacking whereas Mn has a slight preference of the AA over the AB configuration. The composite systems, specifically when intercalated with Fe and Co atoms, favor a hybridization which is far away from sp3-like hybridization along the plane of Si atoms in bilayer silicene.

Structural Evolution of Reversible Mg Insertion into a Bilayer Structure of V 2 O 5 · n H 2 O Xerogel Material

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

Sa, Niya; Kinnibrugh, Tiffany L.; Wang, Hao

Functional multivalent intercalation cathodes represent one of the largest hurdles in the development of Mg batteries. While there are many reports of Mg cathodes, many times the evidence of intercalation chemistry is only circumstantial. In this work, direct evidence of Mg intercalation into a bilayer structure of V2O5·nH2O xerogel is confirmed, and the nature of the Mg intercalated species is reported. The interlayer spacing of V2O5·nH2O contracts upon Mg intercalation and expands for Mg deintercalation due to the strong electrostatic interaction between the divalent cation and the cathode. A combination of NMR, pair distribution function (PDF) analysis, and X-ray absorptionmore » near edge spectroscopy (XANES) confirmed reversible Mg insertion into the V2O5·nH2O material, and structural evolution of Mg intercalation leads to the formation of multiple new phases. Structures of V2O5·nH2O with Mg intercalation were further supported by the first principle simulations. A solvent cointercalated Mg in V2O5·nH2O is observed for the first time, and the 25Mg magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy was used to elucidate the structure obtained upon electrochemical cycling. Specifically, existence of a well-defined Mg–O environment is revealed for the Mg intercalated structures. Information reported here reveals the fundamental Mg ion intercalation mechanism in a bilayer structure of V2O5·nH2O material and provides insightful design metrics for future Mg cathodes.« less

Binding modes and pathway of RHPS4 to human telomeric G-quadruplex and duplex DNA probed by all-atom molecular dynamics simulations with explicit solvent.

PubMed

Mulholland, Kelly; Siddiquei, Farzana; Wu, Chun

2017-07-19

RHPS4, a potent binder to human telomeric DNA G-quadruplex, shows high efficacy in tumor cell growth inhibition. However, it's preferential binding to DNA G-quadruplex over DNA duplex (about 10 fold) remains to be improved toward its clinical application. A high resolution structure of the single-stranded telomeric DNA G-quadruplexes, or B-DNA duplex, in complex with RHPS4 is not available yet, and the binding nature of this ligand to these DNA forms remains to be elusive. In this study, we carried out 40 μs molecular dynamics binding simulations with a free ligand to decipher the binding pathway of RHPS4 to a DNA duplex and three G-quadruplex folders (parallel, antiparallel and hybrid) of the human telomeric DNA sequence. The most stable binding mode identified for the duplex, parallel, antiparallel and hybrid G-quadruplexes is an intercalation, bottom stacking, top intercalation and bottom intercalation mode, respectively. The intercalation mode with similar binding strength to both the duplex and the G-quadruplexes, explains the lack of binding selectivity of RHPS4 to the G-quadruplex form. Therefore, a ligand modification that destabilizes the duplex intercalation mode but stabilizes the G-quadruplex intercalation mode will improve the binding selectivity toward G-quadruplex. The intercalation mode of RHPS4 to both the duplex and the antiparallel and the hybrid G-quadruplex follows a base flipping-insertion mechanism rather than an open-insertion mechanism. The groove binding, the side binding and the intercalation with flipping out of base were observed to be intermediate states before the full intercalation state with paired bases.

Acrylate intercalation and in situ polymerization in iron-, cobalt-, or manganese-substituted nickel hydroxides.

PubMed

Vaysse, C; Guerlou-Demourgues, L; Duguet, E; Delmas, C

2003-07-28

A chimie douce route based on successive redox and exchange reactions has allowed us to prepare new hybrid organic-inorganic materials, composed of polyacrylate macromolecules intercalated into layered double hydroxides (LDHs), deriving from Ni(OH)(2). Monomer intercalation and in situ polymerization mechanisms have appeared to be strongly dependent upon the nature of the substituting cation in the slabs. In the case of iron-based LDHs, a phase containing acrylate monomeric intercalates has been isolated and identified by X-ray diffraction and infrared spectroscopy. Second, interslab free-radical polymerization of acrylate anions has been successfully initiated using potassium persulfate. In cobalt- or manganese-based LDHs, one-step polymerization has been observed, leading directly to a material containing polyacrylate intercalate.

Intercalation chemistry of zirconium 4-sulfophenylphosphonate

NASA Astrophysics Data System (ADS)

Svoboda, Jan; Zima, Vítězslav; Melánová, Klára; Beneš, Ludvík; Trchová, Miroslava

2013-12-01

Zirconium 4-sulfophenylphosphonate is a layered material which can be employed as a host for the intercalation reactions with basic molecules. A wide range of organic compounds were chosen to represent intercalation ability of zirconium 4-sulfophenylphosphonate. These were a series of alkylamines from methylamine to dodecylamine, 1,4-phenylenediamine, p-toluidine, 1,8-diaminonaphthalene, 1-aminopyrene, imidazole, pyridine, 4,4‧-bipyridine, poly(ethylene imine), and a series of amino acids from glycine to 6-aminocaproic acid. The prepared compounds were characterized by powder X-ray diffraction, thermogravimetry analysis and IR spectroscopy and probable arrangement of the guest molecules in the interlayer space of the host is proposed based on the interlayer distance of the prepared intercalates and amount of the intercalated guest molecules.

Synthesis of new oligothiophene derivatives and their intercalation compounds: Orientation effects

USGS Publications Warehouse

Ibrahim, M.A.; Lee, B.-G.; Park, N.-G.; Pugh, J.R.; Eberl, D.D.; Frank, A.J.

1999-01-01

The orientation dependence of intercalated oligothiophene derivatives in vermiculite and metal disulfides MS2 (M = Mo, Ti and Zr) on the pendant group on the thiophene ring and the host material was studied by X-ray diffraction (XRD) and solid state nuclear magnetic resonance spectroscopy. Amino and nitro derivatives of bi-, ter- and quarter-thiophenes were synthesized for the first time. The amino-oligothiophenes were intercalated into vermiculite by an exchange reaction with previously intercalated octadecylammonium vermiculite and into MS2 by the intercalation-exfoliation technique. Analysis of the XRD data indicates that a monolayer of amino-oligothiophene orients perpendicularly to the silicate surface in vermiculite and lies flat in the van der Waals gap of MS2.

Rechargeable LiNiO2/carbon cells

NASA Astrophysics Data System (ADS)

Dahn, J. R.; von Sacken, U.; Juzkow, M. W.; Al-Janaby, H.

1991-08-01

Rechargeable cells can be made using two different intercalation compounds, in which the chemical potential of the intercalant differs by several eV, for the electrodes. The factors that play a role in the selection of appropriate lithium intercalation compounds for such cells are discussed. For the ease of cell assembly, the cathode should be stable in air when it is fully intercalated, like LiNiO2. For the anode, the chemical potential of the intercalated Li should be close to that of Li metal, like it is in Li(x)C6. The intercalation of Li in LiNiO2 is discussed, and then in petroleum coke. Then, it is shown that LiNiO2/coke cells have high energy density, long cycle life, excellent high-temperature performance, low self-discharge rates, can be repeatedly discharged to zero volts without damage, and are easily fabricated. It is considered that this type of cell shows far more promise for widespread applications than traditional secondary Li cells using metallic Li anodes.

Manipulation of Dirac cones in metal-intercalated epitaxial graphene

NASA Astrophysics Data System (ADS)

Wang, Cai-Zhuang; Kim, Minsung; Tringides, Michael; Ho, Kai-Ming

Graphene is one of the most attractive materials from both fundamental and practical points of view due to its characteristic Dirac cones. The electronic property of graphene can be modified through the interaction with substrate or another graphene layer as illustrated in few-layer epitaxial graphene. Recently, metal intercalation became an effective method to manipulate the electronic structure of graphene by modifying the coupling between the constituent layers. In this work, we show that the Dirac cones of epitaxial graphene can be manipulated by intercalating rare-earth metals. We demonstrate that rare-earth metal intercalated epitaxial graphene has tunable band structures and the energy levels of Dirac cones as well as the linear or quadratic band dispersion can be controlled depending on the location of the intercalation layer and density. Our results could be important for applications and characterizations of the intercalated epitaxial graphene. Supported by the U.S. DOE-BES under Contract No. DE-AC02-07CH11358.

Mixing Acid Salts and Layered Double Hydroxides in Nanoscale under Solid Condition

PubMed Central

Nakayama, Hirokazu; Hayashi, Aki

2014-01-01

The immobilization of potassium sorbate, potassium aspartate and sorbic acid in layered double hydroxide under solid condition was examined. By simply mixing two solids, immobilization of sorbate and aspartate in the interlayer space of nitrate-type layered double hydroxide, so called intercalation reaction, was achieved, and the uptakes, that is, the amount of immobilized salts and the interlayer distances of intercalation compounds were almost the same as those obtained in aqueous solution. However, no intercalation was achieved for sorbic acid. Although intercalation of sorbate and aspartate into chloride-type layered double hydroxide was possible, the uptakes for these intercalation compounds were lower than those obtained using nitrate-type layered double hydroxide. The intercalation under solid condition could be achieved to the same extent as for ion-exchange reaction in aqueous solution, and the reactivity was similar to that observed in aqueous solution. This method will enable the encapsulation of acidic drug in layered double hydroxide as nano level simply by mixing both solids. PMID:25080007

Mixing Acid Salts and Layered Double Hydroxides in Nanoscale under Solid Condition.

PubMed

Nakayama, Hirokazu; Hayashi, Aki

2014-07-30

The immobilization of potassium sorbate, potassium aspartate and sorbic acid in layered double hydroxide under solid condition was examined. By simply mixing two solids, immobilization of sorbate and aspartate in the interlayer space of nitrate-type layered double hydroxide, so called intercalation reaction, was achieved, and the uptakes, that is, the amount of immobilized salts and the interlayer distances of intercalation compounds were almost the same as those obtained in aqueous solution. However, no intercalation was achieved for sorbic acid. Although intercalation of sorbate and aspartate into chloride-type layered double hydroxide was possible, the uptakes for these intercalation compounds were lower than those obtained using nitrate-type layered double hydroxide. The intercalation under solid condition could be achieved to the same extent as for ion-exchange reaction in aqueous solution, and the reactivity was similar to that observed in aqueous solution. This method will enable the encapsulation of acidic drug in layered double hydroxide as nano level simply by mixing both solids.

High-contrast imager for Complex Aperture Telescopes (HiCAT). 4. Status and wavefront control development

NASA Astrophysics Data System (ADS)

Leboulleux, Lucie; N'Diaye, Mamadou; Riggs, A. J. E.; Egron, Sylvain; Mazoyer, Johan; Pueyo, Laurent; Choquet, Elodie; Perrin, Marshall D.; Kasdin, Jeremy; Sauvage, Jean-François; Fusco, Thierry; Soummer, Rémi

2016-07-01

Segmented telescopes are a possible approach to enable large-aperture space telescopes for the direct imaging and spectroscopy of habitable worlds. However, the increased complexity of their aperture geometry, due to their central obstruction, support structures and segment gaps, makes high-contrast imaging very challenging. The High-contrast imager for Complex Aperture Telescopes (HiCAT) was designed to study and develop solutions for such telescope pupils using wavefront control and starlight suppression. The testbed design has the flexibility to enable studies with increasing complexity for telescope aperture geometries starting with off-axis telescopes, then on-axis telescopes with central obstruction and support structures (e.g. the Wide Field Infrared Survey Telescope [WFIRST]), up to on-axis segmented telescopes e.g. including various concepts for a Large UV, Optical, IR telescope (LUVOIR), such as the High Definition Space Telescope (HDST). We completed optical alignment in the summer of 2014 and a first deformable mirror was successfully integrated in the testbed, with a total wavefront error of 13nm RMS over a 18mm diameter circular pupil in open loop. HiCAT will also be provided with a segmented mirror conjugated with a shaped pupil representing the HDST configuration, to directly study wavefront control in the presence of segment gaps, central obstruction and spider. We recently applied a focal plane wavefront control method combined with a classical Lyot coronagraph on HiCAT, and we found limitations on contrast performance due to vibration effect. In this communication, we analyze this instability and study its impact on the performance of wavefront control algorithms. We present our Speckle Nulling code to control and correct for wavefront errors both in simulation mode and on testbed mode. This routine is first tested in simulation mode without instability to validate our code. We then add simulated vibrations to study the degradation of contrast performance in the presence of these effects.

New X-ray insight into oxygen intercalation in epitaxial graphene grown on 4H-SiC(0001)

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

Kowalski, G., E-mail: kowal@fuw.edu.pl; Tokarczyk, M.; Dąbrowski, P.

Efficient control of intercalation of epitaxial graphene by specific elements is a way to change properties of the graphene. Results of several experimental techniques, such as X-ray photoelectron spectroscopy, micro-Raman mapping, reflectivity, attenuated total reflection, X-ray diffraction, and X-ray reflectometry, gave a new insight into the intercalation of oxygen in the epitaxial graphene grown on 4H-SiC(0001). These results confirmed that oxygen intercalation decouples the graphene buffer layer from the 4H-SiC surface and converts it into the graphene layer. However, in contrast to the hydrogen intercalation, oxygen does not intercalate between carbon planes (in the case of few layer graphene) andmore » the interlayer spacing stays constant at the level of 3.35–3.32 Å. Moreover, X-ray reflectometry showed the presence of an oxide layer having the thickness of about 0.8 Å underneath the graphene layers. Apart from the formation of the nonuniform thin oxide layer, generation of defects in graphene caused by oxygen was also evidenced. Last but not least, water islands underneath defected graphene regions in both intercalated and non-intercalated samples were most probably revealed. These water islands are formed in the case of all the samples stored under ambient laboratory conditions. Water islands can be removed from underneath the few layer graphene stacks by relevant thermal treatment or by UV illumination.« less

Segmental Duplications in Euchromatic Regions of Human Chromosome 5: A Source of Evolutionary Instability and Transcriptional Innovation

PubMed Central

Courseaux, Anouk; Richard, Florence; Grosgeorge, Josiane; Ortola, Christine; Viale, Agnes; Turc-Carel, Claude; Dutrillaux, Bernard; Gaudray, Patrick; Nahon, Jean-Louis

2003-01-01

Recent analyses of the structure of pericentromeric and subtelomeric regions have revealed that these particular regions of human chromosomes are often composed of blocks of duplicated genomic segments that have been associated with rapid evolutionary turnover among the genomes of closely related primates. In the present study, we show that euchromatic regions of human chromosome 5—5p14, 5p13, 5q13, 5q15–5q21—also display such an accumulation of segmental duplications. The structure, organization and evolution of those primate-specific sequences were studied in detail by combining in silico and comparative FISH analyses on human, chimpanzee, gorilla, orangutang, macaca, and capuchin chromosomes. Our results lend support to a two-step model of transposition duplication in the euchromatic regions, with a founder insertional event at the time of divergence between Platyrrhini and Catarrhini (25–35 million years ago) and an apparent burst of inter- and intrachromosomal duplications in the Hominidae lineage. Furthermore, phylogenetic analysis suggests that the chronology and, likely, molecular mechanisms, differ regarding the region of primary insertion—euchromatic versus pericentromeric regions. Lastly, we show that as their counterparts located near the heterochromatic region, the euchromatic segmental duplications have consistently reshaped their region of insertion during primate evolution, creating putative mosaic genes, and they are obvious candidates for causing ectopic rearrangements that have contributed to evolutionary/genomic instability. [Supplemental material is available online at www.genome.org. The following individuals kindly provided reagents, samples, or unpublished information as indicated in the paper: D. Le Paslier, A. McKenzie, J. Melki, C. Sargent, J. Scharf and S. Selig.] PMID:12618367

Segmental duplications and evolutionary plasticity at tumor chromosome break-prone regions

PubMed Central

Darai-Ramqvist, Eva; Sandlund, Agneta; Müller, Stefan; Klein, George; Imreh, Stefan; Kost-Alimova, Maria

2008-01-01

We have previously found that the borders of evolutionarily conserved chromosomal regions often coincide with tumor-associated deletion breakpoints within human 3p12-p22. Moreover, a detailed analysis of a frequently deleted region at 3p21.3 (CER1) showed associations between tumor breaks and gene duplications. We now report on the analysis of 54 chromosome 3 breaks by multipoint FISH (mpFISH) in 10 carcinoma-derived cell lines. The centromeric region was broken in five lines. In lines with highly complex karyotypes, breaks were clustered near known fragile sites, FRA3B, FRA3C, and FRA3D (three lines), and in two other regions: 3p12.3-p13 (∼75 Mb position) and 3q21.3-q22.1 (∼130 Mb position) (six lines). All locations are shown based on NCBI Build 36.1 human genome sequence. The last two regions participated in three of four chromosome 3 inversions during primate evolution. Regions at 75, 127, and 131 Mb positions carry a large (∼250 kb) segmental duplication (tumor break-prone segmental duplication [TBSD]). TBSD homologous sequences were found at 15 sites on different chromosomes. They were located within bands frequently involved in carcinoma-associated breaks. Thirteen of them have been involved in inversions during primate evolution; 10 were reused by breaks during mammalian evolution; 14 showed copy number polymorphism in man. TBSD sites showed an increase in satellite repeats, retrotransposed sequences, and other segmental duplications. We propose that the instability of these sites stems from specific organization of the chromosomal region, associated with location at a boundary between different CG-content isochores and with the presence of TBSDs and “instability elements,” including satellite repeats and retroviral sequences. PMID:18230801

Segmental duplications and evolutionary plasticity at tumor chromosome break-prone regions.

PubMed

Darai-Ramqvist, Eva; Sandlund, Agneta; Müller, Stefan; Klein, George; Imreh, Stefan; Kost-Alimova, Maria

2008-03-01

We have previously found that the borders of evolutionarily conserved chromosomal regions often coincide with tumor-associated deletion breakpoints within human 3p12-p22. Moreover, a detailed analysis of a frequently deleted region at 3p21.3 (CER1) showed associations between tumor breaks and gene duplications. We now report on the analysis of 54 chromosome 3 breaks by multipoint FISH (mpFISH) in 10 carcinoma-derived cell lines. The centromeric region was broken in five lines. In lines with highly complex karyotypes, breaks were clustered near known fragile sites, FRA3B, FRA3C, and FRA3D (three lines), and in two other regions: 3p12.3-p13 ( approximately 75 Mb position) and 3q21.3-q22.1 ( approximately 130 Mb position) (six lines). All locations are shown based on NCBI Build 36.1 human genome sequence. The last two regions participated in three of four chromosome 3 inversions during primate evolution. Regions at 75, 127, and 131 Mb positions carry a large ( approximately 250 kb) segmental duplication (tumor break-prone segmental duplication [TBSD]). TBSD homologous sequences were found at 15 sites on different chromosomes. They were located within bands frequently involved in carcinoma-associated breaks. Thirteen of them have been involved in inversions during primate evolution; 10 were reused by breaks during mammalian evolution; 14 showed copy number polymorphism in man. TBSD sites showed an increase in satellite repeats, retrotransposed sequences, and other segmental duplications. We propose that the instability of these sites stems from specific organization of the chromosomal region, associated with location at a boundary between different CG-content isochores and with the presence of TBSDs and "instability elements," including satellite repeats and retroviral sequences.

Attainment rate as a surrogate indicator of the intervertebral neutral zone length in lateral bending: an in vitro proof of concept study.

PubMed

Breen, Alexander C; Dupac, Mihai; Osborne, Neil

2015-01-01

Lumbar segmental instability is often considered to be a cause of chronic low back pain. However, defining its measurement has been largely limited to laboratory studies. These have characterised segmental stability as the intrinsic resistance of spine specimens to initial bending moments by quantifying the dynamic neutral zone. However these measurements have been impossible to obtain in vivo without invasive procedures, preventing the assessment of intervertebral stability in patients. Quantitative fluoroscopy (QF), measures the initial velocity of the attainment of intervertebral rotational motion in patients, which may to some extent be representative of the dynamic neutral zone. This study sought to explore the possible relationship between the dynamic neutral zone and intervertebral rotational attainment rate as measured with (QF) in an in vitro preparation. The purpose was to find out if further work into this concept is worth pursuing. This study used passive recumbent QF in a multi-segmental porcine model. This assessed the intrinsic intervertebral responses to a minimal coronal plane bending moment as measured with a digital force guage. Bending moments about each intervertebral joint were calculated and correlated with the rate at which global motion was attained at each intervertebral segment in the first 10° of global motion where the intervertebral joint was rotating. Unlike previous studies of single segment specimens, a neutral zone was found to exist during lateral bending. The initial attainment rates for left and right lateral flexion were comparable to previously published in vivo values for healthy controls. Substantial and highly significant levels of correlation between initial attainment rate and neutral zone were found for left (Rho = 0.75, P = 0.0002) and combined left-right bending (Rho = 0.72, P = 0.0001) and moderate ones for right alone (Rho = 0.55, P = 0.0012). This study found good correlation between the initial intervertebral attainment rate and the dynamic neutral zone, thereby opening the possibility to detect segmental instability from clinical studies. However the results must be treated with caution. Further studies with multiple specimens and adding sagittal plane motion are warranted.

Controls on mid-ocean ridge segmentation and transform fault formation from laboratory experiments using fluids of complex rheology.

NASA Astrophysics Data System (ADS)

Sibrant, A.; Mittelstaedt, E. L.; Davaille, A.

2017-12-01

Mid-ocean ridges are tectonically segmented at scales of 10s to 100s of kilometers by several types of offsets including transform faults (TF), overlapping spreading centers (OSC), and slow-spreading non-transform offsets (NTO). Differences in segmentation along axis have been attributed to changes in numerous processes including magma supply from the upwelling mantle, viscous flow in the asthenosphere, ridge migration, and plate spreading direction. The wide variety of proposed mechanisms demonstrate that the origin of tectonic offsets and their relationship to segment-scale magmatic processes remain actively debated; each of the above processes, however, invoke combinations of tectonic and magmatic processes to explain changes in segmentation. To address the role of tectonic deformation and magmatic accretion on the development of ridge offsets, we present a series of analogue experiments using colloidal silica dispersions as an Earth analogue. Saline water solutions placed in contact with these fluids, cause formation of a skin through salt diffusion, whose rheology evolves from purely viscous to elastic and brittle with increasing salinity. Experiments are performed in a Plexiglas tank with two Plexiglas plates suspended above the base of the tank. The tank is filled with the colloidal fluid to just above the suspended plates, a thin layer of saline water is spread across the surface, and spreading initiated by moving the suspended Plexiglas plates apart at a fixed rate. Results show formation of OSCs, NTOs, and TFs. For parameters corresponding to the Earth, TF offsets are < 5 mm and form at all spreading velocities, corresponding to transform offsets of < 100 km on Earth. Measured TF offset size and ridge segment lengths exhibit a Poisson-type distribution with no apparent dependence on spreading rate. Observations of TF offset size on Earth show a similar distribution for TFs <100 km long and supports the hypothesis that TFform spontaneously through a mechanical instability of the axis. Here, we present an analysis of the magmatic and tectonic controls on axis instability leading to the formation of TFs, OSCs, and NTOs, and their implications for the evolution of mid-ocean ridges.

Polysulfide intercalated layered double hydroxides for metal capture applications

DOEpatents

Kanatzidis, Mercouri G.; Ma, Shulan

2017-04-04

Polysulfide intercalated layered double hydroxides and methods for their use in vapor and liquid-phase metal capture applications are provided. The layered double hydroxides comprise a plurality of positively charged host layers of mixed metal hydroxides separated by interlayer spaces. Polysulfide anions are intercalated in the interlayer spaces.

On lunisolar calendars and intercalation schemes in Southeast Asia

NASA Astrophysics Data System (ADS)

Gislén, Lars

2018-04-01

This is a survey of different calendar intercalation schemes, mainly in Southeast Asia. The Thai and Burmese Calendars, superficially very similar, are shown to have quite different and interesting intercalation schemes. We also investigate similarities between the original Burmese Calendar and the Romakasiddhânta from India.

A rechargeable iodine-carbon battery that exploits ion intercalation and iodine redox chemistry.

PubMed

Lu, Ke; Hu, Ziyu; Ma, Jizhen; Ma, Houyi; Dai, Liming; Zhang, Jintao

2017-09-13

Graphitic carbons have been used as conductive supports for developing rechargeable batteries. However, the classic ion intercalation in graphitic carbon has yet to be coupled with extrinsic redox reactions to develop rechargeable batteries. Herein, we demonstrate the preparation of a free-standing, flexible nitrogen and phosphorus co-doped hierarchically porous graphitic carbon for iodine loading by pyrolysis of polyaniline coated cellulose wiper. We find that heteroatoms could provide additional defect sites for encapsulating iodine while the porous carbon skeleton facilitates redox reactions of iodine and ion intercalation. The combination of ion intercalation with redox reactions of iodine allows for developing rechargeable iodine-carbon batteries free from the unsafe lithium/sodium metals, and hence eliminates the long-standing safety issue. The unique architecture of the hierarchically porous graphitic carbon with heteroatom doping not only provides suitable spaces for both iodine encapsulation and cation intercalation but also generates efficient electronic and ionic transport pathways, thus leading to enhanced performance.Carbon-based electrodes able to intercalate Li + and Na + ions have been exploited for high performing energy storage devices. Here, the authors combine the ion intercalation properties of porous graphitic carbons with the redox chemistry of iodine to produce iodine-carbon batteries with high reversible capacities.

Solid-state chelation of metal ions by ethylenediaminetetraacetate intercalated in a layered double hydroxide.

PubMed

Tarasov, Konstantin A; O'Hare, Dermot; Isupov, Vitaly P

2003-03-24

The solid-state chelation of transition metal ions (Co(2+), Ni(2+), and Cu(2+)) from aqueous solutions into the lithium aluminum layered double hydroxide ([LiAl(2)(OH)(6)]Cl x 0.5H(2)O or LDH) which has been pre-intercalated with EDTA (ethylenediaminetetraacetate) ligand has been investigated. The intercalated metal cations form [M(edta)](2)(-) complexes between the LDH layers as indicated by elemental analysis, powder X-ray diffraction, and IR and UV-vis spectroscopies. If metal chloride or nitrate salts are used in the reaction with the LDH then co-intercalation of either the Cl(-) or NO(3)(-) anions is observed. In the case of metal acetate salts the cations intercalate without the accompanying anion. This can be explained by the different intercalation selectivity of the anions in relation to the LDH. In the latter case the introduction of the positive charge into LDH structure was compensated for by the release from the solid of the equivalent quantity of lithium and hydrogen cations. Time-resolved in-situ X-ray diffraction measurements have revealed that the chelation/intercalation reactions proceed very quickly. The rate of the reaction found for nickel acetate depends on concentration as approximately k[Ni(Ac)(2)](3).

Resistivity of Carbon-Carbon Composites Halved

NASA Technical Reports Server (NTRS)

Gaier, James R.

2004-01-01

Carbon-carbon composites have become the material of choice for applications requiring strength and stiffness at very high temperatures (above 2000 C). These composites comprise carbon or graphite fibers embedded in a carbonized or graphitized matrix. In some applications, such as shielding sensitive electronics in very high temperature environments, the performance of these materials would be improved by lowering their electrical resistivity. One method to lower the resistivity of the composites is to lower the resistivity of the graphite fibers, and a proven method to accomplish that is intercalation. Intercalation is the insertion of guest atoms or molecules into a host lattice. In this study the host fibers were highly graphitic pitch-based graphite fibers, or vapor-grown carbon fibers (VGCF), and the intercalate was bromine. Intercalation compounds of graphite are generally thought of as being only metastable, but it has been shown that the residual bromine graphite fiber intercalation compound is remarkably stable, resisting decomposition even at temperatures at least as high as 1000 C. The focus of this work was to fabricate composite preforms, determine whether the fibers they were made from were still intercalated with bromine after processing, and determine the effect on composite resistivity. It was not expected that the resistivity would be lowered as dramatically as with graphite polymer composites because the matrix itself would be much more conductive, but it was hoped that the gains would be substantial enough to warrant its use in high-performance applications. In a collaborative effort supporting a Space Act Agreement between the NASA Glenn Research Center and Applied Sciences, Inc. (Cedarville, OH), laminar preforms were fabricated with pristine and bromine-intercalated pitch-based fibers (P100 and P100-Br) and VGCF (Pyro I and Pyro I-Br). The green preforms were carbonized at 1000 C and then heat treated to 3000 C. To determine whether the fibers in the samples were still intercalated after composite fabrication, they were subjected to X-ray diffraction. The composites containing intercalated graphite fibers showed much higher background scatter than that of pristine fibers, indicating the presence of bromine in the samples. More importantly, faint features indicative of intercalation were visible in the diffraction pattern, showing that the fibers were still intercalated.

Loss of heterozygosity and microsatellite instability in chromosomal segments commonly deleted in squamous cell carcinoma

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

Van Dyke, D.L.; Worsham, M.J.; Zarbo, R.J.

1994-09-01

To evaluate genetic loss in an unselected series of squamous cell carcinoma (SCC) of the head and neck region (SCCHN), including early stage tumors that do not proliferate aggressively in vitro, we have compared microsatellite repeat polymorphisms (MSRP) in normal blood DNA and tumor DNA from 44 patients with SCCHN, using nine MSRPs from 5q15-q21, proximal 8p, 9p21-p23, 18q21-qter, and 21q21. In previous cytogenetic studies, these chromosome segments were deleted in 40-60% of SCCHN and SCC of the female genital tract. Loss of heterozygosity (LOH) was observed from the ANK1 locus (8p21.1-p11.2) in 2/29 informative tumors. LOH was observed atmore » D5S98 (5q15-5q21) in 5/19, and at D21S11 (21q21) in 5/33 informative tumors. These LOH frequencies were lower than expected, which suggests that the critical region of deletion from these chromosome regions exludes the MSRPs studied here, especially for the 8p MSRP, which may reside in proximal 8p. Alternatively, the observed LOH rates may be appropriate for earlier pathologic stage tumors: total genetic loss increases with tumor stage, and the present study included more stage I and II tumors than did the cytogenetic studies. LOH was observed at D9S126, 1FN, and/or D9S199 (at 9p21, 9p22, & 9p23) in 16/38 informative tumors, and at D18S34 and/or MBP (at 18q21 & 18q22-qter) in 17/39 informative tumors. In addition, three tumors demonstrated microsatellite instability at the MBP locus, and one of these had an expansion at D9S199 as well. This tumor, HFH-SCC-20, also demonstrated microsatellite instability at many other MSRP loci. These results confirm that genetic loss from 9p and 18q is frequent in SCCHN, and demonstrate that microsatellite instability also occurs. Of 66 MSRP changes, 62 were LOH and 4 were microsatellite instabilities. These results also show the usefulness of analyses of MSRP LOH and microsatellite instability in squamous cell carcinoma.« less

Segmentation in cohesive systems constrained by elastic environments

PubMed Central

Novak, I.

2017-01-01

The complexity of fracture-induced segmentation in elastically constrained cohesive (fragile) systems originates from the presence of competing interactions. The role of discreteness in such phenomena is of interest in a variety of fields, from hierarchical self-assembly to developmental morphogenesis. In this paper, we study the analytically solvable example of segmentation in a breakable mass–spring chain elastically linked to a deformable lattice structure. We explicitly construct the complete set of local minima of the energy in this prototypical problem and identify among them the states corresponding to the global energy minima. We show that, even in the continuum limit, the dependence of the segmentation topology on the stretching/pre-stress parameter in this problem takes the form of a devil's type staircase. The peculiar nature of this staircase, characterized by locking in rational microstructures, is of particular importance for biological applications, where its structure may serve as an explanation of the robustness of stress-driven segmentation. This article is part of the themed issue ‘Patterning through instabilities in complex media: theory and applications.’ PMID:28373383

Extremely Robust and Patternable Electrodes for Copy-Paper-Based Electronics.

PubMed

Ahn, Jaeho; Seo, Ji-Won; Lee, Tae-Ik; Kwon, Donguk; Park, Inkyu; Kim, Taek-Soo; Lee, Jung-Yong

2016-07-27

We propose a fabrication process for extremely robust and easily patternable silver nanowire (AgNW) electrodes on paper. Using an auxiliary donor layer and a simple laminating process, AgNWs can be easily transferred to copy paper as well as various other substrates using a dry process. Intercalating a polymeric binder between the AgNWs and the substrate through a simple printing technique enhances adhesion, not only guaranteeing high foldability of the electrodes, but also facilitating selective patterning of the AgNWs. Using the proposed process, extremely crease-tolerant electronics based on copy paper can be fabricated, such as a printed circuit board for a 7-segment display, portable heater, and capacitive touch sensor, demonstrating the applicability of the AgNWs-based electrodes to paper electronics.

The analysis of Stability reliability of Qian Tang River seawall

NASA Astrophysics Data System (ADS)

Wu, Xue-Xiong

2017-11-01

Qiantang River seawall due to high water soaking pond by foreshore scour, encountered during the low tide prone slope overall instability. Considering the seawall beach scour in front of random change, using the simplified Bishop method, combined with the variability of soil mechanics parameters, calculation and analysis of Qiantang River Xiasha seawall segments of the overall stability.

A 3-year follow-up study of overdentures retained by mini-dental implants.

PubMed

Preoteasa, Elena; Imre, Marina; Preoteasa, Christina Teodora

2014-01-01

This study evaluated overdentures retained by mini-dental implants (MDIs) as a treatment option for complete edentulism during a 3-year follow-up period. This observational clinical study included completely edentulous patients who were treated with MDI-retained overdentures. The MDIs were supplied by the manufacturer. Twenty-three patients received 7 maxillary and 16 mandibular MDI overdentures retained by 110 MDIs. Of the 36 MDIs placed in the maxilla, 8 failed (in two patients), 2 had compromised survival, 3 displayed satisfactory survival, and 23 were successful. Of the 74 MDIs placed in the mandible, 11 displayed satisfactory survival and 63 were successful. The marginal bone loss was more pronounced for the MDIs placed mesially (intercalated), in areas of decreased ridge width and bone density, and with lower values of insertion torque. The overdentures fractured in seven patients; in 4 of them, this corresponded to the implant housing area. Self-reported reasons for patient dissatisfaction included occasional pain under the overdenture (n = 5) and instability of the maxillary antagonist complete denture (n = 4). Based on this research, considering its limitations, it is possible to conclude that survival rates and health status are better for MDI overdentures applied in the mandible than for those applied in the maxilla. The most severe prosthetic complications encountered were overdenture base fracture, matrix detachment, and instability of the maxillary antagonist denture.

Does superior-segment facet violation or laminectomy destabilize the adjacent level in lumbar transpedicular fixation? An in vitro human cadaveric assessment.

PubMed

Cardoso, Mario J; Dmitriev, Anton E; Helgeson, Melvin; Lehman, Ronald A; Kuklo, Timothy R; Rosner, Michael K

2008-12-15

This is an in vitro biomechanical study. The current investigation was performed to evaluate adjacent level kinematic change following unilateral and bilateral facet violation and laminectomy following 1-, 2-, and 3-level reconstruction. The incidence of superior-segment facet violation with lumbar transpedicular fixation has been reported as high as 35%; however, its contribution to biomechanical instability at the supradjacent level is unknown. In addition, superior-segment laminectomy has been implicated as a risk factor for the development of adjacent level disease. The authors assess the acute biomechanical effects of proximal facet violation and subsequent laminectomy in an instrumented posterior fusion model in 10 cadaveric specimens. Biomechanical testing was performed on 10 human cadaveric spines under axial rotation (AR), flexion-extension (FE), and lateral bending (LB) loading. After intact analysis, pedicle screws were inserted from L5-S1 and testing repeated with: (1) preserved L4-L5 facets, (2) unilateral facet breach, (3) bilateral breach, and (4) L5 laminectomy. Following biomechanical analysis, instrumentation was extended to L4, then L3 and biomechanical testing repeated. Full range of motion (ROM) at the proximal adjacent levels were recorded and normalized to intact (100%). Supradjacent level ROM was increased for all groups under all loading methods relative to intact (P < 0.05). However, AR testing revealed progressive instability at the adjacent level in groups 3 and 4, relative to group 1, following 1-, 2- and 3-level fixation (P < 0.05). During FE, supradjacent level ROM was significantly increased for group 4 specimens compared with group 1 after L5-S1 fixation (P < 0.05), and was greater than all other groups for L3-S1 constructs (P < 0.05). Interestingly, under lateral bending, facet joint destabilization did not change adjacent segment ROM. There were significant changes in proximal level ROM immediately after posterior stabilization. However, an additional increase in supradjacent segment ROM was recorded during AR after bilateral facet breach.Subsequent complete laminectomy at the uppermostfixation level further destabilized the supradjacent segment in FE and AR. Therefore, meticulous preservation of the cephalad-most segment facet joints-is paramount to ensure stability.

Kinetic magnetic resonance imaging analysis of abnormal segmental motion of the functional spine unit.

PubMed

Kong, Min Ho; Hymanson, Henry J; Song, Kwan Young; Chin, Dong Kyu; Cho, Yong Eun; Yoon, Do Heum; Wang, Jeffrey C

2009-04-01

The authors conducted a retrospective observational study using kinetic MR imaging to investigate the relationship between instability, abnormal sagittal segmental motion, and radiographic variables consisting of intervertebral disc degeneration, facet joint osteoarthritis (FJO), degeneration of the interspinous ligaments, ligamentum flavum hypertrophy (LFH), and the status of the paraspinal muscles. Abnormal segmental motion, defined as > 10 degrees angulation and > 3 mm of translation in the sagittal plane, was investigated in 1575 functional spine units (315 patients) in flexion, neutral, and extension postures using kinetic MR imaging. Each segment was assessed based on the extent of disc degeneration (Grades I-V), FJO (Grades 1-4), interspinous ligament degeneration (Grades 1-4), presence of LFH, and paraspinal muscle fatty infiltration observed on kinetic MR imaging. These factors are often noted in patients with degenerative disease, and there are grading systems to describe these changes. For the first time, the authors attempted to address the relationship between these radiographic observations and the effects on the motion and instability of the functional spine unit. The prevalence of abnormal translational motion was significantly higher in patients with Grade IV degenerative discs and Grade 3 arthritic facet joints (p < 0.05). In patients with advanced disc degeneration and FJO, there was a lesser amount of motion in both segmental translation and angulation when compared with lower grades of degeneration, and this difference was statistically significant for angular motion (p < 0.05). Patients with advanced degenerative Grade 4 facet joint arthritis had a significantly lower percentage of abnormal angular motion compared to patients with normal facet joints (p < 0.001). The presence of LFH was strongly associated with abnormal translational and angular motion. Grade 4 interspinous ligament degeneration and the presence of paraspinal muscle fatty infiltration were both significantly associated with excessive abnormal angular motion (p < 0.05). This kinetic MR imaging analysis showed that the lumbar functional unit with more disc degeneration, FJO, and LFH had abnormal sagittal plane translation and angulation. These findings suggest that abnormal segmental motion noted on kinetic MR images is closely associated with disc degeneration, FJO, and the pathological characteristics of interspinous ligaments, ligamentum flavum, and paraspinal muscles. Kinetic MR imaging in patients with mechanical back pain may prove a valuable source of information about the stability of the functional spine unit by measuring abnormal segmental motion and grading of radiographic parameters simultaneously.

Physical nature of ethidium and proflavine interactions with nucleic acid bases in the intercalation plane.

PubMed

Langner, Karol M; Kedzierski, Pawel; Sokalski, W Andrzej; Leszczynski, Jerzy

2006-05-18

On the basis of the crystallographic structures of three nucleic acid intercalation complexes involving ethidium and proflavine, we have analyzed the interaction energies between intercalator chromophores and their four nearest bases, using a hybrid variation-perturbation method at the second-order Møller-Plesset theory level (MP2) with a 6-31G(d,p) basis set. A total MP2 interaction energy minimum precisely reproduces the crystallographic position of the ethidium chromophore in the intercalation plane between UA/AU bases. The electrostatic component constitutes the same fraction of the total energy for all three studied structures. The multipole electrostatic interaction energy, calculated from cumulative atomic multipole moments (CAMMs), was found to converge only after including components above the fifth order. CAMM interaction surfaces, calculated on grids in the intercalation planes of these structures, reasonably reproduce the alignment of intercalators in crystal structures; they exhibit additional minima in the direction of the DNA grooves, however, which also need to be examined at higher theory levels if no crystallographic data are given.

Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites

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

Yi, Tanghong; Chen, Wei; Cheng, Lei

Reversible intercalation reactions provide the basis for modern battery electrodes. In spite of the decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials A xK 1–xFeF 3 (A = Li, Na). By starting with KFeF 3, approximately 75% of K+ ions were subsequently replaced by Li + and Na + through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopymore » confirmed the existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe 2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. Our study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.« less

Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites

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

Yi, Tanghong; Chen, Wei; Cheng, Lei

Reversible intercalation reactions provide the basis for modern battery electrodes. Despite decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials A xK 1–xFeF 3 (A = Li, Na). By starting with KFeF 3, approximately 75% of K + ions were subsequently replaced by Li + and Na + through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopy confirmed themore » existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe 2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. This study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.« less

Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites

DOE PAGES

Yi, Tanghong; Chen, Wei; Cheng, Lei; ...

2017-01-20

Reversible intercalation reactions provide the basis for modern battery electrodes. In spite of the decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials A xK 1–xFeF 3 (A = Li, Na). By starting with KFeF 3, approximately 75% of K+ ions were subsequently replaced by Li + and Na + through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopymore » confirmed the existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe 2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. Our study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.« less

A micrographic and gravimetric study of intercalation and deintercalation of graphite fibers

NASA Technical Reports Server (NTRS)

Hung, C. C.

1985-01-01

Intercalation and deintercalation of Union Carbide P-100 graphite fibers with liquid and vaporous bromine was studied gravimetrically and microscopically. The mass of the bromine intercalated fibers was found to be 17 to 20 percent greater than their pristine counterpart. This variation decreased to 17 to 18 percent after heating in air for 3 days at 200 C and to 14.5 to 18 percent after 6 days of 260 C heating. The fiber length did not change throughout the experiment. The fiber diameter increased during intercalation and decreased slightly upon deintercalation but was not affected by heating to 260 C for 3 days in air. Comparing the mass and volume data to those with highly oriented pyrolitic graphite or natural single crystal graphite suggested the possibility that the intercalated P-100 fibers could be mostly stage 4.

Synthesis of (Hexaconazole-Zinc/Aluminum-Layered Double Hydroxide Nanocomposite) Fungicide Nanodelivery System for Controlling Ganoderma Disease in Oil Palm.

PubMed

Mustafa, Isshadiba F; Hussein, Mohd Zobir; Saifullah, Bullo; Idris, Abu Seman; Hilmi, Nur Hailini Z; Fakurazi, Sharida

2018-01-31

A fungicide, hexaconazole was successfully intercalated into the intergalleries of zinc/aluminum-layered double hydroxide (ZALDH) using the ion-exchange method. Due to the intercalation of hexaconazole, the basal spacing of the ZALDH was increased from 8.7 Å in ZALDH to 29.4 Å in hexaconazole-intercalated ZALDH (HZALDH). The intercalation of hexaconazole into the interlayer of the nanocomposite was confirmed using the Fourier-transform infrared (FTIR) study. This supramolecular chemistry intercalation process enhanced the thermal stability of the hexaconazole moiety. The fungicide loading was estimated to be 51.8%. The nanodelivery system also shows better inhibition toward the Ganoderma boninense growth than the counterpart, free hexaconazole. The results from this work have a great potential to be further explored for combating basal stem rot (BSR) disease in oil palm plantation.

Intercalating dyes for enhanced contrast in second-harmonic generation imaging of protein crystals

PubMed Central

Newman, Justin A.; Scarborough, Nicole M.; Pogranichniy, Nicholas R.; Shrestha, Rashmi K.; Closser, Richard G.; Das, Chittaranjan; Simpson, Garth J.

2015-01-01

The second-harmonic generation (SHG) activity of protein crystals was found to be enhanced by up to ∼1000-fold by the intercalation of SHG phores within the crystal lattice. Unlike the intercalation of fluorophores, the SHG phores produced no significant background SHG from solvated dye or from dye intercalated into amorphous aggregates. The polarization-dependent SHG is consistent with the chromophores adopting the symmetry of the crystal lattice. In addition, the degree of enhancement for different symmetries of dyes is consistent with theoretical predictions based on the molecular nonlinear optical response. Kinetics studies indicate that intercalation arises over a timeframe of several minutes in lysozyme, with detectable enhancements within seconds. These results provide a potential means to increase the overall diversity of protein crystals and crystal sizes amenable to characterization by SHG microscopy. PMID:26143918

Hydroxy double salts loaded with bioactive ions: Synthesis, intercalation mechanisms, and functional performance

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

Kaassis, Abdessamad Y.A.; Xu, Si-Min; Guan, Shanyue

The intercalation of the anions of diclofenac (Dic), naproxen (Nap), and valproic acid (Val) into three hydroxy double salts (HDSs) has been explored in this work. Experiments were performed with [Co{sub 1.2}Zn{sub 3.8}(OH){sub 8}](NO{sub 3}){sub 2}·2H{sub 2}O (CoZn-NO{sub 3}), [Ni{sub 2}Zn{sub 3}(OH){sub 8}](NO{sub 3}){sub 2}·2H{sub 2}O (NiZn-NO{sub 3}) and [Zn{sub 5}(OH){sub 8}](NO{sub 3}){sub 2}·2H{sub 2}O (Zn-NO{sub 3}). It proved possible to intercalate diclofenac and naproxen into all three HDSs. In contrast, Val could be intercalated into CoZn-NO{sub 3} but when it was reacted with Zn-NO{sub 3} the HDS structure was destroyed, and the product comprised ZnO. Successful intercalation was verifiedmore » by X-ray diffraction, IR spectroscopy, and elemental microanalysis. Molecular dynamics simulations showed the Dic and Nap ions to arrange themselves in an “X” shape in the interlayer space, forming a bilayer. Val was found to adopt a position with its aliphatic groups parallel to the HDS layer, again in a bilayer. In situ time resolved X-ray diffraction experiments revealed that intercalation of Dic and Nap into CoZn-NO{sub 3} and Zn-NO{sub 3} is mechanistically complex, with a number of intermediate phases observed. In contrast, the intercalation of all three guests into NiZn-NO{sub 3} and of Val into CoZn-NO{sub 3} are simple one step reactions proceeding directly from the starting material to the product. The HDS-drug composites were found to have sustained release profiles. - Graphical abstract: Seven new drug intercalates of hydroxy double salts (HDSs) have been prepared and characterised. The intercalation mechanisms have been explored, and the drug release properties of the HDS/drug composites quantified. Display Omitted.« less

Highly Conducting Graphite Epoxy Composite Demonstrated

NASA Technical Reports Server (NTRS)

Gaier, James R.

1999-01-01

Weight savings as high as 80 percent could be achieved if graphite polymer composites could replace aluminum in structures such as electromagnetic interference shielding covers and grounding planes. This could result in significant cost savings, especially for the mobile electronics found in spacecraft, aircraft, automobiles, and hand-held consumer electronics. However, such composites had not yet been fabricated with conductivity sufficient to enable these applications. To address this lack, a partnership of the NASA Lewis Research Center, Manchester College, and Applied Sciences, Inc., fabricated nonmetallic composites with unprecedented electrical conductivity. For these composites, heat-treated, vapor-grown graphite fibers were selected which have a resistivity of about 80 mW-cm, more than 20 times more conductive than typical carbon fibers. These fibers were then intercalated with iodine bromide (IBr). Intercalation is the insertion of guest atoms or molecules between the carbon planes of the graphite fibers. Since the carbon planes are not highly distorted in the process, intercalation has little effect on mechanical and thermal properties. Intercalation does, however, lower the carbon fiber resistivity to less than 10 mW-cm, which is comparable to that of metal fibers. Scaleup of the reaction was required since the initial intercalation experiments would be carried out on 20-mg quantities of fibers, and tens of grams of intercalated fibers would be needed to fabricate even small demonstration composites. The reaction was first optimized through a time and temperature study that yielded fibers with a resistivity of 8.7 2 mW-cm when exposed to IBr vapor at 114 C for 24 hours. Stability studies indicated that the intercalated fibers rapidly lost their conductivity when exposed to temperatures as low as 40 C in air. They were not, however, susceptible to degradation by water vapor in the manner of most graphite intercalation compounds. The 1000-fold scaleup experiments concluded that 114 C was near the optimum temperature, but that the intercalation time needed to be lengthened by a factor of 3.

IR study of dickite-formamide intercalate, Al 2Si 2O 5(OH) 4-H 2NCOH

NASA Astrophysics Data System (ADS)

Zamama, M.; Knidiri, Mohamed

2000-05-01

Direct intercalation of formamide (FAM) in dickite occurs spontaneously when samples are treated by ultrason. The X-ray diffraction patterns show that this intercalation increases the d 001 spacing from 7.19 to 10.77 Å. It is concluded from infrared studies that hydrogen bonds are formed between CO groups of formamide and inner surface hydroxyls of dickite, indicated by the shift of the hydroxyl bands from 3708, 3654 cm -1 and 3622 for natural dickite to 3575, 3520, 3450 and 3612 cm -1 for FAM-intercalated dickite.

IR study of dickite-formamide intercalate, Al2Si2O5(OH)4-H2NCOH.

PubMed

Zamama, M; Knidiri, M

2000-05-01

Direct intercalation of formamide (FAM) in dickite occurs spontaneously when samples are treated by ultrason. The X-ray diffraction patterns show that this intercalation increases the d001 spacing from 7.19 to 10.77 A. It is concluded from infrared studies that hydrogen bonds are formed between C=O groups of formamide and inner surface hydroxyls of dickite, indicated by the shift of the hydroxyl bands from 3708, 3654 cm(-1) and 3622 for natural dickite to 3575, 3520, 3450 and 3612 cm(-1) for FAM-intercalated dickite.

Thin-walled nanoscrolls by multi-step intercalation from tubular halloysite-10 Å and its rearrangement upon peroxide treatment

NASA Astrophysics Data System (ADS)

Zsirka, Balázs; Horváth, Erzsébet; Szabó, Péter; Juzsakova, Tatjána; Szilágyi, Róbert K.; Fertig, Dávid; Makó, Éva; Varga, Tamás; Kónya, Zoltán; Kukovecz, Ákos; Kristóf, János

2017-03-01

Surface modification of the halloysite-10 Å mineral with tubular morphology can be achieved by slightly modified procedures developed for the delamination of kaolinite minerals. The resulting delaminated halloysite nanoparticles have unexpected surface/morphological properties that display, new potentials in catalyst development. In this work, a four-step intercalation/delamination procedure is described for the preparation of thin-walled nanoscrolls from the multi-layered hydrated halloysite mineral that consists of (1) intercalation of halloysite with potassium acetate, (2) replacement intercalation with ethylene glycol, (3) replacement intercalation with hexylamine, and (4) delamination with toluene. The intercalation steps were followed by X-ray diffraction, transmission electron microscopy, N2 adsorption-desorption, thermogravimetry, and infrared spectroscopy. Delamination eliminated the crystalline order and the crystallite size along the 'c'-axis, increased the specific surface area, greatly decreased the thickness of the mineral tubes to a monolayer, and shifted the pore diameter toward the micropore region. Unexpectedly, the removal of residual organics from intercalation steps adsorbed at the nanoscroll surface with a peroxide treatment resulted in partial recovery of crystallinity and increase of crystallite size along the 'c'-crystal direction. The d(001) value showed a diffuse pattern at 7.4-7.7 Å due to the rearrangement of the thin-walled nanoscrolls toward the initial tubular morphology of the dehydrated halloysite-7 Å mineral.

Mechanochemical synthesis and intercalation of Ca(II)Fe(III)-layered double hydroxides

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

Ferencz, Zs.; Szabados, M.; Varga, G.

2016-01-15

A mechanochemical method (grinding the components without added water – dry grinding, followed by further grinding in the presence of minute amount of water or NaOH solution – wet grinding) was used in this work for the preparation and intercalation of CaFe-layered double hydroxides (LDHs). Both the pristine LDHs and the amino acid anion (cystinate and tyrosinate) intercalated varieties were prepared by the two-step grinding procedure in a mixer mill. By systematically changing the conditions of the preparation method, a set of parameters could be determined, which led to the formation of close to phase-pure LDH. The optimisation procedure wasmore » also applied for the intercalation processes of the amino acid anions. The resulting materials were structurally characterised by a range of methods (X-ray diffractometry, scanning electron microscopy, energy dispersive analysis, thermogravimetry, X-ray absorption and infra-red spectroscopies). It was proven that this simple mechanochemical procedure was able to produce complex organic–inorganic nanocomposites: LDHs intercalated with amino acid anions. - Graphical abstract: Amino acid anion-Ca(II)Fe(III)-LDHs were successfully prepared by a two-step milling procedure. - Highlights: • Synthesis of pristine and amino acid intercalated CaFe-LDHs by two-step milling. • Identifying the optimum synthesis and intercalation parameters. • Characterisation of the samples with a range of instrumental methods.« less

CDC-42 Orients Cell Migration during Epithelial Intercalation in the Caenorhabditis elegans Epidermis.

PubMed

Walck-Shannon, Elise; Lucas, Bethany; Chin-Sang, Ian; Reiner, David; Kumfer, Kraig; Cochran, Hunter; Bothfeld, William; Hardin, Jeff

2016-11-01

Cell intercalation is a highly directed cell rearrangement that is essential for animal morphogenesis. As such, intercalation requires orchestration of cell polarity across the plane of the tissue. CDC-42 is a Rho family GTPase with key functions in cell polarity, yet its role during epithelial intercalation has not been established because its roles early in embryogenesis have historically made it difficult to study. To circumvent these early requirements, in this paper we use tissue-specific and conditional loss-of-function approaches to identify a role for CDC-42 during intercalation of the Caenorhabditis elegans dorsal embryonic epidermis. CDC-42 activity is enriched in the medial tips of intercalating cells, which extend as cells migrate past one another. Moreover, CDC-42 is involved in both the efficient formation and orientation of cell tips during cell rearrangement. Using conditional loss-of-function we also show that the PAR complex functions in tip formation and orientation. Additionally, we find that the sole C. elegans Eph receptor, VAB-1, functions during this process in an Ephrin-independent manner. Using epistasis analysis, we find that vab-1 lies in the same genetic pathway as cdc-42 and is responsible for polarizing CDC-42 activity to the medial tip. Together, these data establish a previously uncharacterized role for polarized CDC-42, in conjunction with PAR-6, PAR-3 and an Eph receptor, during epithelial intercalation.

CDC-42 Orients Cell Migration during Epithelial Intercalation in the Caenorhabditis elegans Epidermis

PubMed Central

Lucas, Bethany; Chin-Sang, Ian; Reiner, David; Kumfer, Kraig

2016-01-01

Cell intercalation is a highly directed cell rearrangement that is essential for animal morphogenesis. As such, intercalation requires orchestration of cell polarity across the plane of the tissue. CDC-42 is a Rho family GTPase with key functions in cell polarity, yet its role during epithelial intercalation has not been established because its roles early in embryogenesis have historically made it difficult to study. To circumvent these early requirements, in this paper we use tissue-specific and conditional loss-of-function approaches to identify a role for CDC-42 during intercalation of the Caenorhabditis elegans dorsal embryonic epidermis. CDC-42 activity is enriched in the medial tips of intercalating cells, which extend as cells migrate past one another. Moreover, CDC-42 is involved in both the efficient formation and orientation of cell tips during cell rearrangement. Using conditional loss-of-function we also show that the PAR complex functions in tip formation and orientation. Additionally, we find that the sole C. elegans Eph receptor, VAB-1, functions during this process in an Ephrin-independent manner. Using epistasis analysis, we find that vab-1 lies in the same genetic pathway as cdc-42 and is responsible for polarizing CDC-42 activity to the medial tip. Together, these data establish a previously uncharacterized role for polarized CDC-42, in conjunction with PAR-6, PAR-3 and an Eph receptor, during epithelial intercalation. PMID:27861585

An intercalated BSc degree is associated with higher marks in subsequent medical school examinations.

PubMed

Cleland, Jennifer A; Milne, Andrew; Sinclair, Hazel; Lee, Amanda J

2009-05-19

To compare medical students on a modern MBChB programme who did an optional intercalated degree with their peers who did not intercalate; in particular, to monitor performance in subsequent undergraduate degree exams. This was a retrospective, observational study of anonymised databases of medical student assessment outcomes. Data were accessed for graduates, University of Aberdeen Medical School, Scotland, UK, from the years 2003 to 2007 (n = 861). The main outcome measure was marks for summative degree assessments taken after intercalating. Of 861 medical students, 154 (17.9%) students did an intercalated degree. After adjustment for cohort, maturity, gender and baseline (3rd year) performance in matching exam type, having done an IC degree was significantly associated with attaining high (18-20) common assessment scale (CAS) marks in three of the six degree assessments occurring after the IC students rejoined the course: the 4th year written exam (p < 0.001), 4th year OSCE (p = 0.001) and the 5th year Elective project (p = 0.010). Intercalating was associated with improved performance in Years 4 and 5 of the MBChB. This improved performance will further contribute to higher academic ranking for Foundation Year posts. Long-term follow-up is required to identify if doing an optional intercalated degree as part of a modern medical degree is associated with following a career in academic medicine.

An intercalated BSc degree is associated with higher marks in subsequent medical school examinations

PubMed Central

Cleland, Jennifer A; Milne, Andrew; Sinclair, Hazel; Lee, Amanda J

2009-01-01

Background To compare medical students on a modern MBChB programme who did an optional intercalated degree with their peers who did not intercalate; in particular, to monitor performance in subsequent undergraduate degree exams. Methods This was a retrospective, observational study of anonymised databases of medical student assessment outcomes. Data were accessed for graduates, University of Aberdeen Medical School, Scotland, UK, from the years 2003 to 2007 (n = 861). The main outcome measure was marks for summative degree assessments taken after intercalating. Results Of 861 medical students, 154 (17.9%) students did an intercalated degree. After adjustment for cohort, maturity, gender and baseline (3rd year) performance in matching exam type, having done an IC degree was significantly associated with attaining high (18–20) common assessment scale (CAS) marks in three of the six degree assessments occurring after the IC students rejoined the course: the 4th year written exam (p < 0.001), 4th year OSCE (p = 0.001) and the 5th year Elective project (p = 0.010). Conclusion Intercalating was associated with improved performance in Years 4 and 5 of the MBChB. This improved performance will further contribute to higher academic ranking for Foundation Year posts. Long-term follow-up is required to identify if doing an optional intercalated degree as part of a modern medical degree is associated with following a career in academic medicine. PMID:19454007

A systematic review of definitions and classification systems of adjacent segment pathology.

PubMed

Kraemer, Paul; Fehlings, Michael G; Hashimoto, Robin; Lee, Michael J; Anderson, Paul A; Chapman, Jens R; Raich, Annie; Norvell, Daniel C

2012-10-15

Systematic review. To undertake a systematic review to determine how "adjacent segment degeneration," "adjacent segment disease," or clinical pathological processes that serve as surrogates for adjacent segment pathology are classified and defined in the peer-reviewed literature. Adjacent segment degeneration and adjacent segment disease are terms referring to degenerative changes known to occur after reconstructive spine surgery, most commonly at an immediately adjacent functional spinal unit. These can include disc degeneration, instability, spinal stenosis, facet degeneration, and deformity. The true incidence and clinical impact of degenerative changes at the adjacent segment is unclear because there is lack of a universally accepted classification system that rigorously addresses clinical and radiological issues. A systematic review of the English language literature was undertaken and articles were classified using the Grades of Recommendation Assessment, Development, and Evaluation criteria. RESULTS.: Seven classification systems of spinal degeneration, including degeneration at the adjacent segment, were identified. None have been evaluated for reliability or validity specific to patients with degeneration at the adjacent segment. The ways in which terms related to adjacent segment "degeneration" or "disease" are defined in the peer-reviewed literature are highly variable. On the basis of the systematic review presented in this article, no formal classification system for either cervical or thoracolumbar adjacent segment disorders currently exists. No recommendations regarding the use of current classification of degeneration at any segments can be made based on the available literature. A new comprehensive definition for adjacent segment pathology (ASP, the now preferred terminology) has been proposed in this Focus Issue, which reflects the diverse pathology observed at functional spinal units adjacent to previous spinal reconstruction and balances detailed stratification with clinical utility. A comprehensive classification system is being developed through expert opinion and will require validation as well as peer review. Strength of Statement: Strong.

Acceptor-type hydroxide graphite intercalation compounds electrochemically formed in high ionic strength solutions.

PubMed

Miyazaki, Kohei; Iizuka, Asuka; Mikata, Koji; Fukutsuka, Tomokazu; Abe, Takeshi

2017-09-05

The intercalation of hydroxide ions (OH - ) into graphite formed graphite intercalation compounds (GICs) in high ionic strength solutions. GICs of solvated OH - anions with two water molecules (OH - ·2H 2 O) in alkaline aqueous solutions and GICs of only OH - anions in a molten NaOH-KOH salt solution were electrochemically synthesized.

Comparative analysis of topoisomerase IB inhibition and DNA intercalation by flavonoids and similar compounds: structural determinates of activity

PubMed Central

2004-01-01

Flavonoids and other polyphenolic compounds have been shown to inhibit human topoisomerase IB (topo I) through both inhibition of relaxation activity and through stabilization of the cleavable complex (poisoning). Some flavonoids have also been shown to intercalate DNA, and an association of topoisomerase inhibition with intercalation has been noted. We surveyed 34 polyphenolic compounds, primarily flavonoid glycones and aglycones, for their ability to inhibit topo I and to intercalate DNA using an in vitro gel electrophoresis method. We show that the most potent topo I poisons are the flavones and flavonols, and that these generally, but not always, are found to be DNA intercalators. There was no clear correlation, however, of topo-I-poisoning activity with the degree of DNA unwinding. Surprisingly, both DNA intercalation and topo I poisoning were shown to occur with some flavone glycones, including the C-glycosylflavone orientin. Inhibition of relaxation activity by flavonoids was found to be difficult to quantify and was most likely to be due to non-specific inhibition through flavonoid aggregation. As part of a structure–activity analysis, we also investigated the acid–base chemistry of flavonoids and determined that many flavonoids show acid–base activity with a pKa in the physiological pH region. For this reason, subtle pH changes can have significant effects on solution activity of flavonoids and their concomitant biological activity. In addition, these effects may be complicated by pH-dependent aggregation and oxidative degradation. Finally, we develop a simple model for the intercalation of flavonoids into DNA and discuss possible consequences of intercalation and topoisomerase inhibition on a number of cellular processes. PMID:15312049

Large-scale symmetry-adapted perturbation theory computations via density fitting and Laplace transformation techniques: investigating the fundamental forces of DNA-intercalator interactions.

PubMed

Hohenstein, Edward G; Parrish, Robert M; Sherrill, C David; Turney, Justin M; Schaefer, Henry F

2011-11-07

Symmetry-adapted perturbation theory (SAPT) provides a means of probing the fundamental nature of intermolecular interactions. Low-orders of SAPT (here, SAPT0) are especially attractive since they provide qualitative (sometimes quantitative) results while remaining tractable for large systems. The application of density fitting and Laplace transformation techniques to SAPT0 can significantly reduce the expense associated with these computations and make even larger systems accessible. We present new factorizations of the SAPT0 equations with density-fitted two-electron integrals and the first application of Laplace transformations of energy denominators to SAPT. The improved scalability of the DF-SAPT0 implementation allows it to be applied to systems with more than 200 atoms and 2800 basis functions. The Laplace-transformed energy denominators are compared to analogous partial Cholesky decompositions of the energy denominator tensor. Application of our new DF-SAPT0 program to the intercalation of DNA by proflavine has allowed us to determine the nature of the proflavine-DNA interaction. Overall, the proflavine-DNA interaction contains important contributions from both electrostatics and dispersion. The energetics of the intercalator interaction are are dominated by the stacking interactions (two-thirds of the total), but contain important contributions from the intercalator-backbone interactions. It is hypothesized that the geometry of the complex will be determined by the interactions of the intercalator with the backbone, because by shifting toward one side of the backbone, the intercalator can form two long hydrogen-bonding type interactions. The long-range interactions between the intercalator and the next-nearest base pairs appear to be negligible, justifying the use of truncated DNA models in computational studies of intercalation interaction energies.

Large-scale symmetry-adapted perturbation theory computations via density fitting and Laplace transformation techniques: Investigating the fundamental forces of DNA-intercalator interactions

NASA Astrophysics Data System (ADS)

Hohenstein, Edward G.; Parrish, Robert M.; Sherrill, C. David; Turney, Justin M.; Schaefer, Henry F.

2011-11-01

Symmetry-adapted perturbation theory (SAPT) provides a means of probing the fundamental nature of intermolecular interactions. Low-orders of SAPT (here, SAPT0) are especially attractive since they provide qualitative (sometimes quantitative) results while remaining tractable for large systems. The application of density fitting and Laplace transformation techniques to SAPT0 can significantly reduce the expense associated with these computations and make even larger systems accessible. We present new factorizations of the SAPT0 equations with density-fitted two-electron integrals and the first application of Laplace transformations of energy denominators to SAPT. The improved scalability of the DF-SAPT0 implementation allows it to be applied to systems with more than 200 atoms and 2800 basis functions. The Laplace-transformed energy denominators are compared to analogous partial Cholesky decompositions of the energy denominator tensor. Application of our new DF-SAPT0 program to the intercalation of DNA by proflavine has allowed us to determine the nature of the proflavine-DNA interaction. Overall, the proflavine-DNA interaction contains important contributions from both electrostatics and dispersion. The energetics of the intercalator interaction are are dominated by the stacking interactions (two-thirds of the total), but contain important contributions from the intercalator-backbone interactions. It is hypothesized that the geometry of the complex will be determined by the interactions of the intercalator with the backbone, because by shifting toward one side of the backbone, the intercalator can form two long hydrogen-bonding type interactions. The long-range interactions between the intercalator and the next-nearest base pairs appear to be negligible, justifying the use of truncated DNA models in computational studies of intercalation interaction energies.

XRD, SEM and infrared study into the intercalation of sodium hexadecyl sulfate (SHS) into hydrocalumite.

PubMed

Zhang, Ping; Wang, Tianqi; Zhang, Longlong; Wu, Daishe; Frost, Ray L

2015-12-05

Hydrocalumite (CaAl-LDH-Cl) interacted with a natural anionic surfactant, sodium hexadecyl sulfate (SHS), was performed using an intercalation method. To understand the intercalation behavior and characterize the resulting products, powder X-ray diffraction (XRD), scan electron microscopy (SEM) and mid-infrared (MIR) spectroscopy combined with near-infrared (NIR) spectroscopy technique were used. The XRD analysis indicated that SHS was intercalated into CaAl-LDH-Cl successfully, resulting in an expansion of the interlayer (from 0.78 nm to 2.74 nm). The bands of C-H stretching vibrations of SHS were observed in the near-infrared spectra, which indicated that the resulting products were indeed CaAl-LDH-SHS. In addition, the bands of water stretching vibrations and OH groups shifted to higher wavenumbers when SHS was intercalated into CaAl-LDH-Cl interlayer space. Copyright © 2015 Elsevier B.V. All rights reserved.

Calcium intercalation into layered fluorinated sodium iron phosphate

DOE PAGES

Lipson, Albert L.; Kim, Soojeong; Pan, Baofei; ...

2017-10-09

Here, the energy density and cost of battery systems could be improved by moving to alternative battery chemistries such as Ca-ion. However, in order to switch chemistries many problems need to be solved including the identification of cathode materials with high energy density, and electrolytes that can plate and strip calcium metal. Herein, the feasibility and cycling performance of Ca 2+ intercalation into a desodiated layered Na 2FePO 4F host is described. This is the first demonstration of Ca 2+ intercalation into a polyanionic framework, which implies that other polyanionic framework materials may be active for Ca 2+ intercalation. Althoughmore » substantial effort is still needed to identify a high energy density cathode material, this study and others demonstrate the feasibility of Ca 2+ intercalation into multiple materials making it more probable that such a cathode material can be found.« less

Calcium intercalation into layered fluorinated sodium iron phosphate

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

Lipson, Albert L.; Kim, Soojeong; Pan, Baofei

Here, the energy density and cost of battery systems could be improved by moving to alternative battery chemistries such as Ca-ion. However, in order to switch chemistries many problems need to be solved including the identification of cathode materials with high energy density, and electrolytes that can plate and strip calcium metal. Herein, the feasibility and cycling performance of Ca 2+ intercalation into a desodiated layered Na 2FePO 4F host is described. This is the first demonstration of Ca 2+ intercalation into a polyanionic framework, which implies that other polyanionic framework materials may be active for Ca 2+ intercalation. Althoughmore » substantial effort is still needed to identify a high energy density cathode material, this study and others demonstrate the feasibility of Ca 2+ intercalation into multiple materials making it more probable that such a cathode material can be found.« less

Unified picture of the doping dependence of superconducting transition temperatures in alkali metal/ammonia intercalated FeSe

NASA Astrophysics Data System (ADS)

Guterding, Daniel; Jeschke, Harald; Hirschfeld, Peter; Valenti, Roser

2015-03-01

We present a theoretical investigation of alkali metal/ammonia intercalated iron selenide. Using ab-initio density functional theory we unravel how charge doping and dimensionality of the electronic structure can be controlled through the chemical composition of the intercalated molecules. Within random phase approximation spin fluctuation theory we analyze the impact of intercalation on the superconducting pairing strength. We find that high Tc is to be expected away from perfect nesting. While experimental studies have focused on the intercalation of larger molecules in the spacer layer so far, we argue that no higher Tc can be achieved this way. This work was supported by Deutsche Forschungsgemeinschaft under Grant No. SPP 1458, the National Science Foundation under Grant No. PHY11-25915 and the Department of Energy under Grant No. DE-FG02-05ER46236.

Intercalation of paracetamol into the hydrotalcite-like host

NASA Astrophysics Data System (ADS)

Kovanda, František; Maryšková, Zuzana; Kovář, Petr

2011-12-01

Hydrotalcite-like compounds are often used as host structures for intercalation of various anionic species. The product intercalated with the nonionic, water-soluble pharmaceuticals paracetamol, N-(4-hydroxyphenyl)acetamide, was prepared by rehydration of the Mg-Al mixed oxide obtained by calcination of hydrotalcite-like precursor at 500 °C. The successful intercalation of paracetamol molecules into the interlayer space was confirmed by powder X-ray diffraction and infrared spectroscopy measurements. Molecular simulations showed that the phenolic hydroxyl groups of paracetamol interact with hydroxide sheets of the host via the hydroxyl groups of the positively charged sites of Al-containing octahedra; the interlayer water molecules are located mostly near the hydroxide sheets. The arrangement of paracetamol molecules in the interlayer is rather disordered and interactions between neighboring molecules cause their tilting towards the hydroxide sheets. Dissolution tests in various media showed slower release of paracetamol intercalated in the hydrotalcite-like host in comparison with tablets containing the powdered pharmaceuticals.

Supramolecular polymer formation by cyclic dinucleotides and intercalators affects dinucleotide enzymatic processing

PubMed Central

Nakayama, Shizuka; Zhou, Jie; Zheng, Yue; Szmacinski, Henryk; Sintim, Herman O

2016-01-01

Background: Cyclic dinucleotides form supramolecular aggregates with intercalators, and this property could be utilized in nanotechnology and medicine. Methods & results: Atomic force microscopy and electrophoretic mobility shift assays were used to show that cyclic diguanylic acid (c-di-GMP) forms G-wires in the presence of intercalators. The average fluorescence lifetime of thiazole orange, when bound to c-di-GMP was greater than when bound to DNA G-quadruplexes or dsDNA. The stability of c-di-GMP supramolecular polymers is dependent on both the nature of the cation present and the intercalator. C-di-GMP or cyclic diadenylic acid/intercalator complexes are more resistant to cleavage by YybT, a phosphodiesterase, than the uncomplexed nucleotides. Conclusion: Cleavage of bacterial cyclic dinucleotides could be slowed down via complexation with small molecules and that this could be utilized for diverse applications in nanotechnology and medicine. PMID:28031943

Effect of adsorbed/intercalated anionic dyes into the mechanical properties of PVA: layered zinc hydroxide nitrate nanocomposites.

PubMed

Marangoni, Rafael; Mikowski, Alexandre; Wypych, Fernando

2010-11-15

Zinc hydroxide nitrate (ZHN) was adsorbed with anions of blue dyes (Chicago sky blue, CSB; Evans blue, EB; and Niagara blue, NB) and intercalated with anions of orange dyes (Orange G, OG; Orange II, OII; methyl orange, MO). Transparent, homogeneous and colored nanocomposite films were obtained by casting after dispersing the pigments (dye-intercalated/adsorbed into LHSs) into commercial poly(vinyl alcohol) (PVA). The films were characterized by XRD, UV-Vis spectroscopy, and mechanical testing. The mechanical properties of the PVA compounded with the dye-intercalated/adsorbed ZHN were evaluated, and reasonable increases in Young's modulus and ultimate tensile strength were observed, depending on the amount and choice of layered filler. These results demonstrate the possibility of using a new class of layered hydroxide salts intercalated and adsorbed with anionic dyes to prepare multifunctional polymer nanocomposite materials. Copyright © 2010 Elsevier Inc. All rights reserved.

Advantage of straight walk instability in turning maneuver of multilegged locomotion: a robotics approach

PubMed Central

Aoi, Shinya; Tanaka, Takahiro; Fujiki, Soichiro; Funato, Tetsuro; Senda, Kei; Tsuchiya, Kazuo

2016-01-01

Multilegged locomotion improves the mobility of terrestrial animals and artifacts. Using many legs has advantages, such as the ability to avoid falling and to tolerate leg malfunction. However, many intrinsic degrees of freedom make the motion planning and control difficult, and many contact legs can impede the maneuverability during locomotion. The underlying mechanism for generating agile locomotion using many legs remains unclear from biological and engineering viewpoints. The present study used a centipede-like multilegged robot composed of six body segments and twelve legs. The body segments are passively connected through yaw joints with torsional springs. The dynamic stability of the robot walking in a straight line changes through a supercritical Hopf bifurcation due to the body axis flexibility. We focused on a quick turning task of the robot and quantitatively investigated the relationship between stability and maneuverability in multilegged locomotion by using a simple control strategy. Our experimental results show that the straight walk instability does help the turning maneuver. We discuss the importance and relevance of our findings for biological systems and propose a design principle for a simple control scheme to create maneuverable locomotion of multilegged robots. PMID:27444746

Anomalous toluene transport in model segmented polyurethane-urea/clay nanocomposites.

PubMed

Rath, Sangram K; Bahadur, Jitendra; Panda, Himanshu S; Sen, Debasis; Patro, T Umasankar; S, Praveen; Patri, Manornajan; Khakhar, Devang V

2018-05-16

The kinetics of liquid solvent sorption in polymeric systems and their nanocomposites often deviate from normal Fickian behaviour. This needs to be understood and interpreted, in terms of their underlying mechanistic origins. In the present study, the results of time dependent toluene sorption measurements in model segmented polyurethane-urea/clay nanocomposites have been analysed at room temperature. The studies revealed pronounced S-shaped sorption curves and unusually higher swelling of the nanocomposites compared to the neat polyurethane-urea matrix. Dynamic mechanical analysis (DMA) and small angle X-ray scattering (SAXS) measurements on the nanocomposites in the dry and liquid toluene saturated state have been carried out. The DMA studies revealed a significant decrease in the α relaxation temperature and storage modulus of the nanocomposites in the swollen state compared to the dry samples. The SAXS results showed that the nanoclay dispersion morphology transformed from intercalation in the dry state to exfoliation in the swollen state and the interdomain distance between hard segments increased upon swelling. Thermodynamic analysis of the Flory-Huggins interaction parameter (χ) of nanocomposite/toluene systems revealed increasingly negative χ values with increased clay loading. These results imply a significant plasticization effect of toluene on the nanocomposites. An interpretation of these data, which relates the abovementioned results, is presented in the framework of differential swelling stress (DSS) induced deviation from Fickian transport characteristics. We expect that these findings and methods may provide new insight into the analysis of the solvent diffusion process in heterogeneous polymers and their nanocomposites.

Hydroxy double salts intercalated with Mn(II) complexes as potential contrast agents

NASA Astrophysics Data System (ADS)

Jin, Miao; Li, Wanjing; Spillane, Dominic E. M.; Geraldes, Carlos F. G. C.; Williams, Gareth R.; Bligh, S. W. Annie

2016-03-01

A series of Mn(II) aminophosphonate complexes were successfully synthesized and intercalated into the hydroxy double salt [Zn5(OH)8]Cl2·yH2O. Complex incorporation led to an increase in the interlayer spacing from 7.8 to 10-12 Å. Infrared spectroscopy showed the presence of the characteristic vibration peaks of the Mn(II) complexes in the intercalates' spectra, indicating successful incorporation. The complex-loaded composites had somewhat lower proton relaxivities than the pure complexes. Nevertheless, these intercalates may have use as MRI contrast agents for patients with poor kidney function, where traditional Gd(III)-based contrast agents cause severe renal failure.

High voltage and high specific capacity dual intercalating electrode Li-ion batteries

NASA Technical Reports Server (NTRS)

Blanco, Mario (Inventor); West, William C. (Inventor)

2010-01-01

The present invention provides high capacity and high voltage Li-ion batteries that have a carbonaceous cathode and a nonaqueous electrolyte solution comprising LiF salt and an anion receptor that binds the fluoride ion. The batteries can comprise dual intercalating electrode Li ion batteries. Methods of the present invention use a cathode and electrode pair, wherein each of the electrodes reversibly intercalate ions provided by a LiF salt to make a high voltage and high specific capacity dual intercalating electrode Li-ion battery. The present methods and systems provide high-capacity batteries particularly useful in powering devices where minimizing battery mass is important.

Intercalated cell-specific Rh B glycoprotein deletion diminishes renal ammonia excretion response to hypokalemia

PubMed Central

Bishop, Jesse M.; Lee, Hyun-Wook; Handlogten, Mary E.; Han, Ki-Hwan; Verlander, Jill W.

2013-01-01

The ammonia transporter family member, Rh B Glycoprotein (Rhbg), is an ammonia-specific transporter heavily expressed in the kidney and is necessary for the normal increase in ammonia excretion in response to metabolic acidosis. Hypokalemia is a common clinical condition in which there is increased renal ammonia excretion despite the absence of metabolic acidosis. The purpose of this study was to examine Rhbg's role in this response through the use of mice with intercalated cell-specific Rhbg deletion (IC-Rhbg-KO). Hypokalemia induced by feeding a K+-free diet increased urinary ammonia excretion significantly. In mice with intact Rhbg expression, hypokalemia increased Rhbg protein expression in intercalated cells in the cortical collecting duct (CCD) and in the outer medullary collecting duct (OMCD). Deletion of Rhbg from intercalated cells inhibited hypokalemia-induced changes in urinary total ammonia excretion significantly and completely prevented hypokalemia-induced increases in urinary ammonia concentration, but did not alter urinary pH. We conclude that hypokalemia increases Rhbg expression in intercalated cells in the cortex and outer medulla and that intercalated cell Rhbg expression is necessary for the normal increase in renal ammonia excretion in response to hypokalemia. PMID:23220726

Preparation, quantitative surface analysis, intercalation characteristics and industrial implications of low temperature expandable graphite

NASA Astrophysics Data System (ADS)

Peng, Tiefeng; Liu, Bin; Gao, Xuechao; Luo, Liqun; Sun, Hongjuan

2018-06-01

Expandable graphite is widely used as a new functional carbon material, especially as fire-retardant; however, its practical application is limited due to the high expansion temperature. In this work, preparation process of low temperature and highly expandable graphite was studied, using natural flake graphite as raw material and KMnO4/HClO4/NH4NO3 as oxidative intercalations. The structure, morphology, functional groups and thermal properties were characterized during expanding process by Fourier transform infrared spectroscopy (FTIR), Raman spectra, thermo-gravimetry differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), and scanning electron microscope (SEM). The analysis showed that by oxidation intercalation, some oxygen-containing groups were grafted on the edge and within the graphite layer. The intercalation reagent entered the graphite layer to increase the interlayer spacing. After expansion, the original flaky expandable graphite was completely transformed into worm-like expanded graphite. The order of graphite intercalation compounds (GICs) was proposed and determined to be 3 for the prepared expandable graphite, based on quantitative XRD peak analysis. Meanwhile, the detailed intercalation mechanisms were also proposed. The comprehensive investigation paved a benchmark for the industrial application of such sulfur-free expanded graphite.

Durability of Intercalated Graphite Epoxy Composites in Low Earth Orbit

NASA Technical Reports Server (NTRS)

Gaier, James R.; Davidson, Michelle L.; Shively, Rhonda

1996-01-01

The electrical conductivity of graphite epoxy composites can be substantially increased by intercalating (inserting guest atoms or molecules between the graphene planes) the graphite fibers before composite formation. The resulting high strength, low density, electrically conducting composites have been proposed for EMI shielding in spacecraft. Questions have been raised, however, about their durability in the space environment, especially with respect to outgassing of the intercalates, which are corrosive species such as bromine. To answer those concerns, six samples of bromine intercalated graphite epoxy composites were included in the third Evaluation of Oxygen Interaction with Materials (EOIM-3) experiment flown on the Space Shuttle Discovery (STS-46). Changes in electrical conductivity, optical reflectance, surface texture, and mass loss for SiO2 protected and unprotected samples were measured after being exposed to the LEO environment for 42 hours. SiO2 protected samples showed no degradation, verifying conventional protection strategies are applicable to bromine intercalated composites. The unprotected samples showed that bromine intercalation does not alter the degradation of graphite-epoxy composites. No bromine was detected to have been released by the fibers allaying fears that outgassing could be disruptive to the sensitive electronics the EMI shield is meant to protect.

Alternative Splicing of CHEK2 and Codeletion with NF2 Promote Chromosomal Instability in Meningioma1

PubMed Central

Yang, Hong Wei; Kim, Tae-Min; Song, Sydney S; Shrinath, Nihal; Park, Richard; Kalamarides, Michel; Park, Peter J; Black, Peter M; Carroll, Rona S; Johnson, Mark D

2012-01-01

Mutations of the NF2 gene on chromosome 22q are thought to initiate tumorigenesis in nearly 50% of meningiomas, and 22q deletion is the earliest and most frequent large-scale chromosomal abnormality observed in these tumors. In aggressive meningiomas, 22q deletions are generally accompanied by the presence of large-scale segmental abnormalities involving other chromosomes, but the reasons for this association are unknown. We find that large-scale chromosomal alterations accumulate during meningioma progression primarily in tumors harboring 22q deletions, suggesting 22q-associated chromosomal instability. Here we show frequent codeletion of the DNA repair and tumor suppressor gene, CHEK2, in combination with NF2 on chromosome 22q in a majority of aggressive meningiomas. In addition, tumor-specific splicing of CHEK2 in meningioma leads to decreased functional Chk2 protein expression. We show that enforced Chk2 knockdown in meningioma cells decreases DNA repair. Furthermore, Chk2 depletion increases centrosome amplification, thereby promoting chromosomal instability. Taken together, these data indicate that alternative splicing and frequent codeletion of CHEK2 and NF2 contribute to the genomic instability and associated development of aggressive biologic behavior in meningiomas. PMID:22355270

Modification of thermal and electronic properties of bilayer graphene by using slow Na+ ions

NASA Astrophysics Data System (ADS)

Ryu, Mintae; Lee, Paengro; Kim, Jingul; Park, Heemin; Chung, Jinwook

2016-12-01

Bilayer graphene (BLG) has an extensive list of industrial applications in graphene-based nanodevices such as energy storage devices, flexible displays, and thermoelectric devices. By doping slow Na+ ions on Li-intercalated BLG, we find significantly improved thermal and electronic properties of BLG by using angle-resolved photoemission and high-resolution core level spectroscopy (HRCLS) with synchrotron photons. Our HRCLS data reveal that the adsorbed Na+ ions on a BLG produced by Li-intercalation through single layer graphene (SLG) spontaneously intercalate below the BLG, and substitute Li atoms to form Na-Si bonds at the SiC interface while preserving the same phase of BLG. This is in sharp contrast with no intercalation of Na+ ions on SLG though neutral Na atoms intercalate. The Na+-induced BLG is found to be stable upon heating up to T = 400 °C, but returns to SLG when heated at T d = 500 °C. The evolution of the π-bands upon doping the Na+ ions followed by thermal annealing shows that the carrier concentration of the π-band may be artificially controlled without damaging the Dirac nature of the π-electrons. The doubled desorption temperature from that (T d = 250 °C) of the Na-intercalated SLG together with the electronic stability of the Na+-intercalated BLG may find more practical and effective applications in advancing graphene-based thermoelectric devices and anode materials for rechargeable batteries.

Modelling of adsorption and intercalation of hydrogen on/into tungsten disulphide multilayers and multiwall nanotubes.

PubMed

Martínez, José I; Laikhtman, Alex; Moon, Hoi Ri; Zak, Alla; Alonso, Julio A

2018-05-07

Understanding the interaction of hydrogen with layered materials is crucial in the fields of sensors, catalysis, fuel cells and hydrogen storage, among others. Density functional theory, improved by the introduction of van der Waals dispersion forces, provides an efficient and practical workbench to investigate the interaction of molecular and atomic hydrogen with WS 2 multilayers and nanotubes. We find that H 2 physisorbs on the surface of those materials on top of W atoms, while atomic H chemisorbs on top of S atoms. In the case of nanotubes, the chemisorption strength is sensitive to the nanotube diameter. Diffusion of H 2 on the surface of WS 2 encounters quite small activation barriers whose magnitude helps to explain previous and new experimental results for the observed dependence of the hydrogen concentration with temperature. Intercalation of H 2 between adjacent planar WS 2 layers reveals an endothermic character. Intercalating H atoms is energetically favorable, but the intercalation energy does not compensate for the cost of dissociating the molecules. When H 2 molecules are intercalated between the walls of a double wall nanotube, the rigid confinement induces the dissociation of the confined molecules. A remarkable result is that the presence of a full H 2 monolayer adsorbed on top of the first WS 2 layer of a WS 2 multilayer system strongly facilitates the intercalation of H 2 between WS 2 layers underneath. This opens up an additional gate to intercalation processes.

Surgery for failed cervical spine reconstruction.

PubMed

Helgeson, Melvin D; Albert, Todd J

2012-03-01

Review article. To review the indications, operative strategy, and complications of revision cervical spine reconstruction. With many surgeons expanding their indications for cervical spine surgery, the number of patients being treated operatively has increased. Unfortunately, the number of patients requiring revision procedures is also increasing, but very little literature exists reviewing changes in the indications or operative planning for revision reconstruction. Narrative and review of the literature. In addition to the well-accepted indications for primary cervical spine surgery (radiculopathy, myelopathy, instability, and tumor), we have used the following indications for revision surgery: pseudarthrosis, adjacent segment degeneration, inadequate decompression, iatrogenic instability, and deformity. Our surgical goal for pseudarthrosis is obviously to obtain a fusion, which can usually be performed with an approach not done previously. Our surgical goals for instability and deformity are more complex, with a focus on decompression of any neurologic compression, correction of deformity, and stability. Revision cervical spine reconstruction is safe and effective if performed for the appropriate indications and with proper planning.

Sensitivity analysis for future space missions with segmented telescopes for high-contrast imaging

NASA Astrophysics Data System (ADS)

Leboulleux, Lucie; Pueyo, Laurent; Sauvage, Jean-François; Mazoyer, Johan; Soummer, Remi; Fusco, Thierry; Sivaramakrishnan, Anand

2018-01-01

The detection and analysis of biomarkers on earth-like planets using direct-imaging will require both high-contrast imaging and spectroscopy at very close angular separation (10^10 star to planet flux ratio at a few 0.1”). This goal can only be achieved with large telescopes in space to overcome atmospheric turbulence, often combined with a coronagraphic instrument with wavefront control. Large segmented space telescopes such as studied for the LUVOIR mission will generate segment-level instabilities and cophasing errors in addition to local mirror surface errors and other aberrations of the overall optical system. These effects contribute directly to the degradation of the final image quality and contrast. We present an analytical model that produces coronagraphic images of a segmented pupil telescope in the presence of segment phasing aberrations expressed as Zernike polynomials. This model relies on a pair-based projection of the segmented pupil and provides results that match an end-to-end simulation with an rms error on the final contrast of ~3%. This analytical model can be applied both to static and dynamic modes, and either in monochromatic or broadband light. It retires the need for end-to-end Monte-Carlo simulations that are otherwise needed to build a rigorous error budget, by enabling quasi-instantaneous analytical evaluations. The ability to invert directly the analytical model provides direct constraints and tolerances on all segments-level phasing and aberrations.

Cytoplasm enhancement operator of peripheral blood smear images that are instable-stained and overexposed

NASA Astrophysics Data System (ADS)

Zheng, Xin; Wang, Guoyou; Liu, Jianguo

2015-12-01

Nucleus and cytoplasm are both essential for white blood cell recognition but the edges of cytoplasm are too blurry to be detected because of instable staining and overexposure. This paper aims at proposing a cytoplasm enhancement operator (CEO) to achieve accurate convergence of the active contour model. The CEO contains two parts. First, a nonlinear over-exposure enhancer map is yielded to correct over-exposure, which suppresses background noise while preserving details and improving contrast. Second, the over-exposed regions of cytoplasm in particular is further enhanced by a tri- modal histogram specification based on the scale-space filtering. The experimental results show that the proposed CEO and its corresponding GVF snake is superior to other unsupervised segmentation approaches.

The origins and impact of primate segmental duplications.

PubMed

Marques-Bonet, Tomas; Girirajan, Santhosh; Eichler, Evan E

2009-10-01

Duplicated sequences are substrates for the emergence of new genes and are an important source of genetic instability associated with rare and common diseases. Analyses of primate genomes have shown an increase in the proportion of interspersed segmental duplications (SDs) within the genomes of humans and great apes. This contrasts with other mammalian genomes that seem to have their recently duplicated sequences organized in a tandem configuration. In this review, we focus on the mechanistic origin and impact of this difference with respect to evolution, genetic diversity and primate phenotype. Although many genomes will be sequenced in the future, resolution of this aspect of genomic architecture still requires high quality sequences and detailed analyses.

Maximizing power output from continuous-wave single-frequency fiber amplifiers.

PubMed

Ward, Benjamin G

2015-02-15

This Letter reports on a method of maximizing the power output from highly saturated cladding-pumped continuous-wave single-frequency fiber amplifiers simultaneously, taking into account the stimulated Brillouin scattering and transverse modal instability thresholds. This results in a design figure of merit depending on the fundamental mode overlap with the doping profile, the peak Brillouin gain coefficient, and the peak mode coupling gain coefficient. This figure of merit is then numerically analyzed for three candidate fiber designs including standard, segmented acoustically tailored, and micro-segmented acoustically tailored photonic-crystal fibers. It is found that each of the latter two fibers should enable a 50% higher output power than standard photonic crystal fiber.

Electrochemical oxygen intercalation into Sr2IrO4

NASA Astrophysics Data System (ADS)

Fruchter, L.; Brouet, V.; Colson, D.; Moussy, J.-B.; Forget, A.; Li, Z. Z.

2018-01-01

Oxygen was electrochemically intercalated into Sr2IrO4 sintered samples, single crystals and a thin film. We estimate the diffusion length to a few μm and the concentration of the intercalated oxygen to δ ≃ 0.01. The latter is thus much smaller than for the cuprate and nickelate parent compounds, for which δ > 0.1 is obtained, which could be a consequence of larger steric effects. The influence of the oxygen doping state on resistivity is small, indicating also a poor charge transfer to the conduction band. It is shown that electrochemical intercalation of oxygen may also contribute to doping, when gating thin films with ionic liquid in the presence of water.

Synthesis of reduced graphene oxide intercalated ZnO quantum dots nanoballs for selective biosensing detection

NASA Astrophysics Data System (ADS)

Chen, Jing; Zhao, Minggang; Li, Yingchun; Fan, Sisi; Ding, Longjiang; Liang, Jingjing; Chen, Shougang

2016-07-01

ZnO quantum dots (QDs), reduced graphene oxide (rGO) and multi-walled carbon nanotubes (MWCNTs) are always used in sensors due to their excellent electrochemical characteristics. In this work, ZnO QDs were intercalated by rGO sheets with cross-linked MWCNTs to construct intercalation nanoballs. A MWCNTs/rGO/ZnO QDs 3D hierarchical architecture was fabricated on supporting Ni foam, which exhibited excellent mechanical, kinetic and electrochemical properties. The intercalation construction can introduce strong interfacial effects to improve the surface electronic state. The selectively determinate of uric acid, dopamine, and ascorbic acid by an electrode material using distinct applied potentials was realized.

H-1 NMR study of ternary ammonia-alkali metal-graphite intercalation compounds

NASA Technical Reports Server (NTRS)

Tsang, T.; Fronko, R. M.; Resing, H. A.; Qian, X. W.; Solin, S. A.

1987-01-01

For the first-stage ternary ammonia-alkali metal-graphite intercalation compounds M(NH3)(x)C24(x of about 4, M = K, Rb, Cs), three sets of triplet H-1 NMR spectral lines have been observed at various temperatures and orientations due to the H-1 - H-1 and N-14 - H-1 dipolar interactions. The structures of these compounds have been inferred as mobile (liquid-like) intercalant layers of planar M(NH3)4 ions in between the carbon layers. For the intercalated ammonia molecules, the potential barrier is about 0.2 eV and the molecular geometry is very close to the free NH3 in gas phase.

Environmentally benign graphite intercalation compound composition for exfoliated graphite, flexible graphite, and nano-scaled graphene platelets

DOEpatents

Zhamu, Aruna; Jang, Bor Z.

2014-06-17

A carboxylic-intercalated graphite compound composition for the production of exfoliated graphite, flexible graphite, or nano-scaled graphene platelets. The composition comprises a layered graphite with interlayer spaces or interstices and a carboxylic acid residing in at least one of the interstices, wherein the composition is prepared by a chemical oxidation reaction which uses a combination of a carboxylic acid and hydrogen peroxide as an intercalate source. Alternatively, the composition may be prepared by an electrochemical reaction, which uses a carboxylic acid as both an electrolyte and an intercalate source. Exfoliation of the invented composition does not release undesirable chemical contaminants into air or drainage.

A comparative study of graphite electrodes using the co-intercalation phenomenon for rechargeable Li, Na and K batteries.

PubMed

Kim, Haegyeom; Yoon, Gabin; Lim, Kyungmi; Kang, Kisuk

2016-10-18

Here, we demonstrate that graphite can serve as a versatile electrode for various rechargeable battery types by reversibly accommodating solvated alkali ions (such as K, Na, and Li) through co-intercalation in its galleries. The co-intercalation of alkali ions is observed to occur via staging reactions. Notably, their insertion behaviors, including their specific capacity, are remarkably similar regardless of the alkali ion species despite the different solubility limits of K, Na, and Li ions in graphite. Nevertheless, the insertion potentials of the solvated alkali ions differ from each other and are observed to be correlated with the interlayer distance in the intercalated graphite gallery.

Intercalating cobalt between graphene and iridium (111): Spatially dependent kinetics from the edges

NASA Astrophysics Data System (ADS)

Vlaic, Sergio; Rougemaille, Nicolas; Kimouche, Amina; Burgos, Benito Santos; Locatelli, Andrea; Coraux, Johann

2017-10-01

Using low-energy electron microscopy, we image in real time the intercalation of a cobalt monolayer between graphene and the (111) surface of iridium. Our measurements reveal that the edges of a graphene flake represent an energy barrier to intercalation. Based on a simple description of the growth kinetics, we estimate this energy barrier and find small, but substantial, local variations. These local variations suggest a possible influence of the graphene orientation with respect to its substrate and of the graphene edge termination on the energy value of the barrier height. Besides, our measurements show that intercalated cobalt is energetically more favorable than cobalt on bare iridium, indicating a surfactant role of graphene.

Effect of friction on oxidative graphite intercalation and high-quality graphene formation.

PubMed

Seiler, Steffen; Halbig, Christian E; Grote, Fabian; Rietsch, Philipp; Börrnert, Felix; Kaiser, Ute; Meyer, Bernd; Eigler, Siegfried

2018-02-26

Oxidative wet-chemical delamination of graphene from graphite is expected to become a scalable production method. However, the formation process of the intermediate stage-1 graphite sulfate by sulfuric acid intercalation and its subsequent oxidation are poorly understood and lattice defect formation must be avoided. Here, we demonstrate film formation of micrometer-sized graphene flakes with lattice defects down to 0.02% and visualize the carbon lattice by transmission electron microscopy at atomic resolution. Interestingly, we find that only well-ordered, highly crystalline graphite delaminates into oxo-functionalized graphene, whereas other graphite grades do not form a proper stage-1 intercalate and revert back to graphite upon hydrolysis. Ab initio molecular dynamics simulations show that ideal stacking and electronic oxidation of the graphite layers significantly reduce the friction of the moving sulfuric acid molecules, thereby facilitating intercalation. Furthermore, the evaluation of the stability of oxo-species in graphite sulfate supports an oxidation mechanism that obviates intercalation of the oxidant.

First-principles study on interlayer state in alkali and alkaline earth metal atoms intercalated bilayer graphene

NASA Astrophysics Data System (ADS)

Kaneko, Tomoaki; Saito, Riichiro

2017-11-01

Energetics and electronic structures of alkali metal (Li, Na, K, Rb, and Cs) and alkaline earth metal (Be, Mg, Ca, Sr, and Ba) atoms intercalated bilayer graphene are systematically investigated using first-principles calculations based on density functional theory. Formation of alkali and alkaline earth metal atoms intercalated bilayer graphene is exothermic except for Be and Mg. The interlayer state between two graphene layers is occupied for K, Rb, Cs, Ca, Sr, and Ba. We find that the energetic position of the interlayer states between bilayer graphene monotonically shifts downward with increasing of interlayer distance. The interlayer distances of more than 4.5 Å and 4.0 Å, respectively, are necessary for the occupation of the interlayer state in bilayer graphene for alkali and alkaline earth metal atoms, which is almost independent of the intercalant metal species. We discuss the relevance to occurrence of superconductivity for the metal intercalated bilayer graphene in terms of the occupation of the interlayer state and the phonon frequency of metal ions.

Iodine Intercalation of Bundles of Single Wall Carbon Nanotubes (SWNT)

NASA Astrophysics Data System (ADS)

Grigorian, L.; Fang, S. L.; Williams, K. A.; Sumanasekera, G. U.; Dickey, E. C.; Eklund, P. C.; Pennycock, S.; Rinzler, A. G.; Smalley, R. E.

1998-03-01

We have been able to intercalate iodine into the interstitial channels within the rope lattice by direct contact of SWNT mats with molten iodine. These continuously filled channels were observed by Z-contrast STEM imaging. The intercalated iodine atoms provide a ``chemical wedge'' which expands the rope lattice as found from x-ray powder diffraction. At low doping level, Raman-active modes and photoluminescence were used to identify the intercalated species as (I_3)^-I2 linear polyiodide chains. The observed upshift of the high-frequency tangential Raman mode, as well as decreased values of four-probe electrical resistance and thermopower are all consistent with electron transfer from SWNT to iodine. At higher doping level, another iodine-SWNT compound was formed as evidenced by a different x-ray diffraction pattern and Raman spectrum. This new compound exhibits a number of new Raman lines, apparently unrelated to the intercalated iodine, in addition to the usual SWNT Raman modes. We discuss possible mechanisms responsible for activating new Raman modes in SWNT.

Intercalated hybrid of kaolinite with KH2PO4 showing high ionic conductivity (∼10-4 S cm-1) at room temperature

NASA Astrophysics Data System (ADS)

Liu, Shao-Xian; Xue, Chen; Yang, Hao; Huang, Xiao-Qing; Zou, Yang; Ding, Yan-Ni; Li, Li; Ren, Xiao-Ming

2017-12-01

In this paper, we present the study of preparation and ionic conductance for an intercalated hybrid of kaolinite with potassium dihydrogen. The intercalation efficiency is high up to ca. 90%. The intercalated hybrid has been characterized by powder X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. The ionic conductivity (σ) of the hybrid material is strongly dependent on the moisture in the environment, with σ = 8.4 × 10-10 S cm-1 at 293 K and gradually increases to 7.16 × 10-9 S cm-1 under N2 atmosphere (anhydrous environment) at 353 K as well as an activation energy of Ea = 0.618 e V, whereas σ = 2.19 × 10-4 S cm-1 at 100% relative humidity and 293 K with Ea = 0.44 eV. The mechanism that the moisture affects the ionic conductance of the intercalated hybrid is further discussed.

Process to Selectively Distinguish Viable from Non-Viable Bacterial Cells

NASA Technical Reports Server (NTRS)

LaDuc, Myron T.; Bernardini, Jame N.; Stam, Christina N.

2010-01-01

The combination of ethidium monoazide (EMA) and post-fragmentation, randomly primed DNA amplification technologies will enhance the analytical capability to discern viable from non-viable bacterial cells in spacecraft-related samples. Intercalating agents have been widely used since the inception of molecular biology to stain and visualize nucleic acids. Only recently, intercalating agents such as EMA have been exploited to selectively distinguish viable from dead bacterial cells. Intercalating dyes can only penetrate the membranes of dead cells. Once through the membrane and actually inside the cell, they intercalate DNA and, upon photolysis with visible light, produce stable DNA monoadducts. Once the DNA is crosslinked, it becomes insoluble and unable to be fragmented for post-fragmentation, randomly primed DNA library formation. Viable organisms DNA remains unaffected by the intercalating agents, allowing for amplification via post-fragmentation, randomly primed technologies. This results in the ability to carry out downstream nucleic acid-based analyses on viable microbes to the exclusion of all non-viable cells.

Electrochemical and in-situ X-ray diffraction studies of Ti 3C 2T x MXene in ionic liquid electrolyte

DOE PAGES

Lin, Zifeng; Rozier, Patrick; Duployer, Benjamin; ...

2016-08-26

2D titanium carbide (Ti 3C 2T x MXene) showed good capacitance in both organic and neat ionic liquid electrolytes, but its charge storage mechanism is still not fully understood. Here, electrochemical characteristics of Ti 3C 2T x electrode were studied in neat EMI-TFSI electrolyte. A capacitive behavior was observed within a large electrochemical potential range (from – 1.5 to 1.5 V vs. Ag). Intercalation and de-intercalation of EMI + cations and/or TFSI– anions were investigated by in-situ X-ray diffraction. Interlayer spacing of Ti 3C 2T x flakes decreases during positive polarization, which can be ascribed to either electrostatic attraction effectmore » between intercalated TFSI– anions and positively charged Ti 3C 2T x nanosheets or steric effect caused by de-intercalation of EMI + cations. In conclusion, the expansion of interlayer spacing when polarized to negative potentials is explained by steric effect of cation intercalation.« less

Calcium intercalation into layered fluorinated sodium iron phosphate

NASA Astrophysics Data System (ADS)

Lipson, Albert L.; Kim, Soojeong; Pan, Baofei; Liao, Chen; Fister, Timothy T.; Ingram, Brian J.

2017-11-01

The energy density and cost of battery systems, relative to the current state-of-the art, can be improved by developing alternative chemistries utilizing multivalent working ions such as calcium. Many challenges must be overcome, such as the identification of cathode materials with high energy density and an electrolyte with a wide electrochemical stability window that can plate and strip calcium metal, before market implementation. Herein, the feasibility and cycling performance of Ca2+ intercalation into a desodiated layered Na2FePO4F host is described. This is the first demonstration of Ca2+ intercalation into a polyanionic framework, which implies that other polyanionic framework materials may be active for Ca2+ intercalation. Although substantial effort is expected in order to develop a high energy density cathode material, this study demonstrates the feasibility of Ca2+ intercalation into multiple host structures types, thereby extending opportunities for development of Ca insertion host structures, suggesting such a cathode material can be identified and developed.

Mechanochemical synthesis and intercalation of Ca(II)Fe(III)-layered double hydroxides

NASA Astrophysics Data System (ADS)

Ferencz, Zs.; Szabados, M.; Varga, G.; Csendes, Z.; Kukovecz, Á.; Kónya, Z.; Carlson, S.; Sipos, P.; Pálinkó, I.

2016-01-01

A mechanochemical method (grinding the components without added water - dry grinding, followed by further grinding in the presence of minute amount of water or NaOH solution - wet grinding) was used in this work for the preparation and intercalation of CaFe-layered double hydroxides (LDHs). Both the pristine LDHs and the amino acid anion (cystinate and tyrosinate) intercalated varieties were prepared by the two-step grinding procedure in a mixer mill. By systematically changing the conditions of the preparation method, a set of parameters could be determined, which led to the formation of close to phase-pure LDH. The optimisation procedure was also applied for the intercalation processes of the amino acid anions. The resulting materials were structurally characterised by a range of methods (X-ray diffractometry, scanning electron microscopy, energy dispersive analysis, thermogravimetry, X-ray absorption and infra-red spectroscopies). It was proven that this simple mechanochemical procedure was able to produce complex organic-inorganic nanocomposites: LDHs intercalated with amino acid anions.

Localized concentration reversal of lithium during intercalation into nanoparticles

PubMed Central

Zhang, Wei; Yu, Hui-Chia; Wu, Lijun; Liu, Hao; Abdellahi, Aziz; Qiu, Bao; Bai, Jianming; Orvananos, Bernardo; Strobridge, Fiona C.; Zhou, Xufeng; Liu, Zhaoping; Ceder, Gerbrand; Zhu, Yimei; Thornton, Katsuyo; Grey, Clare P.; Wang, Feng

2018-01-01

Nanoparticulate electrodes, such as LixFePO4, have unique advantages over their microparticulate counterparts for the applications in Li-ion batteries because of the shortened diffusion path and access to nonequilibrium routes for fast Li incorporation, thus radically boosting power density of the electrodes. However, how Li intercalation occurs locally in a single nanoparticle of such materials remains unresolved because real-time observation at such a fine scale is still lacking. We report visualization of local Li intercalation via solid-solution transformation in individual LixFePO4 nanoparticles, enabled by probing sub-angstrom changes in the lattice spacing in situ. The real-time observation reveals inhomogeneous intercalation, accompanied with an unexpected reversal of Li concentration at the nanometer scale. The origin of the reversal phenomenon is elucidated through phase-field simulations, and it is attributed to the presence of structurally different regions that have distinct chemical potential functions. The findings from this study provide a new perspective on the local intercalation dynamics in battery electrodes. PMID:29340302

One-step synthesis of layered yttrium hydroxides in immiscible liquid-liquid systems: Intercalation of sterically-bulky hydrophobic organic anions and doping of europium ions

NASA Astrophysics Data System (ADS)

Watanabe, Mebae; Fujihara, Shinobu

2014-02-01

Inorganic-organic layered rare-earth compounds were synthesized on the basis of a biphasic liquid-liquid system in one pot. Layered yttrium hydroxides (LYHs) were chosen as a host material for the intercalation of hydrophobic organic guest anions such as benzoate, sebacate, or laurate. In a typical synthesis, an organic phase dissolving carboxylic acid was placed in contact with an equal amount of an aqueous phase dissolving yttrium nitrate n-hydrate and urea. At elevated temperatures up to 80 °C, urea was hydrolyzed to release hydroxyl anions which were used to form yttrium hydroxide layers. LYHs were then precipitated with the intercalation of carboxylate anions delivered from the organic phase under the distribution law. The structure and the morphology of the LYHs could be modulated by the intercalated anions. Doped with Eu3+ ions, the LYHs exhibited red photoluminescence which was enhanced by the intercalated anions due to the antenna effect.

Preparation of nanostructured and nanosheets of MoS2 oxide using oxidation method.

PubMed

Amini, Majed; Ramazani S A, Ahmad; Faghihi, Morteza; Fattahpour, Seyyedfaridoddin

2017-11-01

Molybdenum disulfide (MoS 2 ), a two-dimensional transition metal has a 2D layered structure and has recently attracted attention due to its novel catalytic properties. In this study, MoS 2 has been successfully intercalated using chemical and physical intercalation techniques, while enhancing its surface properties. The final intercalated MoS 2 is of many interests because of its low-dimensional and potential properties in in-situ catalysis. In this research, we report different methods to intercalate the layers of MoS 2 successfully using acid-treatment, ultrasonication, oxidation and thermal shocking. The other goal of this study is to form SO bonds mainly because of expected enhanced in-situ catalytic operations. The intercalated MoS 2 is further characterized using analyses such as Fourier Transform Infrared Spectroscopy (FTIR), Raman, Contact Angle, X-ray diffraction (XRD), Field Emission Scanning Electron Microscope (FESEM), Energy Dispersive X-Ray Microanalysis (EDAX), Transmission electron microscopy (TEM), and BET. Copyright © 2017. Published by Elsevier B.V.

Borderline Glenoid Bone Defect in Anterior Shoulder Instability: Latarjet Procedure Versus Bankart Repair.

PubMed

Jeon, Yoon Sang; Jeong, Ho Yeon; Lee, Dong Ki; Rhee, Yong Girl

2018-06-01

The optimal procedure for anterior shoulder instability with a borderline (15%-20%) bone defect on the anterior rim of the glenoid is still controversial. To compare the clinical outcome and recurrence rate between the arthroscopic Bankart repair and Latarjet procedure among patients with recurrent anterior shoulder instability and a borderline glenoid bone defect. Cohort study; Level of evidence, 3. The authors retrospectively reviewed cases of arthroscopic Bankart repair and the Latarjet procedure for recurrent anterior shoulder instability with a borderline (15%-20%) glenoid bone defect. Enrollment comprised 149 patients (Bankart group, n = 118; Latarjet group, n = 31). The mean follow-up and age at operation were 28.9 ± 7.3 months (range, 24-73 months) and 26 ± 5 years (range, 16-46 years), respectively. Rowe and UCLA (University of California, Los Angeles) shoulder scores significantly improved from 42.0 ± 14.3 and 22.9 ± 3.2 preoperatively to 90.9 ± 15.4 and 32.5 ± 3.3 postoperatively in the Bankart group ( P < .001) and from 41.0 ± 17.9 and 22.3 ± 3.4 to 91.1 ± 16.1 and 32.3 ± 3.4 in the Latarjet group ( P < .001), respectively. There were no significant between-group differences in Rowe ( P = .920) or UCLA ( P = .715) scores at the final follow-up. Mean postoperative loss of motion during forward flexion, external rotation in abduction, and internal rotation to the posterior was 3.0° ± 6.2°, 11.6° ± 10.2°, and 0.6 spinal segment in the Bankart group and 3.7° ± 9.8°, 10.3° ± 12.8°, and 0.9 spinal segment in the Latarjet group, respectively. These differences were not significant. However, the loss of external rotation at the side was significantly greater in the Bankart group (13.3° ± 12.9°) than in the Latarjet group (7.3° ± 18.1°, P = .034). The overall recurrence rate was significantly higher in the Bankart group (22.9%) than in the Latarjet group (6.5%), ( P = .040). The Latarjet procedure and arthroscopic Bankart repair both provided satisfactory clinical outcome scores and pain relief for anterior shoulder instability with a borderline glenoid bone defect. However, the Latarjet procedure resulted in significantly lower recurrences and less external rotation limitation than the arthroscopic Bankart repair. Therefore, the Latarjet procedure could be a more reliable surgical option in anterior recurrent instability with a borderline glenoid bone defect.

Cam impingement of the posterior femoral condyle in medial meniscal tears.

PubMed

Suganuma, Jun; Mochizuki, Ryuta; Yamaguchi, Kenji; Inoue, Yutaka; Yamabe, Eikou; Ueda, Yoshiyuki; Fujinaka, Tarou

2010-02-01

The aim of this study was to compare the results of meniscal repair of the medial meniscus with or without decompression of the posterior segment of the medial meniscus for the treatment of posteromedial tibiofemoral incongruence at full flexion (PMTFI), which induces deformation of the posterior segment on sagittal magnetic resonance imaging (MRI). For more than 2 years, we followed up 27 patients with PMTFI who were classified into the following 2 groups. Group 1 included 8 patients (5 male joints and 3 female joints) with a medial meniscal tear with instability at the site of the tear who underwent meniscal repair. The mean age was 23.6 years. Group 2 included 19 patients (16 male joints and 3 female joints) who had a meniscal tear with instability at the site of the tear and underwent meniscal repair and decompression. The mean age was 26.5 years. In decompression of the posterior segment, redundant bone tissue on the most proximal part of the medial femoral condyle was excised. The patients were assessed by use of the Lysholm score, sagittal MRI at full flexion, and arthroscopic examination. There were no statistical differences in mean Lysholm score between the 2 groups before surgery, but the mean score in group 2 was significantly higher than that in group 1 after surgery. Meniscal deformation of the posterior segment at full flexion on MRI disappeared in all cases after decompression. On second-look arthroscopy, the rate of complete healing at the site of the tear was 0% in group 1 but 57% in group 2, and it was significantly different between these groups. The addition of decompression of the posterior segment of the medial meniscus to meniscal repair of knee joints with PMTFI allowed more room for the medial meniscus to accommodate and improved both function of the knee joint and the rate of success of repair of isolated medial meniscal tears in patients who regularly performed full knee flexion. (c) 2010 Arthroscopy Association of North America. Published by Elsevier Inc. All rights reserved.

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

Rubinson, Emily H.; Prakasha Gowda, A.S.; Spratt, Thomas E.

DNA glycosylases that remove alkylated and deaminated purine nucleobases are essential DNA repair enzymes that protect the genome, and at the same time confound cancer alkylation therapy, by excising cytotoxic N3-methyladenine bases formed by DNA-targeting anticancer compounds. The basis for glycosylase specificity towards N3- and N7-alkylpurines is believed to result from intrinsic instability of the modified bases and not from direct enzyme functional group chemistry. Here we present crystal structures of the recently discovered Bacillus cereus AlkD glycosylase in complex with DNAs containing alkylated, mismatched and abasic nucleotides. Unlike other glycosylases, AlkD captures the extrahelical lesion in a solvent-exposed orientation,more » providing an illustration for how hydrolysis of N3- and N7-alkylated bases may be facilitated by increased lifetime out of the DNA helix. The structures and supporting biochemical analysis of base flipping and catalysis reveal how the HEAT repeats of AlkD distort the DNA backbone to detect non-Watson-Crick base pairs without duplex intercalation.« less

Nematic and chiral superconductivity induced by odd-parity fluctuations

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

Wu, Fengcheng; Martin, Ivar

Recent experiments indicate that superconductivity in Bi 2Se 3 intercalated with Cu, Nb, or Sr is nematic with rotational symmetry breaking. Motivated by this observation, we present a model study of nematic and chiral superconductivity induced by odd-parity fluctuations. Additionally, we show that odd-parity fluctuations in the two-component E u representation of D 3d crystal point group can generate attractive interaction in both the even-parity s-wave and odd-parity E-u pairing channels, but repulsive interaction in other odd-parity pairing channels. Coulomb repulsion can suppress s-wave pairing relative to E u pairing, and thus the latter can have a higher critical temperature.more » E u pairing has two distinct phases: a nematic phase and a chiral phase, both of which can be realized in our model. Finally, when s-wave and E u pairings have similar instability temperature, we find an intermediate phase in which both types of pairing coexist.« less

Nematic and chiral superconductivity induced by odd-parity fluctuations

DOE PAGES

Wu, Fengcheng; Martin, Ivar

2017-10-09

Recent experiments indicate that superconductivity in Bi 2Se 3 intercalated with Cu, Nb, or Sr is nematic with rotational symmetry breaking. Motivated by this observation, we present a model study of nematic and chiral superconductivity induced by odd-parity fluctuations. Additionally, we show that odd-parity fluctuations in the two-component E u representation of D 3d crystal point group can generate attractive interaction in both the even-parity s-wave and odd-parity E-u pairing channels, but repulsive interaction in other odd-parity pairing channels. Coulomb repulsion can suppress s-wave pairing relative to E u pairing, and thus the latter can have a higher critical temperature.more » E u pairing has two distinct phases: a nematic phase and a chiral phase, both of which can be realized in our model. Finally, when s-wave and E u pairings have similar instability temperature, we find an intermediate phase in which both types of pairing coexist.« less

Effect of taping on foot kinematics in persons with chronic ankle instability.

PubMed

Deschamps, Kevin; Dingenen, Bart; Pans, Femke; Van Bavel, Isabelle; Matricali, Giovanni Arnoldo; Staes, Filip

2016-07-01

To investigate differences in rigid-foot and multi-segmental foot kinematics between healthy (control) and chronic ankle instability (CAI) participants during running and to evaluate the effect of low-Dye (LD) and high-Dye (HD) taping on foot kinematics of CAI subjects. Cross-sectional, comparative study. Kinematic data of 12 controls and 15 CAI participants were collected by a 3D motion analysis system during running. CAI participants performed barefoot (CAI_BF) running trials as well as trials with taping. A rigid Plug-in gait Model and the Rizzoli 3D Multi-Segment Foot Model were used. Groups were compared using one-dimensional statistical parametric mapping. An increased inversion, a decreased dorsiflexion between the foot and tibia and a decreased external foot progression angle were found during terminal swing and early stance in the CAI_BF group. With respect to the taped conditions, post-hoc SPM{t} calculations highlighted a more dorsiflexed rearfoot (38-46% running cycle) in the CAI_HD compared to the CAI_LD, and a more inverted Mid-Met angle (6-24% running cycle) in the CAI_LD compared to the CAI_BF condition. This study revealed significant differences in rigid foot and multi-segmental foot kinematics between all groups. As high-dye taping embraces shank-rearfoot and forefoot, it seems to have better therapeutic features with respect to low-dye taping as the latter created a more inverted forefoot which may not be recommended in this population. Copyright © 2015 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

Electronic properties of carbon fibers intercalated with copper chloride

NASA Technical Reports Server (NTRS)

Oshima, H.; Natarajan, V.; Woollam, J. A.; Yavrouian, A.; Haugland, E. J.; Tsuzuku, T.

1984-01-01

Copper chloride intercalated pitch-based carbon fibers are found to have electrical resistivities as low as 12.9 micro-ohm-cm, and are air- and thermally-stable at and above room temperature. This is therefore a good candidate system for conductor application. In addition, Shubnikov-deHaas quantum oscillatory effects were found, and electronic properties of the intercalated fiber are studied using magnetic fields to 20 tesla.

Kaolinite Nanocomposite Platelets Synthesized by Intercalation and Imidization of Poly(styrene-co-maleic anhydride)

PubMed Central

Samyn, Pieter; Schoukens, Gustaaf; Stanssens, Dirk

2015-01-01

A synthesis route is presented for the subsequent intercalation, exfoliation and surface modification of kaolinite (Kln) by an imidization reaction of high-molecular weight poly(styrene-co-maleic anhydride) or SMA in the presence of ammonium hydroxide. In a first step, the intercalation of ammonolyzed SMA by guest displacement of intercalated dimethylsulfoxide has been proven. In a second step, the imidization of ammonolyzed SMA at 160 °C results in exfoliation of the kaolinite layers and deposition of poly(styrene-co-maleimide) or SMI nanoparticles onto the kaolinite surfaces. Compared with a physical mixture of Kln/SMI, the chemically reacted Kln/SMI provides more efficient exfoliation and hydrogen bonding between the nanoparticles and the kaolinite. The kaolinite nanocomposite particles are synthesized in aqueous dispersion with solid content of 65 wt %. The intercalation and exfoliation are optimized for a concentration ratio of Kln/SMI = 70:30, resulting in maximum intercalation and interlayer distance in combination with highest imide content. After thermal curing at 135 °C, the imidization proceeds towards a maximum conversion of the intermediate amic acid moieties. The changes in O–H stretching and kaolinite lattice vibrations have been illustrated by infrared and FT-Raman spectroscopy, which allow for a good quantification of concentration and imidization effects. PMID:28793445

Structural Analysis of HMGD-DNA Complexes Reveal Influence of Intercalation on Sequence Selectivity and DNA Bending

PubMed Central

Churchill, Mair E.A.; Klass, Janet; Zoetewey, David L.

2010-01-01

The ubiquitous eukaryotic High-Mobility-Group-Box (HMGB) chromosomal proteins promote many chromatin-mediated cellular activities through their non-sequence-specific binding and bending of DNA. Minor groove DNA binding by the HMG box results in substantial DNA bending toward the major groove owing to electrostatic interactions, shape complementarity and DNA intercalation that occurs at two sites. Here, the structures of the complexes formed with DNA by a partially DNA intercalation-deficient mutant of Drosophila melanogaster HMGD have been determined by X-ray crystallography at a resolution of 2.85 Å. The six proteins and fifty base pairs of DNA in the crystal structure revealed a variety of bound conformations. All of the proteins bound in the minor groove, bridging DNA molecules, presumably because these DNA regions are easily deformed. The loss of the primary site of DNA intercalation decreased overall DNA bending and shape complementarity. However, DNA bending at the secondary site of intercalation was retained and most protein-DNA contacts were preserved. The mode of binding resembles the HMGB1-boxA-cisplatin-DNA complex, which also lacks a primary intercalating residue. This study provides new insights into the binding mechanisms used by HMG boxes to recognize varied DNA structures and sequences as well as modulate DNA structure and DNA bending. PMID:20800069

Self-Activating, Capacitive Anion Intercalation Enables High-Power Graphite Cathodes.

PubMed

Wang, Gang; Yu, Minghao; Wang, Jungang; Li, Debao; Tan, Deming; Löffler, Markus; Zhuang, Xiaodong; Müllen, Klaus; Feng, Xinliang

2018-05-01

Developing high-power cathodes is crucial to construct next-generation quick-charge batteries for electric transportation and grid applications. However, this mainly relies on nanoengineering strategies at the expense of low scalability and high battery cost. Another option is provided herein to build high-power cathodes by exploiting inexpensive bulk graphite as the active electrode material, where anion intercalation is involved. With the assistance of a strong alginate binder, the disintegration problem of graphite cathodes due to the large volume variation of >130% is well suppressed, making it possible to investigate the intrinsic electrochemical behavior and to elucidate the charge storage kinetics of graphite cathodes. Ultrahigh power capability up to 42.9 kW kg -1 at the energy density of >300 Wh kg -1 (based on graphite mass) and long cycling life over 10 000 cycles are achieved, much higher than those of conventional cathode materials for Li-ion batteries. A self-activating and capacitive anion intercalation into graphite is discovered for the first time, making graphite a new intrinsic intercalation-pseudocapacitance cathode material. The finding highlights the kinetical difference of anion intercalation (as cathode) from cation intercalation (as anode) into graphitic carbon materials, and new high-power energy storage devices will be inspired. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stochasticity and stereotypy in the Ciona notochord.

PubMed

Carlson, Maia; Reeves, Wendy; Veeman, Michael

2015-01-15

Fate mapping with single cell resolution has typically been confined to embryos with completely stereotyped development. The lineages giving rise to the 40 cells of the Ciona notochord are invariant, but the intercalation of those cells into a single-file column is not. Here we use genetic labeling methods to fate map the Ciona notochord with both high resolution and large sample sizes. We find that the ordering of notochord cells into a single column is not random, but instead shows a distinctive signature characteristic of mediolaterally-biased intercalation. We find that patterns of cell intercalation in the notochord are somewhat stochastic but far more stereotyped than previously believed. Cell behaviors vary by lineage, with the secondary notochord lineage being much more constrained than the primary lineage. Within the primary lineage, patterns of intercalation reflect the geometry of the intercalating tissue. We identify the latest point at which notochord morphogenesis is largely stereotyped, which is shortly before the onset of mediolateral intercalation and immediately after the final cell divisions in the primary lineage. These divisions are consistently oriented along the AP axis. Our results indicate that the interplay between stereotyped and stochastic cell behaviors in morphogenesis can only be assessed by fate mapping experiments that have both cellular resolution and large sample sizes. Copyright © 2014 Elsevier Inc. All rights reserved.

Stochasticity and Stereotypy in the Ciona Notochord

PubMed Central

Carlson, Maia; Reeves, Wendy; Veeman, Michael

2015-01-01

Fate mapping with single cell resolution has typically been confined to embryos with completely stereotyped development. The lineages giving rise to the 40 cells of the Ciona notochord are invariant, but the intercalation of those cells into a single-file column is not. Here we use genetic labeling methods to fate map the Ciona notochord with both high resolution and large sample sizes. We find that the ordering of notochord cells into a single column is not random, but instead shows a distinctive signature characteristic of mediolaterally-biased intercalation. We find that patterns of cell intercalation in the notochord are somewhat stochastic but far more stereotyped than previously believed. Cell behaviors vary by lineage, with the secondary notochord lineage being much more constrained than the primary lineage. Within the primary lineage, patterns of intercalation reflect the geometry of the intercalating tissue. We identify the latest point at which notochord morphogenesis is largely stereotyped, which is shortly before the onset of mediolateral intercalation and immediately after the final cell divisions in the primary lineage. These divisions are consistently oriented along the AP axis. Our results indicate that the interplay between stereotyped and stochastic cell behaviors in morphogenesis can only be assessed by fate mapping experiments that have both cellular resolution and large sample sizes. PMID:25459659

Atomistic Conversion Reaction Mechanism of WO 3 in Secondary Ion Batteries of Li, Na, and Ca

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

He, Yang; Gu, Meng; Xiao, Haiyan

2016-04-13

Reversible insertion and extraction of ionic species into a host lattice governs the basic operating principle for both rechargeable battery (such as lithium batteries) and electrochromic devices (such as ANA Boeing 787-8 Dreamliner electrochromic window). Intercalation and/or conversion are two fundamental chemical processes for some materials in response to the ion insertion. The interplay between these two chemical processes has never been established. It is speculated that the conversion reaction is initiated by ion intercalation. However, experimental evidence of intercalation and subsequent conversion remains unexplored. Here, using in situ HRTEM and spectroscopy, we captured the atomistic conversion reaction processes duringmore » lithium, sodium and calcium ion insertion into tungsten trioxide (WO3) single crystal model electrodes. An intercalation step right prior to conversion is explicitly revealed at atomic scale for the first time for these three ion species. Combining nanoscale diffraction and ab initio molecular dynamics simulations, it is found that, beyond intercalation, the inserted ion-oxygen bonding formation destabilized the transition-metal framework which gradually shrunk, distorted and finally collapsed to a pseudo-amorphous structure. This study provides a full atomistic picture on the transition from intercalation to conversion, which is of essential for material applications in both secondary ion batteries and electrochromic devices.« less

Effect of humidity and water intercalation on the tribological behavior of graphene and graphene oxide.

PubMed

Arif, Taib; Colas, Guillaume; Filleter, Tobin

2018-06-12

In this work, the effect of humidity and water intercalation on the friction and wear behavior of few-layers of graphene and graphene oxide (GO) was studied using friction force microscopy. Thickness measurements demonstrated significant water intercalation within GO affecting its surface topography (roughness and protrusions), whereas negligible water intercalation of graphene was observed. It was found that water intercalation in GO contributed to wearing of layers at a relative humidity as low as ~30%. The influence of surface wettability and water adsorption was also studied by comparing the sliding behavior of SiO2/GO, SiO2/Graphene, and SiO2/SiO2 interfaces. Friction for the SiO2/GO interface increased with relative humidity due to water intercalation and condensation of water. In contrast, it was observed that adsorption of water molecules lubricated the SiO2/SiO2 interface due to easy shearing of water on the hydrophobic surface, particularly once the adsorbed water layers had transitioned from "ice-like water" to "liquid-like water" structures. Lastly, an opposite friction trend was observed for the graphene/SiO2 interface with water molecules failing to lubricate the interface as compared to the dry graphene/SiO2 contact.

Li intercalation in graphite: A van der Waals density-functional study

NASA Astrophysics Data System (ADS)

Hazrati, E.; de Wijs, G. A.; Brocks, G.

2014-10-01

Modeling layered intercalation compounds from first principles poses a problem, as many of their properties are determined by a subtle balance between van der Waals interactions and chemical or Madelung terms, and a good description of van der Waals interactions is often lacking. Using van der Waals density functionals we study the structures, phonons and energetics of the archetype layered intercalation compound Li-graphite. Intercalation of Li in graphite leads to stable systems with calculated intercalation energies of -0.2 to -0.3 eV/Li atom, (referred to bulk graphite and Li metal). The fully loaded stage 1 and stage 2 compounds LiC6 and Li1 /2C6 are stable, corresponding to two-dimensional √{3 }×√{3 } lattices of Li atoms intercalated between two graphene planes. Stage N >2 structures are unstable compared to dilute stage 2 compounds with the same concentration. At elevated temperatures dilute stage 2 compounds easily become disordered, but the structure of Li3 /16C6 is relatively stable, corresponding to a √{7 }×√{7 } in-plane packing of Li atoms. First-principles calculations, along with a Bethe-Peierls model of finite temperature effects, allow for a microscopic description of the observed voltage profiles.

Release behavior and toxicity profiles towards A549 cell lines of ciprofloxacin from its layered zinc hydroxide intercalation compound.

PubMed

Abdul Latip, Ahmad Faiz; Hussein, Mohd Zobir; Stanslas, Johnson; Wong, Charng Choon; Adnan, Rohana

2013-01-01

Layered hydroxides salts (LHS), a layered inorganic compound is gaining attention in a wide range of applications, particularly due to its unique anion exchange properties. In this work, layered zinc hydroxide nitrate (LZH), a family member of LHS was intercalated with anionic ciprofloxacin (CFX), a broad spectrum antibiotic via ion exchange in a mixture solution of water:ethanol. Powder x-ray diffraction (XRD), Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA) confirmed the drug anions were successfully intercalated in the interlayer space of LZH. Specific surface area of the obtained compound was increased compared to that of the host due to the different pore textures between the two materials. CFX anions were slowly released over 80 hours in phosphate-buffered saline (PBS) solution due to strong interactions that occurred between the intercalated anions and the host lattices. The intercalation compound demonstrated enhanced antiproliferative effects towards A549 cancer cells compared to the toxicity of CFX alone. Strong host-guest interactions between the LZH lattice and the CFX anion give rise to a new intercalation compound that demonstrates sustained release mode and enhanced toxicity effects towards A549 cell lines. These findings should serve as foundations towards further developments of the brucite-like host material in drug delivery systems.

Preparation of an anionic azo pigment-pillared layered double hydroxide and the thermo- and photostability of the resulting intercalated material

NASA Astrophysics Data System (ADS)

Guo, Shengchang; Li, Dianqing; Zhang, Weifeng; Pu, Min; Evans, David G.; Duan, Xue

2004-12-01

A large anionic pigment has been intercalated into a layered double hydroxide (LDH) host by ion-exchange of an Mg/Al LDH-nitrate precursor with a solution of C.I. Pigment Red 48:2 (the calcium salt of 4-((5-chloro-4-methyl-2-sulfophenyl)azo)-3-hydroxy-2-naphthalene-carboxylic acid), in ethane-1,2-diol. After intercalation of the pigment, the interlayer distance in the LDH increases from 0.86 to 1.72 nm. Infrared spectra and TG-DTA curves reveal the presence of a complex system of supramolecular host-guest interactions. The UV-visible diffuse reflectance spectra of C.I. Pigment Red 48:2 show marked changes after heating at 200 °C and above, whereas there are no significant changes in the spectra of the intercalated pigment after heating at temperatures up to 300 °C, showing that the thermostability is markedly enhanced by intercalation in the LDH host. The pigment-intercalated LDHs exhibits much higher photostability to UV light than the pristine pigment, in the case of both the pure solids and their composites with polypropylene, as shown by measurement of CIE 1976 L*a*b* color difference ( ΔE) values.

Intercalation of paracetamol into the hydrotalcite-like host

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

Kovanda, Frantisek, E-mail: Frantisek.Kovanda@vscht.cz; Maryskova, Zuzana; Kovar, Petr

2011-12-15

Hydrotalcite-like compounds are often used as host structures for intercalation of various anionic species. The product intercalated with the nonionic, water-soluble pharmaceuticals paracetamol, N-(4-hydroxyphenyl)acetamide, was prepared by rehydration of the Mg-Al mixed oxide obtained by calcination of hydrotalcite-like precursor at 500 Degree-Sign C. The successful intercalation of paracetamol molecules into the interlayer space was confirmed by powder X-ray diffraction and infrared spectroscopy measurements. Molecular simulations showed that the phenolic hydroxyl groups of paracetamol interact with hydroxide sheets of the host via the hydroxyl groups of the positively charged sites of Al-containing octahedra; the interlayer water molecules are located mostly nearmore » the hydroxide sheets. The arrangement of paracetamol molecules in the interlayer is rather disordered and interactions between neighboring molecules cause their tilting towards the hydroxide sheets. Dissolution tests in various media showed slower release of paracetamol intercalated in the hydrotalcite-like host in comparison with tablets containing the powdered pharmaceuticals. - Graphical abstract: Molecular simulations showed disordered arrangement of paracetamol molecules in the interlayer; most of the interlayer water molecules are located near the hydroxide sheets. Black-Small-Square Highlights: Black-Right-Pointing-Pointer Paracetamol was intercalated in Mg-Al hydrotalcite-like host by rehydration/reconstruction procedure. Black-Right-Pointing-Pointer Paracetamol phenolic groups interact with positively charged sites in hydroxide sheets. Black-Right-Pointing-Pointer Molecular simulations showed disordered arrangement of guest molecules in the interlayer. Black-Right-Pointing-Pointer Slower release of paracetamol intercalated in the hydrotalcite-like host was observed.« less

Mobilisation of the thoracic spine in the management of spondylolisthesis.

PubMed

Mohanty, P P; Pattnaik, Monalisa

2016-07-01

Segmental instability due to lumbar spondylolisthesis is a potential cause of chronic low back pain. Hypomobility of the spine results in compensatory segmental hypermobility of the segment above or below restricted segments. Therefore, the aim of the study is to determine the effects of mobilisation of the hypomobile upper thoracic spine along with conventional flexion exercises and stretching of short hip flexors on the degree of slippage and the functions of the persons with lumbar spondylolisthesis. All patients with spondylolisthesis were randomly assigned into two groups: Group I - Experimental group, treated with mobilisation of the thoracic spine along with the conventional physiotherapy and Group II - Conventional group, treated with conventional stretching, strengthening, and lumbar flexion exercise programme. The experimental group treated with mobilisation of the thoracic spine shows a significant reduction in the percentage of vertebral slip from pre-treatment to post-treatment measurements. Low back pain due to spondylolisthesis may be benefited by mobilisation of the thoracic spine along with stretching of short hip flexors, piriformis, lumbar flexion range of motion exercises, core strengthening exercises, etc. Copyright © 2016 Elsevier Ltd. All rights reserved.

Intercalated organic-inorganic perovskites stabilized by fluoroaryl-aryl interactions.

PubMed

Mitzi, David B; Medeiros, David R; Malenfant, Patrick R L

2002-04-22

Crystals of several new hybrid tin(II) iodide-based perovskites, involving 2,3,4,5,6- pentafluorophenethylammonium or phenethylammonium cation bilayers and intercalated aryl or perfluoroaryl molecules, were grown by slow evaporation of a methanol solution containing the hybrid perovskite and the intercalating species. The (C(6)F(5)C(2)H(4)NH(3))(2)SnI(4).(C(6)H(6)) structure was solved at -75 degrees C in a monoclinic C2/c subcell [a = 41.089(12) A, b = 6.134(2) A, c = 12.245(3) A, beta = 94.021(5) degrees, Z = 4] and consists of sheets of corner-sharing distorted SnI(6) octahedra separated by bilayers of pentafluorophenethylammonium cations. The intercalated benzene molecules form a single well-ordered layer interposed between adjacent fluoroaryl cation layers. The corresponding hybrid with an unfluorinated organic cation and fluorinated intercalating molecule, (C(6)H(5)C(2)H(4)NH(3))(2)SnI(4).(C(6)F(6)), is isostructural [a = 40.685(4) A, b = 6.0804(6) A, c = 12.163(1) A, beta = 93.136(2) degrees, Z = 4]. For each intercalated system, close C...C contacts (3.44-3.50 A) between the aromatic cation and the intercalated molecule are indicative of a significant face-to-face interaction, similar to that found in the complex C(6)H(6).C(6)F(6). Crystal growth runs with the organic cation and prospective intercalating molecule either both fluorinated or both unfluorinated did not yield stable intercalated compounds, demonstrating the significance of fluoroaryl-aryl interactions in the current intercalated structures. Thermal analysis of (C(6)F(5)C(2)H(4)NH(3))(2)SnI(4).(C(6)H(6)) and (C(6)H(5)C(2)H(4)NH(3))(2)SnI(4).(C(6)F(6)) crystals yields, in addition to the characteristic transitions of the parent perovskite, endothermic transitions [12.6(5) and 32.1(8) kJ/mol, respectively] with an onset at 145 degrees C and a weight loss corresponding to the complete loss of the intercalated molecule. The relatively high deintercalation temperature (well above the boiling point of benzene and hexafluorobenzene) demonstrates the usefulness of the hybrid perovskites in providing a stable framework for the examination of the fluoroaryl-aryl interaction, as well as the potential importance of this interaction in tailoring new hybrid perovskites. UV-vis absorption measurements on (C(6)H(5)C(2)H(4)NH(3))(2)SnI(4).(C(6)F(6)) thin films indicate a small reversible wavelength shift to higher energy for the tin(II) iodide framework exciton peak (with respect to that of the parent perovskite spectrum), from 608(2) nm [2.04 eV] to 595(2) nm [2.08 eV], and a corresponding shift in the band edge position. This spectral shift can most reasonably be attributed to subtle structural changes induced in the tin(II) iodide sheets by the intercalated hexafluorobenzene molecules.

Organo-Soluble Porphyrin Mixed Monolayer-Protected Gold Nanorods with Intercalated Fullerenes

DTIC Science & Technology

2012-03-16

Mixed Monolayer- Protected Gold Nanorods with Intercalated Fullerenes Chenming Xue, Yongqian Xu, Yi Pang, Dingshan Yu, Liming Dai, Min Gao, Augustine...Protected Gold Nanorods with Intercalated Fullerenes 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT... Fullerenes Chenming Xue, † Yongqian Xu, ‡ Yi Pang, ‡ Dingshan Yu, § Liming Dai, § Min Gao, † Augustine Urbas ± and Quan

Evaluation of Carbon Anodes for Rechargeable Lithium Cells

NASA Technical Reports Server (NTRS)

Huang, C-K.; Surampudi, S.; Attia, A.; Halpert, G.

1993-01-01

Both liquid phase intercalation technique and electrochemical intercalation technique were examined for the Li-carbon material preparation. The electrochemical techniques include a intermittent discharge method and a two step method. These two electrochemical techniques can ensure to achieve the maximum reversible Li capacity for common commercially available carbon materials. The carbon materials evaluated by the intercalacation method includes: pitch coke, petroleum cole, PAN fiber and graphite materials. Their reversible Li capacity were determined and compared. In this paper, we also demonstrate the importance of EPDM binder composition in the carbon electrode. Our results indicated that it can impact the Li intercalation and de-intercalation capacity in carbon materials. Finally, two possibilities that may help explain the capacity degradation during practical cell cycling were proposed.

Effect of metal ion intercalation on the structure of MXene and water dynamics on its internal surfaces

DOE PAGES

Osti, Naresh C.; Naguib, Michael; Ostadhossein, Alireza; ...

2016-03-24

MXenes are a recently discovered class of 2D materials with an excellent potential for energy storage applications. Because MXene surfaces are hydrophilic and attractive interaction forces between the layers are relatively weak, water molecules can spontaneously intercalate at ambient humidity and significantly influence the key properties of this 2D material. Using complementary X-ray and neutron scattering techniques, we demonstrate that intercalation with potassium cations significantly improves structural homogeneity and water stability in MXenes. Furthermore, in agreement with molecular dynamics simulations, intercalated potassium ions reduce the water self-diffusion coefficient by 2 orders of magnitude, suggesting greater stability of hydrated MXene againstmore » changing environmental conditions.« less

Preparation of 5-benzotriazolyl-4-hydroxy-3- sec-butylbenzenesulfonate anion-intercalated layered double hydroxide and its photostabilizing effect on polypropylene

NASA Astrophysics Data System (ADS)

Li, Dianqing; Tuo, Zhenjun; Evans, David G.; Duan, Xue

2006-10-01

An organic UV absorber has been intercalated into a layered double hydroxide (LDH) host by ion-exchange method using ZnAl-NO 3-LDH as a precursor with an aqueous solution of the sodium salt of 5-benzotriazolyl-4-hydroxy-3- sec-butylbenzenesulfonic acid (BZO). After intercalation of the UV absorber, the interlayer distance in the LDHs increases from 0.89 to 2.32 nm. Infrared spectra and thermogravimetry and differential thermal analysis (TG-DTA) curves reveal the presence of a complex system of supramolecular host-guest interactions. The thermostability of BZO is markedly enhanced by intercalation in the LDH host. ZnAl-BZO-LDHs/polypropylene composite materials exhibit excellent UV photostability.

Comparing cervical spine motion with different halo devices in a cadaveric cervical instability model.

PubMed

DiPaola, Christian P; Sawers, Andrew; Conrad, Bryan P; Horodyski, MaryBeth; DiPaola, Matthew J; Del Rossi, Gianluca; Rechtine, Glenn R

2009-01-15

Biomechanical evaluation of conventional and noninvasive halos in cadaveric C1-C2 and C5-C6 instability models. To compare the ability of a conventional halo and noninvasive halo (NIH) to immobilize the unstable cervical spine at the C1-C2 and C5-C6 levels. Many successful outcomes have been reported in cervical spine injury treatment with the conventional halo (CH); however, complications related to pin sites have been reported. The NIH was designed to overcome these complications. To date, no investigation has compared the biomechanical efficacy of the NIH with that of the CH in restricting three-dimensional cervical spine motion. A global instability was created at the C1-C2 level in 4 cadavers and at C5-C6 in 4 others. Relative motion was measured between the superior and inferior vertebrae during the donning process, execution of the log roll technique, and during the process of sitting up. This testing sequence was followed for all treatment conditions. During the application of the orthoses there was a significant increase in motion at C1-C2 instability and a trend toward increased motion at the C5-C6 instability with CH compared with NIH. In the log roll maneuver, the CH and NIH restrict motion to a similar degree at the C1-C2 instability level, except in frontal plane translation, where CH immobilizes the segment to a greater extent. For the C5-C6 instability the CH provides significantly better immobilization for lateral bending and axial translation. No significant differences were found between the NIH and CH for the sit-up maneuver at either of the levels. Donning of the NIH generates significantly less cervical spine motion than application of the CH. The CH provides superior immobilization for a C5-C6 instability during the log roll maneuver and a C1-C2 instability in the frontal plane during the log-roll maneuver. The CH and NIH immobilize the C1-C2 and C5-C6 instability to a similar degree during the sit-up maneuver.

Metal complexes as DNA intercalators.

PubMed

Liu, Hong-Ke; Sadler, Peter J

2011-05-17

DNA has a strong affinity for many heterocyclic aromatic dyes, such as acridine and its derivatives. Lerman in 1961 first proposed intercalation as the source of this affinity, and this mode of DNA binding has since attracted considerable research scrutiny. Organic intercalators can inhibit nucleic acid synthesis in vivo, and they are now common anticancer drugs in clinical therapy. The covalent attachment of organic intercalators to transition metal coordination complexes, yielding metallointercalators, can lead to novel DNA interactions that influence biological activity. Metal complexes with σ-bonded aromatic side arms can act as dual-function complexes: they bind to DNA both by metal coordination and through intercalation of the attached aromatic ligand. These aromatic side arms introduce new modes of DNA binding, involving mutual interactions of functional groups held in close proximity. The biological activity of both cis- and trans-diamine Pt(II) complexes is dramatically enhanced by the addition of σ-bonded intercalators. We have explored a new class of organometallic "piano-stool" Ru(II) and Os(II) arene anticancer complexes of the type [(η(6)-arene)Ru/Os(XY)Cl](+). Here XY is, for example, ethylenediamine (en), and the arene ligand can take many forms, including tetrahydroanthracene, biphenyl, or p-cymene. Arene-nucleobase stacking interactions can have a significant influence on both the kinetics and thermodynamics of DNA binding. In particular, the cytotoxic activity, conformational distortions, recognition by DNA-binding proteins, and repair mechanisms are dependent on the arene. A major difficulty in developing anticancer drugs is cross-resistance, a phenomenon whereby a cell that is resistant to one drug is also resistant to another drug in the same class. These new complexes are non-cross-resistant with cisplatin towards cancer cells: they constitute a new class of anticancer agents, with a mechanism of action that differs from the anticancer drug cisplatin and its analogs. The Ru-arene complexes with dual functions are more potent towards cancer cells than their nonintercalating analogs. In this Account, we focus on recent studies of dual-function organometallic Ru(II)- and Os(II)-arene complexes and the methods used to detect arene-DNA intercalation. We relate these interactions to the mechanism of anticancer activity and to structure-activity relationships. The interactions between these complexes and DNA show close similarities to those of covalent polycyclic aromatic carcinogens, especially to N7-alkylating intercalation compounds. However, Ru-arene complexes exhibit some new features. Classical intercalation and base extrusion next to the metallated base is observed for {(η(6)-biphenyl)Ru(ethylenediamine)}(2+) adducts of a 14-mer duplex, while penetrating arene intercalation occurs for adducts of the nonaromatic bulky intercalator {(η(6)-tetrahydroanthracene)Ru(ethylenediamine)}(2+) with a 6-mer duplex. The introduction of dual-function Ru-arene complexes introduces new mechanisms of antitumor activity, novel mechanisms for attack on DNA, and new concepts for developing structure- activity relationships. We hope this discussion will stimulate thoughtful and focused research on the design of anticancer chemotherapeutic agents using these unique approaches.

Higher Improvement in Patient-Reported Outcomes Can Be Achieved After Transforaminal Lumbar Interbody Fusion for Clinical and Radiographic Degenerative Spondylolisthesis Classification Type D Degenerative Lumbar Spondylolisthesis.

PubMed

Chen, Xi; Xu, Liang; Qiu, Yong; Chen, Zhong-Hui; Zhou, Qing-Shuang; Li, Song; Sun, Xu

2018-06-01

Clinical and radiographic degenerative spondylolisthesis (CARDS) classification defines a distinct subset of patients with kyphotic angulation at the involved segment (type D). Research using CARDS classification to investigate motion characteristics at involved segments or patient-related outcomes (PROs) following surgical intervention is sparse. We investigated the relationship between CARDS type D spondylolisthesis and dynamic instability and PROs in type D versus non-type D spondylolisthesis. We reviewed consecutive patients who received transforaminal lumbar interbody fusion for L4-5 spondylolisthesis between 2009 and 2015. Patients were assigned into type D and non-type D groups. Translational motion was determined by upright lumbar lateral radiography with supine sagittal magnetic resonance imaging or flexion and extension radiography. Demographics, radiographic parameters, and PROs were evaluated. Type D and non-type D groups comprised 34 and 163 patients, respectively. Compared with non-type D, type D group was characterized by lordotic angulation loss and higher degree of olisthesis on upright radiographs and demonstrated higher translational motion on upright lumbar lateral radiography with supine sagittal magnetic resonance imaging analysis. After surgery, mean reduction rate was significantly higher in type D group; type D had less slippage, but differences in slip angle and disc height were not significant. Preoperative Oswestry Disability Index and visual analog scale for back pain scores were higher in type D group. Type D spondylolisthesis and dynamic instability were associated with achieving minimal clinically important differences in PROs. CARDS type D spondylolisthesis is a distinct subset associated with dynamic instability and worse PROs. Higher improvement in PROs can be achieved in CARDS type D spondylolisthesis after surgery. Copyright © 2018 Elsevier Inc. All rights reserved.

Intercalated graphitic carbon nitride: a fascinating two-dimensional nanomaterial for an ultra-sensitive humidity nanosensor

NASA Astrophysics Data System (ADS)

Zhang, Zhenyi; Huang, Jindou; Yuan, Qing; Dong, Bin

2014-07-01

We develop a novel humidity nanosensor based on intercalated graphitic carbon nitride (g-C3N4) nanosheets fabricated by a facile thermal polymerization of common urea in the presence of LiCl as the intercalated guest under air and ambient pressure. The response and recovery times of an optimal nanosensor can reach ~0.9 s and ~1.4 s, respectively, which are superior to most of the traditional oxide ceramic-based humidity nanosensors tested under similar conditions. By combining with the theoretical calculations, it is proposed that the ultrafast response-recovery time for this nanosensor is attributed to their unique 2D intercalated nanostructure by which Li species linked with the ``nitrogen pots'' of g-C3N4 can make the protons conduct in the first adsorbed water layer. Meanwhile, the physically adsorbed water on the surface of LiCl-intercalated g-C3N4 nanosheets can be desorbed rapidly at a relative lower RH environment due to their high adsorption energy and the strong diffusion effect of water molecules.We develop a novel humidity nanosensor based on intercalated graphitic carbon nitride (g-C3N4) nanosheets fabricated by a facile thermal polymerization of common urea in the presence of LiCl as the intercalated guest under air and ambient pressure. The response and recovery times of an optimal nanosensor can reach ~0.9 s and ~1.4 s, respectively, which are superior to most of the traditional oxide ceramic-based humidity nanosensors tested under similar conditions. By combining with the theoretical calculations, it is proposed that the ultrafast response-recovery time for this nanosensor is attributed to their unique 2D intercalated nanostructure by which Li species linked with the ``nitrogen pots'' of g-C3N4 can make the protons conduct in the first adsorbed water layer. Meanwhile, the physically adsorbed water on the surface of LiCl-intercalated g-C3N4 nanosheets can be desorbed rapidly at a relative lower RH environment due to their high adsorption energy and the strong diffusion effect of water molecules. Electronic supplementary information (ESI) available: Fig. S1-S8 and Table S1 including SEM, TEM and theoretical calculations. See DOI: 10.1039/c4nr01570c

Zerovalent Copper Intercalated Birnessite as a Cathode for Lithium Ion Batteries: Extending Cycle Life

DOE PAGES

Li, Yue Ru; Poyraz, Altug S.; Hu, Xiaobing; ...

2017-01-01

Birnessite type layered manganese dioxides (δ-MnO 2) have attracted considerable attention in recent years as 2D intercalation cathodes for rechargeable Li +, Na +, and Mg 2+ batteries due to fast ion diffusion through their negatively charged δ-MnO 2 sheets separated by interlayer cations and a stable Mn 3+/4+ redox couple. Here we report the preparation and electrochemistry of zero and divalent copper co-intercalated birnessite type manganese dioxide (Cu 0 0.03Cu 2+ 0.21Na 0.12MnO 2·0.9H 2O). The copper intercalated birnessite materials were fully characterized utilizing powder X-ray diffraction (XRD), inductively coupled plasma optical emission spectroscopy (ICP-OES), transmission electron microscopy (TEM).more » The mixed valent nature of intercalated Cu 0 and Cu 2+ was confirmed by X-ray photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS). Electrochemical evaluation results show that zero valent copper intercalated birnessite exhibits higher discharge capability, improved cyclability, and lower impedance compared to the Cu 2+ only intercalated (Cu 0.26MnO 2·1.0H 2O) and Cu free Na birnessite (Na 0.40MnO 2·1.0H 2O) materials. Remarkably, zero valent copper birnessite shows almost no fade after 10 cycles at 0.1 mV/s. Electrochemical impedance spectroscopy results suggest that charge transfer resistivity of Cu 0 modified samples was much lower than that of Cu 2+ and Cu free birnessite, indicating that the presence of a small amount of Cu 0 improves the conductivity of birnessite and results in better electrochemical cyclability, rate capability, and lower impedance.« less

Ultrastructural and biochemical localization of N-RAP at the interface between myofibrils and intercalated disks in the mouse heart.

PubMed

Zhang, J Q; Elzey, B; Williams, G; Lu, S; Law, D J; Horowits, R

2001-12-11

N-RAP is a recently discovered muscle-specific protein found at cardiac intercalated disks. Double immunogold labeling of mouse cardiac muscle reveals that vinculin is located immediately adjacent to the fascia adherens region of the intercalated disk membrane, while N-RAP extends approximately 100 nm further toward the interior of the cell. We partially purified cardiac intercalated disks using low- and high-salt extractions followed by density gradient centrifugation. Immunoblots show that this preparation is highly enriched in desmin and junctional proteins, including N-RAP, talin, vinculin, beta1-integrin, N-cadherin, and connexin 43. Electron microscopy and immunolabeling demonstrate that N-RAP and vinculin are associated with the large fragments of intercalated disks that are present in this preparation, which also contains numerous membrane vesicles. Detergent treatment of the partially purified intercalated disks removed the membrane vesicles and extracted vinculin and beta1-integrin. Further separation on a sucrose gradient removed residual actin and myosin and yielded a fraction morphologically similar to fasciae adherentes that was highly enriched in N-RAP, N-cadherin, connexin 43, talin, desmin, and alpha-actinin. The finding that N-RAP copurifies with detergent-extracted intercalated disk fragments even though beta-integrin and vinculin have been completely removed suggests that N-RAP association with the adherens junction region is mediated by the cadherin system. Consistent with this hypothesis, we found that recombinant N-RAP fragments bind alpha-actinin in a gel overlay assay. In addition, immunofluorescence shows that N-RAP remains bound at the ends of isolated, detergent-treated cardiac myofibrils. These results demonstrate that N-RAP remains tightly bound to myofibrils and fasciae adherentes during biochemical purification and may be a key constituent in the mechanical link between these two structures.

Preparation of graphite intercalation compounds containing oligo and polyethers

NASA Astrophysics Data System (ADS)

Zhang, Hanyang; Lerner, Michael M.

2016-02-01

Layered host-polymer nanocomposites comprising polymeric guests between inorganic sheets have been prepared with many inorganic hosts, but there is limited evidence for the incorporation of polymeric guests into graphite. Here we report for the first time the preparation, and structural and compositional characterization of graphite intercalation compounds (GICs) containing polyether bilayers. The new GICs are obtained by either (1) reductive intercalation of graphite with an alkali metal in the presence of an oligo or polyether and an electrocatalyst, or (2) co-intercalate exchange of an amine for an oligo or polyether in a donor-type GIC. Structural characterization of products using powder X-ray diffraction, Raman spectroscopy, and thermal analyses supports the formation of well-ordered, first-stage GICs containing alkali metal cations and oligo or polyether bilayers between reduced graphene sheets.Layered host-polymer nanocomposites comprising polymeric guests between inorganic sheets have been prepared with many inorganic hosts, but there is limited evidence for the incorporation of polymeric guests into graphite. Here we report for the first time the preparation, and structural and compositional characterization of graphite intercalation compounds (GICs) containing polyether bilayers. The new GICs are obtained by either (1) reductive intercalation of graphite with an alkali metal in the presence of an oligo or polyether and an electrocatalyst, or (2) co-intercalate exchange of an amine for an oligo or polyether in a donor-type GIC. Structural characterization of products using powder X-ray diffraction, Raman spectroscopy, and thermal analyses supports the formation of well-ordered, first-stage GICs containing alkali metal cations and oligo or polyether bilayers between reduced graphene sheets. Electronic supplementary information (ESI) available: Domain size, additional Raman spectra info, compositional calculation, and packing fractions. See DOI: 10.1039/c5nr08226a

Enhancing the efficiency of lithium intercalation in carbon nanotube bundles using surface functional groups.

PubMed

Xiao, Shiyan; Zhu, Hong; Wang, Lei; Chen, Liping; Liang, Haojun

2014-08-14

The effect of surface functionalization on the ability and kinetics of lithium intercalation in carbon nanotube (CNT) bundles has been studied by comparing the dynamical behaviors of lithium (Li) ions in pristine and -NH2 functionalized CNTs via ab initio molecular dynamics simulations. It was observed that lithium intercalation has been achieved quickly for both the pristine and surface functionalized CNT bundle. Our calculations demonstrated for the first time that CNT functionalization improved the efficiency of lithium intercalation significantly at both low and high Li ion density. Moreover, we found that keeping the nanotubes apart with an appropriate distance and charging the battery at a rational rate were beneficial to achieve a high rate of lithium intercalation. Besides, the calculated adsorption energy curves indicated that the potential wells in the system of -NH2 functionalized CNT were deeper than that of the pristine CNT bundle by 0.74 eV, and a third energy minimum with a value of 2.64 eV existed at the midpoint of the central axis of the nanotube. Thus, it would be more difficult to remove Li ions from the nanotube interior after surface functionalization. The barrier for lithium diffusion in the interior of the nanotube is greatly decreased because of the surface functional groups. Based on these results, we would suggest to "damage" the nanotube by introducing defects at its sidewall in order to improve not only the capacity of surface functionalized CNTs but also the efficiency of lithium intercalation and deintercalation processes. Our results presented here are helpful in understanding the mechanism of lithium intercalation into nanotube bundles, which may potentially be applied in the development of CNT based electrodes.

Electrochemical potassium-ion intercalation in NaxCoO2: a novel cathode material for potassium-ion batteries.

PubMed

Sada, Krishnakanth; Senthilkumar, Baskar; Barpanda, Prabeer

2017-07-27

Reversible electrochemical potassium-ion intercalation in P2-type Na x CoO 2 was examined for the first time. Hexagonal Na 0.84 CoO 2 platelets prepared by a solution combustion synthesis technique were found to work as an efficient host for K + intercalation. They deliver a high reversible capacity of 82 mA h g -1 , good rate capability and excellent cycling performance up to 50 cycles.

Small molecule-mediated duplex formation of nucleic acids with 'incompatible' backbones.

PubMed

Cafferty, Brian J; Musetti, Caterina; Kim, Keunsoo; Horowitz, Eric D; Krishnamurthy, Ramanarayanan; Hud, Nicholas V

2016-04-07

Proflavine, a known intercalator of DNA and RNA, promotes duplex formation by nucleic acids with natural and non-natural backbones that otherwise form duplexes with low thermal stability, and even some that show no sign of duplex formation in the absence of proflavine. These findings demonstrate the potential for intercalators to be used as cofactors for the assembly of rationally designed nucleic acid structures, and could provide fundamental insights regarding intercalation of natural nucleic acid duplexes.

A molecular model for proflavine-DNA intercalation.

PubMed Central

Neidle, S; Pearl, L H; Herzyk, P; Berman, H M

1988-01-01

A molecular model has been derived for the intercalation of proflavine into the CpG site of the decamer duplex of d(GATACGATAC). The starting geometry of the intercalation site was taken from previous crystallographic studies on the d(CpG)-proflavine complex, and molecular mechanics used to obtain a stereochemically acceptable structure. This has widened grooves compared to standard A- or B- double helices, as well as distinct conformational, roll, twist and tilt features. PMID:3174439

Lithium ion intercalation in thin crystals of hexagonal TaSe2 gated by a polymer electrolyte

NASA Astrophysics Data System (ADS)

Wu, Yueshen; Lian, Hailong; He, Jiaming; Liu, Jinyu; Wang, Shun; Xing, Hui; Mao, Zhiqiang; Liu, Ying

2018-01-01

Ionic liquid gating has been used to modify the properties of layered transition metal dichalcogenides (TMDCs), including two-dimensional (2D) crystals of TMDCs used extensively recently in the device work, which has led to observations of properties not seen in the bulk. The main effect comes from the electrostatic gating due to the strong electric field at the interface. In addition, ionic liquid gating also leads to ion intercalation when the ion size of the gate electrolyte is small compared to the interlayer spacing of TMDCs. However, the microscopic processes of ion intercalation have rarely been explored in layered TMDCs. Here, we employed a technique combining photolithography device fabrication and electrical transport measurements on the thin crystals of hexagonal TaSe2 using multiple channel devices gated by a polymer electrolyte LiClO4/Polyethylene oxide (PEO). The gate voltage and time dependent source-drain resistances of these thin crystals were used to obtain information on the intercalation process, the effect of ion intercalation, and the correlation between the ion occupation of allowed interstitial sites and the device characteristics. We found a gate voltage controlled modulation of the charge density waves and a scattering rate of charge carriers. Our work suggests that ion intercalation can be a useful tool for layered materials engineering and 2D crystal device design.

Influence of metal ions intercalation on the vibrational dynamics of water confined between MXene layers

DOE PAGES

Osti, Naresh C.; Naguib, Michael; Ganeshan, Karthik; ...

2017-11-21

Two-dimensional carbides and nitrides of early transition metals (MXenes) combine high conductivity with hydrophilic surfaces, which make them promising for energy storage, electrocatalysis, and water desalination. Effects of intercalated metal ions on the vibrational states of water confined in Ti 3C 2T x MXenes have been explored using inelastic neutron scattering (INS) and molecular dynamics simulations to better understand the mechanisms that control MXenes’ behavior in aqueous electrolytes, water purification and other important applications. Here, we observe INS signal from water in all samples, pristine and with lithium, sodium or potassium ions intercalated between the 2D Ti 3C 2T xmore » layers. However, only a small amount of water is found to reside in Ti 3C 2T x intercalated with metal ions. Water in pristine Ti 3C 2T x is more disordered, with bulk-like characteristics, in contrast to intercalated Ti 3C 2T x, where water is more ordered, irrespective of the metal ions used for intercalation. The ordering of the confined water increases with the ion size. Lastly, this finding is further confirmed from molecular dynamics simulation which showed an increase in interference of water molecules with increasing ion size resulting in a concomitant decrease in water mobility, therefore, providing a guidance to tailor MXene properties for energy and environmental applications.« less

Decreasing the electronic confinement in layered perovskites through intercalation.

PubMed

Smith, Matthew D; Pedesseau, Laurent; Kepenekian, Mikaël; Smith, Ian C; Katan, Claudine; Even, Jacky; Karunadasa, Hemamala I

2017-03-01

We show that post-synthetic small-molecule intercalation can significantly reduce the electronic confinement of 2D hybrid perovskites. Using a combined experimental and theoretical approach, we explain structural, optical, and electronic effects of intercalating highly polarizable molecules in layered perovskites designed to stabilize the intercalants. Polarizable molecules in the organic layers substantially alter the optical and electronic properties of the inorganic layers. By calculating the spatially resolved dielectric profiles of the organic and inorganic layers within the hybrid structure, we show that the intercalants afford organic layers that are more polarizable than the inorganic layers. This strategy reduces the confinement of excitons generated in the inorganic layers and affords the lowest exciton binding energy for an n = 1 perovskite of which we are aware. We also demonstrate a method for computationally evaluating the exciton's binding energy by solving the Bethe-Salpeter equation for the exciton, which includes an ab initio determination of the material's dielectric profile across organic and inorganic layers. This new semi-empirical method goes beyond the imprecise phenomenological approximation of abrupt dielectric-constant changes at the organic-inorganic interfaces. This work shows that incorporation of polarizable molecules in the organic layers, through intercalation or covalent attachment, is a viable strategy for tuning 2D perovskites towards mimicking the reduced electronic confinement and isotropic light absorption of 3D perovskites while maintaining the greater synthetic tunability of the layered architecture.

New Lithium- and Diamine-Intercalated Superconductors Lix(CnH2n+4N2)yMoSe2 (n = 2,6)

NASA Astrophysics Data System (ADS)

Sato, Kazuki; Noji, Takashi; Hatakeda, Takehiro; Kawamata, Takayuki; Kato, Masatsune; Koike, Yoji

2018-05-01

We have succeeded in synthesizing new intercalation superconductors Lix(C2H8N2)yMoSe2 and Lix(C6H16N2)yMoSe2 with Tc = 4.2 and 3.8-6.0 K, respectively, via the co-intercalation of lithium and ethylenediamine or hexamethylenediamine into semiconducting 2H-MoSe2. It has been found that the Tc values are related not to the interlayer spacing between MoSe2 layers so much but to the electronic density of states (EDOS) at the Fermi level. Moreover, only Li-intercalated LixMoSe2 with a small interlayer spacing has been found to be non-superconducting. Accordingly, it has been concluded that not only a sufficient amount of EDOS at the Fermi level due to the charge transfer from intercalated Li to MoSe2 layers but also the enhancement of the two-dimensionality of the crystal structure and/or electronic structure due to the expansion of the interlayer spacing between MoSe2 layers is necessary for the appearance of superconductivity in MoSe2-based intercalation superconductors. The pairing mechanism and the analogy to the superconductivity in the electric double-layer transistors of 2H-MoX2 (X = S, Se, Te) are discussed.

Influence of metal ions intercalation on the vibrational dynamics of water confined between MXene layers

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

Osti, Naresh C.; Naguib, Michael; Ganeshan, Karthik

Two-dimensional carbides and nitrides of early transition metals (MXenes) combine high conductivity with hydrophilic surfaces, which make them promising for energy storage, electrocatalysis, and water desalination. Effects of intercalated metal ions on the vibrational states of water confined in Ti 3C 2T x MXenes have been explored using inelastic neutron scattering (INS) and molecular dynamics simulations to better understand the mechanisms that control MXenes’ behavior in aqueous electrolytes, water purification and other important applications. Here, we observe INS signal from water in all samples, pristine and with lithium, sodium or potassium ions intercalated between the 2D Ti 3C 2T xmore » layers. However, only a small amount of water is found to reside in Ti 3C 2T x intercalated with metal ions. Water in pristine Ti 3C 2T x is more disordered, with bulk-like characteristics, in contrast to intercalated Ti 3C 2T x, where water is more ordered, irrespective of the metal ions used for intercalation. The ordering of the confined water increases with the ion size. Lastly, this finding is further confirmed from molecular dynamics simulation which showed an increase in interference of water molecules with increasing ion size resulting in a concomitant decrease in water mobility, therefore, providing a guidance to tailor MXene properties for energy and environmental applications.« less

Stability of bromine, iodine monochloride, copper (II) chloride, and nickel (II) chloride intercalated pitch-based graphite fibers

NASA Technical Reports Server (NTRS)

Gaier, James R.; Slabe, Melissa E.; Shaffer, Nanette

1987-01-01

Four different grades of pitch-based graphite fibers (Amoco P-55, P-75, P-100. and P-120) were intercalated with each of four different intercalates: bromine (Br2), iodine monochloride (ICl), copper (II) chloride (CuCl2), and nickel (II) chloride (NiCl2). The P-55 fibers did not react with Br2 or NiCl2, and the P-75 did not react with NiCl2. The stability of the electrical resistance of the intercalated fibers was monitored over long periods of time in ambient, high humidity (100 percent at 60 C), vacuum (10 to the -6 torr), and high temperature (up to 400 C) conditions. Fibers with lower graphitization form graphite intercalation compounds (GIC's) which are more stable than those with higher graphitization (i.e., P-55 (most stable) greater than P-75 greater than P-100 greater than P-120 (least stable). Br2 formed the most stable GIC's followed in order of decreasing stability by ICl, CuCl2, and NiCl2. While Br2 GIC's had the most stability, ICl had the advantages of forming GIC's with slightly greater reduction in resistance (by about 10%) than Br2, and the ability to intercalate P-55 fiber. Transition metal chlorides are susceptible to water vapor and high temperature. The stability of fibers in composites differs.

Release behavior and toxicity profiles towards A549 cell lines of ciprofloxacin from its layered zinc hydroxide intercalation compound

PubMed Central

2013-01-01

Background Layered hydroxides salts (LHS), a layered inorganic compound is gaining attention in a wide range of applications, particularly due to its unique anion exchange properties. In this work, layered zinc hydroxide nitrate (LZH), a family member of LHS was intercalated with anionic ciprofloxacin (CFX), a broad spectrum antibiotic via ion exchange in a mixture solution of water:ethanol. Results Powder x-ray diffraction (XRD), Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA) confirmed the drug anions were successfully intercalated in the interlayer space of LZH. Specific surface area of the obtained compound was increased compared to that of the host due to the different pore textures between the two materials. CFX anions were slowly released over 80 hours in phosphate-buffered saline (PBS) solution due to strong interactions that occurred between the intercalated anions and the host lattices. The intercalation compound demonstrated enhanced antiproliferative effects towards A549 cancer cells compared to the toxicity of CFX alone. Conclusions Strong host-guest interactions between the LZH lattice and the CFX anion give rise to a new intercalation compound that demonstrates sustained release mode and enhanced toxicity effects towards A549 cell lines. These findings should serve as foundations towards further developments of the brucite-like host material in drug delivery systems. PMID:23849189

Chromosomal instability mediated by non-B DNA: cruciform conformation and not DNA sequence is responsible for recurrent translocation in humans.

PubMed

Inagaki, Hidehito; Ohye, Tamae; Kogo, Hiroshi; Kato, Takema; Bolor, Hasbaira; Taniguchi, Mariko; Shaikh, Tamim H; Emanuel, Beverly S; Kurahashi, Hiroki

2009-02-01

Chromosomal aberrations have been thought to be random events. However, recent findings introduce a new paradigm in which certain DNA segments have the potential to adopt unusual conformations that lead to genomic instability and nonrandom chromosomal rearrangement. One of the best-studied examples is the palindromic AT-rich repeat (PATRR), which induces recurrent constitutional translocations in humans. Here, we established a plasmid-based model that promotes frequent intermolecular rearrangements between two PATRRs in HEK293 cells. In this model system, the proportion of PATRR plasmid that extrudes a cruciform structure correlates to the levels of rearrangement. Our data suggest that PATRR-mediated translocations are attributable to unusual DNA conformations that confer a common pathway for chromosomal rearrangements in humans.

Role of subunit assembly in autosomal dominant retinitis pigmentosa linked to mutations in peripherin 2.

PubMed

Molday, Robert S; Molday, Laurie L; Loewen, Christopher J R

2004-01-01

Peripherin 2 is a photoreceptor-specific membrane protein implicated in outer segment disk morphogenesis and linked to various retinopathies including autosomal dominant retinitis pigmentosa (ADRP). Peripherin 2 and ROM1 assemble as a mixture of core noncovalent homomeric and heteromeric tetramers that further link together through disulfide bonds to form higher order oligomers. These complexes are critical for disk rim formation and outer segment structure through interaction with the cGMP-gated channel and other photoreceptor proteins. We have examined the role of subunit assembly in peripherin 2 targeting to disks, outer segment structure, and photoreceptor degeneration by examining molecular and cellular properties of peripherin 2 mutants in COS-1 cells and transgenic Xenopus laevis rod photoreceptors. Wild-type (WT) and the ADRP-linked P216L mutant were transported and incorporated into newly formed outer segment disks of transgenic X. laevis. The P216L mutant, however, induced progressive outer segment instability and photoreceptor degeneration possibly through the introduction of a new N-linked oligosaccharide chain. In contrast, the C214S and L185P disease-linked, tetramerization-defective mutants, were retained in the inner segment, but did not affect outer segment structure or induce photoreceptor degeneration. Together, these results indicate that peripherin 2 mutations can cause ADRP either through a deficiency in WT peripherin 2 (C214S, 1.185P) or by a dominant negative effect on disk stability (P216L).

Dynamic origin of segment magnetization reversal in thin-film Penrose tilings

NASA Astrophysics Data System (ADS)

Montoncello, F.; Giovannini, L.; Farmer, B.; De Long, L.

2017-02-01

We investigate the low-frequency spin wave dynamics involved in the magnetization reversal of a Penrose P2 tiling using the dynamical matrix method. This system consists of a two-dimensional, connected wire network of elongated thin-film segments, whose complete reversal occurs as a cascade of successive local segment reversals. Using soft mode theory, we interpret the reversal of an individual segment as a first order magnetic transition, in which magnetization curve of the system suffers a small discontinuity. Near this discontinuity a specific mode of the spin wave spectrum goes soft (i.e., its frequency goes to zero), triggering a local instability of the magnetization. We show that this mode is localized, and is at the origin of the local reversal. We discuss the correlation of the mode spatial profile with the ;reversal mechanism;, which is the passage of a domain wall through the segment. This process differs from reversal in periodic square or honeycomb artificial spin ices, where a cascade of reversing segments (e.g., ;Dirac string;) follows an extended (though irregular) path across the sample; here the spatial distribution of successive segment reversals is discontinuous, but strictly associated with the area where a soft mode is localized. The migration of the localization area across the P2 tiling (during reversal in decreasing applied fields) depends on changes in the internal effective field map. We discuss these results in the context of spin wave localization due to the unique topology of the P2 tiling.

Polyethylene organo-clay nanocomposites: the role of the interface chemistry on the extent of clay intercalation/exfoliation.

PubMed

Mainil, Michaël; Alexandre, Michaël; Monteverde, Fabien; Dubois, Philippe

2006-02-01

High density polyethylene (HDPE)/clay nanocomposites have been prepared using three different functionalized polyethylene compatibilizers: an ethylene/vinyl acetate copolymer, a polyethylene grafted with maleic anhydride functions and a (styrene-b-ethylene/butylene-b-styrene) block copolymer. The nanocomposites were prepared via two different routes: (1) the dispersion in HDPE of a masterbatch prepared from the compatibilizer and the clay or (2) the direct melt blending of the three components. For each compatibilizer, essentially intercalated nanocomposites were formed as determined by X-ray diffraction and transmission electron microscopy. With the ethylene/vinyl acetate copolymer, a significant delamination of the intercalated clay in thin stacks was observed. This dispersion of thin intercalated stacks within the polymer matrix allowed increasing significantly the stiffness and the flame resistance of the nanocomposite. A positive effect of shear rate and blending time has also been put into evidence, especially for the process based on the masterbatch preparation, improving both the formation of thin stacks of intercalated clay and the mechanical properties and the flame resistance of the formed nanocomposites.

From nicotinate-containing layered double hydroxides (LDHs) to NAD coenzyme-LDH nanocomposites - Syntheses and structural characterization by various spectroscopic methods

NASA Astrophysics Data System (ADS)

Muráth, Szabolcs; Dudás, Csilla; Kukovecz, Ákos; Kónya, Zoltán; Sipos, Pál; Pálinkó, István

2017-07-01

The syntheses of nicotinate anion- and NAD coenzyme-layered double hydroxide (LDH) composites were performed with the aim of having the organic component among the layers. In-house prepared CaAl-LDHs were the host materials. Intercalation was attempted by direct ion exchange or by the dehydration-rehydration method applying aqueous solvent mixtures (containing ethanol, propanol, acetone, N,N-dimethylformamide). For structural characterization, beside X-ray diffractometry, X-ray photoelectron and IR spectroscopies, transmission and scanning electron microscopies as well as energy-dispersive X-ray analysis were used. Molecular modelling served for the visualization of the arrangements of the intercalated ions among the layers of the LDH samples. Although not all the intercalation methods and solvent mixtures led to intercalated composite materials, successful ones could be identified. The combination of spectroscopic methods helped in proposing sensible spatial arrangements for the intercalated anions. The NAD-CaAl-LDH composite proved to be an active catalyst in the oxidation of hydroquinone to 1,4-bezoquinoe in the presence of H2O2.

Structural consequences of hydrogen intercalation of epitaxial graphene on SiC(0001)

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

Emery, Jonathan D., E-mail: jdemery@anl.gov, E-mail: bedzyk@northwestern.edu; Johns, James E.; McBriarty, Martin E.

2014-10-20

The intercalation of various atomic species, such as hydrogen, to the interface between epitaxial graphene (EG) and its SiC substrate is known to significantly influence the electronic properties of the graphene overlayers. Here, we use high-resolution X-ray reflectivity to investigate the structural consequences of the hydrogen intercalation process used in the formation of quasi-free-standing (QFS) EG/SiC(0001). We confirm that the interfacial layer is converted to a layer structurally indistinguishable from that of the overlying graphene layers. This newly formed graphene layer becomes decoupled from the SiC substrate and, along with the other graphene layers within the film, is vertically displacedmore » by ∼2.1 Å. The number of total carbon layers is conserved during the process, and we observe no other structural changes such as interlayer intercalation or expansion of the graphene d-spacing. These results clarify the under-determined structure of hydrogen intercalated QFS-EG/SiC(0001) and provide a precise model to inform further fundamental and practical understanding of the system.« less

Localized concentration reversal of lithium during intercalation into nanoparticles

DOE PAGES

Zhang, Wei; Yu, Hui -Chia; Wu, Lijun; ...

2018-01-12

Nanoparticulate electrodes, such as Li xFePO 4, have unique advantages over their microparticulate counterparts for the applications in Li-ion batteries because of the shortened diffusion path and access to nonequilibrium routes for fast Li incorporation, thus radically boosting power density of the electrodes. However, how Li intercalation occurs locally in a single nanoparticle of such materials remains unresolved because real-time observation at such a fine scale is still lacking. We report visualization of local Li intercalation via solid-solution transformation in individual Li xFePO 4 nanoparticles, enabled by probing sub-angstrom changes in the lattice spacing in situ. The real-time observation revealsmore » inhomogeneous intercalation, accompanied with an unexpected reversal of Li concentration at the nanometer scale. The origin of the reversal phenomenon is elucidated through phase-field simulations, and it is attributed to the presence of structurally different regions that have distinct chemical potential functions. Furthermore, the findings from this study provide a new perspective on the local intercalation dynamics in battery electrodes.« less

Electron doping through lithium intercalation to interstitial channels in tetrahedrally bonded SiC

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

Sakai, Yuki; Center for Computational Materials, Institute for Computational Engineering and Sciences, The University of Texas at Austin, Austin, Texas 78712; Oshiyama, Atsushi

2015-11-07

We report on first-principles calculations that clarify the effect of lithium atom intercalation into zinc blende 3C-silicon carbide (3C-SiC) on electronic and structural properties. Lithium atoms inside 3C-SiC are found to donate electrons to 3C-SiC that is an indication of a new way of electron doping through the intercalation. The electrons doped into the conduction band interact with lithium cations and reduce the band spacing between the original valence and conduction bands. We have also found that a silicon monovacancy in 3C-SiC promotes the lithium intercalation, showing that the vacancy generation makes SiC as a possible anode material for lithium-ionmore » battery.« less

Direct observation of strain-induced orbital valence band splitting in HfSe2 by sodium intercalation

NASA Astrophysics Data System (ADS)

Eknapakul, T.; Fongkaew, I.; Siriroj, S.; Jindata, W.; Chaiyachad, S.; Mo, S.-K.; Thakur, S.; Petaccia, L.; Takagi, H.; Limpijumnong, S.; Meevasana, W.

2018-05-01

By using angle-resolved photoemission spectroscopy (ARPES), the variation of the electronic structure of HfSe2 has been studied as a function of sodium intercalation. We observe how this drives a band splitting of the p -orbital valence bands and a simultaneous reduction of the indirect band gap by values of up to 400 and 280 meV, respectively. Our calculations indicate that such behavior is driven by the band deformation potential, which is a result of our observed strain induced by sodium intercalation. The applied uniaxial strain calculations based on density functional theory agree strongly with the experimental ARPES data. These findings should assist in studying the physical relationship between intercalation and strain, as well as for large-scale two-dimensional straintronics.

Heat capacities of kaolinite from 7 to 380 K and of DMSO- intercalated kaolinite from 20 to 310 K. The entropy of kaolinite Al2Si2O5(OH)4

USGS Publications Warehouse

Robie, Richard A.; Hemingway, Bruce S.

1991-01-01

The heat capacities of kaolinite (7 to 380 K) and of dimethyl sulfoxide (DMSO) intercalated kaolinite (20 to 310 K) were measured by adiabatically shielded calorimetry. The third law entropy of kaolinite, S°298, is 200.9 ± 0.5 J ⋅ mol-1 ⋅ K-1.The "melting point" of the DMSO in the intercalate, 288.0 ± 0.2 K, is 3.7 K lower than that of pure DMSO, 291.67 K. The heat capacity of DMSO in the intercalate above 290 K is approximately 5.2 J ⋅ mol-1 ⋅ K-1 smaller than that of pure liquid DMSO at the same temperature.

Molecular mechanism of direct proflavine-DNA intercalation: evidence for drug-induced minimum base-stacking penalty pathway.

PubMed

Sasikala, Wilbee D; Mukherjee, Arnab

2012-10-11

DNA intercalation, a biophysical process of enormous clinical significance, has surprisingly eluded molecular understanding for several decades. With appropriate configurational restraint (to prevent dissociation) in all-atom metadynamics simulations, we capture the free energy surface of direct intercalation from minor groove-bound state for the first time using an anticancer agent proflavine. Mechanism along the minimum free energy path reveals that intercalation happens through a minimum base stacking penalty pathway where nonstacking parameters (Twist→Slide/Shift) change first, followed by base stacking parameters (Buckle/Roll→Rise). This mechanism defies the natural fluctuation hypothesis and provides molecular evidence for the drug-induced cavity formation hypothesis. The thermodynamic origin of the barrier is found to be a combination of entropy and desolvation energy.

Formation Dynamics of Potassium-Based Graphite Intercalation Compounds: An Ab Initio Study

NASA Astrophysics Data System (ADS)

Jiang, Xiankai; Song, Bo; Tománek, David

2018-04-01

This paper is a contribution to the Physical Review Applied collection in memory of Mildred S. Dresselhaus. We use ab initio molecular dynamics simulations to study the microscopic dynamics of potassium intercalation in graphite. Upon adsorbing on graphite from the vapor phase, K atoms transfer their valence charge to the substrate. K atoms adsorbed on the surface diffuse rapidly along the graphene basal plane and eventually enter the interlayer region following a "U -turn" across the edge, gaining additional energy. This process is promoted at higher coverages associated with higher K pressure, leading to the formation of a stable intercalation compound. We find that the functionalization of graphene edges is an essential prerequisite for intercalation since bare edges reconstruct and reconnect, closing off the entry channels for the atoms.

Intercalation of biomolecules into NiAl-NO 3 layered double hydroxide films synthesized in situ on anodic alumina/aluminium support

NASA Astrophysics Data System (ADS)

Zhao, Hua-Zhang; Chang, Ying-Yue; Yang, Jing; Yang, Qin-Zheng

2013-03-01

Layered double hydroxide (LDH) films were synthesized in situ on anodic alumina/aluminium (AAO/Al). Glucose oxidase (GOD) and L-ascorbic acid (vitamin C, VC) were intercalated respectively into the in-situ grown LDH films by anion-exchange in aqueous solutions. Dodecylsulfate (SDS) was used to expand the lamellar structure before GOD intercalation into the LDH film. The resulting products were characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and thermo gravimetric analysis (TGA). The results showed that VC and GOD were successfully intercalated into the in-situ synthesized LDH film. These biomolecules loaded LDH films could have potential applications in electrode modification, safe storage and effective delivery of bioactive compounds.

Feasibility of intercalated graphite railgun armatures

NASA Technical Reports Server (NTRS)

Gaier, James R.; Gooden, Clarence E.; Yashan, Doreen; Naud, Steven

1990-01-01

Graphite intercalation compounds may provide an excellent material for the fabrication of electro-magnetic railgun armatures. As a pulse of power is fed into the armature the intercalate could be excited into the plasma state around the edges of the armature, while the bulk of the current would be carried through the graphite block. Such an armature would have the desirable characteristics of both diffuse plasma armatures and bulk conduction armatures. In addition, the highly anisotropic nature of these materials could enable the electrical and thermal conductivity to be tailored to meet the specific requirements of electromagnetic railgun armatures. Preliminary investigations were performed in an attempt to determine the feasibility of using graphite intercalation compounds as railgun armatures. Issues of fabrication, resistivity, stability, and electrical current spreading are addressed for the case of highly oriented pyrolytic graphite.

Neural basis of postural instability identified by VTC and EEG

PubMed Central

Cao, Cheng; Jaiswal, Niharika; Newell, Karl M.

2010-01-01

In this study, we investigated the neural basis of virtual time to contact (VTC) and the hypothesis that VTC provides predictive information for future postural instability. A novel approach to differentiate stable pre-falling and transition-to-instability stages within a single postural trial while a subject was performing a challenging single leg stance with eyes closed was developed. Specifically, we utilized wavelet transform and stage segmentation algorithms using VTC time series data set as an input. The VTC time series was time-locked with multichannel (n = 64) EEG signals to examine its underlying neural substrates. To identify the focal sources of neural substrates of VTC, a two-step approach was designed combining the independent component analysis (ICA) and low-resolution tomography (LORETA) of multichannel EEG. There were two major findings: (1) a significant increase of VTC minimal values (along with enhanced variability of VTC) was observed during the transition-to-instability stage with progression to ultimate loss of balance and falling; and (2) this VTC dynamics was associated with pronounced modulation of EEG predominantly within theta, alpha and gamma frequency bands. The sources of this EEG modulation were identified at the cingulate cortex (ACC) and the junction of precuneus and parietal lobe, as well as at the occipital cortex. The findings support the hypothesis that the systematic increase of minimal values of VTC concomitant with modulation of EEG signals at the frontal-central and parietal–occipital areas serve collectively to predict the future instability in posture. PMID:19655130

The surgical treatment of instability of the upper part of the cervical spine in children and adolescents.

PubMed

Koop, S E; Winter, R B; Lonstein, J E

1984-03-01

In a retrospective review of the cases of thirteen skeletally immature children and adolescents (four to eighteen years old) with instability of the upper part of the cervical spine (occiput to fifth cervical vertebra), we determined the efficacy of posterior arthrodesis and halo-cast immobilization in the management of this condition. The patients were divided into two groups: those with congenital vertebral anomalies alone (fusion or structural defects, or both) and those with cervical anomalies and systemic disorders (dwarfism, juvenile rheumatoid arthritis, Down syndrome, and cerebral palsy). Two patterns of instability were found: instabilities at intervertebral joints adjacent to vertebral fusions, and instabilities located in vertebral defects. For all patients treatment included a posterior arthrodesis with external immobilization by a halo cast, and in two patients internal fixation with wire was also used. Solid arthrodesis was obtained in the twelve patients who were treated with autogenous grafts (iliac cancellous bone in eleven and rib bone in one), and a non-union developed in a child who was treated with bank-bone rib segments. Posterior cervical arthrodesis with wire fixation carries some risk of neural injury and often is not applicable in children with anomalous vertebrae. Spine fusion using delicate exposure, decortication using an air-drill, and placement of autogenous cancellous iliac grafts with external immobilization by a halo cast minimizes the risk of neural damage and is a reliable way to obtain a solid arthrodesis.

High Mitochondrial DNA Stability in B-Cell Chronic Lymphocytic Leukemia

PubMed Central

Cerezo, María; Bandelt, Hans-Jürgen; Martín-Guerrero, Idoia; Ardanaz, Maite; Vega, Ana; Carracedo, Ángel; García-Orad, África; Salas, Antonio

2009-01-01

Background Chronic Lymphocytic Leukemia (CLL) leads to progressive accumulation of lymphocytes in the blood, bone marrow, and lymphatic tissues. Previous findings have suggested that the mtDNA could play an important role in CLL. Methodology/Principal Findings The mitochondrial DNA (mtDNA) control-region was analyzed in lymphocyte cell DNA extracts and compared with their granulocyte counterpart extract of 146 patients suffering from B-Cell CLL; B-CLL (all recruited from the Basque country). Major efforts were undertaken to rule out methodological artefacts that would render a high false positive rate for mtDNA instabilities and thus lead to erroneous interpretation of sequence instabilities. Only twenty instabilities were finally confirmed, most of them affecting the homopolymeric stretch located in the second hypervariable segment (HVS-II) around position 310, which is well known to constitute an extreme mutational hotspot of length polymorphism, as these mutations are frequently observed in the general human population. A critical revision of the findings in previous studies indicates a lack of proper methodological standards, which eventually led to an overinterpretation of the role of the mtDNA in CLL tumorigenesis. Conclusions/Significance Our results suggest that mtDNA instability is not the primary causal factor in B-CLL. A secondary role of mtDNA mutations cannot be fully ruled out under the hypothesis that the progressive accumulation of mtDNA instabilities could finally contribute to the tumoral process. Recommendations are given that would help to minimize erroneous interpretation of sequencing results in mtDNA studies in tumorigenesis. PMID:19924307

Probing Atomic, Electronic, and Optical Structures of Nanoparticle Photocatalysts Using Fast Electrons

NASA Astrophysics Data System (ADS)

Liu, Qianlang

Graphene has attracted great interest in many fields due to its outstanding electronic and chemical properties. Among them, its surface inertness and high thermal stability makes graphene a promising candidate as a protective material for transition metal surfaces. Recent studies show, however, that small molecules, such as O2, CO and H2O, intercalate between a graphene film and a metal substrate at particular temperatures. The intercalation of O2 between graphene and Ru(0001) is studied with 3 keV helium ion scattering and low energy electron diffraction. It is shown that O2 intercalates between the graphene and the Ru(0001) substrate at a temperature of 650 K and does not adsorb onto the graphene surface. Nevertheless, the graphene layer efficiently avoids both intercalation and adsorption of oxygen at room temperature. It is also found that the intercalated oxygen thermally desorbs from the surface after it is heated to 800 K. Such a desorption is not, however, observed for oxygen dissociatively adsorbed on a bare Ru(0001) surface until 1200 K. It is thus inferred that the oxygen intercalated between graphene and Ru(0001) is in a molecular form. In addition, part of the graphene overlayer is etched by a chemical reaction during the thermal desorption of oxygen. The role of the defects on the graphene layer is also studied. Defects are introduced by 50 eV Ar+ sputtering, which creates single vacancies with a quick sputtering or larger open areas of substrate following a prolonged sputtering. It is found that oxygen molecularly adsorbs at single carbon vacancies even at room temperature, which does not occur on a complete graphene layer. Following post-annealing to 600 K, it is observed that such adsorbed oxygen diffuses to become intercalated between graphene and Ru(0001). Oxygen dissociatively adsorbs in the large open areas of exposed substrate by forming strong oxygen-metal bonds. It is also found that the presence of defects facilitates the intercalation of oxygen and improves the etching efficiency of the graphene during the desorption of oxygen.

Gait kinematics of subjects with ankle instability using a multisegmented foot model.

PubMed

De Ridder, Roel; Willems, Tine; Vanrenterghem, Jos; Robinson, Mark; Pataky, Todd; Roosen, Philip

2013-11-01

Many patients who sustain an acute lateral ankle sprain develop chronic ankle instability (CAI). Altered ankle kinematics have been reported to play a role in the underlying mechanisms of CAI. In previous studies, however, the foot was modeled as one rigid segment, ignoring the complexity of the ankle and foot anatomy and kinematics. The purpose of this study was to evaluate stance phase kinematics of subjects with CAI, copers, and controls during walking and running using both a rigid and a multisegmented foot model. Foot and ankle kinematics of 77 subjects (29 subjects with self-reported CAI, 24 copers, and 24 controls) were measured during barefoot walking and running using a rigid foot model and a six-segment Ghent Foot Model. Data were collected on a 20-m-long instrumented runway embedded with a force plate and a six-camera optoelectronic system. Groups were compared using statistical parametric mapping. Both the CAI and the coper group showed similar differences during midstance and late stance compared with the control group (P < 0.05). The rigid foot segment showed a more everted position during walking compared with the control group. Based on the Ghent Foot Model, the rear foot also showed a more everted position during running. The medial forefoot showed a more inverted position for both running and walking compared with the control group. Our study revealed significant midstance and late stance differences in rigid foot, rear foot, and medial forefoot kinematics The multisegmented foot model demonstrated intricate behavior of the foot that is not detectable with rigid foot modeling. Further research using these models is necessary to expand knowledge of foot kinematics in subjects with CAI.

Adaptive Stress Response in Segmental Progeria Resembles Long-Lived Dwarfism and Calorie Restriction in Mice

PubMed Central

Holcomb, Valerie B; von Lindern, Marieke; Jong, Willeke M. C; Zeeuw, Chris I. De; Suh, Yousin; Hasty, Paul; Hoeijmakers, Jan H. J; van der Horst, Gijsbertus T. J; Mitchell, James R

2006-01-01

How congenital defects causing genome instability can result in the pleiotropic symptoms reminiscent of aging but in a segmental and accelerated fashion remains largely unknown. Most segmental progerias are associated with accelerated fibroblast senescence, suggesting that cellular senescence is a likely contributing mechanism. Contrary to expectations, neither accelerated senescence nor acute oxidative stress hypersensitivity was detected in primary fibroblast or erythroblast cultures from multiple progeroid mouse models for defects in the nucleotide excision DNA repair pathway, which share premature aging features including postnatal growth retardation, cerebellar ataxia, and death before weaning. Instead, we report a prominent phenotypic overlap with long-lived dwarfism and calorie restriction during postnatal development (2 wk of age), including reduced size, reduced body temperature, hypoglycemia, and perturbation of the growth hormone/insulin-like growth factor 1 neuroendocrine axis. These symptoms were also present at 2 wk of age in a novel progeroid nucleotide excision repair-deficient mouse model (XPDG602D/R722W/XPA−/−) that survived weaning with high penetrance. However, despite persistent cachectic dwarfism, blood glucose and serum insulin-like growth factor 1 levels returned to normal by 10 wk, with hypoglycemia reappearing near premature death at 5 mo of age. These data strongly suggest changes in energy metabolism as part of an adaptive response during the stressful period of postnatal growth. Interestingly, a similar perturbation of the postnatal growth axis was not detected in another progeroid mouse model, the double-strand DNA break repair deficient Ku80 −/− mouse. Specific (but not all) types of genome instability may thus engage a conserved response to stress that evolved to cope with environmental pressures such as food shortage. PMID:17173483

Adaptive stress response in segmental progeria resembles long-lived dwarfism and calorie restriction in mice.

PubMed

van de Ven, Marieke; Andressoo, Jaan-Olle; Holcomb, Valerie B; von Lindern, Marieke; Jong, Willeke M C; De Zeeuw, Chris I; Suh, Yousin; Hasty, Paul; Hoeijmakers, Jan H J; van der Horst, Gijsbertus T J; Mitchell, James R

2006-12-15

How congenital defects causing genome instability can result in the pleiotropic symptoms reminiscent of aging but in a segmental and accelerated fashion remains largely unknown. Most segmental progerias are associated with accelerated fibroblast senescence, suggesting that cellular senescence is a likely contributing mechanism. Contrary to expectations, neither accelerated senescence nor acute oxidative stress hypersensitivity was detected in primary fibroblast or erythroblast cultures from multiple progeroid mouse models for defects in the nucleotide excision DNA repair pathway, which share premature aging features including postnatal growth retardation, cerebellar ataxia, and death before weaning. Instead, we report a prominent phenotypic overlap with long-lived dwarfism and calorie restriction during postnatal development (2 wk of age), including reduced size, reduced body temperature, hypoglycemia, and perturbation of the growth hormone/insulin-like growth factor 1 neuroendocrine axis. These symptoms were also present at 2 wk of age in a novel progeroid nucleotide excision repair-deficient mouse model (XPD(G602D/R722W)/XPA(-/-)) that survived weaning with high penetrance. However, despite persistent cachectic dwarfism, blood glucose and serum insulin-like growth factor 1 levels returned to normal by 10 wk, with hypoglycemia reappearing near premature death at 5 mo of age. These data strongly suggest changes in energy metabolism as part of an adaptive response during the stressful period of postnatal growth. Interestingly, a similar perturbation of the postnatal growth axis was not detected in another progeroid mouse model, the double-strand DNA break repair deficient Ku80(-/-) mouse. Specific (but not all) types of genome instability may thus engage a conserved response to stress that evolved to cope with environmental pressures such as food shortage.

Mutation mechanisms that underlie turnover of a human telomere-adjacent segmental duplication containing an unstable minisatellite.

PubMed

Hills, Mark; Jeyapalan, Jennie N; Foxon, Jennifer L; Royle, Nicola J

2007-04-01

Subterminal regions, juxtaposed to telomeres on human chromosomes, contain a high density of segmental duplications, but relatively little is known about the evolutionary processes that underlie sequence turnover in these regions. We have characterized a segmental duplication adjacent to the Xp/Yp telomere, each copy containing a hypervariable array of the DXYS14 minisatellite. Both DXYS14 repeat arrays mutate at a high rate (0.3 and 0.2% per gamete) but linkage disequilibrium analysis across 27 SNPs and a direct crossover assay show that recombination during meiosis is suppressed. Therefore instability at DXYS14a and b is dominated by intra-allelic processes or possibly conversion limited to the repeat arrays. Furthermore some chromosomes (14%) carry only one copy of the duplicon, including one DXYS14 repeat array that is also highly mutable (1.2% per gamete). To explain these and other observations, we propose there is another low-rate mutation process that causes copy number change in part or all of the duplicon.

Ab initio study of the adsorption, diffusion, and intercalation of alkali metal atoms on the (0001) surface of the topological insulator Bi{sub 2}Se{sub 3}

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

Ryabishchenkova, A. G., E-mail: ryaange@gmail.com; Otrokov, M. M.; Kuznetsov, V. M.

2015-09-15

Ab initio study of the adsorption, diffusion, and intercalation of alkali metal adatoms on the (0001) step surface of the topological insulator Bi{sub 2}Se{sub 3} has been performed for the case of low coverage. The calculations of the activation energies of diffusion of adatoms on the surface and in van der Waals gaps near steps, as well as the estimate of diffusion lengths, have shown that efficient intercalation through steps is possible only for Li and Na. Data obtained for K, Rb, and Cs atoms indicate that their thermal desorption at high temperatures can occur before intercalation. The results havemore » been discussed in the context of existing experimental data.« less

Effect of lightning strike on bromine intercalated graphite fiber/epoxy composites

NASA Technical Reports Server (NTRS)

Gaier, James R.; Slabe, Melissa E.; Brink, Norman O.

1991-01-01

Laminar composites were fabricated from pristine and bromine intercalated pitch based graphite fibers. It was found that laminar composites could be fabricated using either pristine or intercalated graphite fibers using standard fabrication techniques. The intercalated graphite fiber composites had electrical properties which were markedly improved over both the corresponding pitch based and polyacrylonitrile (PAN) based composites. Despite composites resistivities more than an order of magnitude lower for pitch based fiber composites, the lightning strike resistance was poorer than that of the Pan based fiber composites. This leads to the conclusion that the mechanical properties of the pitch fibers are more important than electrical or thermal properties in determining the lightning strike resistance. Based on indicated lightning strike tolerance for high elongation to failure materials, the use of vapor grown, rather than pitch based graphite fibers appears promising.

Graphite fiber intercalation: Basic properties of copper chloride intercalated fibers

NASA Technical Reports Server (NTRS)

Jaworske, D. A.; Miller, J. D.

1986-01-01

In situ resistance measurements were used to follow the intercalation of copper chloride in pitch-based fibers. Subsequent single fiber resistivity measurements reveal a large range of resistivities, from 13 to 160 micro-ohms cm. Additional density measurements reveal a bimodal distribution of mass densities. The dense fibers have lower resistivities and correspond to the stage III compound identified by X-ray diffraction. Neither resistivity nor density correlate with diameter. Both energy dispersive spectroscopy and mass density data suggest that excess chlorine resides in the intercalated fiber, resulting in a stoichiometry of C4.9n CuCl2.5 (where n is the stage number) for the denser fibers. Finally, thermogravimetric analysis shows a 33 percent loss in mass upon heating to 700C. This loss in mass is attributed to loss of both chlorine and carbon.

Stable loop in the crystal structure of the intercalated four-stranded cytosine-rich metazoan telomere

NASA Technical Reports Server (NTRS)

Kang, C.; Berger, I.; Lockshin, C.; Ratliff, R.; Moyzis, R.; Rich, A.

1995-01-01

In most metazoans, the telomeric cytosine-rich strand repeating sequence is d(TAACCC). The crystal structure of this sequence was solved to 1.9-A resolution. Four strands associate via the cytosine-containing parts to form a four-stranded intercalated structure held together by C.C+ hydrogen bonds. The base-paired strands are parallel to each other, and the two duplexes are intercalated into each other in opposite orientations. One TAA end forms a highly stabilized loop with the 5' thymine Hoogsteen-base-paired to the third adenine. The 5' end of this loop is in close proximity to the 3' end of one of the other intercalated cytosine strands. Instead of being entirely in a DNA duplex, this structure suggests the possibility of an alternative conformation for the cytosine-rich telomere strands.

Structural and thermal properties of inorganic-organic montmorillonite: Implications for their potential environmental applications.

PubMed

Rathnayake, Suramya I; Xi, Yunfei; Frost, Ray L; Ayoko, Godwin A

2015-12-01

Inorganic-organic clays (IOCs), clays intercalated with both organic cations such as cationic surfactants and inorganic cations such as metal hydroxy polycations have the properties of both organic and pillared clays, and thereby the ability to remove both inorganic and organic contaminants from water simultaneously. In this study, IOCs were synthesised using three different methods with different surfactant concentrations. Octadecyltrimethylammonium bromide (ODTMA) and hydroxy aluminium ([Al13O4(OH)24(H2O)12](7+) or Al13) are used as the organic and inorganic modifiers (intercalation agents). According to the results, the interlayer distance, the surfactant loading amount and the Al/Si ratio of IOCs strictly depend on the intercalation method and the intercalation agent ratio. Interlayers of IOCs synthesised by intercalating ODTMA before Al13 and IOCs synthesised by simultaneous intercalation of ODTMA and Al13 were increased with increasing the ODTMA concentration used in the synthesis procedure and comparatively high loading amounts could be observed in them. In contrast, Al/Si decreased with increasing ODTMA concentration in these two types of IOCs. The results suggest that Al-pillars can be fixed within the interlayers by calcination and any increment in the amount of ODTMA used in the synthesis procedure did not affect the interlayer distance of the IOCs. Overall the study provides valuable insights into the structure and properties of the IOCs and their potential environmental applications. Copyright © 2015 Elsevier Inc. All rights reserved.

Direct Investigation of Mg Intercalation into the Orthorhombic V 2O 5 Cathode Using Atomic-Resolution Transmission Electron Microscopy [Direct Investigation of Mg intercalation into orthorhombic V 2O 5 cathode using Atomic Resolution Electron Microscopy Methods

DOE PAGES

Mukherjee, Arijita; Sa, Niya; Phillips, Patrick J.; ...

2017-02-13

Batteries based on Mg metal anode can promise much higher specific volumetric capacity and energy density compared to Li-ion systems and are, at the same time, safer and more cost-effective. While previous experimental reports have claimed reversible Mg intercalation into beyond Chevrel phase cathodes, they provide limited evidence of true Mg intercalation other than electrochemical data. Transmission electron microscopy techniques provide unique capabilities to directly image Mg intercalation and quantify the redox reaction within the cathode material. Here, we present a systematic study of Mg insertion into orthorhombic V 2O 5, combining aberration-corrected scanning transmission electron microscopy (STEM) imaging, electronmore » energy-loss spectroscopy (EELS), and energy-dispersive X-ray spectroscopy (EDX) analysis. We compare the results from an electrochemically cycled V 2O 5 cathode in a prospective full cell with Mg metal anode with a chemically synthesized MgV 2O 5 sample. Results suggest that the electrochemically cycled orthorhombic V 2O 5 cathode shows a local formation of the theoretically predicted ϵ-Mg0.5V2O5 phase; however, the intercalation levels of Mg are lower than predicted. Lastly, this phase is different from the chemically synthesized sample, which is found to represent the δ-MgV 2O 5 phase.« less

Intercalation and controlled release properties of vitamin C intercalated layered double hydroxide

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

Gao, Xiaorui, E-mail: gxr_1320@sina.com; School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189; Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA

Two drug-inorganic composites involving vitamin C (VC) intercalated in Mg–Al and Mg–Fe layered double hydroxides (LDHs) have been synthesized by the calcination–rehydration (reconstruction) method. Powder X-ray diffraction (XRD), Fourier transform infrared (FTIR), and UV–vis absorption spectroscopy indicate a successful intercalation of VC into the interlayer galleries of the LDH host. Studies of VC release from the LDHs in deionised water and in aqueous CO{sub 3}{sup 2−} solutions imply that Mg{sub 3}Al–VC LDH is a better controlled release system than Mg{sub 3}Fe–VC LDH. Analysis of the release profiles using a number of kinetic models suggests a solution-dependent release mechanism, and amore » diffusion-controlled deintercalation mechanism in deionised water, but an ion exchange process in CO{sub 3}{sup 2−} solution. - Graphical abstract: Vitamin C anions have been intercalated in the interlayer space of layered double hydroxide and released in CO{sub 3}{sup 2−} solution and deionised water. - Highlights: • Vitamin C intercalated Mg–Al and Mg–Fe layered double hydroxides were prepared. • Release property of vitamin C in aqueous CO{sub 3}{sup 2−} solution is better. • Avrami-Erofe’ev and first-order models provide better fit for release results. • Diffusion-controlled and ion exchange processes occur in deionised water. • An ion exchange process occurs in CO{sub 3}{sup 2−} solution.« less

A ruthenium dimer complex with a flexible linker slowly threads between DNA bases in two distinct steps.

PubMed

Bahira, Meriem; McCauley, Micah J; Almaqwashi, Ali A; Lincoln, Per; Westerlund, Fredrik; Rouzina, Ioulia; Williams, Mark C

2015-10-15

Several multi-component DNA intercalating small molecules have been designed around ruthenium-based intercalating monomers to optimize DNA binding properties for therapeutic use. Here we probe the DNA binding ligand [μ-C4(cpdppz)2(phen)4Ru2](4+), which consists of two Ru(phen)2dppz(2+) moieties joined by a flexible linker. To quantify ligand binding, double-stranded DNA is stretched with optical tweezers and exposed to ligand under constant applied force. In contrast to other bis-intercalators, we find that ligand association is described by a two-step process, which consists of fast bimolecular intercalation of the first dppz moiety followed by ∼10-fold slower intercalation of the second dppz moiety. The second step is rate-limited by the requirement for a DNA-ligand conformational change that allows the flexible linker to pass through the DNA duplex. Based on our measured force-dependent binding rates and ligand-induced DNA elongation measurements, we are able to map out the energy landscape and structural dynamics for both ligand binding steps. In addition, we find that at zero force the overall binding process involves fast association (∼10 s), slow dissociation (∼300 s), and very high affinity (Kd ∼10 nM). The methodology developed in this work will be useful for studying the mechanism of DNA binding by other multi-step intercalating ligands and proteins. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

Antiproliferative, DNA intercalation and redox cycling activities of dioxonaphtho[2,3-d]imidazolium analogs of YM155: A structure-activity relationship study.

PubMed

Ho, Si-Han Sherman; Sim, Mei-Yi; Yee, Wei-Loong Sherman; Yang, Tianming; Yuen, Shyi-Peng John; Go, Mei-Lin

2015-11-02

The anticancer agent YM155 is widely investigated as a specific survivin suppressant. More recently, YM155 was found to induce DNA damage and this has raised doubts as to whether survivin is its primary target. In an effort to assess the contribution of DNA damage to the anticancer activity of YM155, several analogs were prepared and evaluated for antiproliferative activity on malignant cells, participation in DNA intercalation and free radical generation by redox cycling. The intact positively charged scaffold was found to be essential for antiproliferative activity and intercalation but was less critical for redox cycling where the minimal requirement was a pared down bicyclic quinone. Side chain requirements at the N(1) and N(3) positions of the scaffold were more alike for redox cycling and intercalation than antiproliferative activity, underscoring yet again, the limited structural overlaps for these activities. Furthermore, antiproliferative activities were poorly correlated to DNA intercalation and redox cycling. Potent antiproliferative activity (IC50 9-23 nM), exceeding that of YM155, was found for a minimally substituted methyl analog AB7. Like YM155 and other dioxonaphthoimidazoliums, AB7 was a modest DNA intercalator but with weak redox cycling activity. Thus, the capacity of this scaffold to inflict direct DNA damage leading to cell death may not be significant and YM155 should not be routinely classified as a DNA damaging agent. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

Direct intercalation of cisplatin into zirconium phosphate nanoplatelets for potential cancer nanotherapy

PubMed Central

Díaz, Agustín; González, Millie L.; Pérez, Riviam J.; David, Amanda; Mukherjee, Atashi; Báez, Adriana; Clearfield, Abraham

2014-01-01

We report the use of zirconium phosphate nanoplatelets (ZrP) for the encapsulation of the anticancer drug cisplatin and its delivery to tumor cells. Cisplatin was intercalated into ZrP by direct-ion exchange and was tested in-vitro for cytotoxicity in the human breast cancer (MCF-7) cell line. The structural characterization of the intercalated cisplatin in ZrP suggests that during the intercalation process, the chloride ligands of the cisplatin complex were substituted by phosphate groups within the layers. Consequently, a new phosphate phase with the platinum complex directly bound to ZrP (cisPt@ZrP) is produced with an interlayer distance of 9.3 Å. The in-vitro release profile of the intercalated drug by pH stimulus shows that at low pH under lysosomal conditions the platinum complex is released with simultaneous hydrolysis of the zirconium phosphate material, while at higher pH the complex is not released. Experiments with the MCF-7 cell line show that cisPt@ZrP reduced the cell viability up to 40%. The cisPt@ZrP intercalation product is envisioned as a future nanotherapy agent for cancer. Taking advantage of the shape and sizes of the ZrP particles and controlled release of the drug at low pH, it is intended to exploit the enhanced permeability and retention effect of tumors, as well as their intrinsic acidity, for the destruction of malignant cells. PMID:24072038

Probing the recognition surface of a DNA triplex: binding studies with intercalator-neomycin conjugates.

PubMed

Xue, Liang; Xi, Hongjuan; Kumar, Sunil; Gray, David; Davis, Erik; Hamilton, Paris; Skriba, Michael; Arya, Dev P

2010-07-06

Thermodynamic studies on the interactions between intercalator-neomycin conjugates and a DNA polynucleotide triplex [poly(dA).2poly(dT)] were conducted. To draw a complete picture of such interactions, naphthalene diimide-neomycin (3) and anthraquinone-neomycin (4) conjugates were synthesized and used together with two other analogues, previously synthesized pyrene-neomycin (1) and BQQ-neomycin (2) conjugates, in our investigations. A combination of experiments, including UV denaturation, circular dichroism (CD) titration, differential scanning calorimetry (DSC), and isothermal titration calorimetry (ITC), revealed that all four conjugates (1-4) stabilized poly(dA).2poly(dT) much more than its parent compound, neomycin. UV melting experiments clearly showed that the temperature (T(m3-->2)) at which poly(dA).2poly(dT) dissociated into poly(dA).poly(dT) and poly(dT) increased dramatically (>12 degrees C) in the presence of intercalator-neomycin conjugates (1-4) even at a very low concentration (2 muM). In contrast to intercalator-neomycin conjugates, the increment of T(m3-->2) of poly(dA).2poly(dT) induced by neomycin was negligible under the same conditions. The binding preference of intercalator-neomycin conjugates (1-4) to poly(dA).2poly(dT) was also confirmed by competition dialysis and a fluorescent intercalator displacement assay. Circular dichroism titration studies revealed that compounds 1-4 had slightly larger binding site size ( approximately 7-7.5) with poly(dA).2poly(dT) as compared to neomycin ( approximately 6.5). The thermodynamic parameters of these intercalator-neomycin conjugates with poly(dA).2poly(dT) were derived from an integrated van't Hoff equation using the T(m3-->2) values, the binding site size numbers, and other parameters obtained from DSC and ITC. The binding affinity of all tested ligands with poly(dA).2poly(dT) increased in the following order: neomycin < 1 < 3 < 4 < 2. Among them, the binding constant [(2.7 +/- 0.3) x 10(8) M(-1)] of 2 with poly(dA).2poly(dT) was the highest, almost 1000-fold greater than that of neomycin. The binding of compounds 1-4 with poly(dA).2poly(dT) was mostly enthalpy-driven and gave negative DeltaC(p) values. The results described here suggest that the binding affinity of intercalator-neomycin conjugates for poly(dA).2poly(dT) increases as a function of the surface area of the intercalator moiety.

Electronic and Structural Studies of Intercalated Graphite and Buckminsterfullerene.

NASA Astrophysics Data System (ADS)

Kelty, Stephen Paul

Under the direction of Prof. C. M. Lieber, the surface electronic and structural properties of binary MC_{rm x} and ternary rm MM^' C_{x } donor graphite intercalation compounds (GICs) were investigated using scanning tunneling microscopy (STM) and other surface sensitive techniques. The STM images revealed previously unobserved superstructures in the local density of states contours. These new superstructures include a commensurate 4.9 A periodicity (MC_8, where M = Li, K, Rb, Cs, KHg, rm K_2Hg_2 and rm K_2Tl _3). This superstructure has been interpreted as a modulation of the surface density of states due to the underlying commensurate intercalate lattice. Other GICs exhibit longer wavelength incommensurate superstructures, including: 19 A rm (KH_{0.8}C _8), 12 A rm (KH_{0.8 }C_4), 8.9 A rm (KHgC _4) and 7.5 A rm (KTl_ {1.5}C_8) periodicities. The direct -space wavelength of these incommensurate superstructures was found to scale inversely with the amount of charge transferred from the intercalate to the graphite layers. Such a correlation is consistent with the wavelength dependence on Fermi surface expansion of a charge density wave (CDW) state. STM investigations of adsorbed films of colloidal BiI_3, prepared by a solution-phase method, revealed the presence of mono-disperse 10-50 A single-layer particles with atomic resolution. This investigation demonstrated both the validity of the preparative method for the BiI_3 particles and the capability of the STM to atomically resolve small semiconducting particles. The structural and superconducting properties of alkali metal intercalated Buckminsterfullerene (C _{60}) were also investigated. A new preparatory method was developed using heavy metal alloys instead of pure alkali metal. Using these alloys, it was discovered that high superconducting fraction intercalation compounds could be prepared under milder conditions than by using the pure alkali metal. In addition, intercalation of Hg, Tl and Bi alloys of Cs was found to form a superconducting phase which has never been prepared by direct intercalation of Cs metal. Finally, other investigators have empirically derived a linear dependence of T_{ rm c} on lattice constant for intercalated C_{60}. This dependence has been used to model the electron pairing mechanism for the superconducting state. Investigations presented herein indicate that for lattice constants greater than 14.5 A, no further increases in T_{rm c} are observed. This finding places constraints on the above mentioned electron pairing models.

Clinical evaluation of semi-automatic open-source algorithmic software segmentation of the mandibular bone: Practical feasibility and assessment of a new course of action.

PubMed

Wallner, Jürgen; Hochegger, Kerstin; Chen, Xiaojun; Mischak, Irene; Reinbacher, Knut; Pau, Mauro; Zrnc, Tomislav; Schwenzer-Zimmerer, Katja; Zemann, Wolfgang; Schmalstieg, Dieter; Egger, Jan

2018-01-01

Computer assisted technologies based on algorithmic software segmentation are an increasing topic of interest in complex surgical cases. However-due to functional instability, time consuming software processes, personnel resources or licensed-based financial costs many segmentation processes are often outsourced from clinical centers to third parties and the industry. Therefore, the aim of this trial was to assess the practical feasibility of an easy available, functional stable and licensed-free segmentation approach to be used in the clinical practice. In this retrospective, randomized, controlled trail the accuracy and accordance of the open-source based segmentation algorithm GrowCut was assessed through the comparison to the manually generated ground truth of the same anatomy using 10 CT lower jaw data-sets from the clinical routine. Assessment parameters were the segmentation time, the volume, the voxel number, the Dice Score and the Hausdorff distance. Overall semi-automatic GrowCut segmentation times were about one minute. Mean Dice Score values of over 85% and Hausdorff Distances below 33.5 voxel could be achieved between the algorithmic GrowCut-based segmentations and the manual generated ground truth schemes. Statistical differences between the assessment parameters were not significant (p<0.05) and correlation coefficients were close to the value one (r > 0.94) for any of the comparison made between the two groups. Complete functional stable and time saving segmentations with high accuracy and high positive correlation could be performed by the presented interactive open-source based approach. In the cranio-maxillofacial complex the used method could represent an algorithmic alternative for image-based segmentation in the clinical practice for e.g. surgical treatment planning or visualization of postoperative results and offers several advantages. Due to an open-source basis the used method could be further developed by other groups or specialists. Systematic comparisons to other segmentation approaches or with a greater data amount are areas of future works.

Mechanisms of nanoclay-enhanced plastic foaming processes: effects of nanoclay intercalation and exfoliation

NASA Astrophysics Data System (ADS)

Wong, Anson; Wijnands, Stephan F. L.; Kuboki, Takashi; Park, Chul B.

2013-08-01

The foaming behaviors of high-density polypropylene-nanoclay composites with intercalated and exfoliated nanoclay particles blown with carbon dioxide were examined via in situ observation of the foaming processes in a high-temperature/high-pressure view-cell. The intercalated nanoclay particles were 300-600 nm in length and 50-200 nm in thickness, while the exfoliated nanoclay particles were 100-200 nm in length and 1 nm in thickness. Contrary to common belief, it was discovered that intercalated nanoclay yielded higher cell density than exfoliated nanoclay despite its lower particle density. This was attributed to the higher tensile stresses generated around the larger and stiffer intercalated nanoclay particles, which led to increase in supersaturation level for cell nucleation. Also, the coupling agent used to exfoliate nanoclay would increase the affinity between polymer and surface of nanoclay particles. Consequently, the critical work needed for cell nucleation would be increased; pre-existing microvoids, which could act as seeds for cell nucleation, were also less likely to exist. Meanwhile, exfoliated nanoclay had better cell stabilization ability to prevent cell coalescence and cell coarsening. This investigation clarifies the roles of nanoclay in plastic foaming processes and provides guidance for the advancement of polymer nanocomposite foaming technology.

Chemical Intercalation of Topological Insulator Grid Nanostructures for High-Performance Transparent Electrodes.

PubMed

Guo, Yunfan; Zhou, Jinyuan; Liu, Yujing; Zhou, Xu; Yao, Fengrui; Tan, Congwei; Wu, Jinxiong; Lin, Li; Liu, Kaihui; Liu, Zhongfan; Peng, Hailin

2017-11-01

2D layered nanomaterials with strong covalent bonding within layers and weak van der Waals' interactions between layers have attracted tremendous interest in recent years. Layered Bi 2 Se 3 is a representative topological insulator material in this family, which holds promise for exploration of the fundamental physics and practical applications such as transparent electrode. Here, a simultaneous enhancement of optical transmittancy and electrical conductivity in Bi 2 Se 3 grid electrodes by copper-atom intercalation is presented. These Cu-intercalated 2D Bi 2 Se 3 electrodes exhibit high uniformity over large area and excellent stabilities to environmental perturbations, such as UV light, thermal fluctuation, and mechanical distortion. Remarkably, by intercalating a high density of copper atoms, the electrical and optical performance of Bi 2 Se 3 grid electrodes is greatly improved from 900 Ω sq -1 , 68% to 300 Ω sq -1 , 82% in the visible range; with better performance of 300 Ω sq -1 , 91% achieved in the near-infrared region. These unique properties of Cu-intercalated topological insulator grid nanostructures may boost their potential applications in high-performance optoelectronics, especially for infrared optoelectronic devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Use of anionic clays for photoprotection and sunscreen photostability: Hydrotalcites and phenylbenzimidazole sulfonic acid

NASA Astrophysics Data System (ADS)

Perioli, Luana; Ambrogi, Valeria; Rossi, Carlo; Latterini, Loredana; Nocchetti, Morena; Costantino, Umberto

2006-05-01

Layered double hydroxides of hydrotalcite (HTlc) type have many applications as matrices in pharmaceutical and cosmetic fields when intercalated with active species in anionic form. The aim of this work was to intercalate 2-phenyl-1H-benzimidazole-5-sulfonic acid (Eusolex 232) (EUS) as sunscreen molecule into hydrotalcites in order to obtain the sunscreen stabilization, the reduction of its photodegradation and the elimination of close contact between skin and filter. Hydrotalcites MgAl and ZnAl were used as hosts and the intercalation products obtained were characterized by TG, RX and DSC. They were also submitted to spectrophotometric assays in order to study the matrix influence on sunlight protection and on sunscreen photostability. These experiments showed that both MgAl and ZnAl HTlc intercalation products maintained the sunscreen properties and eusolex photodegradation was reduced. The in vitro EUS release from both formulations was almost negligible when compared with formulations containing free EUS. The EUS intercalation in HTlc and the respective formulations provided advantages in the maintenance of photoprotection efficacy, filter photostabilization and avoidance of a close contact between skin and filter, with consequent elimination of allergy problems and photocross reactions.

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

Osiry, H.; Cano, A.; Lemus-Santana, A.A.

This contribution discusses the intercalation of imidazole and its 2-ethyl derivative, and pyridine in 2D copper nitroprusside. In the interlayer region, neighboring molecules remain interacting throu gh their dipole and quadrupole moments, which supports the solid 3D crystal structure. The crystal structure of this series of intercalation compounds was solved and refined from powder X-ray diffraction patterns complemented with spectroscopic information. The intermolecular interactions were studied from the refined crystal structures and low temperature magnetic measurements. Due to strong attractive forces between neighboring molecules, the resulting π–π cloud overlapping enables the ferromagnetic coupling between metal centers on neighboring layers, which wasmore » actually observed for the solids containing imidazole and pyridine as intercalated molecules. For these two solids, the magnetic data were properly described with a model of six neighbors. For the solid containing 2-ethylimidazole and for 2D copper nitroprusside, a model of four neighbors in a plane is sufficient to obtain a reliable data fitting. - Highlights: • Intercalation of organic molecules in 2D copper (II) nitroprusside. • Molecular properties of intercalation compounds of 2D copper (II) nitroprusside. • Magnetic properties of hybrid inorganic–organic solids. • Hybrid inorganic–organic 3D framework.« less

Correlation of intercalation potential with d-electron configurations for cathode compounds of lithium-ion batteries.

PubMed

Chen, Zhenlian; Zhang, Caixia; Zhang, Zhiyong; Li, Jun

2014-07-14

The d-electron localization is widely recognized as important to transport properties of transition metal compounds, but its role in the energy conversion of intercalation reactions of cathode compounds is still not fully explored. In this work, the correlation of intercalation potential with electron affinity, a key energy term controlling electron intercalation, then with d-electron configuration, is investigated. Firstly, we find that the change of the intercalation potential with respect to the transition metal cations within the same structure class is correlated in an approximately mirror relationship with the electron affinity, based on first-principles calculations on three typical categories of cathode compounds including layered oxides and polyoxyanions Then, by using a new model Hamiltonian based on the crystal-field theory, we reveal that the evolution is governed by the combination of the crystal-field splitting and the on-site d-d exchange interactions. Further, we show that the charge order in solid-solution composites and the compatibility of multi-electron redox steps could be inferred from the energy terms with the d-electron configuration alternations. These findings may be applied to rationally designing new chemistry for the lithium-ion batteries and other metal-ion batteries.

Capacitive Sensing of Intercalated H2O Molecules Using Graphene.

PubMed

Olson, Eric J; Ma, Rui; Sun, Tao; Ebrish, Mona A; Haratipour, Nazila; Min, Kyoungmin; Aluru, Narayana R; Koester, Steven J

2015-11-25

Understanding the interactions of ambient molecules with graphene and adjacent dielectrics is of fundamental importance for a range of graphene-based devices, particularly sensors, where such interactions could influence the operation of the device. It is well-known that water can be trapped underneath graphene and its host substrate; however, the electrical effect of water beneath graphene and the dynamics of how the interfacial water changes with different ambient conditions has not been quantified. Here, using a metal-oxide-graphene variable-capacitor (varactor) structure, we show that graphene can be used to capacitively sense the intercalation of water between graphene and HfO2 and that this process is reversible on a fast time scale. Atomic force microscopy is used to confirm the intercalation and quantify the displacement of graphene as a function of humidity. Density functional theory simulations are used to quantify the displacement of graphene induced by intercalated water and also explain the observed Dirac point shifts as being due to the combined effect of water and oxygen on the carrier concentration in the graphene. Finally, molecular dynamics simulations indicate that a likely mechanism for the intercalation involves adsorption and lateral diffusion of water molecules beneath the graphene.

Two-dimensional triangular lattice and its application to lithium-intercalated layered compounds

NASA Astrophysics Data System (ADS)

Decerqueira, R. O.

1982-08-01

Good rechargeable batteries are being searched for use in electric vehicles and in energy storage during off-peak consumption periods and from solar sources. The interest in lithium intercalation compounds has been recently enhanced by the search for such batteries. The process of intercalation of lithium in several transition metal dichalcogenides can provide an emf of several volts. The progress achieved in the last decade in the investigation of these intercalates has been facilitated by the availability of the dichalcogenides as single crystals and by their chemical stability. The transition-metal dichalcogenides and their Li-intercalates are studied, with emphasis on the Li/su xTa/sub yTi/sub l-y/S2 series. The interactions between the Li atoms and the applicability of a lattice gas model to the problem of ordering of these atoms is discussed. A formulation is presented of the cluster-variation aproximation to the lattice gas problem. The single-site and the nearest-neighbor triangle basic clusters are considered as models for Li/sub x TiS2. Also a theory is presented for the effects of a random distribution of different species of host atoms, as in Ta/sub y/Ti/sub l-y/S2.

Superconductivity and magnetism in iron sulfides intercalated by metal hydroxides† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc05268a Click here for additional data file.

PubMed Central

Zhou, Xiuquan; Eckberg, Christopher; Wilfong, Brandon; Liou, Sz-Chian; Vivanco, Hector K.; Paglione, Johnpierre

2017-01-01

Inspired by naturally occurring sulfide minerals, we present a new family of iron-based superconductors. A metastable form of FeS known as the mineral mackinawite forms two-dimensional sheets that can be readily intercalated by various cationic guest species. Under hydrothermal conditions using alkali metal hydroxides, we prepare three different cation and metal hydroxide-intercalated FeS phases including (Li1–xFexOH)FeS, [(Na1–xFex)(OH)2]FeS, and KxFe2–yS2. Upon successful intercalation of the FeS layer, the superconducting critical temperature T c of mackinawite is enhanced from 5 K to 8 K for the (Li1–xFexOH)δ+ intercalate. Layered heterostructures of [(Na1–xFex)(OH)2]FeS resemble the natural mineral tochilinite, which contains an iron square lattice interleaved with a hexagonal hydroxide lattice. Whilst heterostructured [(Na1–xFex)(OH)2]FeS displays long-range magnetic ordering near 15 K, KxFe2–yS2 displays short range antiferromagnetism. PMID:28580110

Method for intercalating alkali metal ions into carbon electrodes

DOEpatents

Doeff, Marca M.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard

1995-01-01

A low cost, relatively flexible, carbon electrode for use in a secondary battery is described. A method is provided for producing same, including intercalating alkali metal salts such as sodium and lithium into carbon.

Method for intercalating alkali metal ions into carbon electrodes

DOEpatents

Doeff, M.M.; Ma, Y.; Visco, S.J.; DeJonghe, L.

1995-08-22

A low cost, relatively flexible, carbon electrode for use in a secondary battery is described. A method is provided for producing same, including intercalating alkali metal salts such as sodium and lithium into carbon.

Coverage dependent work function of graphene on a Cu(111) substrate with intercalated alkali metals

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

Cook, Brandon G.; Russakoff, Arthur; Varga, Kalman

2015-05-26

Using first-principles calculations, it is shown that the work function of graphene on copper can be adjusted by varying the concentration of intercalated alkali metals. Using density functional theory, we calculate the modulation of work function when Li, Na, or K are intercalated between graphene and a Cu(111) surface. Furthermore, the physical origins of the change in work function are explained in terms of phenomenological models accounting for the formation and depolarization of interfacial dipoles and the shift in the Fermi-level induced via charge transfer.

Stereochemical model for proflavin intercalation in A-DNA.

PubMed Central

Alden, C J; Arnott, S

1977-01-01

Linked-atom molecular modelling was employed to determine the steric and torsional requirements for intercalation of proflavine into a double-stranded region of DNA compatible with adjacent regions of cohelical A-DNA. The optimum intercalation conformation is characterized by the dihedral angles xi and psi becoming trans, with all sugars retaining the characteristics C3'-endo pucker. This extended conformation results in virtually no helical unwinding, suggesting it may be an appropriate model for an intercalative intermediary in mutagenesis by virtue of its similarity to standard helical DNA. PMID:593890

Processing of monolayer materials via interfacial reactions

DOEpatents

Sutter, Peter Werner; Sutter, Eli Anguelova

2014-05-20

A method of forming and processing of graphene is disclosed based on exposure and selective intercalation of the partially graphene-covered metal substrate with atomic or molecular intercalation species such as oxygen (O.sub.2) and nitrogen oxide (NO.sub.2). The process of intercalation lifts the strong metal-carbon coupling and restores the characteristic Dirac behavior of isolated monolayer graphene. The interface of graphene with metals or metal-decorated substrates also provides for controlled chemical reactions based on novel functionality of the confined space between a metal surface and a graphene sheet.

STM/STS studies of Ca-intercalated bilayer graphene

NASA Astrophysics Data System (ADS)

Shimizu, Ryota; Sugawara, Katsuaki; Kanetani, Kohei; Iwaya, Katsuya; Sato, Takafumi; Takahashi, Takashi; Hitosugi, Taro

2013-03-01

We have performed low temperature scanning tunneling microscopy/spectroscopy (STM/STS) measurements on a two-dimensional Ca-intercalated bilayer graphene epitaxially grown on a 6H-SiC(0001) substrate. The STM topographic images clearly resolve each intercalated Ca atom with graphene-based honeycomb lattice. Furthermore, we found a clear ×2.5 modulation in the topography, implying charge density wave or Moiré pattern originated from the interaction with the SiC substrate. Comparison with ARPES measurements provided us of further insight into the Fermi surface deduced from STS.

Ferric chloride-graphite intercalation compounds as anode materials for Li-ion batteries.

PubMed

Wang, Lili; Zhu, Yongchun; Guo, Cong; Zhu, Xiaobo; Liang, Jianwen; Qian, Yitai

2014-01-01

Ferric chloride-graphite intercalation compounds (FeCl3 -GICs) with stage 1 and stage 2 structures were synthesized by reacting FeCl3 and expanded graphite (EG) in air in a stainless-steel autoclave. As rechargeable Li-ion batteries, these FeCl3 -GICs exhibit high capacity, excellent cycling stability, and superior rate capability, which could be attributed to their unique intercalation features. This work may enable new possibilities for the fabrication of Li-ion batteries. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coiled-Coil Irregularities and Instabilities in Group A Streptococcus M1 Are Required for Virulence

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

McNamara, Case; Zinkernagel, Annelies S.; Macheboeuf, Pauline

2008-07-21

Antigenically variable M proteins are major virulence factors and immunogens of the human pathogen group A Streptococcus (GAS). Here, we report the -3 angstrom resolution structure of a GAS M1 fragment containing the regions responsible for eliciting type-specific, protective immunity and for binding fibrinogen, which promotes M1 proinflammatory and antiphagocytic functions. The structure revealed substantial irregularities and instabilities throughout the coiled coil of the M1 fragment. Similar structural irregularities occur in myosin and tropomyosin, explaining the patterns of cross-reactivity seen in autoimmune sequelae of GAS infection. Sequence idealization of a large segment of the M1 coiled coil enhanced stability butmore » diminished fibrinogen binding, proinflammatory effects, and antibody cross-reactivity, whereas it left protective immunogenicity undiminished. Idealized M proteins appear to have promise as vaccine immunogens.« less

Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CO2: Implications for Caprock Integrity

NASA Astrophysics Data System (ADS)

Loring, J. S.; Chen, J.; Thompson, C.; Schaef, T.; Miller, Q. R.; Martin, P. F.; Ilton, E. S.; Qafoku, O.; Felmy, A. R.; Rosso, K. M.

2012-12-01

The effectiveness of geologic sequestration as an enterprise for CO2 storage depends partly on the reactivity of supercritical CO2 (scCO2) with caprock minerals. Injection of scCO2 will displace formation water, and the pore space adjacent to overlying caprocks could eventually be dominated by dry to water-saturated scCO2. Caprock formations have high concentrations of clay minerals, including expandable montmorillonites. Water-bearing scCO2 is highly reactive and capable of hydrating or dehydrating clays, possibly leading to porosity and permeability changes that directly impact caprock performance. Dehydration will cause montmorillonite clay minerals in caprocks to contract, thereby decreasing solid volume and possibly increasing caprock permeability and porosity. On the other hand, water intercalation will cause these clays to expand, thereby increasing solid volume and possibly leading to self-sealing of caprock fractures. Pacific Northwest National Laboratory's Carbon Sequestration Initiative is developing capabilities for studying wet scCO2-mineral reactions in situ. Here, we introduce novel in situ infrared (IR) spectroscopic instrumentation that enables quantitative titrations of reactant minerals with water in scCO2. Results are presented for the infrared spectroscopic titrations of Na-, Ca-, and Mg-saturated Wyoming betonites with water over concentrations ranging from zero to scCO2 saturated. These experiments were carried out at 50°C and 90 bar. Transmission IR spectroscopy was used to measure concentrations of water dissolved in the scCO2 or intercalated into the clays. The titration curves evaluated from the transmission-IR data are compared between the three types of clays to assess the effects of the cation on water partitioning. Single-reflection attenuated total reflection (ATR) IR spectroscopy was used to collect the spectrum of the clays as they hydrate at every total water concentration during the titration. Clay hydration is evidenced by increases in absorbance of the OH stretching and HOH bending modes of the intercalated waters. The ATR-IR data also indicate that CO2 is intercalated in the clay. The asymmetric stretching band of the CO2 molecules that are intercalated in the clay is narrower than that stretching band of bulk scCO2, which indicates that the spectral contribution from rotational fine structure is minimal and the intercalated CO2 is rotationally constrained. A chemometrics analysis of the complete set of ATR-IR spectra spanning the range of total water concentrations covered in the titration finds that there are at least two types of intercalated waters, two types of intercalated CO2 molecules, and the concentrations of these intercalated waters and CO2 molecules are correlated. These quantitative data, when coupled with in situ XRD results that predict interlayer spacing and clay volume, demonstrate that water and CO2 intercalation processes in expandable montmorillonite clays could lead to porosity and permeability changes that directly impact caprock performance.

Segmentation of humeral head from axial proton density weighted shoulder MR images

NASA Astrophysics Data System (ADS)

Sezer, Aysun; Sezer, Hasan Basri; Albayrak, Songul

2015-01-01

The purpose of this study is to determine the effectiveness of segmentation of axial MR proton density (PD) images of bony humeral head. PD sequence images which are included in standard shoulder MRI protocol are used instead of T1 MR images. Bony structures were reported to be successfully segmented in the literature from T1 MR images. T1 MR images give more sharp determination of bone and soft tissue border but cannot address the pathological process which takes place in the bone. In the clinical settings PD images of shoulder are used to investigate soft tissue alterations which can cause shoulder instability and are better in demonstrating edema and the pathology but have a higher noise ratio than other modalities. Moreover the alteration of humeral head intensity in patients and soft tissues in contact with the humeral head which have the very similar intensities with bone makes the humeral head segmentation a challenging problem in PD images. However segmentation of the bony humeral head is required initially to facilitate the segmentation of the soft tissues of shoulder. In this study shoulder MRI of 33 randomly selected patients were included. Speckle reducing anisotropic diffusion (SRAD) method was used to decrease noise and then Active Contour Without Edge (ACWE) and Signed Pressure Force (SPF) models were applied on our data set. Success of these methods is determined by comparing our results with manually segmented images by an expert. Applications of these methods on PD images provide highly successful results for segmentation of bony humeral head. This is the first study to determine bone contours in PD images in literature.

Controlling the actuation properties of MXene paper electrodes upon cation intercalation

DOE PAGES

Come, Jeremy E.; Black, Jennifer M.; Naguib, Michael; ...

2015-08-05

Atomic force microscopy was used to monitor the macroscopic deformation in a delaminated Ti₃C₂ paper electrode in-situ, during charge/discharge in a variety of aqueous electrolytes to examine the effect of the cation intercalation on the electrochemical behavior and mechanical response. The results show a strong dependence of the electrode deformation on cation size and charge. The electrode undergoes a large contraction during Li⁺, Na⁺ or Mg²⁺ intercalation, differentiating the Ti₃C₂ paper from conventional electrodes where redox intercalation of ions (e.g. Li⁺) into the bulk phase (e.g. graphite, silicon) results in volumetric expansion. This feature may explain the excellent rate performancemore » and cyclability reported for MXenes. We also demonstrated that the variation of the electromechanical contraction can be easily adjusted by electrolyte exchange, and shows interesting characteristics for the design of actuators based on 2D metal carbides.« less

Alternate-strand triple-helix formation by the 3'-3'-linked oligodeoxynucleotides with the intercalators at the junction point.

PubMed

Ueno, Y; Mikawa, M; Hoshika, S; Takeba, M; Kitade, Y; Matsuda, A

2001-01-01

3'-3'-Linked oligodeoxynucleotides (ODNs) with the anthraquinonyl group at the junction point were synthesized on a DNA synthesizer using a controlled pore glass (CPG), which has pentaerythritol carrying the intercalator at one of the four hydroxymethyl groups. Stability of the triplexes with the target duplexes was studied by thermal denaturation. The 3'-3'-linked ODNs with the anthraquinonyl group enhanced the thermal stability of the triplexes when compared with those without the intercalator and the unmodified nonamer. The inhibitory activity of the 3'-3'-linked ODNs against the cleavage of the target DNA by the restriction enzyme Hind III was tested. It was found that the 3'-3'-linked ODN with the anthraquinonyl group at the junction point inhibited the cleavage by the enzyme more effectively than the nonamer and the 3'-3'-linked ODN without the intercalator.

Intercalated europium metal in epitaxial graphene on SiC

DOE PAGES

Anderson, Nathaniel; Hupalo, Myron; Keavney, David; ...

2017-10-25

X-ray magnetic circular dichroism (XMCD) reveals the magnetic properties of intercalated europium metal under graphene on SiC(0001). Intercalation of Eu nanoclusters (average size 2.5 nm) between graphene and SiC substate are formed by deposition of Eu on epitaxially grown graphene that is subsequently annealed at various temperatures while keeping the integrity of the graphene layer. Using sum-rules analysis of the XMCD of Eu M 4,5 edges at T = 15 K, our samples show paramagnetic-like behavior with distinct anomaly at T ≈ 90 K, which may be related to the Nèel transition, T N = 91 K, of bulk metalmore » Eu. Here, we find no evidence of ferromagnetism due to EuO or antiferromagnetism due to Eu 2 O 3, indicating that the graphene layer protects the intercalated metallic Eu against oxidation over months of exposure to atmospheric environment.« less

Tuning Fullerene Intercalation in a Poly (thiophene) derivative by Controlling the Polymer Degree of Self-Organisation

NASA Astrophysics Data System (ADS)

Paternò, G. M.; Skoda, M. W. A.; Dalgliesh, Robert; Cacialli, F.; Sakai, V. García

2016-10-01

Controlling the nanoscale arrangement in polymer-fullerene organic solar cells is of paramount importance to boost the performance of such promising class of photovoltaic diodes. In this work, we use a pseudo-bilayer system made of poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene (PBTTT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), to acquire a more complete understanding of the diffusion and intercalation of the fullerene-derivative within the polymer layer. By exploiting morphological and structural characterisation techniques, we observe that if we increase the film solidification time the polymer develops a higher crystalline order, and, as a result, it does not allow fullerene molecules to intercalate between the polymer side-chains. Gaining insight into the detailed fullerene intercalation mechanism is important for the development of organic photovoltaic diodes (PVDs).

Preparation and Characterization of Novel Montmorillonite Nanocomposites

NASA Astrophysics Data System (ADS)

Mansa, Rola

Clay minerals have historically played a consequential role in human health. While the beginnings were rooted in geophagy, a primitive act of consuming earth, the health-related uses of clay minerals have evolved and diversified over time.. As excipients in pharmaceutical formulations, clay minerals can attribute novel properties onto intercalated compounds. Intercalating oxybenzone, a UV filter, within the interlamellar space of montmorillonite is desirable in order to minimize direct contact with skin. Intercalating resveratrol, a compound known for attributing beneficial effects onto human health, may be advantageous since this compound is susceptible to cis-trans isomerisation. The strategy of using alkylammonium--modified clay was undertaken and proved successful for the intercalation of oxybenzone. The field of biopolymer/layered silicate nanocomposites is heavily researched for use in a multitude of applications. Novel montmorillonite nanocomposites were prepared with neutral guar gum and cationic guar gum, using an environmentally friendly process and are fully characterized.

Tunable thermal expansion in framework materials through redox intercalation

PubMed Central

Chen, Jun; Gao, Qilong; Sanson, Andrea; Jiang, Xingxing; Huang, Qingzhen; Carnera, Alberto; Rodriguez, Clara Guglieri; Olivi, Luca; Wang, Lei; Hu, Lei; Lin, Kun; Ren, Yang; Lin, Zheshuai; Wang, Cong; Gu, Lin; Deng, Jinxia; Attfield, J. Paul; Xing, Xianran

2017-01-01

Thermal expansion properties of solids are of fundamental interest and control of thermal expansion is important for practical applications but can be difficult to achieve. Many framework-type materials show negative thermal expansion when internal cages are empty but positive thermal expansion when additional atoms or molecules fill internal voids present. Here we show that redox intercalation offers an effective method to control thermal expansion from positive to zero to negative by insertion of Li ions into the simple negative thermal expansion framework material ScF3, doped with 10% Fe to enable reduction. The small concentration of intercalated Li ions has a strong influence through steric hindrance of transverse fluoride ion vibrations, which directly controls the thermal expansion. Redox intercalation of guest ions is thus likely to be a general and effective method for controlling thermal expansion in the many known framework materials with phonon-driven negative thermal expansion. PMID:28181576

Hexagonal boron nitride intercalated multi-layer graphene: a possible ultimate solution to ultra-scaled interconnect technology

NASA Astrophysics Data System (ADS)

Li, Yong-Jun; Sun, Qing-Qing; Chen, Lin; Zhou, Peng; Wang, Peng-Fei; Ding, Shi-Jin; Zhang, David Wei

2012-03-01

We proposed intercalation of hexagonal boron nitride (hBN) in multilayer graphene to improve its performance in ultra-scaled interconnects for integrated circuit. The effect of intercalated hBN layer in bilayer graphene is investigated using non-equilibrium Green's functions. We find the hBN intercalated bilayer graphene exhibit enhanced transport properties compared with pristine bilayer ones, and the improvement is attributed to suppression of interlayer scattering and good planar bonding condition of inbetween hBN layer. Based on these results, we proposed a via structure that not only benefits from suppressed interlayer scattering between multilayer graphene, but also sustains the unique electrical properties of graphene when many graphene layers are stacking together. The ideal current density across the structure can be as high as 4.6×109 A/cm2 at 1V, which is very promising for the future high-performance interconnect.

Intercalation of Li Ions into a Graphite Anode Material: Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Abou Hamad, Ibrahim; Novotny, Mark

2008-03-01

Large-scale molecular dynamics simulations of the anode half-cell of a lithium-ion battery are presented. The model system is composed of an anode represented by a stack of graphite sheets, an electrolyte of ethylene carbonate and propylene carbonate molecules, and lithium and hexafluorophosphate ions. The simulations are done in the NVT ensemble and at room temperature. One charging scheme explored is normal charging in which intercalation is enhanced by electric charges on the graphitic sheets. The second charging mechanism has an external applied oscillatory electric field of amplitude A and frequency f. The simulations were performed on 2.6 GHz Opteron processors, using 160 processors at a time. Our simulation results show an improvement in the intercalation time of the lithium ions for the second charging mechanism. The dependence of the intercalation time on A and f will be discussed.

Potassium-intercalated H2Pc films: Alkali-induced electronic and geometrical modifications

NASA Astrophysics Data System (ADS)

Nilson, K.; Åhlund, J.; Shariati, M.-N.; Schiessling, J.; Palmgren, P.; Brena, B.; Göthelid, E.; Hennies, F.; Huismans, Y.; Evangelista, F.; Rudolf, P.; Göthelid, M.; Mârtensson, N.; Puglia, C.

2012-07-01

X-ray spectroscopy studies of potassium intercalated metal-free phthalocyanine multilayers adsorbed on Al(110) have been undertaken. Photoelectron spectroscopy measurements show the presence of several charge states of the molecules upon K intercalation, due to a charge transfer from the alkali. In addition, the comparison of valence band photoemission spectra with the density functional theory calculations of the density of states of the H2Pc- anion indicates a filling of the formerly lowest unoccupied molecular orbital by charge transfer from the alkali. This is further confirmed by x-ray absorption spectroscopy (XAS) studies, which show a decreased density of unoccupied states. XAS measurements in different experimental geometries reveal that the molecules in the pristine film are standing upright on the surface or are only slightly tilted away from the surface normal but upon K intercalation, the molecular orientation is changed in that the tilt angle of the molecules increases.

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

Danial, Wan Hazman, E-mail: hazmandanial@gmail.com; Majid, Zaiton Abdul, E-mail: zaiton@kimia.fs.utm.my; Aziz, Madzlan

The present work reports the synthesis and characterization of graphene via electrochemical exfoliation of graphite rod using two-electrode system assisted by Sodium Dodecyl Sulphate (SDS) as a surfactant. The electrochemical process was carried out with sequence of intercalation of SDS onto the graphite anode followed by exfoliation of the SDS-intercalated graphite electrode when the anode was treated as cathode. The effect of intercalation potential from 5 V to 9 V and concentration of the SDS surfactant of 0.1 M and 0.01 M were investigated. UV-vis Spectroscopic analysis indicated an increase in the graphene production with higher intercalation potential. Transmission Electron Microscopy (TEM)more » analysis showed a well-ordered hexagonal lattice of graphene image and indicated an angle of 60° between two zigzag directions within the honeycomb crystal lattice. Raman spectroscopy analysis shows the graphitic information effects after the exfoliation process.« less

Intercalation complex of proflavine with DNA: Structure and dynamics by solid-state NMR

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

Tang, Pei; Juang, Chilong; Harbison, G.S.

1990-07-06

The structure of the complex formed between the intercalating agent proflavine and fibrous native DNA was studied by one- and two-dimensional high-resolution solid-state nuclear magnetic resonance (NMR). Carbon-13-labeled proflavine was used to show that the drug is stacked with the aromatic ring plane perpendicular to the fiber axis and that it is essentially immobile. Natural abundance carbon-13 NMR of the DNA itself shows that proflavine binding does not change the puckering of the deoxyribose ring. However, phosphorus-31 NMR spectra show profound changes in the orientation of the phosphodiester grouping on proflavine binding, with some of the phosphodiesters tilting almost parallelmore » to the helix axis, and a second set almost perpendicular. The first group to the phosphodiesters probably spans the intercalation sites, whereas the tilting of the second set likely compensates for the unwinding of the DNA by the intercalator.« less

Synthesis and characterization of intercalated few-layer graphenes

NASA Astrophysics Data System (ADS)

Sato, Shogo; Ichikawa, Hiroaki; Iwata, Nobuyuki; Yamamoto, Hiroshi

2014-02-01

Toward achieving room-temperature superconductivity, FeCl3-intercalated few-layer graphenes (FeCl3-FLGs) and Ca-intercalated few-layer graphenes (Ca-FLGs) were synthesized. FeCl3-FLGs were synthesized by the two-zone method and Ca-FLGs were synthesized using Ca-Li alloy. The Raman spectra of the FeCl3-FLGs showed a lower-intensity peak at 1607 cm-1 than that of the corresponding bare G. The peak at 1607 cm-1 suggested that the sample was stage 4-5 FeCl3-FLGs. The room-temperature electrical resistivity of FeCl3-FLGs was 2.65 × 10-5 Ω·m, which linearly decreased with decreasing temperature with a marked change occurring at approximately 200 K. From a XRD pattern of Ca-FLGs, we concluded that Ca is intercalated in FLGs. The room-temperature resistivity of Ca-FLGs was 3.45 × 10-5 Ω·m, which increased with decreasing temperature.

Nano-scaled graphene platelets with a high length-to-width aspect ratio

DOEpatents

Zhamu, Aruna; Guo, Jiusheng; Jang, Bor Z.

2010-09-07

This invention provides a nano-scaled graphene platelet (NGP) having a thickness no greater than 100 nm and a length-to-width ratio no less than 3 (preferably greater than 10). The NGP with a high length-to-width ratio can be prepared by using a method comprising (a) intercalating a carbon fiber or graphite fiber with an intercalate to form an intercalated fiber; (b) exfoliating the intercalated fiber to obtain an exfoliated fiber comprising graphene sheets or flakes; and (c) separating the graphene sheets or flakes to obtain nano-scaled graphene platelets. The invention also provides a nanocomposite material comprising an NGP with a high length-to-width ratio. Such a nanocomposite can become electrically conductive with a small weight fraction of NGPs. Conductive composites are particularly useful for shielding of sensitive electronic equipment against electromagnetic interference (EMI) or radio frequency interference (RFI), and for electrostatic charge dissipation.

Preparation and enhanced properties of polyaniline/grafted intercalated ZnAl-LDH nanocomposites

NASA Astrophysics Data System (ADS)

Hu, Jinlong; Gan, Mengyu; Ma, Li; Zhang, Jun; Xie, Shuang; Xu, Fenfang; Shen, JiYue Zheng Xiaoyu; Yin, Hui

2015-02-01

The polymeric nanocomposites (PANI/AD-LDH) were prepared by in situ polymerization based on polyaniline (PANI) and decavanadate-intercalated and γ-aminopropyltriethoxysilane (APTS)-grafted ZnAl-layered double hydroxide (AD-LDH). FTIR and XRD studies confirm the grafting of APTS with decavanadate-intercalated LDH (D-LDH). The extent of grafting (wt%) has also been estimated on the basis of the residue left in nitrogen atmosphere at 800 °C in TGA. SEM and XPS studies show the partial exfoliation of grafted LDH in the PANI matrix and the interfacial interaction between PANI and grafted LDH, respectively. The grafted intercalated layered double hydroxide in reinforcing the properties of the PANI nanocomposites has also been investigated by open circuit potential (OCP), tafel polarization curves (TAF), electrochemical impendence spectroscopy (EIS), salt spray test and TGA-DTA. The experimental results indicate that the PANI/AD-LDH has a higher thermal stability and anticorrosion properties relative to the PANI.

Tunable thermal expansion in framework materials through redox intercalation

NASA Astrophysics Data System (ADS)

Chen, Jun; Gao, Qilong; Sanson, Andrea; Jiang, Xingxing; Huang, Qingzhen; Carnera, Alberto; Rodriguez, Clara Guglieri; Olivi, Luca; Wang, Lei; Hu, Lei; Lin, Kun; Ren, Yang; Lin, Zheshuai; Wang, Cong; Gu, Lin; Deng, Jinxia; Attfield, J. Paul; Xing, Xianran

2017-02-01

Thermal expansion properties of solids are of fundamental interest and control of thermal expansion is important for practical applications but can be difficult to achieve. Many framework-type materials show negative thermal expansion when internal cages are empty but positive thermal expansion when additional atoms or molecules fill internal voids present. Here we show that redox intercalation offers an effective method to control thermal expansion from positive to zero to negative by insertion of Li ions into the simple negative thermal expansion framework material ScF3, doped with 10% Fe to enable reduction. The small concentration of intercalated Li ions has a strong influence through steric hindrance of transverse fluoride ion vibrations, which directly controls the thermal expansion. Redox intercalation of guest ions is thus likely to be a general and effective method for controlling thermal expansion in the many known framework materials with phonon-driven negative thermal expansion.

Tuning Fullerene Intercalation in a Poly (thiophene) derivative by Controlling the Polymer Degree of Self-Organisation.

PubMed

Paternò, G M; Skoda, M W A; Dalgliesh, Robert; Cacialli, F; Sakai, V García

2016-10-04

Controlling the nanoscale arrangement in polymer-fullerene organic solar cells is of paramount importance to boost the performance of such promising class of photovoltaic diodes. In this work, we use a pseudo-bilayer system made of poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene (PBTTT) and [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM), to acquire a more complete understanding of the diffusion and intercalation of the fullerene-derivative within the polymer layer. By exploiting morphological and structural characterisation techniques, we observe that if we increase the film solidification time the polymer develops a higher crystalline order, and, as a result, it does not allow fullerene molecules to intercalate between the polymer side-chains. Gaining insight into the detailed fullerene intercalation mechanism is important for the development of organic photovoltaic diodes (PVDs).

Tuning Fullerene Intercalation in a Poly (thiophene) derivative by Controlling the Polymer Degree of Self-Organisation

PubMed Central

Paternò, G. M.; Skoda, M. W. A.; Dalgliesh, Robert; Cacialli, F.; Sakai, V. García

2016-01-01

Controlling the nanoscale arrangement in polymer-fullerene organic solar cells is of paramount importance to boost the performance of such promising class of photovoltaic diodes. In this work, we use a pseudo-bilayer system made of poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene (PBTTT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), to acquire a more complete understanding of the diffusion and intercalation of the fullerene-derivative within the polymer layer. By exploiting morphological and structural characterisation techniques, we observe that if we increase the film solidification time the polymer develops a higher crystalline order, and, as a result, it does not allow fullerene molecules to intercalate between the polymer side-chains. Gaining insight into the detailed fullerene intercalation mechanism is important for the development of organic photovoltaic diodes (PVDs). PMID:27698410

Carbon Nanotube Anodes Being Evaluated for Lithium Ion Batteries

NASA Technical Reports Server (NTRS)

Raffaelle, Ryne P.; Gennett, Tom; VanderWal, Randy L.; Hepp, Aloysius F.

2001-01-01

The NASA Glenn Research Center is evaluating the use of carbon nanotubes as anode materials for thin-film lithium-ion (Li) batteries. The motivation for this work lies in the fact that, in contrast to carbon black, directed structured nanotubes and nanofibers offer a superior intercalation media for Li-ion batteries. Carbon lamellas in carbon blacks are circumferentially oriented and block much of the particle interior, rendering much of the matrix useless as intercalation material. Nanofibers, on the other hand, can be grown so as to provide 100-percent accessibility of the entire carbon structure to intercalation. These tubes can be visualized as "rolled-up" sheets of carbon hexagons (see the following figure). One tube is approximately 1/10,000th the diameter of a human hair. In addition, the high accessibility of the structure confers a high mobility to ion-exchange processes, a fundamental for the batteries to respond dynamically because of intercalation.

Intercalated europium metal in epitaxial graphene on SiC

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

Anderson, Nathaniel; Hupalo, Myron; Keavney, David

X-ray magnetic circular dichroism (XMCD) reveals the magnetic properties of intercalated europium metal under graphene on SiC(0001). Intercalation of Eu nanoclusters (average size 2.5 nm) between graphene and SiC substate are formed by deposition of Eu on epitaxially grown graphene that is subsequently annealed at various temperatures while keeping the integrity of the graphene layer. Using sum-rules analysis of the XMCD of Eu M 4,5 edges at T = 15 K, our samples show paramagnetic-like behavior with distinct anomaly at T ≈ 90 K, which may be related to the Nèel transition, T N = 91 K, of bulk metalmore » Eu. Here, we find no evidence of ferromagnetism due to EuO or antiferromagnetism due to Eu 2 O 3, indicating that the graphene layer protects the intercalated metallic Eu against oxidation over months of exposure to atmospheric environment.« less

Preparation of C.I. Pigment 52:1 anion-pillared layered double hydroxide and the thermo- and photostability of the resulting intercalated material

NASA Astrophysics Data System (ADS)

Guo, Shengchang; Evans, David G.; Li, Dianqing

2006-05-01

Intercalation of 2-naphthalenecarboxylic acid, 4-((4-chloro-5-methyl-2-sulfophenyl) azo)-3-hydroxy-, calcium salt (1:1) (C.I. Pigment Red 52:1, also known as New Rubine S6B) into a layered double hydroxide (LDHs) host was carried out using MgAl NO3 LDHs as a precursor in an effort to improve the thermal and photo stability of the pigment. After intercalation, the powder X-ray diffraction (XRD) pattern shows that the basal spacing of the LDHs increased from 0.86 to 1.92 nm. Infrared spectra and TG DTA curves demonstrate that there are supramolecular host guest interactions. It was found that the intercalated material is more stable than the pristine pigment at high temperatures. The pigment anion-pillared LDHs also exhibit much higher photostablity to UV-light than the pristine pigment.

Pnrc2 regulates 3'UTR-mediated decay of segmentation clock-associated transcripts during zebrafish segmentation.

PubMed

Gallagher, Thomas L; Tietz, Kiel T; Morrow, Zachary T; McCammon, Jasmine M; Goldrich, Michael L; Derr, Nicolas L; Amacher, Sharon L

2017-09-01

Vertebrate segmentation is controlled by the segmentation clock, a molecular oscillator that regulates gene expression and cycles rapidly. The expression of many genes oscillates during segmentation, including hairy/Enhancer of split-related (her or Hes) genes, which encode transcriptional repressors that auto-inhibit their own expression, and deltaC (dlc), which encodes a Notch ligand. We previously identified the tortuga (tor) locus in a zebrafish forward genetic screen for genes involved in cyclic transcript regulation and showed that cyclic transcripts accumulate post-splicing in tor mutants. Here we show that cyclic mRNA accumulation in tor mutants is due to loss of pnrc2, which encodes a proline-rich nuclear receptor co-activator implicated in mRNA decay. Using an inducible in vivo reporter system to analyze transcript stability, we find that the her1 3'UTR confers Pnrc2-dependent instability to a heterologous transcript. her1 mRNA decay is Dicer-independent and likely employs a Pnrc2-Upf1-containing mRNA decay complex. Surprisingly, despite accumulation of cyclic transcripts in pnrc2-deficient embryos, we find that cyclic protein is expressed normally. Overall, we show that Pnrc2 promotes 3'UTR-mediated decay of developmentally-regulated segmentation clock transcripts and we uncover an additional post-transcriptional regulatory layer that ensures oscillatory protein expression in the absence of cyclic mRNA decay. Copyright © 2017 Elsevier Inc. All rights reserved.

Rare earth and zinc layered hydroxide salts intercalated with the 2-aminobenzoate anion as organic luminescent sensitizer

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

Cursino, Ana Cristina Trindade, E-mail: anacursino@ufpr.br; Rives, Vicente, E-mail: vrives@usal.es; Arizaga, Gregorio Guadalupe Carbajal, E-mail: gregoriocarbajal@yahoo.com.mx

2015-10-15

Rare earth (RE = Eu, Y and Tb) and zinc layered hydroxide salts intercalated with nitrate anions were synthesized, followed by exchange with 2-aminobenzoate. The UV absorption ability was improved after intercalation/grafting in relation to that shown by the parent material. - Highlights: • Rare earth (RE = Eu, Y and Tb) and zinc layered hydroxide were synthesized. • Intercalated nitrate anions were exchanged by 2-aminobenzoate. • In all the 2-aminobenzoate containing compounds, the grafting reaction was detected. • The UV absorption ability was improved after the exchange reactions. • Rare earth hydroxide salts are potential matrixes to produce luminescentmore » materials. - Abstract: Rare earth (RE = Eu, Y and Tb) and zinc layered hydroxide salts intercalated with nitrate anions were synthesized, followed by exchange with 2-aminobenzoate. The obtained compounds were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared (FTIR) and ultraviolet visible (UV–vis) spectroscopies, fluorescence measurements and thermal analysis (TGA/DTA). The results from FTIR spectroscopy suggest a direct coordination of 2-aminobenzoate to the metal cations of the inorganic layered structure. The organic derivative products from the intercalation reactions absorb a broader range of UV-light in relation to that shown by the parent material; the photoluminescence measurements present a strong violet, blue and green luminescence under UV-light excitation for layered compounds with, Zn, Y and Tb, respectively. Rare earth hydroxide salts (RE-LHS) are potential alternative matrices for the immobilization of organic species to produce luminescent materials.« less

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

Li, Yue Ru; Poyraz, Altug S.; Hu, Xiaobing

Birnessite type layered manganese dioxides (δ-MnO 2) have attracted considerable attention in recent years as 2D intercalation cathodes for rechargeable Li +, Na +, and Mg 2+ batteries due to fast ion diffusion through their negatively charged δ-MnO 2 sheets separated by interlayer cations and a stable Mn 3+/4+ redox couple. Here we report the preparation and electrochemistry of zero and divalent copper co-intercalated birnessite type manganese dioxide (Cu 0 0.03Cu 2+ 0.21Na 0.12MnO 2·0.9H 2O). The copper intercalated birnessite materials were fully characterized utilizing powder X-ray diffraction (XRD), inductively coupled plasma optical emission spectroscopy (ICP-OES), transmission electron microscopy (TEM).more » The mixed valent nature of intercalated Cu 0 and Cu 2+ was confirmed by X-ray photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS). Electrochemical evaluation results show that zero valent copper intercalated birnessite exhibits higher discharge capability, improved cyclability, and lower impedance compared to the Cu 2+ only intercalated (Cu 0.26MnO 2·1.0H 2O) and Cu free Na birnessite (Na 0.40MnO 2·1.0H 2O) materials. Remarkably, zero valent copper birnessite shows almost no fade after 10 cycles at 0.1 mV/s. Electrochemical impedance spectroscopy results suggest that charge transfer resistivity of Cu 0 modified samples was much lower than that of Cu 2+ and Cu free birnessite, indicating that the presence of a small amount of Cu 0 improves the conductivity of birnessite and results in better electrochemical cyclability, rate capability, and lower impedance.« less

Stability of Ruddlesden–Popper-structured oxides in humid conditions

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

Lehtimäki, M.; Yamauchi, H.; Karppinen, M., E-mail: maarit.karppinen@aalto.fi

2013-08-15

Some of layered transition-metal oxides are known to react with atmospheric humidity to form through topotactic intercalation reactions new water-containing layered structures. Here we investigate the influence of oxygen content (7−δ) of the Ruddlesden–Popper-structured Sr{sub 3}FeMO{sub 7−δ} (M=Ni, Mn, Ti) oxides on the water-intercalation reaction. It is found that their oxygen contents influence greatly the reactivity of the phases with water. Other factors possibly affecting the reactivity are discussed on the basis of the present data in combination with a comprehensive review of previous works on Ruddlesden–Popper and related layered oxide phases. - Graphical abstract: Many of the Ruddlesden–Popper-structured A{submore » 3}B{sub 2}O{sub 7−δ} oxides readily react with water via intercalation reactions. Three possible factors affecting the water intercalation are identified: oxygen content of the phase, ionic radius of cation A and valence state of cation B. The resultant layered water-derivative phases can be categorised into two groups, depending on the crystal symmetry of the phase. Highlights: • Ruddlesden–Popper oxides A{sub 3}B{sub 2}O{sub 7−δ} often accommodate water via intercalation reaction. • The lower the oxygen content 7−δ is the more readily the intercalation reaction occurs. • The second factor promoting the reaction is the large size of cation A. • The third possible factor is the high valence state of cation B. • Resultant water-derivatives can be categorised into two groups depending on symmetry.« less

Electrochemical behavior of LiV3O8 positive electrode in hybrid Li,Na-ion batteries

NASA Astrophysics Data System (ADS)

Maletti, S.; Sarapulova, A.; Tsirlin, A. A.; Oswald, S.; Fauth, F.; Giebeler, L.; Bramnik, N. N.; Ehrenberg, H.; Mikhailova, D.

2018-01-01

Vanadium(V)-containing oxides show superior intercalation properties for alkaline ions, although the performance of the material strongly depends on its surface morphology. In this work, intercalation activity of LiV3O8, prepared by a conventional solid state synthesis, is demonstrated for the first time in non-aqueous Li,Na-ion hybrid batteries with Na as negative electrode, and different Na/Li ratios in the electrolyte. In the pure Na-ion cell, one Na per formula unit of LiV3O8 can be reversibly inserted at room temperature via a two-step process, while further intercalation leads to gradual amorphisation of the material, with a specific capacity of 190 mAhg-1 after 10 cycles in the potential window of 0.8-3.4 V. Hybrid Li,Na-ion batteries feature simultaneous intercalation of Li+ and Na+ cations into LiV3O8, resulting in the formation of a second phase. Depending on the electrolyte composition, this second phase bears structural similarities either to Li0.7Na0.7V3O8 in Na-rich electrolytes, or to Li4V3O8 in Li-rich electrolytes. The chemical diffusion coefficients of Na+ and Li+ in crystalline LiV3O8 are very close, hence explaining the co-intercalation of these cations. As DFT calculations show, once formed, the Li0.7Na0.7V3O8-type structure favors intercalation of Na+, whereas the LiV3O8-type prefers to accommodate Li+ cations.

Kinematic predictors of star excursion balance test performance in individuals with chronic ankle instability.

PubMed

Hoch, Matthew C; Gaven, Stacey L; Weinhandl, Joshua T

2016-06-01

The Star Excursion Balance Test has identified dynamic postural control deficits in individuals with chronic ankle instability. While kinematic predictors of Star Excursion Balance Test performance have been evaluated in healthy individuals, this has not been thoroughly examined in individuals with chronic ankle instability. Fifteen individuals with chronic ankle instability completed the anterior reach direction of the Star Excursion Balance Test and weight-bearing dorsiflexion assessments. Maximum reach distances on the Star Excursion Balance Test were measured in cm and normalized to leg length. Three-dimensional trunk, hip, knee, and ankle motion of the stance limb were recorded during each anterior reach trial using a motion capture system. Sagittal, frontal, and transverse plane displacement observed from trial initiation to the point of maximum reach was calculated for each joint or segment and averaged for analysis. Pearson product-moment correlations were performed to examine the relationships between kinematic variables, maximal reach, and weight-bearing dorsiflexion. A backward multiple linear regression model was developed with maximal reach as the criterion variable and kinematic variables as predictors. Frontal plane displacement of the trunk, hip, and ankle and sagittal plane knee displacement were entered into the analysis. The final model (p=0.004) included all three frontal plane variables and explained 81% of the variance in maximal reach. Maximal reach distance and several kinematic variables were significantly related to weight-bearing dorsiflexion. Individuals with chronic ankle instability who demonstrated greater lateral trunk displacement toward the stance limb, hip adduction, and ankle eversion achieved greater maximal reach. Copyright © 2016. Published by Elsevier Ltd.

Lifeline in Danger. An Assessment of the United States Defense Industrial Base

DTIC Science & Technology

1988-09-01

reserves. In- furizing catalyst in crude oil refining, and (4) as a creasing U.S. production of vanadium would be 35 Petroleum and Fossil Fuels CHART 16...industry. Technical manpower. 4. Raw Materials 31 U.S. dependency in minerals and fuels . Excesses and shortages in the stockpile. 5. Key Segments of...power. rating. Instability in funding and in the defense The decline in manufacturing and technol- acquisition process undercut capital investment ogy

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage.

PubMed

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine; Neuefeind, Joerg; Xu, Wenqian; Teng, Xiaowei

2017-05-23

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because the large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate of 5 mV s -1 , corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full cells after 5,000 cycles at 10 C). The promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage

DOE PAGES

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine; ...

2017-05-23

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate ofmore » 5 mV s -1, corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full-cells after 5,000 cycles at 10 C). Finally, the promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.« less

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage

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

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate ofmore » 5 mV s -1, corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full-cells after 5,000 cycles at 10 C). Finally, the promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.« less

Metallic conductivity and air stability in copper chloride intercalated carbon fibers

NASA Astrophysics Data System (ADS)

Oshima, H.; Woollam, J. A.; Yavrouian, A.

1982-12-01

Carbon-copper chloride intercalation compounds have been obtained by using variously graphitized carbon fibers as host materials. The resultant conductors are air stable, thermally stable to 450 K, have electrical resistivities as low as 12.9 microohm cm at room temperature, and have metallic conductivity temperature dependencies. These intercalated fibers have tensile strengths of 160000 psi, and Young's moduli of 25 x 10 to the 6th psi. For aerospace use, 1/(resistivity x density) is a figure of merit. On this basis, a reduction in resistivity by a factor of two will make this conductor competitive with copper.

The effect of hydrazine intercalation on the structure and capacitance of 2D titanium carbide (MXene)

DOE PAGES

Mashtalir, O.; Lukatskaya, Maria R.; Kolesnikov, Alexander I.; ...

2016-03-25

Herein we show that hydrazine intercalation into 2D titanium carbide (Ti 3C 2-based MXene) results in changes in its surface chemistry by decreasing the amounts of fluorine, OH surface groups and intercalated water. It also creates a pillaring effect between Ti 3C 2T x layers pre-opening the structure and improving the accessability to active sites. Furthermore, the hydrazine treated material has demonstrated a greatly improved capacitance of 250 F g –1 in acidic electrolytes with an excellent cycling ability for electrodes as thick as 75 μm.

Intercalation and structural aspects of macroRAFT agents into MgAl layered double hydroxides.

PubMed

Kostadinova, Dessislava; Cenacchi Pereira, Ana; Lansalot, Muriel; D'Agosto, Franck; Bourgeat-Lami, Elodie; Leroux, Fabrice; Taviot-Guého, Christine; Cadars, Sylvian; Prevot, Vanessa

2016-01-01

Increasing attention has been devoted to the design of layered double hydroxide (LDH)-based hybrid materials. In this work, we demonstrate the intercalation by anion exchange process of poly(acrylic acid) (PAA) and three different hydrophilic random copolymers of acrylic acid (AA) and n -butyl acrylate (BA) with molar masses ranging from 2000 to 4200 g mol -1 synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization, into LDH containing magnesium(II) and aluminium(III) intralayer cations and nitrates as counterions (MgAl-NO 3 LDH). At basic pH, the copolymer chains (macroRAFT agents) carry negative charges which allowed the establishment of electrostatic interactions with the LDH interlayer and their intercalation. The resulting hybrid macroRAFT/LDH materials displayed an expanded interlamellar domain compared to pristine MgAl-NO 3 LDH from 1.36 nm to 2.33 nm. Depending on the nature of the units involved into the macroRAFT copolymer (only AA or AA and BA), the intercalation led to monolayer or bilayer arrangements within the interlayer space. The macroRAFT intercalation and the molecular structure of the hybrid phases were further characterized by Fourier transform infrared (FTIR) and solid-state 13 C, 1 H and 27 Al nuclear magnetic resonance (NMR) spectroscopies to get a better description of the local structure.

Combination probes with intercalating anchors and proximal fluorophores for DNA and RNA detection

PubMed Central

Qiu, Jieqiong; Wilson, Adam; El-Sagheer, Afaf H.; Brown, Tom

2016-01-01

A new class of modified oligonucleotides (combination probes) has been designed and synthesised for use in genetic analysis and RNA detection. Their chemical structure combines an intercalating anchor with a reporter fluorophore on the same thymine nucleobase. The intercalator (thiazole orange or benzothiazole orange) provides an anchor, which upon hybridisation of the probe to its target becomes fluorescent and simultaneously stabilizes the duplex. The anchor is able to communicate via FRET to a proximal reporter dye (e.g. ROX, HEX, ATTO647N, FAM) whose fluorescence signal can be monitored on a range of analytical devices. Direct excitation of the reporter dye provides an alternative signalling mechanism. In both signalling modes, fluorescence in the unhybridised probe is switched off by collisional quenching between adjacent intercalator and reporter dyes. Single nucleotide polymorphisms in DNA and RNA targets are identified by differences in the duplex melting temperature, and the use of short hybridization probes, made possible by the stabilisation provided by the intercalator, enhances mismatch discrimination. Unlike other fluorogenic probe systems, placing the fluorophore and quencher on the same nucleobase facilitates the design of short probes containing multiple modifications. The ability to detect both DNA and RNA sequences suggests applications in cellular imaging and diagnostics. PMID:27369379

Copper intercalation at the interface of graphene and Ir(111) studied by scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Sicot, M.; Fagot-Revurat, Y.; Kierren, B.; Vasseur, G.; Malterre, D.

2014-11-01

We report on the intercalation of a submonolayer of copper at 775 K underneath graphene epitaxially grown on Ir(111) studied by means of low energy electron diffraction (LEED) and scanning tunneling microscopy (STM) at 77 K. Nucleation and growth dynamics of Cu below graphene have been investigated, and, most importantly, the intercalation mechanism has been identified. First, LEED patterns reveal the pseudomorphic growth of Cu on Ir under the topmost graphene layer resulting in a large Cu in-plane lattice parameter expansion of about 6% compared to Cu(111). Second, large-scale STM topographs as a function of Cu coverage show that Cu diffusion on Ir below graphene exhibits a low energy barrier resulting in Cu accumulation at Ir step edges. As a result, the graphene sheet undergoes a strong edges reshaping. Finally, atomically-resolved STM images reveal a damaged graphene sheet at the atomic scale after metal intercalation. Point defects in graphene were shown to be carbon vacancies. According to these results, a Cu penetration path beneath graphene is proposed to occur via metal aided defect formation with no or poor self healing of the graphene sheet. This work illustrates the fact that Cu intercalation is harmful for graphene grown on Ir(111) at the atomic scale.

Structure, molecular simulation, and release of aspirin from intercalated Zn-Al-layered double hydroxides.

PubMed

Meng, Zilin; Li, Xiaowei; Lv, Fengzhu; Zhang, Qian; Chu, Paul K; Zhang, Yihe

2015-11-01

Aspirin or acetylsalicylic acid (AA), a non-steroidal anti-inflammatory drug, is intercalated into Zn-Al-layered double hydroxides (ZnAl-LDHs) by co-precipitation and reconstruction methods. The composition, structure, and morphology of the intercalated products as well as their release behavior are determined experimentally and theoretically by Material Studio 5.5. Experimental results disclose the strong interaction between the LDHs sheets and AA in the intercalated ZnAl-LDHs produced by co-precipitation and slow release of AA from the intercalated ZnAl-LDHs in both phosphate buffered saline (PBS) and borate buffered saline (BBS) solutions. The percentage of AA released from the ZnAl-LDHs prepared by both methods in PBS (96.87% and 98.12%) are much more than those in BBS (68.59% and 81.22%) implying that both H4BO4(-) and H2PO4(-) can exchange with AA in the ZnAl-LDHs. After AA is released to PBS, ZnAl-LDHs break into small pieces. The experimental results are explained theoretically based on the calculation of the bonding energy between the anions and LDHs sheets as well as the AlO bond length change in the LDHs sheets. Copyright © 2015 Elsevier B.V. All rights reserved.

First-Principles evaluation of the Chevrel phase intercalated with Be, Mg, Ca, Sr, and Ba

NASA Astrophysics Data System (ADS)

Juran, Taylor; Smeu, Manuel

Li ion batteries are extremely useful when an item requires portability and compactness, such as laptops and cell phones; due to the lightweight/compact nature of Li ion batteries. The lightweight and compact nature of Li ion batteries comes at a high cost. It is sensible to consider Li ion battery alternatives, which are more cost effective and useable when portability is not a priority. An option for a less expensive battery source is the Ca ion battery. The Ca ion battery is interesting as many researchers overlook the potential battery source due to the perplexity of finding suitable anode materials and electrolytes. In order for this technology to work, cathodes that allow for the reversible intercalation of Ca2+ ions and also provide a preferred voltage must be identified. We investigate the Chevrel phase compounds of Mo6X8 (X = S, Se, Te) which can intercalate various ions. The concentration of the ion intercalated with the Chevrel cathode is studied. We consider doped versions of the Chevrel phase, using various dopants to substitute Mo. We use density functional theory to calculate the voltage of several intercalation ions with the Chevrel material. The resulting electronic properties of the aforementioned materials will be investigated.

Modulating the electronic and magnetic properties of bilayer borophene via transition metal atoms intercalation: from metal to half metal and semiconductor

NASA Astrophysics Data System (ADS)

Zhang, Xiuyun; Sun, Yi; Ma, Liang; Zhao, Xinli; Yao, Xiaojing

2018-07-01

Borophene, a two-dimensional monolayer made of boron atoms, has attracted wide attention due to its appealing properties. Great efforts have been devoted to fine tuning its electronic and magnetic properties for desired applications. Herein, we theoretically investigate the versatile electronic and magnetic properties of bilayer borophene (BLB) intercalated by 3d transition metal (TM) atoms, TM@BLBs (TM = Ti-Fe), using ab initio calculations. Four allotropes of AA-stacking (α 1-, β-, β 12- and χ 3-) BLBs with different intercalation concentrations of TM atoms are considered. Our results show that the TM atoms are strongly bonded to the borophene layers with fairly large binding energies, around 6.31 ∼ 15.44 eV per TM atom. The BLBs with Cr and Mn intercalation have robust ferromagnetism, while for the systems decorated with Fe atoms, fruitful magnetic properties, such as nonmagnetic, ferromagnetic or antiferromagnetic, are identified. In particular, the α 1- and β-BLBs intercalated by Mn or Fe atom can be transformed into a semiconductor, half metal or graphene-like semimetal. Moreover, some heavily doped TM@BLBs expose high Curie temperatures above room temperature. The attractive properties of TM@BLBs entail an efficient way to modulate the electronic and magnetic properties of borophene sheets for advanced applications.

Local corrugation and persistent charge density wave in ZrTe 3 with Ni intercalation

NASA Astrophysics Data System (ADS)

Ganose, Alex M.; Gannon, Liam; Fabrizi, Federica; Nowell, Hariott; Barnett, Sarah A.; Lei, Hechang; Zhu, Xiangde; Petrovic, Cedomir; Scanlon, David O.; Hoesch, Moritz

2018-04-01

The mechanism of emergent bulk superconductivity in transition-metal intercalated ZrTe3 is investigated by studying the effect of Ni doping on the band structure and charge density wave (CDW). The study reports theoretical and experimental results in the range of Ni0.01ZrTe3 to Ni0.05ZrTe3 . In the highest doped samples, bulk superconductivity with Tc

Exfoliation of Hexagonal Boron Nitride via Ferric Chloride Intercalation

NASA Technical Reports Server (NTRS)

Hung, Ching-cheh; Hurst, Janet; Santiago, Diana; Rogers, Richard B.

2014-01-01

Sodium fluoride (NaF) was used as an activation agent to successfully intercalate ferric chloride (FeCl3) into hexagonal boron nitride (hBN). This reaction caused the hBN mass to increase by approx.100 percent, the lattice parameter c to decrease from 6.6585 to between 6.6565 and 6.6569 ?, the x-ray diffraction (XRD) (002) peak to widen from 0.01deg to 0.05deg of the full width half maximum value, the Fourier transform infrared (FTIR) spectrum's broad band (1277/cm peak) to change shape, and new FTIR bands to emerge at 3700 to 2700 and 1600/cm. This indicates hBN's structural and chemical properties are significantly changed. The intercalated product was hygroscopic and interacted with moisture in the air to cause further structural and chemical changes (from XRD and FTIR). During a 24-h hold at room temperature in air with 100 percent relative humidity, the mass increased another 141 percent. The intercalated product, hydrated or not, can be heated to 750 C in air to cause exfoliation. Exfoliation becomes significant after two intercalation-air heating cycles, when 20-nm nanosheets are commonly found. Structural and chemical changes indicated by XRD and FTIR data were nearly reversed after the product was placed in hydrochloric acid (HCl), resulting in purified, exfoliated, thin hBN products.

Stand-alone lumbar cage subsidence: A biomechanical sensitivity study of cage design and placement.

PubMed

Calvo-Echenique, Andrea; Cegoñino, José; Chueca, Raúl; Pérez-Del Palomar, Amaya

2018-08-01

Spinal degeneration and instability are commonly treated with interbody fusion cages either alone or supplemented with posterior instrumentation with the aim to immobilise the segment and restore intervertebral height. The purpose of this work is to establish a tool which may help to understand the effects of intervertebral cage design and placement on the biomechanical response of a patient-specific model to help reducing post-surgical complications such as subsidence and segment instability. A 3D lumbar functional spinal unit (FSU) finite element model was created and a parametric model of an interbody cage was designed and introduced in the FSU. A Drucker-Prager Cap plasticity formulation was used to predict plastic strains and bone failure in the vertebrae. The effect of varying cage size, cross-sectional area, apparent stiffness and positioning was evaluated under 500 N preload followed by 7.5 Nm multidirectional rotation and the results were compared with the intact model. The most influential cage parameters on the FSU were size, curvature congruence with the endplates and cage placement. Segmental stiffness was higher when increasing the cross-sectional cage area in all loading directions and when the cage was anteriorly placed in all directions but extension. In general, the facet joint forces were reduced by increasing segmental stiffness. However, these forces were higher than in the intact model in most of the cases due to the displacement of the instantaneous centre of rotation. The highest plastic deformations took place at the caudal vertebra under flexion and increased for cages with greater stiffness. Thus, wider cages and a more anteriorly placement would increase the volume of failed bone and, therefore, the risk of subsidence. Cage geometry plays a crucial role in the success of lumbar surgery. General considerations such as larger cages may be applied as a guideline, but parameters such as curvature or cage placement should be determined for each specific patient. This model provides a proof-of-concept of a tool for the preoperative evaluation of lumbar surgical outcomes. Copyright © 2018 Elsevier B.V. All rights reserved.

Geomorphic evidence for post-10 Ma uplift of the western flank of the central Andes 18°30'-22°S

NASA Astrophysics Data System (ADS)

Hoke, Gregory D.; Isacks, Bryan L.; Jordan, Teresa E.; Blanco, NicoláS.; Tomlinson, Andrew J.; Ramezani, Jahandar

2007-10-01

The western Andean mountain front forms the western edge of the central Andean Plateau. Between 18.5° and 22°S latitude, the mountain front has ˜3000 m of relief over ˜50 km horizontal distance that has developed in the absence of major local Neogene deformation. Models of the evolution of the plateau, as well as paleoaltimetry estimates, all call for continued large-magnitude uplift of the plateau surface into the late Miocene (i.e., younger than 10 Ma). Longitudinal river profiles from 20 catchments that drain the western Andean mountain front contain several streams with knickpoint-bounded segments that we use to reconstruct the history of post-10 Ma surface uplift of the western flank of the central Andean Plateau. The generation of knickpoints is attributed to tectonic processes and is not a consequence of base level change related to Pacific Ocean capture, eustatic change, or climate change as causes for creating the knickpoint-bounded stream segments observed. Minor valley-filling alluvial gravels intercalated with the 5.4 Ma Carcote ignimbrite suggest uplift related river incision was well under way by 5.4 Ma. The maximum age of river incision is provided by the regionally extensive, approximately 10 Ma El Diablo-Altos de Pica paleosurface. The river profiles reveal that relative surface uplift of at least1 km occurred after 10 Ma.

Evolving concepts on regulation and function of renin in distal nephron

PubMed Central

Prieto, Minolfa C.; Gonzalez, Alexis A.

2012-01-01

Sustained stimulation of the intrarenal/intratubular renin–angiotensin system in a setting of elevated arterial pressure elicits renal vasoconstriction, increased sodium reabsorption, proliferation, fibrosis, and eventual renal injury. Activation of luminal AT1 receptors in proximal and distal nephron segments by local Ang II formation stimulates various transport systems. Augmented angiotensinogen (AGT) production by proximal tubule cells increases AGT secretion contributing to increased proximal Ang II levels and leading to spillover of AGT into the distal nephron segments, as reflected by increased urinary AGT excretion. The increased distal delivery of AGT provides substrate for renin, which is expressed in principal cells of the collecting tubule and collecting ducts, and is also stimulated by AT1 receptor activation. Renin and prorenin are secreted into the tubular lumen and act on the AGT delivered from the proximal tubule to form more Ang I. The catalytic actions of renin and or prorenin may be enhanced by binding to prorenin receptors on the intercalated cells or soluble prorenin receptor secreted into the tubular fluid. There is also increased luminal angiotensin converting enzyme in collecting ducts facilitating Ang II formation leading to stimulation of sodium reabsorption via sodium channel and sodium/chloride co-transporter. Thus, increased collecting duct renin contributes to Ang II-dependent hypertension by augmenting distal nephron intra-tubular Ang II formation leading to sustained stimulation of sodium reabsorption and progression of hypertension. PMID:22990760

Superconducting selenides intercalated with organic molecules: synthesis, crystal structure, electric and magnetic properties, superconducting properties, and phase separation in iron based-chalcogenides and hybrid organic-inorganic superconductors

NASA Astrophysics Data System (ADS)

Krzton-Maziopa, Anna; Pesko, Edyta; Puzniak, Roman

2018-06-01

Layered iron-based superconducting chalcogenides intercalated with molecular species are the subject of intensive studies, especially in the field of solid state chemistry and condensed matter physics, because of their intriguing chemistry and tunable electric and magnetic properties. Considerable progress in the research, revealing superconducting inorganic–organic hybrid materials with transition temperatures to superconducting state, T c, up to 46 K, has been brought in recent years. These novel materials are synthesized by low-temperature intercalation of molecular species, such as solvates of alkali metals and nitrogen-containing donor compounds, into layered FeSe-type structure. Both the chemical nature as well as orientation of organic molecules between the layers of inorganic host, play an important role in structural modifications and may be used for fine tuning of superconducting properties. Furthermore, a variety of donor species compatible with alkali metals, as well as the possibility of doping also in the host structure (either on Fe or Se sites), makes this system quite flexible and gives a vast array of new materials with tunable electric and magnetic properties. In this review, the main aspects of intercalation chemistry are discussed with a particular attention paid to the influence of the unique nature of intercalating species on the crystal structure and physical properties of the hybrid inorganic–organic materials. To get a full picture of these materials, a comprehensive description of the most effective chemical and electrochemical methods, utilized for synthesis of intercalated species, with critical evaluation of their strong and weak points, related to feasibility of synthesis, phase purity, crystal size and morphology of final products, is included as well.

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

Xia Shengjie; Ni Zheming; Xu Qian

Zn/Al layered double hydroxides (LDHs) were intercalated with the anionic antihypertensive drugs Enalpril, Lisinopril, Captopril and Ramipril by using coprecipitation or ion-exchange technique. TG-MS analyses suggested that the thermal stability of Ena{sup -}, Lis{sup -} (arranged with monolayer, resulted from X-ray diffraction (XRD) and Fourier transform infrared spectra (FT-IR) analysis was enhanced much more than Cap{sup -} and Ram{sup -} (arranged with bilayer). The release studies show that the release rate of all samples markedly decreased in both pH 4.25 and 7.45. However, the release time of Ena{sup -}, Lis{sup -} were much longer compared with Cap{sup -}, Ram{sup -}more » in both pH 4.25 and 7.45, it is possible that the intercalated guests, arranged with monolayer in the interlayer, show lesser repulsive force and strong affinity with the LDH layers. And the release data followed both the Higuchi-square-root law and the first-order equation well. Based on the analysis of batch release, intercalated structural models as well as the TG-DTA results, we conclude that for drug-LDH, stronger the affinity between intercalated anions and the layers is, better the thermal property and the stability to the acid attack of drug-LDH, and the intercalated anions are easier apt to monolayer arrangement within the interlayer, were presented. - Graphical abstract: A series of antihypertensive drugs including Enalpril, Lisinopril, Captopril and Ramipril were intercalated into Zn/Al-NO{sub 3}-LDHs successfully by coprecipitation or ion-exchange technique. We focus on the structure, thermal property and low/controlled release property of as-synthesized drug-LDH composite intended for the possibility of applying these LDH-antihypertensive nanohybrids in drug delivery and controlled release systems.« less

Layered zinc hydroxide nanocones: synthesis, facile morphological and structural modification, and properties

NASA Astrophysics Data System (ADS)

Ma, Wei; Ma, Renzhi; Liang, Jianbo; Wang, Chengxiang; Liu, Xiaohe; Zhou, Kechao; Sasaki, Takayoshi

2014-10-01

Layered zinc hydroxide nanocones intercalated with DS- have been synthesized for the first time via a convenient synthetic approach, using homogeneous precipitation in the presence of urea and sodium dodecyl sulfate (SDS). SDS plays a significant role in controlling the morphologies of as-synthesized samples. Conical samples intercalated with various anions were transformed through an anion-exchange route in ethanol solution, and the original conical structure was perfectly maintained. Additionally, these DS--inserted nanocones can be transformed into square-like nanoplates in aqueous solution at room temperature, fulfilling the need for different morphology-dependent properties. Corresponding ZnO nanocones and nanoplates have been further obtained through the thermal calcination of NO3--intercalating zinc hydroxide nanocones/nanoplates. These ZnO nanostructures with different morphologies exhibit promising photocatalytic properties.Layered zinc hydroxide nanocones intercalated with DS- have been synthesized for the first time via a convenient synthetic approach, using homogeneous precipitation in the presence of urea and sodium dodecyl sulfate (SDS). SDS plays a significant role in controlling the morphologies of as-synthesized samples. Conical samples intercalated with various anions were transformed through an anion-exchange route in ethanol solution, and the original conical structure was perfectly maintained. Additionally, these DS--inserted nanocones can be transformed into square-like nanoplates in aqueous solution at room temperature, fulfilling the need for different morphology-dependent properties. Corresponding ZnO nanocones and nanoplates have been further obtained through the thermal calcination of NO3--intercalating zinc hydroxide nanocones/nanoplates. These ZnO nanostructures with different morphologies exhibit promising photocatalytic properties. Electronic supplementary information (ESI) available: Typical SEM images, TGA curves and XRD patterns of as-prepared samples. See DOI: 10.1039/c4nr04166f

Dynamic stability experiment of Maglev systems

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

Cai, Y.; Mulcahy, T.M.; Chen, S.S.

1995-04-01

This report summarizes the research performed on Maglev vehicle dynamic stability at Argonne National Laboratory during the past few years. It also documents magnetic-force data obtained from both measurements and calculations. Because dynamic instability is not acceptable for any commercial Maglev system, it is important to consider this phenomenon in the development of all Maglev systems. This report presents dynamic stability experiments on Maglev systems and compares their numerical simulation with predictions calculated by a nonlinear dynamic computer code. Instabilities of an electrodynamic system (EDS)-type vehicle model were obtained from both experimental observations and computer simulations for a five-degree-of-freedom Maglevmore » vehicle moving on a guideway consisting of double L-shaped aluminum segments attached to a rotating wheel. The experimental and theoretical analyses developed in this study identify basic stability characteristics and future research needs of Maglev systems.« less

Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction

PubMed Central

Wang, Haotian; Lu, Zhiyi; Xu, Shicheng; Kong, Desheng; Cha, Judy J.; Zheng, Guangyuan; Hsu, Po-Chun; Yan, Kai; Bradshaw, David; Prinz, Fritz B.; Cui, Yi

2013-01-01

The ability to intercalate guest species into the van der Waals gap of 2D layered materials affords the opportunity to engineer the electronic structures for a variety of applications. Here we demonstrate the continuous tuning of layer vertically aligned MoS2 nanofilms through electrochemical intercalation of Li+ ions. By scanning the Li intercalation potential from high to low, we have gained control of multiple important material properties in a continuous manner, including tuning the oxidation state of Mo, the transition of semiconducting 2H to metallic 1T phase, and expanding the van der Waals gap until exfoliation. Using such nanofilms after different degree of Li intercalation, we show the significant improvement of the hydrogen evolution reaction activity. A strong correlation between such tunable material properties and hydrogen evolution reaction activity is established. This work provides an intriguing and effective approach on tuning electronic structures for optimizing the catalytic activity. PMID:24248362

Mechanism Responsible for Intercalation of Dimethyl Sulfoxide in Kaolinite: Molecular Dynamics Simulations.

PubMed

Zhang, Shuai; Liu, Qinfu; Cheng, Hongfei; Gao, Feng; Liu, Cun; Teppen, Brian J

2018-01-01

Intercalation is the promising strategy to expand the interlayer region of kaolinite for their further applications. Herein, the adaptive biasing force (ABF) accelerated molecular dynamics simulations were performed to calculate the free energies involved in the kaolinite intercalation by dimethyl sulfoxide (DMSO). Additionally, the classical all atom molecular dynamics simulations were carried out to calculate the interfacial interactions between kaolinite interlayer surfaces and DMSO with the aim at exploring the underlying force that drives the DMSO to enter the interlayer space. The results showed that the favorable interaction of DMSO with both kaolinite interlayer octahedral surface and tetrahedral surface can help in introducing DMSO enter kaolinite interlayer. The hydroxyl groups on octahedral surface functioned as H-donors attracting the S=O groups of DMSO through hydrogen bonding interaction. The tetrahedral surface featuring hydrophobic property attracted the methyl groups of DMSO through hydrophobic interaction. The results provided a detailed picture of the energetics and interlayer structure of kaolinite-DMSO intercalate.

Ion-Transport Design for High-Performance Na+-Based Electrochromics.

PubMed

Li, Ran; Li, Kerui; Wang, Gang; Li, Lei; Zhang, Qiangqiang; Yan, Jinhui; Chen, Yao; Zhang, Qinghong; Hou, Chengyi; Li, Yaogang; Wang, Hongzhi

2018-04-24

Sodium ion (Na + )-based electrochemical systems have been extensively investigated in batteries and supercapacitors and also can be quality candidates for electrochromic (EC) devices. However, poor diffusion kinetics and severe EC performance degradation occur during the intercalation/deintercalation processes because the ionic radii of Na + are larger than those of conventional intercalation ions. Here, through intentional design of ion-transport channels in metal-organic frameworks (MOFs), Na + serves as an efficient intercalation ion for incorporation into a nanostructured electrode with a high diffusion coefficient of approximately 10 -8 cm 2 s -1 . As a result, the well-designed MOF-based EC device demonstrates desirable Na + EC performance, including fast switching speed, multicolor switching, and high stability. A smart "quick response code" display is fabricated using a mask-free laser writing method for application in the "Internet of Things". In addition, the concept of ion transport pathway design can be widely adopted for fabricating high-performance ion intercalation materials and devices for consumer electronics.

Exfoliation and van der Waals heterostructure assembly of intercalated ferromagnet Cr1/3TaS2

NASA Astrophysics Data System (ADS)

Yamasaki, Yuji; Moriya, Rai; Arai, Miho; Masubuchi, Satoru; Pyon, Sunseng; Tamegai, Tsuyoshi; Ueno, Keiji; Machida, Tomoki

2017-12-01

Ferromagnetic van der Waals (vdW) materials are in demand for spintronic devices with all-two-dimensional-materials heterostructures. Here, we demonstrate mechanical exfoliation of magnetic-atom-intercalated transition metal dichalcogenide Cr1/3TaS2 from its bulk crystal; previously such intercalated materials were thought difficult to exfoliate. Magnetotransport in exfoliated tens-of-nanometres-thick flakes revealed ferromagnetic ordering below its Curie temperature T C ~ 110 K as well as strong in-plane magnetic anisotropy; these are identical to its bulk properties. Further, van der Waals heterostructure assembly of Cr1/3TaS2 with another intercalated ferromagnet Fe1/4TaS2 is demonstrated using a dry-transfer method. The fabricated heterojunction composed of Cr1/3TaS2 and Fe1/4TaS2 with a native Ta2O5 oxide tunnel barrier in between exhibits tunnel magnetoresistance (TMR), revealing possible spin injection and detection with these exfoliatable ferromagnetic materials through the vdW junction.

Effect of length of chopped pristine and intercalated graphite fibers on the resistivity of fiber networks

NASA Technical Reports Server (NTRS)

Gaier, James R.; Stahl, Mark

1988-01-01

Samples of Amoco P-100 fibers were chopped to lengths of 3.14, 2.53, 1.90, 1.27, 0.66 mm, or milled for 2 hours. The two-point resistivity of compacts of these fibers were measured as a function of pressure from 34 kPa to 143 MPa. Samples of each fiber length were intercalated with bromine at room temperature and similarly measured. The low pressure resistivity of the compacts decreased with increasing fiber length. Intercalation lowered the resistivity of each of the chopped length compacts, but raised the resistivity of the milled fiber compacts. Bulk resistivity of all samples decreased with increasing pressure at similar rates. Even though fiber volumes were as low as 5 percent, all measurements exhibited measurable resistivity. A greater change with pressure in the resistance was observed for shorter fibers than for longer, probably an indication of tighter fiber packing. Intercalation appeared to have no effect on the fiber to fiber contact resistance.

Superconductivity and hybrid soft modes in Ti Se 2

DOE PAGES

Maschek, M.; Rosenkranz, S.; Hott, R.; ...

2016-12-12

The interplay between superconductivity and charge-density-wave (CDW) order plays a central role in the layered transition-metal dichalcogenides. 1 T-TiSe 2 forms a prime example, featuring superconducting domes on intercalation as well as under applied pressure. Here, we present high energy-resolution inelastic x-ray scattering measurements of the CDW soft phonon mode in intercalated Cu xTiSe 2 and pressurized 1 T-TiSe 2 along with detailed ab-initio calculations for the lattice dynamical properties and phonon-mediated superconductivity. We find that the intercalation-induced superconductivity can be explained by a solely phonon-mediated pairing mechanism, while this is not possible for the superconducting phase under pressure. Wemore » argue that a hybridization of phonon and exciton modes in the pairing mechanism is necessary to explain the full observed temperature-pressure-intercalation phase diagram. Finally, these results indicate that 1 T-TiSe 2 under pressure is close to the elusive state of the excitonic insulator.« less

Tunable thermal expansion in framework materials through redox intercalation

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

Chen, Jun; Gao, Qilong; Sanson, Andrea

Thermal expansion properties of solids are of fundamental interest and control of thermal expansion is important for practical applications but can be difficult to achieve. Many framework type materials show negative thermal expansion when internal cages are empty but positive thermal expansion when additional atoms or molecules fill internal voids present, offering a potential route for control. Here we show that redox intercalation offers an effective method to control thermal expansion from positive to zero to negative by insertion of Li ions into the simple negative thermal expansion framework material ScF 3, doped with 10% Fe to enable reduction. Themore » small concentration of intercalated Li ions has a strong influence through steric hindrance of transverse fluoride ion vibrations, which directly controls the thermal expansion. As a result, redox intercalation of guest ions is thus likely to be a general and effective method for controlling thermal expansion in the many known framework materials with phonon-driven negative thermal expansion.« less

High Energy-Density and Reversibility of Iron Fluoride Cathode Enabled Via an Intercalation-Extrusion Reaction

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

Fan, Xiulin; Hu, Enyuan; Ji, Xiao

Iron fluoride, an intercalation-conversion cathode for lithium ion batteries, promises a high theoretical energy density of 1922 Wh Kg –1. However, poor electrochemical reversibility due to repeated breaking/reformation of metal-fluoride bonds poses a grand challenge for its practical application. Here we report that both a high reversibility over 1000 cycles and a high capacity of 420 mAh g –1 can be realized by concerted doping of cobalt and oxygen into iron fluoride. In the doped nanorods, an energy density of ~1000 Wh Kg –1 with a decay rate of 0.03% per cycle is achieved. The anion and cation’s co-substitutions thermodynamicallymore » reduce conversion-reaction potential and shift the reaction from less reversible intercalation-conversion reaction in iron fluoride to a highly reversible intercalation-extrusion reaction in doped material. Furthermore, the co-substitution strategy to tune the thermodynamic features of the reactions could be extended to other high energy conversion materials for improved performance.« less

Method for fabricating carbon/lithium-ion electrode for rechargeable lithium cell

NASA Technical Reports Server (NTRS)

Attia, Alan I. (Inventor); Halpert, Gerald (Inventor); Huang, Chen-Kuo (Inventor); Surampudi, Subbarao (Inventor)

1995-01-01

The method includes steps for forming a carbon electrode composed of graphitic carbon particles adhered by an ethylene propylene diene monomer binder. An effective binder composition is disclosed for achieving a carbon electrode capable of subsequent intercalation by lithium ions. The method also includes steps for reacting the carbon electrode with lithium ions to incorporate lithium ions into graphitic carbon particles of the electrode. An electrical current is repeatedly applied to the carbon electrode to initially cause a surface reaction between the lithium ions and to the carbon and subsequently cause intercalation of the lithium ions into crystalline layers of the graphitic carbon particles. With repeated application of the electrical current, intercalation is achieved to near a theoretical maximum. Two differing multi-stage intercalation processes are disclosed. In the first, a fixed current is reapplied. In the second, a high current is initially applied, followed by a single subsequent lower current stage. Resulting carbon/lithium-ion electrodes are well suited for use as an anode in a reversible, ambient temperature, lithium cell.

Incommensurate Graphene Foam as a High Capacity Lithium Intercalation Anode

PubMed Central

Paronyan, Tereza M.; Thapa, Arjun Kumar; Sherehiy, Andriy; Jasinski, Jacek B.; Jangam, John Samuel Dilip

2017-01-01

Graphite’s capacity of intercalating lithium in rechargeable batteries is limited (theoretically, 372 mAh g−1) due to low diffusion within commensurately-stacked graphene layers. Graphene foam with highly enriched incommensurately-stacked layers was grown and applied as an active electrode in rechargeable batteries. A 93% incommensurate graphene foam demonstrated a reversible specific capacity of 1,540 mAh g−1 with a 75% coulombic efficiency, and an 86% incommensurate sample achieves above 99% coulombic efficiency exhibiting 930 mAh g−1 specific capacity. The structural and binding analysis of graphene show that lithium atoms highly intercalate within weakly interacting incommensurately-stacked graphene network, followed by a further flexible rearrangement of layers for a long-term stable cycling. We consider lithium intercalation model for multilayer graphene where capacity varies with N number of layers resulting LiN+1C2N stoichiometry. The effective capacity of commonly used carbon-based rechargeable batteries can be significantly improved using incommensurate graphene as an anode material. PMID:28059110

X-ray Spectroscopy and Imaging as Multiscale Probes of Intercalation Phenomena in Cathode Materials

NASA Astrophysics Data System (ADS)

Horrocks, Gregory A.; De Jesus, Luis R.; Andrews, Justin L.; Banerjee, Sarbajit

2017-09-01

Intercalation phenomena are at the heart of modern electrochemical energy storage. Nevertheless, as out-of-equilibrium processes involving concomitant mass and charge transport, such phenomena can be difficult to engineer in a predictive manner. The rational design of electrode architectures requires mechanistic understanding of physical phenomena spanning multiple length scales, from atomistic distortions and electron localization at individual transition metal centers to phase inhomogeneities and intercalation gradients in individual particles and concentration variances across ensembles of particles. In this review article, we discuss the importance of the electronic structure in mediating electrochemical storage and mesoscale heterogeneity. In particular, we discuss x-ray spectroscopy and imaging probes of electronic and atomistic structure as well as statistical regression methods that allow for monitoring of the evolution of the electronic structure as a function of intercalation. The layered α-phase of V2O5 is used as a model system to develop fundamental ideas on the origins of mesoscale heterogeneity.

Understanding self-photorechargeability of WO(3) for H(2) generation without light illumination.

PubMed

Ng, Charlene; Iwase, Akihide; Ng, Yun Hau; Amal, Rose

2013-02-01

This work presents insight into the self-photorechargeability of WO(3), whereby the intercalation of positive alkali cations is accompanied by the simultaneous storage of photo-excited electrons. The cyclic voltammetry studies verify the photo-assisted intercalation and de-intercalation of Na(+) and K(+) from the flower structured WO(3). A storage capacity of up to 0.722 C cm(-2) can be achieved in a saturated (0.68 M) K(2)SO(4) electrolyte solution. However, the best photo recharge-discharge stability of the electrode are observed at a lower (0.1 M) cation concentration. At high electrolyte concentrations, the intercalated cations are firmly trapped, as indicated by the structural modifications observed in Raman analysis, resulting in much less photocharging and discharging abilities in subsequent cycles. The study also shows that the stored electrons can be successfully used to generate H(2) with 100 % faradaic efficiency in the absence of light. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox-controlled potassium intercalation into two polyaromatic hydrocarbon solids

NASA Astrophysics Data System (ADS)

Romero, F. Denis; Pitcher, M. J.; Hiley, C. I.; Whitehead, G. F. S.; Kar, S.; Ganin, A. Y.; Antypov, D.; Collins, C.; Dyer, M. S.; Klupp, G.; Colman, R. H.; Prassides, K.; Rosseinsky, M. J.

2017-07-01

Alkali metal intercalation into polyaromatic hydrocarbons (PAHs) has been studied intensely after reports of superconductivity in a number of potassium- and rubidium-intercalated materials. There are, however, no reported crystal structures to inform our understanding of the chemistry and physics because of the complex reactivity of PAHs with strong reducing agents at high temperature. Here we present the synthesis of crystalline K2Pentacene and K2Picene by a solid-solid insertion protocol that uses potassium hydride as a redox-controlled reducing agent to access the PAH dianions, and so enables the determination of their crystal structures. In both cases, the inserted cations expand the parent herringbone packings by reorienting the molecular anions to create multiple potassium sites within initially dense molecular layers, and thus interact with the PAH anion π systems. The synthetic and crystal chemistry of alkali metal intercalation into PAHs differs from that into fullerenes and graphite, in which the cation sites are pre-defined by the host structure.

High Energy-Density and Reversibility of Iron Fluoride Cathode Enabled Via an Intercalation-Extrusion Reaction

DOE PAGES

Fan, Xiulin; Hu, Enyuan; Ji, Xiao; ...

2018-05-30

Iron fluoride, an intercalation-conversion cathode for lithium ion batteries, promises a high theoretical energy density of 1922 Wh Kg –1. However, poor electrochemical reversibility due to repeated breaking/reformation of metal-fluoride bonds poses a grand challenge for its practical application. Here we report that both a high reversibility over 1000 cycles and a high capacity of 420 mAh g –1 can be realized by concerted doping of cobalt and oxygen into iron fluoride. In the doped nanorods, an energy density of ~1000 Wh Kg –1 with a decay rate of 0.03% per cycle is achieved. The anion and cation’s co-substitutions thermodynamicallymore » reduce conversion-reaction potential and shift the reaction from less reversible intercalation-conversion reaction in iron fluoride to a highly reversible intercalation-extrusion reaction in doped material. Furthermore, the co-substitution strategy to tune the thermodynamic features of the reactions could be extended to other high energy conversion materials for improved performance.« less

Effect of molecular intercalation on the local structure of superconducting Nax(NH3)yMoSe2 system

NASA Astrophysics Data System (ADS)

Simonelli, L.; Paris, E.; Wakita, T.; Marini, C.; Terashima, K.; Miao, X.; Olszewski, W.; Ramanan, N.; Heinis, D.; Kubozono, Y.; Yokoya, T.; Saini, N. L.

2017-12-01

We have studied the local structure of layered Nax(NH3)yMoSe2 system by Mo K-edge extended X-ray absorption fine structure (EXAFS) measurements performed as a function of temperature. We find that molecular intercalation in MoSe2 largely affects the Mo-Se network while Mo-Mo seems to sustain small changes. The Einstein temperature (ΘE) of Mo-Mo distance hardly changes (∼264 K) indicating that bond strength of this distance remains unaffected by intercalation. On the other hand, Mo-Se distance suffers a softening, revealed by the decrease of ΘE from ∼364 K to ∼350 K. The results indicate that Na+ ion transported by NH3 molecules may enter between the two MoSe-layers resulting reduced Se-Se coupling. Therefore, increased hybridization between Se 4p and Mo 4d orbitals due to inter-layer disorder is the likely reason of metallicity in intercalated MoSe2 and superconductivity at low temperature.

Tunable thermal expansion in framework materials through redox intercalation

DOE PAGES

Chen, Jun; Gao, Qilong; Sanson, Andrea; ...

2017-02-09

Thermal expansion properties of solids are of fundamental interest and control of thermal expansion is important for practical applications but can be difficult to achieve. Many framework type materials show negative thermal expansion when internal cages are empty but positive thermal expansion when additional atoms or molecules fill internal voids present, offering a potential route for control. Here we show that redox intercalation offers an effective method to control thermal expansion from positive to zero to negative by insertion of Li ions into the simple negative thermal expansion framework material ScF 3, doped with 10% Fe to enable reduction. Themore » small concentration of intercalated Li ions has a strong influence through steric hindrance of transverse fluoride ion vibrations, which directly controls the thermal expansion. As a result, redox intercalation of guest ions is thus likely to be a general and effective method for controlling thermal expansion in the many known framework materials with phonon-driven negative thermal expansion.« less

Herbicide-Intercalated Zinc Layered Hydroxide Nanohybrid for a Dual-Guest Controlled Release Formulation

PubMed Central

Hussein, Mohd Zobir; Rahman, Nor Shazlirah Shazlyn Abdul; Sarijo, Siti H.; Zainal, Zulkarnain

2012-01-01

Herbicides, namely 4-(2,4-dichlorophenoxy) butyrate (DPBA) and 2-(3-chlorophenoxy) propionate (CPPA), were intercalated simultaneously into the interlayers of zinc layered hydroxide (ZLH) by direct reaction of zinc oxide with both anions under aqueous environment to form a new nanohybrid containing both herbicides labeled as ZCDX. Successful intercalation of both anions simultaneously into the interlayer gallery space of ZLH was studied by PXRD, with basal spacing of 28.7 Å and supported by FTIR, TGA/DTG and UV-visible studies. Simultaneous release of both CPPA and DPBA anions into the release media was found to be governed by a pseudo second-order equation. The loading and percentage release of the DPBA is higher than the CPPA anion, which indicates that the DPBA anion was preferentially intercalated into and released from the ZLH interlayer galleries. This work shows that layered single metal hydroxide, particularly ZLH, is a suitable host for the controlled release formulation of two herbicides simultaneously. PMID:22837696

Room temperature deintercalation of alkali metal atoms from epitaxial graphene by formation of charge-transfer complexes

NASA Astrophysics Data System (ADS)

Shin, H.-C.; Ahn, S. J.; Kim, H. W.; Moon, Y.; Rai, K. B.; Woo, S. H.; Ahn, J. R.

2016-08-01

Atom (or molecule) intercalations and deintercalations have been used to control the electronic properties of graphene. In general, finite energies above room temperature (RT) thermal energy are required for the intercalations and deintercalations. Here, we demonstrate that alkali metal atoms can be deintercalated from epitaxial graphene on a SiC substrate at RT, resulting in the reduction in density of states at the Fermi level. The change in density of states at the Fermi level at RT can be applied to a highly sensitive graphene sensor operating at RT. Na atoms, which were intercalated at a temperature of 80 °C, were deintercalated at a high temperature above 1000 °C when only a thermal treatment was used. In contrast to the thermal treatment, the intercalated Na atoms were deintercalated at RT when tetrafluorotetracyanoquinodimethane (F4-TCNQ) molecules were adsorbed on the surface. The RT deintercalation occurred via the formation of charge-transfer complexes between Na atoms and F4-TCNQ molecules.

A method of inversion of satellite magnetic anomaly data

NASA Technical Reports Server (NTRS)

Mayhew, M. A.

1977-01-01

A method of finding a first approximation to a crustal magnetization distribution from inversion of satellite magnetic anomaly data is described. Magnetization is expressed as a Fourier Series in a segment of spherical shell. Input to this procedure is an equivalent source representation of the observed anomaly field. Instability of the inversion occurs when high frequency noise is present in the input data, or when the series is carried to an excessively high wave number. Preliminary results are given for the United States and adjacent areas.

Mitochondrial nucleoid clusters protect newly synthesized mtDNA during Doxorubicin- and Ethidium Bromide-induced mitochondrial stress

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

Alán, Lukáš, E-mail: lukas.alan@fgu.cas.cz; Špaček

Mitochondrial DNA (mtDNA) is compacted in ribonucleoprotein complexes called nucleoids, which can divide or move within the mitochondrial network. Mitochondrial nucleoids are able to aggregate into clusters upon reaction with intercalators such as the mtDNA depletion agent Ethidium Bromide (EB) or anticancer drug Doxorobicin (DXR). However, the exact mechanism of nucleoid clusters formation remains unknown. Resolving these processes may help to elucidate the mechanisms of DXR-induced cardiotoxicity. Therefore, we addressed the role of two key nucleoid proteins; mitochondrial transcription factor A (TFAM) and mitochondrial single-stranded binding protein (mtSSB); in the formation of mitochondrial nucleoid clusters during the action of intercalators.more » We found that both intercalators cause numerous aberrations due to perturbing their native status. By blocking mtDNA replication, both agents also prevented mtDNA association with TFAM, consequently causing nucleoid aggregation into large nucleoid clusters enriched with TFAM, co-existing with the normal nucleoid population. In the later stages of intercalation (> 48 h), TFAM levels were reduced to 25%. In contrast, mtSSB was released from mtDNA and freely distributed within the mitochondrial network. Nucleoid clusters mostly contained nucleoids with newly replicated mtDNA, however the nucleoid population which was not in replication mode remained outside the clusters. Moreover, the nucleoid clusters were enriched with p53, an anti-oncogenic gatekeeper. We suggest that mitochondrial nucleoid clustering is a mechanism for protecting nucleoids with newly replicated DNA against intercalators mediating genotoxic stress. These results provide new insight into the common mitochondrial response to mtDNA stress and can be implied also on DXR-induced mitochondrial cytotoxicity. - Highlights: • The mechanism for mitochondrial nucleoid clustering is proposed. • DNA intercalators (Doxorubicin or Ethidium Bromide) prevent TFAM binding to mtDNA. • Replicating nucleoids are less prone to DNA intercalator and preserve more TFAM. • Nucleoid clusters mostly contain nucleoids with newly replicated mtDNA. • Recently replicated nucleoids are protected in clusters by increased TFAM and p53.« less

Influence of sodium dodecyl sulfate concentration on the photocatalytic activity and dielectric properties of intercalated sodium dodecyl sulfate into Zn–Cd–Al layered double hydroxide

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

Ahmed, Abdullah Ahmed Ali, E-mail: abdullah2803@gmail.com; Talib, Zainal Abidin; Hussein, Mohd Zobir

2015-02-15

Highlights: • Zn–Cd–Al–LDH–DS were synthesized with different SDS concentrations. • Photocatalytic activity of samples was improved by increasing SDS concentration. • Dielectric response of LDH can be described by anomalous low frequency dispersion. • The dc conductivity values were calculated for Zn–Cd–Al–LDH–DS samples. • ESR spectra exhibited the successful intercalation of DS molecule into LDH gallery. - Abstract: Sodium dodecyl sulfate (SDS) has been successfully intercalated into Zn–Cd–Al–LDH precursor with different SDS concentrations (0.2, 0.3, 0.4, 0.5 and 1 mol L{sup −1}) using the coprecipitation method at (Zn{sup 2+} + Cd{sup 2+})/Al{sup 3+} molar ratio of 13 and pH 8.more » The structural, morphological, texture and composition properties of the synthesized (Zn–Cd–Al–LDH–DS) nanostructure were investigated using powder X-ray diffraction (PXRD), scanning electron microscope (SEM), thermogravimetric analysis (TGA) and Fourier transform infrared (FT-IR), respectively. The photocatalytic activity of these materials was developed by increasing the concentration of intercalated SDS. The absorbance spectra have been used to detect an anion in the LDH interlayer before and after the intercalation process, which confirmed the presence of the dodecyl sulfate (DS{sup −}) anion into LDH gallery after intercalation. The anomalous low frequency dispersion (ALFD) has been used to describe the dielectric response of Zn–Cd–Al–LDH–DS nanostructure using the second type of universal power law. At low frequency, the polarization effect of electrodes caused the rising in dielectric constant and loss values. An important result of the dielectric measurements is the calculated dc conductivity values, which are new in dielectric spectroscopy of LDH materials. An important result of the electron spin resonance (ESR) spectra exhibited the successful intercalation of DS molecule into LDH gallery. The g-factor value was affected by the SDS concentration which indicated changes to the environment around the DS molecule in LDH interlayer.« less

Generation of a variety of stable Influenza A reporter viruses by genetic engineering of the NS gene segment

PubMed Central

Reuther, Peter; Göpfert, Kristina; Dudek, Alexandra H.; Heiner, Monika; Herold, Susanne; Schwemmle, Martin

2015-01-01

Influenza A viruses (IAV) pose a constant threat to the human population and therefore a better understanding of their fundamental biology and identification of novel therapeutics is of upmost importance. Various reporter-encoding IAV were generated to achieve these goals, however, one recurring difficulty was the genetic instability especially of larger reporter genes. We employed the viral NS segment coding for the non-structural protein 1 (NS1) and nuclear export protein (NEP) for stable expression of diverse reporter proteins. This was achieved by converting the NS segment into a single open reading frame (ORF) coding for NS1, the respective reporter and NEP. To allow expression of individual proteins, the reporter genes were flanked by two porcine Teschovirus-1 2A peptide (PTV-1 2A)-coding sequences. The resulting viruses encoding luciferases, fluorescent proteins or a Cre recombinase are characterized by a high genetic stability in vitro and in mice and can be readily employed for antiviral compound screenings, visualization of infected cells or cells that survived acute infection. PMID:26068081

Isolation of high quality graphene from Ru by solution phase intercalation

NASA Astrophysics Data System (ADS)

Koren, E.; Sutter, E.; Bliznakov, S.; Ivars-Barcelo, F.; Sutter, P.

2013-09-01

We introduce a method for isolating graphene grown on epitaxial Ru(0001)/α-Al2O3. The strong graphene/Ru(0001) coupling is weakened by electrochemically driven intercalation of hydrogen underpotentially deposited in aqueous KOH solution, which allows the penetration of water molecules at the graphene/Ru(0001) interface. Following these electrochemically driven processes, the graphene can be isolated by electrochemical hydrogen evolution and transferred to arbitrary supports. Raman and transport measurements demonstrate the high quality of the transferred graphene. Our results show that intercalation, typically carried out in vacuum, can be extended to solution environments for graphene processing under ambient conditions.

Absence of photoemission from the Fermi level in potassium intercalated picene and coronene films: structure, polaron, or correlation physics?

PubMed

Mahns, Benjamin; Roth, Friedrich; Knupfer, Martin

2012-04-07

The electronic structure of potassium intercalated picene and coronene films has been studied using photoemission spectroscopy. Picene has additionally been intercalated using sodium. Upon alkali metal addition core level as well as valence band photoemission data signal a filling of previously unoccupied states of the two molecular materials due to charge transfer from potassium. In contrast to the observation of superconductivity in K(x)picene and K(x)coronene (x ~ 3), none of the films studied shows emission from the Fermi level, i.e., we find no indication for a metallic ground state. Several reasons for this observation are discussed.

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

Zhou, Yinghui; Lii-Rosales, Ann; Kim, Minsung

Here, we show that 3 metals – Dy, Ru, and Cu – can form multilayer intercalated (encapsulated) islands at the graphite (0001) surface if 2 specific conditions are met: Defects are introduced on the graphite terraces to act as entry portals, and the metal deposition temperature is well above ambient. Focusing on Dy as a prototype, we show that surface encapsulation is much different than bulk intercalation, because the encapsulated metal takes the form of bulk-like rafts of multilayer Dy, rather than the dilute, single-layer structure known for the bulk compound. Carbon-covered metallic rafts even form for relatively unreactive metalsmore » (Ru and Cu) which have no known bulk intercalation compound.« less

Semiconductor cooling apparatus

NASA Technical Reports Server (NTRS)

Banks, Bruce A. (Inventor); Gaier, James R. (Inventor)

1993-01-01

Gas derived graphite fibers generated by the decomposition of an organic gas are joined with a suitable binder. This produces a high thermal conductivity composite material which passively conducts heat from a source, such as a semiconductor, to a heat sink. The fibers may be intercalated. The intercalate can be halogen or halide salt, alkaline metal, or any other species which contributes to the electrical conductivity improvement of the graphite fiber. The fibers are bundled and joined with a suitable binder to form a high thermal conductivity composite material device. The heat transfer device may also be made of intercalated highly oriented pyrolytic graphite and machined, rather than made of fibers.

Plasma synthesis of lithium based intercalation powders for solid polymer electrolyte batteries

DOEpatents

Kong, Peter C [Idaho Falls, ID; Pink, Robert J [Pocatello, ID; Nelson, Lee O [Idaho Falls, ID

2005-01-04

The invention relates to a process for preparing lithium intercalation compounds by plasma reaction comprising the steps of: forming a feed solution by mixing lithium nitrate or lithium hydroxide or lithium oxide and the required metal nitrate or metal hydroxide or metal oxide and between 10-50% alcohol by weight; mixing the feed solution with O.sub.2 gas wherein the O.sub.2 gas atomizes the feed solution into fine reactant droplets, inserting the atomized feed solution into a plasma reactor to form an intercalation powder; and if desired, heating the resulting powder to from a very pure single phase product.

Intercalation Pseudocapacitance of Exfoliated Molybdenum Disulfide for Ultrafast Energy Storage

DOE PAGES

Yoo, Hyun Deog; Li, Yifei; Liang, Yanliang; ...

2016-05-23

In this study, we report intercalation pseudocapacitance of 250 F g -1 for exfoliated molybdenum disulfide (MoS 2) in non-aqueous electrolytes that contain lithium ions. The exfoliated MoS 2 shows surface-limited reaction kinetics with high rate capability up to 3 min of charge or discharge. The intercalation pseudocapacitance originates from the extremely fast kinetics due to the enhanced ionic and electronic transport enabled by the slightly expanded layer structure as well as the metallic 1T-phase. The exfoliated MoS 2 could be also used in a Li-Mg-ion hybrid capacitor, which shows full cell specific capacitance of 240 F g -1.

First-principles study of Ti intercalation between graphene and Au surface

NASA Astrophysics Data System (ADS)

Kaneko, T.; Imamura, H.

2011-06-01

We investigate the effects of Ti intercalation between graphene and Au surface on binding energy and charge doping by using the first-principles calculations. We show that the largest binding energy is realized by the intercalation of single mono-layer of Ti. We also show that electronic structure is very sensitive to the arrangement of metal atoms at the interface. If the composition of the interface layer is Ti0.33Au0.67 and the Ti is located at the top site, the Fermi level lies closely at the Dirac point, i.e., the Dirac cone of the ideal free-standing graphene is recovered.

Intercalation of P atoms in Fullerene-like CP x

NASA Astrophysics Data System (ADS)

Gueorguiev, G. K.; Czigány, Zs.; Furlan, A.; Stafström, S.; Hultman, L.

2011-01-01

The energy cost for P atom intercalation and corresponding structural implications during formation of Fullerene-like Phosphorus carbide (FL-CPx) were evaluated within the framework of Density Functional Theory. Single P atom interstitial defects in FL-CPx are energetically feasible and exhibit energy cost of 0.93-1.21 eV, which is comparable to the energy cost for experimentally confirmed tetragon defects and dangling bonds in CPx. A single P atom intercalation event in FL-CPx can increase the inter-sheet distance from 3.39-3.62 Å to 5.81-7.04 Å. These theoretical results are corroborated by Selected Area Electron Diffraction characterization of FL-CPx samples.

Scaling of Linking and Writhing Numbers for Spherically Confined and Topologically Equilibrated Flexible Polymers

PubMed Central

Marko, John F.

2011-01-01

Scaling laws for Gauss linking number Ca and writhing number Wr for spherically confined flexible polymers with thermally fluctuating topology are analyzed. For ideal (phantom) polymers each of N segments of length unity confined to a spherical pore of radius R there are two scaling regimes: for sufficiently weak confinement (R ⪢ N1/3) each chain has |Wr| ≈ N1/2, and each pair of chains has average |Ca| ≈ N/R3/2; alternately for sufficiently tight confinement (N1/3 ⪢ R), |Wr| ≈ |CA| ≈ N/R3/2. Adding segment-segment avoidance modifies this result: for n chains with excluded volume interactions |Ca| ≈ (N/n)1/2f(ϕ) where f is a scaling function that depends approximately linearly on the segment concentration ϕ = nN/R3. Scaling results for writhe are used to estimate the maximum writhe of a polymer; this is demonstrated to be realizable through a writhing instability that occurs for a polymer which is able to change knotting topology and which is subject to an applied torque. Finally, scaling results for linking are used to estimate bounds on the entanglement complexity of long chromosomal DNA molecules inside cells, and to show how “lengthwise” chromosome condensation can suppress DNA entanglement. PMID:21686050

Highly Efficient Iodine Capture by Layered Double Hydroxides Intercalated with Polysulfides

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

Ma, Shulan; Islam, Saiful M.; Shim, Yurina

2014-12-23

We demonstrate strong iodine (I-2) vapor adsorption using Mg/Al layered double hydroxide (MgAl-LDH) nanocomposites intercalated with polysulfide (S-x(2-)) groups (S-x-LDH, x = 2, 4, 6). The as-prepared LDH/polysulfide hybrid materials display highly efficient iodine capture resulting from the reducing property of the intercalated polysulfides. During adsorption, the I-2 molecules are reduced to I-3(-) anions by the intercalated [S-x](2-) groups that simultaneously are oxidized to form S8. In addition to the chemical adsorption, additional molecular I-2 is physically captured by the LDH composites. As a result of these parallel processes, and despite their very low BET surface areas, the iodine capturemore » capacities of S-2-LDH, S-4-LDH, and S-6-LDH are similar to 1.32, 1.52, and 1.43 g/g, respectively, with a maximum adsorption of 152% (wt %). Thermogravimetric and differential thermal analysis (TG-DTA), energy dispersive X-ray spectroscopy (EDS), and temperature-variable powder X-ray diffraction (XRD) measurements show the resulting I-3(-) ions that intercalated into the LDH gallery have high thermal stability (>= 350 degrees C). The excellent iodine adsorption performance combined with the facile preparation points to the S-x-LDH systems as potential superior materials for adsorption of radioactive iodine, a waste product of the nuclear power industry.« less

Modulating the electronic and magnetic properties of bilayer borophene via transition metal atoms intercalation: from metal to half metal and semiconductor.

PubMed

Zhang, Xiuyun; Sun, Yi; Ma, Liang; Zhao, Xinli; Yao, Xiaojing

2018-07-27

Borophene, a two-dimensional monolayer made of boron atoms, has attracted wide attention due to its appealing properties. Great efforts have been devoted to fine tuning its electronic and magnetic properties for desired applications. Herein, we theoretically investigate the versatile electronic and magnetic properties of bilayer borophene (BLB) intercalated by 3d transition metal (TM) atoms, TM@BLBs (TM = Ti-Fe), using ab initio calculations. Four allotropes of AA-stacking (α 1 -, β-, β 12 - and χ 3 -) BLBs with different intercalation concentrations of TM atoms are considered. Our results show that the TM atoms are strongly bonded to the borophene layers with fairly large binding energies, around 6.31 ∼ 15.44 eV per TM atom. The BLBs with Cr and Mn intercalation have robust ferromagnetism, while for the systems decorated with Fe atoms, fruitful magnetic properties, such as nonmagnetic, ferromagnetic or antiferromagnetic, are identified. In particular, the α 1 - and β-BLBs intercalated by Mn or Fe atom can be transformed into a semiconductor, half metal or graphene-like semimetal. Moreover, some heavily doped TM@BLBs expose high Curie temperatures above room temperature. The attractive properties of TM@BLBs entail an efficient way to modulate the electronic and magnetic properties of borophene sheets for advanced applications.

Effects of redox-active interlayer anions on the oxygen evolution reactivity of NiFe-layered double hydroxide nanosheets

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

Zhou, Daojin; Cai, Zhao; Bi, Yongmin

Nickel-iron layered double hydroxide (NiFe-LDH) nanosheets have shown optimal oxygen evolution reaction (OER) performance; however, the role of the intercalated ions in the OER activity remains unclear. In this work, we show that the activity of the NiFe-LDHs can be tailored by the intercalated anions with different redox potentials. The intercalation of anions with low redox potential (high reducing ability), such as hypophosphites, leads to NiFe-LDHs with low OER overpotential of 240 mV and a small Tafel slope of 36.9 mV/dec, whereas NiFe-LDHs intercalated with anions of high redox potential (low reducing ability), such as fluorion, show a high overpotentialmore » of 370 mV and a Tafel slope of 80.8 mV/dec. The OER activity shows a surprising linear correlation with the standard redox potential. Density functional theory calculations and X-ray photoelectron spectroscopy analysis indicate that the intercalated anions alter the electronic structure of metal atoms which exposed at the surface. Anions with low standard redox potential and strong reducing ability transfer more electrons to the hydroxide layers. Finally, this increases the electron density of the surface metal sites and stabilizes their high-valence states, whose formation is known as the critical step prior to the OER process.« less

Temperature dependent local atomic displacements in ammonia intercalated iron selenide superconductor

NASA Astrophysics Data System (ADS)

Paris, E.; Simonelli, L.; Wakita, T.; Marini, C.; Lee, J.-H.; Olszewski, W.; Terashima, K.; Kakuto, T.; Nishimoto, N.; Kimura, T.; Kudo, K.; Kambe, T.; Nohara, M.; Yokoya, T.; Saini, N. L.

2016-06-01

Recently, ammonia-thermal reaction has been used for molecular intercalation in layered FeSe, resulting a new Lix(NH3)yFe2Se2 superconductor with Tc ~ 45 K. Here, we have used temperature dependent extended x-ray absorption fine structure (EXAFS) to investigate local atomic displacements in single crystals of this new superconductor. Using polarized EXAFS at Fe K-edge we have obtained direct information on the local Fe-Se and Fe-Fe bondlengths and corresponding mean square relative displacements (MSRD). We find that the Se-height in the intercalated system is lower than the one in the binary FeSe, suggesting compressed FeSe4 tetrahedron in the title system. Incidentally, there is hardly any effect of the intercalation on the bondlengths characteristics, revealed by the Einstein temperatures, that are similar to those found in the binary FeSe. Therefore, the molecular intercalation induces an effective compression and decouples the FeSe slabs. Furthermore, the results reveal an anomalous change in the atomic correlations across Tc, appearing as a clear decrease in the MSRD, indicating hardening of the local lattice mode. Similar response of the local lattice has been found in other families of superconductors, e.g., A15-type and cuprates superconductors. This observation suggests that local atomic correlations should have some direct correlation with the superconductivity.

Spatially controlled doping of two-dimensional SnS 2 through intercalation for electronics

DOE PAGES

Gong, Yongji; Yuan, Hongtao; Wu, Chun-Lan; ...

2018-02-26

Doped semiconductors are the most important building elements for modern electronic devices. In silicon-based integrated circuits, facile and controllable fabrication and integration of these materials can be realized without introducing a high-resistance interface. Besides, the emergence of two-dimensional (2D) materials enables the realization of atomically thin integrated circuits. However, the 2D nature of these materials precludes the use of traditional ion implantation techniques for carrier doping and further hinders device development10. Here, we demonstrate a solvent-based intercalation method to achieve p-type, n-type and degenerately doped semiconductors in the same parent material at the atomically thin limit. In contrast to naturallymore » grown n-type S-vacancy SnS 2, Cu intercalated bilayer SnS 2 obtained by this technique displays a hole field-effect mobility of ~40 cm 2 V -1 s -1, and the obtained Co-SnS 2 exhibits a metal-like behaviour with sheet resistance comparable to that of few-layer graphene. Combining this intercalation technique with lithography, an atomically seamless p–n–metal junction could be further realized with precise size and spatial control, which makes in-plane heterostructures practically applicable for integrated devices and other 2D materials. Therefore, the presented intercalation method can open a new avenue connecting the previously disparate worlds of integrated circuits and atomically thin materials.« less

Possible Mg intercalation mechanism at the Mo6 S8 cathode surface proposed by first-principles methods

NASA Astrophysics Data System (ADS)

Wan, Liwen; Prendergast, David

2015-03-01

In recent years, great attention has been paid to the development of divalent Mg-ion batteries, which can potentially double the energy density and volumetric capacity compared to monovalent Li-ion batteries. The prototype Mg-ion battery, comprising Mg(anode)/Mg(AlCl2BuEt)2.THF(electrolyte)/Mo6S8(cathode), was established in 2000 by Aurbach et al. Despite the remarkable success of this prototype system, we still lack a clear understanding of the fundamental Mg intercalation/deposition mechanism at the electrolyte/electrode interfaces that perhaps results in the observed sluggish Mg transport process. Our previous work has shown that Mg-ions are strongly coordinated in the bulk electrolyte by a combination of counterion, Cl-, and organic aprotic solvent, THF. In this work, we use first-principles methods to study Mg intercalation behavior at the Mo6S8 cathode surface with the presence of solvent molecules. It is found that the image charge, formed on this metallic cathode surface, can effectively weaken the solvent-surface interactions and facilitate Mg intercalation. A detailed Mg intercalation mechanism is proposed and the unique role of Mo6S8 as the cathode material is emphasized. This work is supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.

Effects of redox-active interlayer anions on the oxygen evolution reactivity of NiFe-layered double hydroxide nanosheets

DOE PAGES

Zhou, Daojin; Cai, Zhao; Bi, Yongmin; ...

2018-02-02

Nickel-iron layered double hydroxide (NiFe-LDH) nanosheets have shown optimal oxygen evolution reaction (OER) performance; however, the role of the intercalated ions in the OER activity remains unclear. In this work, we show that the activity of the NiFe-LDHs can be tailored by the intercalated anions with different redox potentials. The intercalation of anions with low redox potential (high reducing ability), such as hypophosphites, leads to NiFe-LDHs with low OER overpotential of 240 mV and a small Tafel slope of 36.9 mV/dec, whereas NiFe-LDHs intercalated with anions of high redox potential (low reducing ability), such as fluorion, show a high overpotentialmore » of 370 mV and a Tafel slope of 80.8 mV/dec. The OER activity shows a surprising linear correlation with the standard redox potential. Density functional theory calculations and X-ray photoelectron spectroscopy analysis indicate that the intercalated anions alter the electronic structure of metal atoms which exposed at the surface. Anions with low standard redox potential and strong reducing ability transfer more electrons to the hydroxide layers. Finally, this increases the electron density of the surface metal sites and stabilizes their high-valence states, whose formation is known as the critical step prior to the OER process.« less

Binding of DNA-binding alkaloids berberine and palmatine to tRNA and comparison to ethidium: Spectroscopic and molecular modeling studies

NASA Astrophysics Data System (ADS)

Islam, Md. Maidul; Pandya, Prateek; Chowdhury, Sebanti Roy; Kumar, Surat; Kumar, Gopinatha Suresh

2008-11-01

The interaction of two natural protoberberine plant alkaloids berberine and palmatine with tRNA phe was studied using various biophysical techniques and molecular modeling and the data were compared with the binding of the classical DNA intercalator, ethidium. Circular dichroic studies revealed that the tRNA conformation was moderately perturbed on binding of the alkaloids. The cooperative binding of both the alkaloids and ethidium to tRNA was revealed from absorbance and fluorescence studies. Fluorescence quenching studies advanced a conclusion that while berberine and palmatine are partially intercalated, ethidium is fully intercalated on the tRNA molecule. The binding of the alkaloids as well as ethidium stabilized the tRNA melting, and the binding constant evaluated from the averaged optical melting temperature data was in agreement with fluorescence spectral-binding data. Differential scanning calorimetry revealed that the tRNA melting showed three close transitions that were affected on binding of these small molecules. Molecular docking calculations performed showed the preferred regions of binding of these small molecules on the tRNA. Taken together, the results suggest that the binding of the alkaloids berberine and palmatine on the tRNA structure appears to be mostly by partial intercalation while ethidium intercalates fully on the tRNA. These results further advance our knowledge on the molecular aspects on the interaction of these alkaloids to tRNA.

Multi-Step Lithiation of Tin Sulfide: An Investigation Using In Situ Electron Microscopy

DOE PAGES

Hwang, Sooyeon; Yao, Zhenpeng; Zhang, Lei; ...

2018-04-03

Two-dimensional metal sulfides have been widely explored as promising electrodes for lithium ion batteries since their two-dimensional layered structure allows lithium ions to intercalate between layers. For tin disulfide, the lithiation process proceeds via a sequence of three different types of reactions: intercalation, conversion, and alloying but the full scenario of reaction dynamics remains nebulous. In this paper, we investigate the dynamical process of the multi-step reactions using in situ electron microscopy and discover an intermediate rock-salt phase with the disordering of Li and Sn cations, after the initial 2-dimensional intercalation. The disordered cations occupy all the octahedral sites andmore » block the channels for intercalation, which alter the reaction pathways during further lithiation. Our first principles calculations of the non-equilibrium lithiation of SnS2 corroborate the energetic preference of the disordered rock-salt structure over known layered polymorphs. The in situ observations and calculations suggest a two-phase reaction nature for intercalation, disordering, and following conversion reactions. In addition, in situ de-lithiation observation confirms that the alloying reaction is reversible while the conversion reaction is not, which is consistent to the ex situ analysis. This work reveals the full lithiation characteristic of SnS2 and sheds light on the understanding of complex multistep reactions in two-dimensional materials.« less

Spatially controlled doping of two-dimensional SnS 2 through intercalation for electronics

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

Gong, Yongji; Yuan, Hongtao; Wu, Chun-Lan

Doped semiconductors are the most important building elements for modern electronic devices. In silicon-based integrated circuits, facile and controllable fabrication and integration of these materials can be realized without introducing a high-resistance interface. Besides, the emergence of two-dimensional (2D) materials enables the realization of atomically thin integrated circuits. However, the 2D nature of these materials precludes the use of traditional ion implantation techniques for carrier doping and further hinders device development10. Here, we demonstrate a solvent-based intercalation method to achieve p-type, n-type and degenerately doped semiconductors in the same parent material at the atomically thin limit. In contrast to naturallymore » grown n-type S-vacancy SnS 2, Cu intercalated bilayer SnS 2 obtained by this technique displays a hole field-effect mobility of ~40 cm 2 V -1 s -1, and the obtained Co-SnS 2 exhibits a metal-like behaviour with sheet resistance comparable to that of few-layer graphene. Combining this intercalation technique with lithography, an atomically seamless p–n–metal junction could be further realized with precise size and spatial control, which makes in-plane heterostructures practically applicable for integrated devices and other 2D materials. Therefore, the presented intercalation method can open a new avenue connecting the previously disparate worlds of integrated circuits and atomically thin materials.« less

Effects of Applied Potential and Water Intercalation on the Surface Chemistry of Ti 2C and Mo 2C MXenes

DOE PAGES

Fredrickson, Kurt D.; Anasori, Babak; Seh, Zhi Wei; ...

2016-12-09

Here, two-dimensional transition metal carbides and nitrides, also known as MXenes, represent an attractive class of materials for a multitude of electrochemical and other applications. While single sheets of MXenes have been widely studied theoretically, there have been much fewer studies on layered bulk MXenes, which are more representative of multi- or few-layer MXenes used in actual applications. Herein, we investigate the structural and electronic effects of water intercalation, multiple functional groups and applied potential on layered bulk Ti 2C and Mo 2C MXenes using density functional theory. The out-of plane lattice parameter, c, was found to vary significantly withmore » the functional group, and is greatly increased upon intercalation of water. Experimental results confirm the change in lattice constant due to addition or removal of intercalated water. Under zero applied potential, both Ti 2C and Mo 2C were found to be functionalized by one monolayer of O; bare MXenes were never found to be stable, regardless of the applied potential. Applying a potential changed the adsorbate coverage, changing the systems from O covered to H covered at negative potentials and, in some cases, giving rise to a metal–insulator transition. Understanding of the effects of surface functionalization and water intercalation of MXenes provides a better insight of their use for catalytic and electronic applications.« less

Multi-Step Lithiation of Tin Sulfide: An Investigation Using In Situ Electron Microscopy

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

Hwang, Sooyeon; Yao, Zhenpeng; Zhang, Lei

Two-dimensional metal sulfides have been widely explored as promising electrodes for lithium ion batteries since their two-dimensional layered structure allows lithium ions to intercalate between layers. For tin disulfide, the lithiation process proceeds via a sequence of three different types of reactions: intercalation, conversion, and alloying but the full scenario of reaction dynamics remains nebulous. In this paper, we investigate the dynamical process of the multi-step reactions using in situ electron microscopy and discover an intermediate rock-salt phase with the disordering of Li and Sn cations, after the initial 2-dimensional intercalation. The disordered cations occupy all the octahedral sites andmore » block the channels for intercalation, which alter the reaction pathways during further lithiation. Our first principles calculations of the non-equilibrium lithiation of SnS2 corroborate the energetic preference of the disordered rock-salt structure over known layered polymorphs. The in situ observations and calculations suggest a two-phase reaction nature for intercalation, disordering, and following conversion reactions. In addition, in situ de-lithiation observation confirms that the alloying reaction is reversible while the conversion reaction is not, which is consistent to the ex situ analysis. This work reveals the full lithiation characteristic of SnS2 and sheds light on the understanding of complex multistep reactions in two-dimensional materials.« less

Spatially controlled doping of two-dimensional SnS2 through intercalation for electronics

NASA Astrophysics Data System (ADS)

Gong, Yongji; Yuan, Hongtao; Wu, Chun-Lan; Tang, Peizhe; Yang, Shi-Ze; Yang, Ankun; Li, Guodong; Liu, Bofei; van de Groep, Jorik; Brongersma, Mark L.; Chisholm, Matthew F.; Zhang, Shou-Cheng; Zhou, Wu; Cui, Yi

2018-04-01

Doped semiconductors are the most important building elements for modern electronic devices1. In silicon-based integrated circuits, facile and controllable fabrication and integration of these materials can be realized without introducing a high-resistance interface2,3. Besides, the emergence of two-dimensional (2D) materials enables the realization of atomically thin integrated circuits4-9. However, the 2D nature of these materials precludes the use of traditional ion implantation techniques for carrier doping and further hinders device development10. Here, we demonstrate a solvent-based intercalation method to achieve p-type, n-type and degenerately doped semiconductors in the same parent material at the atomically thin limit. In contrast to naturally grown n-type S-vacancy SnS2, Cu intercalated bilayer SnS2 obtained by this technique displays a hole field-effect mobility of 40 cm2 V-1 s-1, and the obtained Co-SnS2 exhibits a metal-like behaviour with sheet resistance comparable to that of few-layer graphene5. Combining this intercalation technique with lithography, an atomically seamless p-n-metal junction could be further realized with precise size and spatial control, which makes in-plane heterostructures practically applicable for integrated devices and other 2D materials. Therefore, the presented intercalation method can open a new avenue connecting the previously disparate worlds of integrated circuits and atomically thin materials.

Reversible intercalation of ammonia molecules into a layered double hydroxide structure without exchanging nitrate counter-ions

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

Carbajal Arizaga, Gregorio Guadalupe, E-mail: gregoriocarbajal@yahoo.com.m; Wypych, Fernando; Castillon Barraza, Felipe

2010-10-15

A zinc/aluminum LDH was precipitated with recycled ammonia from a chemical vapor deposition reaction. The LDH presented a crystalline phase with basal distance of 8.9 A, typical for nitrate-containing LDHs, and another phase with a basal distance of 13.9 A. Thermal treatment at 150 {sup o}C eliminated the phase with the bigger basal distance leaving only the anhydrous nitrate-intercalated LDH structure with 8.9 A. Intense N-H stretching modes in the FTIR spectra suggested that the expansion was due to intercalation of ammonia in the form of [NH{sub 4}(NH{sub 3}){sub n}]{sup +} species. When additional samples were precipitated with pure ammonia,more » the conventional LDH nitrate structure was obtained (8.9 A basal distance) at pH=7, as well as a pure crystalline phase with 13.9 A basal distance at pH=10 due to ammonia intercalation that can be removed by heating at 150 {sup o}C or by stirring in acetone, confirming a unusual sensu stricto intercalation process into a LDH without exchanging nitrate ions. - Graphical abstract: LDH-nitrate precipitated with ammonia expands the interlayer space if ammonia is bubbled up to pH 10. The basal distance decreased when the compound was heated at 150 {sup o}C or stirred in acetone. Nitrate ions are not exchanged.« less

Synthesis and characterization of Mg-Al-layered double hydroxides intercalated with cubane-1,4-dicarboxylate anions.

PubMed

Rezvani, Zolfaghar; Arjomandi Rad, Farzad; Khodam, Fatemeh

2015-01-21

In the present work, Mg2Al-layered double hydroxide (LDH) intercalated with cubane-1,4-dicarboxylate anions was prepared from the reaction of solutions of Mg(ii) and Al(iii) nitrate salts with an alkaline solution of cubane-1,4-dicarboxylic acid by using the coprecipitation method. The successful preparation of a nanohybrid of cubane-1,4-dicarboxylate(cubane-dc) anions with LDH was confirmed by powder X-ray diffraction, FTIR spectroscopy and thermal gravimetric analysis (TGA). The increase in the basal spacing of LDHs from 8.67 Å to 13.40 Å shows that cubane-dc anions were successfully incorporated into the interlayer space. Thermogravimetric analyses confirm that the thermal stability of the intercalated cubane-dc anions is greater than that of the pure form before intercalation because of host-guest interactions involving hydrogen bonds. The interlayer structure, hydrogen bonding, and subsequent distension of LDH compounds containing cubane-dc anions were shown by molecular simulation. The RDF (radial distribution function), mean square displacement (MSD), and self-diffusion coefficient were calculated using the trajectory files on the basis of molecular dynamics (MD) simulations, and the results indicated that the cubane-dc anions were more stable when intercalated into the LDH layers. A good agreement was obtained between calculated and measured X-ray diffraction patterns and between experimental and calculated basal spacings.

Methotrexate intercalated ZnAl-layered double hydroxide

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

Chakraborty, Manjusha; Dasgupta, Sudip; Soundrapandian, Chidambaram

2011-09-15

The anticancerous drug methotrexate (MTX) has been intercalated into an ZnAl-layered double hydroxide (LDH) using an anion exchange technique to produce LDH-MTX hybrids having particle sizes in the range of 100-300 nm. X-ray diffraction studies revealed increases in the basal spacings of ZnAl-LDH-MTX hybrid on MTX intercalation. This was corroborated by the transmission electron micrographs, which showed an increase in average interlayer spacing from 8.9 A in pristine LDH to 21.3 A in LDH-MTX hybrid. Thermogravimetric analyses showed an increase in the decomposition temperature for the MTX molecule in the LDH-MTX hybrid indicating enhanced thermal stability of the drug moleculemore » in the LDH nanovehicle. The cumulative release profile of MTX from ZnAl-LDH-MTX hybrids in phosphate buffer saline (PBS) at pH 7.4 was successfully sustained for 48 h following Rigter-Peppas model release kinetics via diffusion. - Graphical abstract: ZnAl-layered double hydroxide intercalated with methotrexate ({approx}34% loading) promises the possibility of use of ZnAl-LDH material as drug carrier and in controlled delivery. Highlights: > ZnAl-layered double hydroxide methotrexate nanohybrid has been synthesized. > XRD and TEM studies on nanohybrid revealed successful intercalation of methotrexate. > TG and CHN analyses showed {approx}34 wt% of methotrexate loading into the nanohybrid. > Possibility of use of ZnAl-LDH material as drug carrier and in delivery.« less

Synthesis and investigation of proton conductivity for intercalated kaolinite with 4-amidinopyridinium chloride

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

Ren, Li-Te; College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009; Li, Xiao-Pei

2015-12-15

The proton-conducting materials have potential application in devices such as fuel cells. In this study, a mineral kaolinite-based proton conducting material, kaolinite-4-amidinopyridinium hydrochloride (K-4-APy–HCl), was synthesized by the intercalated compound kaolinite-4-amidinopyridine (K-4-APy) adsorbing volatilizing HCl. The thermogravimetric analysis (TG), powder X-ray diffraction (PXRD) and IR spectrum confirmed the HCl successfully inserting into the interlayer space of kaolinite and the 4-aminopyridine being protonated. The intercalation efficiency is estimated to be ca. 85.6%. With respect to K-4-APy, the interlayer space expends by 1.53 Å. The thermal decomposition mechanism was studied by PXRD and TG techniques. The K-4-APy–HCl shows proton conductivity with σ=3.379×10{supmore » −8} S cm{sup −1} at 373 K and E{sub a}=1.159 eV in the anhydrous condition, which are comparable to MOFs-based proton conducting materials. - Graphical abstract: The intercalated hybrid of mineral kaolinite with 4-amidinopyridinium hydrochloride is prepared to use as proton conducting material. - Highlights: • A new strategy is proposed for preparation of kaolinite-based proton conductor. • Intercalatied hybrid was prepared by sequentially inserting 4-amidinopyridine and adsorbing HCl. • The proton conductivity of intercalated hybrid is comparable to MOFs-based proton-conductors.« less

Clinical evaluation of semi-automatic open-source algorithmic software segmentation of the mandibular bone: Practical feasibility and assessment of a new course of action

PubMed Central

Wallner, Jürgen; Hochegger, Kerstin; Chen, Xiaojun; Mischak, Irene; Reinbacher, Knut; Pau, Mauro; Zrnc, Tomislav; Schwenzer-Zimmerer, Katja; Zemann, Wolfgang; Schmalstieg, Dieter

2018-01-01

Introduction Computer assisted technologies based on algorithmic software segmentation are an increasing topic of interest in complex surgical cases. However—due to functional instability, time consuming software processes, personnel resources or licensed-based financial costs many segmentation processes are often outsourced from clinical centers to third parties and the industry. Therefore, the aim of this trial was to assess the practical feasibility of an easy available, functional stable and licensed-free segmentation approach to be used in the clinical practice. Material and methods In this retrospective, randomized, controlled trail the accuracy and accordance of the open-source based segmentation algorithm GrowCut was assessed through the comparison to the manually generated ground truth of the same anatomy using 10 CT lower jaw data-sets from the clinical routine. Assessment parameters were the segmentation time, the volume, the voxel number, the Dice Score and the Hausdorff distance. Results Overall semi-automatic GrowCut segmentation times were about one minute. Mean Dice Score values of over 85% and Hausdorff Distances below 33.5 voxel could be achieved between the algorithmic GrowCut-based segmentations and the manual generated ground truth schemes. Statistical differences between the assessment parameters were not significant (p<0.05) and correlation coefficients were close to the value one (r > 0.94) for any of the comparison made between the two groups. Discussion Complete functional stable and time saving segmentations with high accuracy and high positive correlation could be performed by the presented interactive open-source based approach. In the cranio-maxillofacial complex the used method could represent an algorithmic alternative for image-based segmentation in the clinical practice for e.g. surgical treatment planning or visualization of postoperative results and offers several advantages. Due to an open-source basis the used method could be further developed by other groups or specialists. Systematic comparisons to other segmentation approaches or with a greater data amount are areas of future works. PMID:29746490

Studies of hexafluorophosphate, tetrafluoroborate, and perchlorate electro-intercalation into graphitic carbon

NASA Astrophysics Data System (ADS)

Seel, Jennifer Ann

There has been some interest in using carbon materials as both working electrodes in electrochemical cells and rechargeable batteries [1--6]. This would result in the intercalation of not only of lithium ions into one carbon electrode but the anion component of the lithium salt, such as PF 6-, into the other carbon electrode. The intercalation of the anion component of the salt into carbon electrodes has not been studied extensively and it is not completely understood. The work presented here will expand on this rarely touched subject through electrochemical cycling as well as in-situ and ex-situ X-ray diffraction experiments. The anions that will be studied are: PF6- , BF4- and ClO4 -. It will be shown that anion intercalation occurs for various types of soft carbons and that the process can be greatly affected by the amount of turbostratic disorder present in the carbon material as well as by the specific anion used. It was discovered that using ethyl methyl sulfone, EMS, as the solvent component of the electrolyte resulted in more stable electrochemical cells than ethylene carbonate/diethyl carbonate, a more common solvent, at the high potentials required for anion intercalation. It was also discovered that PF 6 and BF4 formed staged phases during electrochemical cycling whereas ClO4 did not. The amount of disorder present in the carbon electrode did affect the intercalation of the anion. The samples with a greater amount of disorder present had a larger amount of capacity loss between charge and discharge capacities. It was also found that purer and more distinct staged phases occurred in the more ordered carbon samples. The turbostratically disordered carbon layers may rotate to accommodate PF6 and therefore become slightly more ordered. X-ray diffraction evidence suggests that intercalated PF6 molecules may be free-rotating between the carbon layers. However, the orientation of BF4 molecules between the carbon layers could not be determined. There may also be some co-intercalation of the solvent, mainly with ClO 4 and to a lesser extent BF4 and PF6. It is thought that a large amount of solvent co-intercalation occurs with ClO4 and this is the most probable reason why staged phases were not observed. An unfortunate aspect of this study is that dual carbon cells are not at all viable as commercial cells. The energy densities of dual carbon cells are much lower than the currently available lithium-ion cells. For dual carbon cells to become viable new inexpensive salts and solvents that can operate at high potentials and high concentrations must be discovered. With further investigation, combinations of different anions and solvents may result in higher specific capacities that would also make dual carbon cells more viable.

Clinical Outcomes of Posterior C1 and C2 Screw-Rod Fixation for Atlantoaxial Instability.

PubMed

Işik, Hasan Serdar; Sandal, Evren; Çağli, Sedat

2017-06-14

In this study, we aimed at sharing our experiences and contributing to the literature by making a retrospective analysis of the patients we operated with screw-rod system for atlantoaxial instability in our clinic. Archive files of adult patients, who were operated for posterior C1-C2 stabilization with screw and rod in our clinic between January 2006 and January 2016, were analyzed. 28 patients, who had pre and post-operative images, follow-up forms and who were followed for at least one year, were analyzed. Preoperative clinical and radiological records, preoperative observations, postoperative complications, and clinical responses were evaluated. The average age of 28 patients (F:13 M:19) was 44.7 (21-73). Fixation was performed with C1-C2 screw-rod system on the basis of the following diagnoses; type 2 odontoid fracture (16), basilar invagination (5), C1-C2 instability (5), and atlantoaxial subluxation secondary to rheumatoid arthritis (2). Lateral mass screws were inserted at C1 segment. C2 screws inserted were bilateral pedicle in 12 cases, bilateral pars in 4, bilateral laminar in 8 and one side pars, one side laminar in 4 cases. There was no screw malposition. Neither implant failure nor recurrent instability was observed during follow-up. Significant clinical improvement was reported according to the assessments done with JOA and VAS scores. C1-C2 screw fixation is regarded as a more successful and safe method than other fixation methods in surgical treatment of atlantoaxial instability considering complications, success in reduction, fusion and fixation strength. C2 laminar screw technique is as successful as the other alternatives in fixation and fusion.

[Atlanto-axial pedicle screw fixation through posterior approach for treatment of atlanto-axial joint instability].

PubMed

Zuo, Chun-Guang; Liu, Xia-Jun; Wang, Xin-Hu; Wang, Jian-shun

2013-01-01

To discuss the therapeutic effects of the atlantoaxial pedicle screw system fixation in treatment of atlantoaxial instability. From June 2003 to March 2010, 32 patients with atlantoaxial instability were treated by atlantoaxial pedicle screw system fixation, included 21 males and 11 females wiht an average age of 42.5 years old ranging from 28 to 66 years. Among them, 18 cases were odontoid process fractures, 7 were congenital dissociate odontoid process, 4 were Jefferson fracture combined with odontoid fracture, 3 were rheumatic arthritis causing atlantoaxial instability. All patients suffered from the atlantoaxial subluxation and atlantoaxial instability. The JOA score ranged from 4 to 14 (means 9.1 +/- 0.3) before operation. The patients had some image examination including the X-ray of cervical vertebrae (include of dynamic position film), spiral CT 3D reconstruction and/or MRI. The position of pedicle screw system implantation,the angle of pedicle screw system implantation and screw length were measured. Operating skull traction. Operation undewent general anesthesia, implanted the pedicle screw, reduction and bone fusion under direct vision. The bone was fixated between posterior arch of atlas and lamina of axis by the lateral combination bended to posterior. One hundred and twenty-eight atlantoaxial pedicle screws were implanted in 32 patients. No patient had the injure of spinal cord, nerve root and vertebral artery. All patients were followed-up from 6 to 48 months (averaged 16 months). After operation, the JOA score ranged from 11 to 17 (averaged 15.9 +/- 0.2), improvement rate was 86.1%. The fracture of odontoid process were healing completely. All fusion bone were combinated. The internal fixation wasn't loosening and breaking. The atlantoaxial pedicle screw system fixation was effective method to treat atlantoaxial instability. The method had many advantages, such as provide rigid and short segment fixation, safe and simple, high fusion rate. The method was worth in clinical application.

Spatial instability of the rift in the St. Paul multifault transform fracture system, Atlantic Ocean

NASA Astrophysics Data System (ADS)

Sokolov, S. Yu.; Zaraiskaya, Yu. A.; Mazarovich, A. O.; Efimov, V. N.; Sokolov, N. S.

2016-05-01

The structure of the acoustic basement of the eastern part of the St. Paul multifault transform fracture system hosts rift paleovalleys and a paleonodal depression that mismatch the position of the currently active zones. This displacement zone, which is composed of five fault troughs, is unstable in terms of the position of the rift segments, which jumped according to redistribution of stresses. The St. Paul system is characterized by straightening of the transform transition between two remote segments of the Mid-Atlantic Ridge (MAR). The eastern part of the system contains anomalous bright-spot-like reflectors on the flattened basement, which is a result of atypical magmatism, that forms the standard ridge relief of the acoustic basement. Deformations of the acoustic basement have a presedimentation character. The present-day deformations with lower amplitude in comparison to the basement are accompanied by acoustic brightening of the sedimentary sequence. The axial Bouguer anomalies in the east of the system continue to the north for 120 km from the active segments of the St. Paul system. Currently seismically active segments of the spreading system are characterized by increasing amplitudes of the E-W displacement along the fault troughs. Cross-correlation of the lengths of the active structural elements of the MAR zone (segments of the ridge and transform fracture zones of displacement) indicates that, statistically, the multifault transform fracture system is a specific type of oceanic strike-slip faults.

Preparation of poly(vinyl alcohol)/kaolinite nanocomposites via in situ polymerization

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

Jia Xin; Department of Chemistry, Hexi University, Zhangye 734000; Li Yanfeng

2008-03-04

Poly(vinyl alcohol)/kaolinite intercalated nanocomposites (Kao-PVA) were prepared via in situ intercalation radical polymerization. Vinyl acetate (VAc) was intercalated into kaolinite by a displacement method using dimethyl sulfoxide/kaolinite (Kao-DMSO) as the intermediate. Then, PVAc/kaolinite (Kao-PVAc) was obtained via radical polymerization with benzoyl peroxide (BPO) as initiator. Last, PVAc/kaolinite was saponified via direct-hydrolysis with NaOH solution in order to obtain PVA/kaolinite nanocomposites, which was characterized by Fourier-Transformation spectroscopy (FTIR), wide X-ray diffraction (WXRD) and transmission electron microscopy (TEM). Their differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) results of the obtained PVA/kaolinite suggested that the thermal properties had an obvious improvement.

The structure of drug-deoxydinucleoside phosphate complex; generalized conformational behavior of intercalation complexes with RNA and DNA fragments.

PubMed Central

Shieh, H S; Berman, H M; Dabrow, M; Neidle, S

1980-01-01

A 2:2 complex of proflavine and deoxycytidylyl-3', 5'-guanosine has been crystallized and its structure determined by x-ray crystallography. The two dinucleoside phosphate strands form self complementary duplexes with Watson Crick hydrogen bonds. One proflavin is asymmetrically intercalated between the base pairs and the other is stacked above them. The conformations of the nucleotides are unusual in that one strand has C3',C2'endomixed sugar puckering and the other has C3',C3' endo deoxyribose sugars. These results show that the conformation of the 3'sugar is of secondary importance to the intercalated geometry. PMID:7355129

Interaction of proflavine with DNA studied by colloid surface enhanced resonance Raman spectroscopy

NASA Astrophysics Data System (ADS)

Koglin, E.; Séquaris, J.-M.

1986-03-01

The interaction of the mutagenic highly fluourescing proflavine (3,6-diaminoacridine: PF) dye with calf thymus DNA has been studied by Surface Enhanced Resonance Raman Scattering (SERRS). Since the Ag-colloids almost completely quenche the strong fluorescence it is possible to obtain excellent vibrational spectra in a wide frequency range providing valuable information about the intercalation. The intercalation does not affect the vibrational frequencies of the proflavine dye. On the other hand, intensity changes are observed in some of the ring- and NH 2-modes of proflavine upon intercalation. This Raman hypochromism is characteristic for ring stacking interactions and in the SERRS spetroscopy for an additional effects of the dye orientation to the surface.

Process for producing advanced ceramics

DOEpatents

Kwong, Kyei-Sing

1996-01-01

A process for the synthesis of homogeneous advanced ceramics such as SiC+AlN, SiAlON, SiC+Al.sub.2 O.sub.3, and Si.sub.3 N.sub.4 +AlN from natural clays such as kaolin, halloysite and montmorillonite by an intercalation and heat treatment method. Included are the steps of refining clays, intercalating organic compounds into the layered structure of clays, drying the intercalated mixture, firing the treated atmospheres and grinding the loosely agglomerated structure. Advanced ceramics produced by this procedure have the advantages of homogeneity, cost effectiveness, simplicity of manufacture, ease of grind and a short process time. Advanced ceramics produced by this process can be used for refractory, wear part and structure ceramics.

Metallization and superconductivity in Ca-intercalated bilayer MoS2

NASA Astrophysics Data System (ADS)

Szczȱśniak, R.; Durajski, A. P.; Jarosik, M. W.

2017-12-01

A two-dimensional molybdenum disulfide (MoS2) has attracted significant interest recently due to its outstanding physical, chemical and optoelectronic properties. In this paper, using the first-principles calculations, the dynamical stability, electronic structure and superconducting properties of Ca-intercalated bilayer MoS2 are investigated. The calculated electron-phonon coupling constant implies that the stable form of investigated system is a strong-coupling superconductor (λ = 1.05) with a low value of critical temperature (TC = 13.3 K). Moreover, results obtained within the framework of the isotropic Migdal-Eliashberg formalism proved that Ca-intercalated bilayer MoS2 exhibits behavior that goes beyond the scope of the conventional BCS theory.

Intercalation of the layered solid acid HCa/sub 2/Nb/sub 3/O/sub 10/ by organic amines

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

Jacobson, A.J.; Johnson, J.W.; Lewandowski, J.T.

1987-01-01

Layered compounds of formula C/sub n/H/sub 2n+1/NH/sub 3/Ca/sub 2/Nb/sub 3/O/sub 10/ are formed by reaction of n-alkylamines with the solid acid HCa/sub 2/Nb/sub 3/O/sub 10/. Other organic bases such as pyridine can also be intercalated. The lattice constants of the new compounds have been determined by powder X-ray diffraction. The unit cells are tetragonal with a axes that are unchanged with variation of the intercalated amine. The c axes lengths (layer spacings) vary systematically with the hydrocarbon chain length of the alkylamine.

Impact of Infralimbic Inputs on Intercalated Amygdale Neurons: A Biophysical Modeling Study

ERIC Educational Resources Information Center

Li, Guoshi; Amano, Taiju; Pare, Denis; Nair, Satish S.

2011-01-01

Intercalated (ITC) amygdala neurons regulate fear expression by controlling impulse traffic between the input (basolateral amygdala; BLA) and output (central nucleus; Ce) stations of the amygdala for conditioned fear responses. Previously, stimulation of the infralimbic (IL) cortex was found to reduce fear expression and the responsiveness of Ce…

Superlattice Effects in Graphite Intercalation Compounds.

DTIC Science & Technology

1986-04-15

away from ;le[ Isy.st,.mns (r lin( nl :; atars ) and look for nonlinear dynamical effects -. m,,5,: U~ i,: ,1 : s y’t, rns, a3iioh m i Josephson...Intercalation Coaanm, Chemistry Dept., Northeast(.rn,, February 25, 1935. ( iv) "Giant Magnetic Interaction and Domain Dynamics in Twe -. "Dimensions," hoston

Hydrogenation and hydrogen intercalation of hexagonal boron nitride on Ni(1 1 1): reactivity and electronic structure

NASA Astrophysics Data System (ADS)

Späth, F.; Gebhardt, J.; Düll, F.; Bauer, U.; Bachmann, P.; Gleichweit, C.; Görling, A.; Steinrück, H.-P.; Papp, C.

2017-09-01

We investigate the reactivity of hexagonal boron nitride (h-BN) on a Ni(1 1 1) single crystal towards atomic hydrogen over a wide exposure range. Near edge x-ray absorption fine structure and x-ray photoelectron spectroscopy (XPS) show that for low hydrogen exposures hydrogenation of the h-BN sheet is found. In contrast, intercalation of hydrogen between h-BN and the Ni(1 1 1) substrate occurs for high exposures. For intermediate regimes, a mixture of intercalation and hydrogenation is observed. From temperature-programmed desorption and temperature-programmed XPS experiments, we conclude that the hydrogen covalently bound to h-BN is rather stable with a desorption temperature of 600 K, while intercalated hydrogen is desorbing already at 390 K. Further insight into the structural arrangements and the thermodynamics of the system is obtained by comparing our experimental results with extensive density-functional theory calculations. Together with ultraviolet photoelectron spectroscopy measurements, the calculations provide detailed insight into the influence of hydrogenation on the electronic structure of h-BN.

Synthesis and reversible hydration behavior of the thiosulfate intercalated layered double hydroxide of Zn and Al

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

Radha, S.; Milius, Wolfgang; Breu, Josef, E-mail: josef.breu@uni-bayreuth.de

2013-08-15

The thiosulfate-intercalated layered double hydroxide of Zn and Al undergoes reversible hydration with a variation in the relative humidity of the ambient. The hydrated and dehydrated phases, which represent the end members of the hydration cycle, both adopt the structure of the 3R{sub 1} polytype. In the intermediate range of relative humidity values (40–60%), the hydrated and dehydrated phases coexist. The end members of the hydration cycle adopt the structure of the same polytype, and vary only in their basal spacings. This points to the possibility that all the intermediate phases have a kinetic origin. - Graphical abstract: Basal spacingmore » evolution of the thiosulfate ion intercalated [Zn–Al] LDH during one complete hydration–dehydration cycle as a function of relative humidity. Display Omitted - Highlights: • Thiosulfate intercalated [Zn–Al] LDHs were synthesized by co-precipitation. • The LDH exhibits reversible hydration with variation in humidity. • Both the end members of the hydration cycle adopt the same polytype structure. • The interstratified intermediates observed are kinetic in origin.« less

Intercalating graphene with clusters of Fe3O4 nanocrystals for electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Ke, Qingqing; Tang, Chunhua; Liu, Yanqiong; Liu, Huajun; Wang, John

2014-04-01

A hierarchical nanostructure consisting of graphene sheets intercalated by clusters of Fe3O4 nanocystals is developed for high-performance supercapacitor electrode. Here we show that the negatively charged graphene oxide (GO) and positively charged Fe3O4 clusters enable a strong electrostatic interaction, generating a hierarchical 3D nanostructure, which gives rise to the intercalated composites through a rational hydrothermal process. The electrocapacitive behavior of the resultant composites is systematically investigated by cyclic voltammeter and galvanostatic charge-discharge techniques, where a positive synergistic effect between graphene and Fe3O4 clusters is identified. A maximum specific capacitance of 169 F g-1 is achieved in the Fe3O4 clusters decorated with effectively reduced graphene oxide (Fe3O4-rGO-12h), which is much higher than those of rGO (101 F g-1) and Fe3O4 (68 F g-1) at the current density of 1 Ag-1. Moreover, this intercalated hierarchical nanostructure demonstrates a good capacitance retention, retaining over 88% of the initial capacity after 1000 cycles.

Superconducting Continuous Graphene Fibers via Calcium Intercalation.

PubMed

Liu, Yingjun; Liang, Hui; Xu, Zhen; Xi, Jiabin; Chen, Genfu; Gao, Weiwei; Xue, Mianqi; Gao, Chao

2017-04-25

Superconductors are important materials in the field of low-temperature magnet applications and long-distance electrical power transmission systems. Besides metal-based superconducting materials, carbon-based superconductors have attracted considerable attention in recent years. Up to now, five allotropes of carbon, including diamond, graphite, C 60 , CNTs, and graphene, have been reported to show superconducting behavior. However, most of the carbon-based superconductors are limited to small size and discontinuous phases, which inevitably hinders further application in macroscopic form. Therefore, it raises a question of whether continuously carbon-based superconducting wires could be accessed, which is of vital importance from viewpoints of fundamental research and practical application. Here, inspired by superconducting graphene, we successfully fabricated flexible graphene-based superconducting fibers via a well-established calcium (Ca) intercalation strategy. The resultant Ca-intercalated graphene fiber (Ca-GF) shows a superconducting transition at ∼11 K, which is almost 2 orders of magnitude higher than that of early reported alkali metal intercalated graphite and comparable to that of commercial superconducting NbTi wire. The combination of lightness and easy scalability makes Ca-GF highly promising as a lightweight superconducting wire.

Room temperature deintercalation of alkali metal atoms from epitaxial graphene by formation of charge-transfer complexes

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

Shin, H.-C.; Ahn, S. J.; Kim, H. W.

2016-08-22

Atom (or molecule) intercalations and deintercalations have been used to control the electronic properties of graphene. In general, finite energies above room temperature (RT) thermal energy are required for the intercalations and deintercalations. Here, we demonstrate that alkali metal atoms can be deintercalated from epitaxial graphene on a SiC substrate at RT, resulting in the reduction in density of states at the Fermi level. The change in density of states at the Fermi level at RT can be applied to a highly sensitive graphene sensor operating at RT. Na atoms, which were intercalated at a temperature of 80 °C, were deintercalatedmore » at a high temperature above 1000 °C when only a thermal treatment was used. In contrast to the thermal treatment, the intercalated Na atoms were deintercalated at RT when tetrafluorotetracyanoquinodimethane (F4-TCNQ) molecules were adsorbed on the surface. The RT deintercalation occurred via the formation of charge-transfer complexes between Na atoms and F4-TCNQ molecules.« less

First Principles Studies for Lithium Intercalation and Diffusion Behaviors in MoS2 treated with the Compressive Sensing Cluster Expansion

NASA Astrophysics Data System (ADS)

Liu, Chi-Ping; Zhou, Fei; Ozolins, Vidvuds

2014-03-01

Molybdenum disulfide (MoS2) is a good candidate electrode material for high capacity energy storage applications, such as lithium ion batteries and supercapacitors. In this work, we investigate lithium intercalation and diffusion kinetics in MoS2 by using first-principles density-functional theory (DFT) calculations. Two different lithium intercalation sites (1-H and 2-T) in MoS2 are found to be stable for lithium intercalation at different van der Waals' (vdW) gap distances. It is found that both thermodynamic and kinetic properties are highly related to the interlayer vdW gap distance, and that the optimal gap distance leads to effective solid-state diffusion in MoS2. Additionally, through the use of compressive sensing, we build accurate cluster expansion models to study the thermodynamic properties of MoS2 at high lithium content by truncating the higher order effective clusters with significant contributions. The results show that compressive sensing cluster expansion is a rigorous and powerful tool for model construction for advanced electrochemical applications in the future.

A mediator-free glucose biosensor based on glucose oxidase/chitosan/α-zirconium phosphate ternary biocomposite.

PubMed

Liu, Li-Min; Wen, Jiwu; Liu, Lijun; He, Deyong; Kuang, Ren-yun; Shi, Taqing

2014-01-15

A novel glucose oxidase/chitosan/α-zirconium phosphate (GOD/chitosan/α-ZrP) ternary biocomposite was prepared by co-intercalating glucose oxidase (GOD) and chitosan into the interlayers of α-zirconium phosphate (α-ZrP) via a delamination-reassembly procedure. The results of X-ray diffraction, infrared spectroscopy, circular dichroism, and ultraviolet spectrum characterizations indicated not only the layered and hybrid structure of the GOD/chitosan/α-ZrP ternary biocomposite but also the recovered activity of the intercalated GOD improved by the co-intercalated chitosan. By depositing the GOD/chitosan/α-ZrP biocomposite film onto a glassy carbon electrode, the direct electrochemistry of the intercalated GOD was achieved with a fast electron transfer rate constant, k(s), of 7.48±3.52 s(-1). Moreover, this GOD/chitosan/α-ZrP biocomposite modified electrode exhibited a sensitive response to glucose in the linear range of 0.25-8.0 mM (R=0.9994, n=14), with a determination limit of 0.076 mM. Copyright © 2013 Elsevier Inc. All rights reserved.

Immobilization of kojic acid in ZnAl-hydrotalcite like compounds

NASA Astrophysics Data System (ADS)

Ambrogi, Valeria; Perioli, Luana; Nocchetti, Morena; Latterini, Loredana; Pagano, Cinzia; Massetti, Elena; Rossi, Carlo

2012-01-01

Kojic acid (KOJ) is a melanin synthesis inhibitor widely used as skin lightening agent in topical preparations. Unfortunately it is easily susceptible to photo-oxidation, phenomenon responsible for chemical and organoleptic modifications. The aim of this work was the intercalation of KOJ in hydrotalcite-like compounds (HTlc) in order to stabilize KOJ and to reduce its photolability. Hydrotalcite containing Zn and Al (ZnAl-HTlc) was used as host to obtain the final compound ZnAl-HTlc-KOJ. The intercalation was carried out, after many attempts, by ionic exchange mechanism by means of the strong base EtO- in anhydrous ethanol/dimethylsulfoxide (DMSO) mixture as solvent in order to generate KOJ- anions. The final product was characterized by the X-ray powder diffraction (XRPD), FT-IR spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and elemental analysis. The intercalated compound was formulated in a siliconic water free self-emulsifying ointment and the in vitro release profile was evaluated. All samples (intercalation compound and its formulation) were submitted also to spectrophotometric assays in order to evaluate the matrix protective effect towards ultraviolet rays.

AgI -Induced Switching of DNA Binding Modes via Formation of a Supramolecular Metallacycle.

PubMed

Basak, Shibaji; Léon, J Christian; Ferranco, Annaleizle; Sharma, Renu; Hebenbrock, Marian; Lough, Alan; Müller, Jens; Kraatz, Heinz-Bernhard

2018-03-12

The histidine derivative L1 of the DNA intercalator naphthalenediimide (NDI) forms a triangular Ag I complex (C2). The interactions of L1 and of C2 with DNA were studied by circular dichroism (CD) and UV/Vis spectroscopy and by viscosity studies. Different binding modes were observed for L1 and for C2, as the Ag I complex C2 is too large in size to act as an intercalator. If Ag I is added to the NDI molecule that is already intercalated into a duplex, higher order complexes are formed within the DNA duplex and cause disruptions in the helical duplex structure, which leads to a significant decrease in the characteristic CD features of B-DNA. Thus, via addition of a metal we show how a classic and well-known organic intercalator unit can be turned into a partial metallo insertor. We also show how electrochemical impedance spectroscopy (EIS) can be used to probe DNA binding modes on DNA films that are immobilized on gold surfaces. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intercalated Water and Organic Molecules for Electrode Materials of Rechargeable Batteries.

PubMed

Lee, Hyeon Jeong; Shin, Jaeho; Choi, Jang Wook

2018-03-24

The intrinsic limitations of lithium-ion batteries (LIBs) with regard to safety, cost, and the availability of raw materials have promoted research on so-called "post-LIBs". The recent intense research of post-LIBs provides an invaluable lesson that existing electrode materials used in LIBs may not perform as well in post-LIBs, calling for new material designs compliant with emerging batteries based on new chemistries. One promising approach in this direction is the development of materials with intercalated water or organic molecules, as these materials demonstrate superior electrochemical performance in emerging battery systems. The enlarged ionic channel dimensions and effective shielding of the electrostatic interaction between carrier ions and the lattice host are the origins of the observed electrochemical performance. Moreover, these intercalants serve as interlayer pillars to sustain the framework for prolonged cycles. Representative examples of such intercalated materials applied to batteries based on Li + , Na + , Mg 2+ , and Zn 2+ ions and supercapacitors are considered, along with their impact in materials research. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cell migration, intercalation and growth regulate mammalian cochlear extension.

PubMed

Driver, Elizabeth Carroll; Northrop, Amy; Kelley, Matthew W

2017-10-15

Developmental remodeling of the sensory epithelium of the cochlea is required for the formation of an elongated, tonotopically organized auditory organ, but the cellular processes that mediate these events are largely unknown. We used both morphological assessments of cellular rearrangements and time-lapse imaging to visualize cochlear remodeling in mouse. Analysis of cell redistribution showed that the cochlea extends through a combination of radial intercalation and cell growth. Live imaging demonstrated that concomitant cellular intercalation results in a brief period of epithelial convergence, although subsequent changes in cell size lead to medial-lateral spreading. Supporting cells, which retain contact with the basement membrane, exhibit biased protrusive activity and directed movement along the axis of extension. By contrast, hair cells lose contact with the basement membrane, but contribute to continued outgrowth through increased cell size. Regulation of cellular protrusions, movement and intercalation within the cochlea all require myosin II. These results establish, for the first time, many of the cellular processes that drive the distribution of sensory cells along the tonotopic axis of the cochlea. © 2017. Published by The Company of Biologists Ltd.

Organic or organometallic template mediated clay synthesis

DOEpatents

Gregar, Kathleen C.; Winans, Randall E.; Botto, Robert E.

1994-01-01

A method for incorporating diverse Varieties of intercalants or templates directly during hydrothermal synthesis of clays such as hectorite or montmorillonite-type layer-silicate clays. For a hectorite layer-silicate clay, refluxing a gel of silica sol, magnesium hydroxide sol and lithium fluoride for two days in the presence of an organic or organometallic intercalant or template results in crystalline products containing either (a) organic dye molecules such as ethyl violet and methyl green, (b) dye molecules such as alcian blue that are based on a Cu(II)-phthalocyannine complex, or (c) transition metal complexes such as Ru(II)phenanthroline and Co(III)sepulchrate or (d) water-soluble porphyrins and metalloporphyrins. Montmorillonite-type clays are made by the method taught by U.S. Pat. No. 3,887,454 issued to Hickson, Jun. 13, 1975; however, a variety of intercalants or templates may be introduced. The intercalants or templates should have (i) water-solubility, (ii) positive charge, and (iii) thermal stability under moderately basic (pH 9-10) aqueous reflux conditions or hydrothermal pressurized conditions for the montmorillonite-type clays.

Relaxation kinetics of the interaction between RNA and metal-intercalators: the Poly(A).Poly(U)/platinum-proflavine system.

PubMed

Biver, Tarita; Secco, Fernando; Venturini, Marcella

2005-05-15

The interactions of Poly(A).Poly(U) with the cis-platinum derivative of proflavine [{PtCl(tmen)}(2){HNC(13)H(7)(NHCH(2)CH(2))(2)}](+) (PRPt) and proflavine (PR) are investigated by spectrophotometry, spectrofluorimetry and T-jump relaxation at I=0.2M, pH 7.0, and T=25 degrees C. Base-dye interactions prevail at high RNA/dye ratio and binding isotherms analysis reveals that both dyes bind to Poly(A).Poly(U) according to the excluded site model (n=2). Only one relaxation effect is observed for the Poly(A).Poly(U)/PRPt system, whereas two effects are observed with Poly(A).Poly(U)/PR. The results agree with the sequence D+S <==> D, S <==> DS(I) <==> DS(II), where D,S is an external complex, DS(I) is a partially intercalated species, and DS(II) is the fully intercalated complex. Formation of DS(II) could be observed in the case of proflavine only. This result is interpreted by assuming that the platinum-containing residue of PRPt hinders the full intercalation of the acridine residue.

Reversible calcium alloying enables a practical room-temperature rechargeable calcium-ion battery with a high discharge voltage

NASA Astrophysics Data System (ADS)

Wang, Meng; Jiang, Chunlei; Zhang, Songquan; Song, Xiaohe; Tang, Yongbing; Cheng, Hui-Ming

2018-06-01

Calcium-ion batteries (CIBs) are attractive candidates for energy storage because Ca2+ has low polarization and a reduction potential (-2.87 V versus standard hydrogen electrode, SHE) close to that of Li+ (-3.04 V versus SHE), promising a wide voltage window for a full battery. However, their development is limited by difficulties such as the lack of proper cathode/anode materials for reversible Ca2+ intercalation/de-intercalation, low working voltages (<2 V), low cycling stability, and especially poor room-temperature performance. Here, we report a CIB that can work stably at room temperature in a new cell configuration using graphite as the cathode and tin foils as the anode as well as the current collector. This CIB operates on a highly reversible electrochemical reaction that combines hexafluorophosphate intercalation/de-intercalation at the cathode and a Ca-involved alloying/de-alloying reaction at the anode. An optimized CIB exhibits a working voltage of up to 4.45 V with capacity retention of 95% after 350 cycles.

Multistage Mechanism of Lithium Intercalation into Graphite Anodes in the Presence of the Solid Electrolyte Interface.

PubMed

Dinkelacker, Franz; Marzak, Philipp; Yun, Jeongsik; Liang, Yunchang; Bandarenka, Aliaksandr S

2018-04-25

A so-called solid electrolyte interface (SEI) in a lithium-ion battery largely determines the performance of the whole system. However, it is one of the least understood objects in these types of batteries. SEIs are formed during the initial charge-discharge cycles, prevent the organic electrolytes from further decomposition, and at the same time govern lithium intercalation into the graphite anodes. In this work, we use electrochemical impedance spectroscopy and atomic force microscopy to investigate the properties of a SEI film and an electrified "graphite/SEI/electrolyte interface". We reveal a multistage mechanism of lithium intercalation and de-intercalation in the case of graphite anodes covered by SEI. On the basis of this mechanism, we propose a relatively simple model, which perfectly explains the impedance response of the "graphite/SEI/electrolyte" interface at different temperatures and states of charge. From the whole data obtained in this work, it is suggested that not only Li + but also negatively charged species, such as anions from the electrolyte or functional groups of the SEI, likely interact with the surface of the graphite anode.

DNA mismatch-specific targeting and hypersensitivity of mismatch-repair-deficient cells to bulky rhodium(III) intercalators

PubMed Central

Hart, Jonathan R.; Glebov, Oleg; Ernst, Russell J.; Kirsch, Ilan R.; Barton, Jacqueline K.

2006-01-01

Mismatch repair (MMR) is critical to maintaining the integrity of the genome, and deficiencies in MMR are correlated with cancerous transformations. Bulky rhodium intercalators target DNA base mismatches with high specificity. Here we describe the application of bulky rhodium intercalators to inhibit cellular proliferation differentially in MMR-deficient cells compared with cells that are MMR-proficient. Preferential inhibition by the rhodium complexes associated with MMR deficiency is seen both in a human colon cancer cell line and in normal mouse fibroblast cells; the inhibition of cellular proliferation depends strictly on the MMR deficiency of the cell. Furthermore, our assay of cellular proliferation is found to correlate with DNA mismatch targeting by the bulky metallointercalators. It is the Δ-isomer that is active both in targeting base mismatches and in inhibiting DNA synthesis. Additionally, the rhodium intercalators promote strand cleavage at the mismatch site with photoactivation, and we observe that the cellular response is enhanced with photoactivation. Targeting DNA mismatches may therefore provide a cell-selective strategy for chemotherapeutic design. PMID:17030786

Organic or organometallic template mediated clay synthesis

DOEpatents

Gregar, K.C.; Winans, R.E.; Botto, R.E.

1994-05-03

A method is described for incorporating diverse varieties of intercalates or templates directly during hydrothermal synthesis of clays such as hectorite or montmorillonite-type layer-silicate clays. For a hectorite layer-silicate clay, refluxing a gel of silica sol, magnesium hydroxide sol and lithium fluoride for two days in the presence of an organic or organometallic intercalate or template results in crystalline products containing either (a) organic dye molecules such as ethyl violet and methyl green, (b) dye molecules such as alcian blue that are based on a Cu(II)-phthalocyannine complex, or (c) transition metal complexes such as Ru(II)phenanthroline and Co(III)sepulchrate or (d) water-soluble porphyrins and metalloporphyrins. Montmorillonite-type clays are made by the method taught by U.S. Pat. No. 3,887,454 issued to Hickson, Jun. 13, 1975; however, a variety of intercalates or templates may be introduced. The intercalates or templates should have (i) water-solubility, (ii) positive charge, and (iii) thermal stability under moderately basic (pH 9-10) aqueous reflux conditions or hydrothermal pressurized conditions for the montmorillonite-type clays. 22 figures.

Reversible Intercalation of Fluoride-Anion Receptor Complexes in Graphite

NASA Technical Reports Server (NTRS)

West, William C.; Whitacre, Jay F.; Leifer, Nicole; Greenbaum, Steve; Smart, Marshall; Bugga, Ratnakumar; Blanco, Mario; Narayanan, S. R.

2007-01-01

We have demonstrated a route to reversibly intercalate fluoride-anion receptor complexes in graphite via a nonaqueous electrochemical process. This approach may find application for a rechargeable lithium-fluoride dual-ion intercalating battery with high specific energy. The cell chemistry presented here uses graphite cathodes with LiF dissolved in a nonaqueous solvent through the aid of anion receptors. Cells have been demonstrated with reversible cathode specific capacity of approximately 80 mAh/g at discharge plateaus of upward of 4.8 V, with graphite staging of the intercalant observed via in situ synchrotron X-ray diffraction during charging. Electrochemical impedance spectroscopy and B-11 nuclear magnetic resonance studies suggest that cointercalation of the anion receptor with the fluoride occurs during charging, which likely limits the cathode specific capacity. The anion receptor type dictates the extent of graphite fluorination, and must be further optimized to realize high theoretical fluorination levels. To find these optimal anion receptors, we have designed an ab initio calculations-based scheme aimed at identifying receptors with favorable fluoride binding and release properties.

Regenerable Cu-intercalated MnO2 layered cathode for highly cyclable energy dense batteries

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

Yadav, Gautam G.; Gallaway, Joshua W.; Turney, Damon E.

2017-03-06

Manganese dioxide cathodes are inexpensive and have high theoretical capacity (based on two electrons) of 617 mAh g-1, making them attractive for low-cost, energy-dense batteries. They are used in non-rechargeable batteries with anodes like zinc. Only ~10% of the theoretical capacity is currently accessible in rechargeable alkaline systems. Attempts to access the full capacity using additives have been unsuccessful. We report a class of Bi-birnessite (a layered manganese oxide polymorph mixed with bismuth oxide (Bi2O3)) cathodes intercalated with Cu2+ that deliver near-full two-electron capacity reversibly for >6,000 cycles. The key to rechargeability lies in exploiting the redox potentials of Cumore » to reversibly intercalate into the Bi-birnessite-layered structure during its dissolution and precipitation process for stabilizing and enhancing its charge transfer characteristics. This process holds promise for other applications like catalysis and intercalation of metal ions into layered structures. A large prismatic rechargeable Zn-birnessite cell delivering ~140 Wh l-1 is shown.« less

Synthesis and characterization of Zn-Ti layered double hydroxide intercalated with cinnamic acid for cosmetic application

NASA Astrophysics Data System (ADS)

Li, Yong; Tang, Liping; Ma, Xinxu; Wang, Xinrui; Zhou, Wei; Bai, Dongsheng

2017-08-01

The use of sunscreen is recently growing and their efficacy and safety must be taken into account since they are applied on the skin frequently. In this work, an organic ultraviolet (UV) ray absorbent, cinnamic acid (CA) was intercalated into Zn-Ti layered double hydroxide (LDH) by anion-exchange reaction. ZnTi-CA-LDH, a new type of host-guest UV-blocking material has been synthesized. Detailed structural and surface morphology of ZnTi-CA-LDH were characterized by XRD, FT-IR, SEM and TEM. ZnTi-CA-LDH exhibits a superior UV blocking ability compared to pure CA and ZnTi-CO3-LDH. The thermal stability of the intercalated ZnTi-CA-LDH was investigated by TG-DTA, which showed that the thermostability of CA was markedly enhanced after intercalation into ZnTi-CO3-LDH. The EPR data showed greatly decreased photocatalytic activity compared to common inorganic UV blocking agents TiO2 and ZnO. Furthermore, the sample was formulated in a sunscreen cream to study the matrix protective effect towards UV rays.

Tests of spool models for DNA packaging in phage lambda.

PubMed

Widom, J; Baldwin, R L

1983-12-25

Experiments are reported which bear on two spool models proposed for packaging the DNA of phage lambda. Both spool models fill an assumed spherical cavity with DNA wrapped in cylindrical or quasi-cylindrical layers composed of adjacent circular turns. In the curved-spool model, a single continuous segment of DNA, about 20% of the DNA length and probably located near the left end of the DNA, is in contact with the coat protein of the phage capsid. In the straight spool model, there are several DNA segments in contact with the capsid; they are concentrated in one half (probably the left half) of lambda DNA. We have identified the loci on the DNA which are in contact with the capsid by chemical crosslinking, induced by ultraviolet-irradiation of phage containing 5-bromodeoxyuridine in place of thymine. In an electron microscope experiment, phage are first lysed with EDTA, and then spread in a cytochrome c film by the formamide method. The disrupted capsid, which has the appearance of a phage ghost, serves as a marker showing where the DNA is crosslinked to the coat. The left end of the DNA is not distinguished from the right end, and so the map of DNA-capsid contacts is folded over on itself. Contacts are found nearly randomly over the entire map. In a second experiment, DNA from lysed, crosslinked phage is cut either with EcoRI or HindIII restriction endonucleases and the cut restriction fragments are labeled at their ends with 32P. Density centrifugation in a CsCl gradient separates free DNA from restriction fragments crosslinked to protein. After digestion with proteinase k, the DNA fragments previously crosslinked to protein are identified by size after agarose gel electrophoresis. DNA fragments from all parts of the genome are found. These two experiments show that, if the DNA of each phage is packaged identically, then the curved-spool model is ruled out and the straight spool model is unlikely. Alternatively, the manner of packaging the DNA may vary from one phage to the next. These results agree with other recent experiments on lambda DNA packaging by Hall & Schellman (1982a,b), and by Haas et al. (1982). A different experiment is also reported. The psoralen derivative aminomethyltrioxalen (AMT) is allowed to intercalate into lambda phage and then the DNA strands are crosslinked by ultraviolet-irradiation after the rapid phase of AMT intercalation is complete. The DNA is subsequently denatured by glyoxal modification and spread for electron microscopy in a cytochrome c film by the formamide method.(ABSTRACT TRUNCATED AT 400 WORDS)

Synthesis, characterization, and controlled release antibacterial behavior of antibiotic intercalated Mg–Al layered double hydroxides

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

Wang, Yi; Zhang, Dun, E-mail: zhangdun@qdio.ac.cn

Graphical abstract: The antibiotic anion released from Mg–Al LDHs provides a controlled release antibacterial activity against the growth of Micrococcus lysodeikticus in 3.5% NaCl solution. Highlights: ► Antibiotic anion intercalated LDHs were synthesized and characterized. ► The ion-exchange one is responsible for the release process. ► The diffusion through particle is the release rate limiting step. ► LDHs loaded with antibiotic anion have high antibacterial capabilities. -- Abstract: Antibiotic–inorganic clay composites including four antibiotic anions, namely, benzoate (BZ), succinate (SU), benzylpenicillin (BP), and ticarcillin (TC) anions, intercalated Mg–Al layered double hydroxides (LDHs) were synthesized via ion-exchange. Powder X-ray diffraction andmore » Fourier transform infrared spectrum analyses showed the successful intercalation of antibiotic anion into the LDH interlayer. BZ and BP anions were accommodated in the interlayer region as a bilayer, whereas SU and TC anions were intercalated in a monolayer arrangement. Kinetic simulation of the release data indicated that ion-exchange was responsible for the release process, and the diffusion through the particles was the rate-limiting step. The antibacterial capabilities of LDHs loaded with antibiotic anion toward Micrococcus lysodeikticus growth were analyzed using a turbidimetric method. Significant high inhibition rate was observed when LDH nanohybrid was introduced in 3.5% NaCl solution. Therefore, this hybrid material may be applied as nanocontainer in active antifouling coating for marine equipment.« less

Atomic-scale recognition of surface structure and intercalation mechanism of Ti3C2X.

PubMed

Wang, Xuefeng; Shen, Xi; Gao, Yurui; Wang, Zhaoxiang; Yu, Richeng; Chen, Liquan

2015-02-25

MXenes represent a large family of functionalized two-dimensional (2D) transition-metal carbides and carbonitrides. However, most of the understanding on their unique structures and applications stops at the theoretical suggestion and lack of experimental support. Herein, the surface structure and intercalation chemistry of Ti3C2X are clarified at the atomic scale by aberration-corrected scanning transmission electron microscope (STEM) and density functional theory (DFT) calculations. The STEM studies show that the functional groups (e.g., OH(-), F(-), O(-)) and the intercalated sodium (Na) ions prefer to stay on the top sites of the centro-Ti atoms and the C atoms of the Ti3C2 monolayer, respectively. Double Na-atomic layers are found within the Ti3C2X interlayer upon extensive Na intercalation via two-phase transition and solid-solution reactions. In addition, aluminum (Al)-ion intercalation leads to horizontal sliding of the Ti3C2X monolayer. On the basis of these observations, the previous monolayer surface model of Ti3C2X is modified. DFT calculations using the new modeling help to understand more about their physical and chemical properties. These findings enrich the understanding of the MXenes and shed light on future material design and applications. Moreover, the Ti3C2X exhibits prominent rate performance and long-term cycling stability as an anode material for Na-ion batteries.

A ruthenium polypyridyl intercalator stalls DNA replication forks, radiosensitizes human cancer cells and is enhanced by Chk1 inhibition

NASA Astrophysics Data System (ADS)

Gill, Martin R.; Harun, Siti Norain; Halder, Swagata; Boghozian, Ramon A.; Ramadan, Kristijan; Ahmad, Haslina; Vallis, Katherine A.

2016-08-01

Ruthenium(II) polypyridyl complexes can intercalate DNA with high affinity and prevent cell proliferation; however, the direct impact of ruthenium-based intercalation on cellular DNA replication remains unknown. Here we show the multi-intercalator [Ru(dppz)2(PIP)]2+ (dppz = dipyridophenazine, PIP = 2-(phenyl)imidazo[4,5-f][1,10]phenanthroline) immediately stalls replication fork progression in HeLa human cervical cancer cells. In response to this replication blockade, the DNA damage response (DDR) cell signalling network is activated, with checkpoint kinase 1 (Chk1) activation indicating prolonged replication-associated DNA damage, and cell proliferation is inhibited by G1-S cell-cycle arrest. Co-incubation with a Chk1 inhibitor achieves synergistic apoptosis in cancer cells, with a significant increase in phospho(Ser139) histone H2AX (γ-H2AX) levels and foci indicating increased conversion of stalled replication forks to double-strand breaks (DSBs). Normal human epithelial cells remain unaffected by this concurrent treatment. Furthermore, pre-treatment of HeLa cells with [Ru(dppz)2(PIP)]2+ before external beam ionising radiation results in a supra-additive decrease in cell survival accompanied by increased γ-H2AX expression, indicating the compound functions as a radiosensitizer. Together, these results indicate ruthenium-based intercalation can block replication fork progression and demonstrate how these DNA-binding agents may be combined with DDR inhibitors or ionising radiation to achieve more efficient cancer cell killing.

Superconductivity in Li{sub 3}Ca{sub 2}C{sub 6} intercalated graphite

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

Emery, Nicolas; Herold, Claire; Mareche, Jean-Francois

2006-04-15

In this paper, we report the discovery of superconductivity in Li{sub 3}Ca{sub 2}C{sub 6}. Several graphite intercalation compounds (GICs) with electron donors, are well known as superconductors [T. Enoki, S. Masatsugu, E. Morinobu, Graphite Intercalation Compounds and Applications, Oxford University Press, Oxford, 2003]. It is probably not astonishing, since it is generally admitted that low dimensionality promotes high superconducting transition temperatures. Superconductivity is lacking in pristine graphite, but after charging the graphene planes by intercalation, its electronic properties change considerably and superconducting behaviour can appear. Li{sub 3}Ca{sub 2}C{sub 6} is a ternary GIC [S. Pruvost, C. Herold, A. Herold, P.more » Lagrange, Eur. J. Inorg. Chem. 8 (2004) 1661-1667], for which the intercalated sheets are very thick and poly layered (five lithium layers and two calcium ones). It contains a great amount of metal (five metallic atoms for six carbon ones). Its critical temperature of 11.15 K is very close to that of CaC{sub 6} GIC [T.E. Weller, M. Ellerby, S.S. Saxena, R.P. Smith, N.T. Skipper, Nat. Phys. 1 (2005) 39-41; N. Emery, C. Herold, M. d'Astuto, V. Garcia, Ch. Bellin, J.F. Mareche, P. Lagrange, G. Loupias, Phys. Rev. Lett. 95 (2005) 087003] (11.5 K). Both CaC{sub 6} and Li{sub 3}Ca{sub 2}C{sub 6} GICs possess currently the highest transition temperatures among all the GICs.« less

Eph regulates dorsoventral asymmetry of the notochord plate and convergent extension-mediated notochord formation.

PubMed

Oda-Ishii, Izumi; Ishii, Yasuo; Mikawa, Takashi

2010-10-29

The notochord is a signaling center required for the patterning of the vertebrate embryonic midline, however, the molecular and cellular mechanisms involved in the formation of this essential embryonic tissue remain unclear. The urochordate Ciona intestinalis develops a simple notochord from 40 specific postmitotic mesodermal cells. The precursors intercalate mediolaterally and establish a single array of disk-shaped notochord cells along the midline. However, the role that notochord precursor polarization, particularly along the dorsoventral axis, plays in this morphogenetic process remains poorly understood. Here we show that the notochord preferentially accumulates an apical cell polarity marker, aPKC, ventrally and a basement membrane marker, laminin, dorsally. This asymmetric accumulation of apicobasal cell polarity markers along the embryonic dorsoventral axis was sustained in notochord precursors during convergence and extension. Further, of several members of the Eph gene family implicated in cellular and tissue morphogenesis, only Ci-Eph4 was predominantly expressed in the notochord throughout cell intercalation. Introduction of a dominant-negative Ci-Eph4 to notochord precursors diminished asymmetric accumulation of apicobasal cell polarity markers, leading to defective intercalation. In contrast, misexpression of a dominant-negative mutant of a planar cell polarity gene Dishevelled preserved asymmetric accumulation of aPKC and laminin in notochord precursors, although their intercalation was incomplete. Our data support a model in which in ascidian embryos Eph-dependent dorsoventral polarity of notochord precursors plays a crucial role in mediolateral cell intercalation and is required for proper notochord morphogenesis.

A ruthenium polypyridyl intercalator stalls DNA replication forks, radiosensitizes human cancer cells and is enhanced by Chk1 inhibition.

PubMed

Gill, Martin R; Harun, Siti Norain; Halder, Swagata; Boghozian, Ramon A; Ramadan, Kristijan; Ahmad, Haslina; Vallis, Katherine A

2016-08-25

Ruthenium(II) polypyridyl complexes can intercalate DNA with high affinity and prevent cell proliferation; however, the direct impact of ruthenium-based intercalation on cellular DNA replication remains unknown. Here we show the multi-intercalator [Ru(dppz)2(PIP)](2+) (dppz = dipyridophenazine, PIP = 2-(phenyl)imidazo[4,5-f][1,10]phenanthroline) immediately stalls replication fork progression in HeLa human cervical cancer cells. In response to this replication blockade, the DNA damage response (DDR) cell signalling network is activated, with checkpoint kinase 1 (Chk1) activation indicating prolonged replication-associated DNA damage, and cell proliferation is inhibited by G1-S cell-cycle arrest. Co-incubation with a Chk1 inhibitor achieves synergistic apoptosis in cancer cells, with a significant increase in phospho(Ser139) histone H2AX (γ-H2AX) levels and foci indicating increased conversion of stalled replication forks to double-strand breaks (DSBs). Normal human epithelial cells remain unaffected by this concurrent treatment. Furthermore, pre-treatment of HeLa cells with [Ru(dppz)2(PIP)](2+) before external beam ionising radiation results in a supra-additive decrease in cell survival accompanied by increased γ-H2AX expression, indicating the compound functions as a radiosensitizer. Together, these results indicate ruthenium-based intercalation can block replication fork progression and demonstrate how these DNA-binding agents may be combined with DDR inhibitors or ionising radiation to achieve more efficient cancer cell killing.

First-principles investigation of aluminum intercalation and diffusion in TiO2 materials: Anatase versus rutile

NASA Astrophysics Data System (ADS)

Tang, Weiqiang; Xuan, Jin; Wang, Huizhi; Zhao, Shuangliang; Liu, Honglai

2018-04-01

Aluminum-ion batteries, emerging as a promising post-lithium battery solution, have been a subject of increasing research interest. Yet, most existing aluminum-ion research has focused on electrode materials development and synthesis. There has been a lack of fundamental understanding of the electrode processes and thus theoretical guidelines for electrode materials selection and design. In this study, by using density functional theory, we for the first time report a first-principles investigation on the thermodynamic and kinetic properties of aluminum intercalation into two common TiO2 polymorphs, i.e., anatase and rutile. After examining the aluminum intercalation sites, intercalation voltages, storage capacities and aluminum diffusion paths in both cases, we demonstrate that the stable aluminum intercalation site locates at the center of the O6 octahedral for TiO2 rutile and off center for TiO2 anatase. The maximum achievable Al/Ti ratios for rutile and anatase are 0.34375 and 0.36111, respectively. Although rutile is found to have an aluminum storage capacity slightly higher than anatase, the theoretical specific energy of rutile can reach 20.90 Wh kg-1, nearly twice as high as anatase (9.84 Wh kg-1). Moreover, the diffusion coefficient of aluminum ions in rutile is 10-9 cm2 s-1, significantly higher than that in anatase (10-20 cm2 s-1). In this regard, TiO2 rutile appears to be a better candidate than anatase as an electrode material for aluminum-ion batteries.

Pemetrexed-carboplatin with intercalated icotinib in the treatment of patient with advanced EGFR wild-type lung adenocarcinoma: A case report.

PubMed

Xu, Tongpeng; Wu, Hao; Jin, Shidai; Min, Huang; Zhang, Zhihong; Shu, Yongqian; Wen, Wei; Guo, Renhua

2017-08-01

Tyrosine kinase inhibitors (TKIs) are known to have greater efficacy in epidermal growth factor receptor (EGFR) mutation nonsmall cell lung cancer (NSCLC). However, about 10% of EGFR wild-type (wt) patients respond to TKIs. Several strategies to increase the efficacy of TKIs in wt NSCLC are the subjects of ongoing investigations. One of them is combining EGFR TKI with intercalated chemotherapy. We describe a patient with EGFR wt NSCLC, who was found with ovarian and lung metastasis, was treated with pemetrexed and intercalated icotinib. In this case, we reported the successful long-term maintenance treatment of a patient with EGFR wt NSCLC with pemetrexed and Icotinib. The patient (40-year-old female) was found with ovarian masses and lung masses. Pathological, immunohistochemical, and amplification refractory mutation system (ARMS) assay examinations of ovarian specimen suggested the expression of metastatic lung adenocarcinoma with wt EGFR. After failure treatment with paclitaxel-carboplatin, the patient received 4 cycles of pemetrexed plus platinum with intercalated icotinib and then remained on pemetrexed and icotinib. A partial response was achieved after the treatment. The patient's condition had remained stable on pemetrexed and icotinib for more than 20 months, with no evidence of progression. To our knowledge, this is the first report using the long-term maintenance treatment with pemetrexed and intercalated icotinib in EGFR wt patient. The therapeutic strategies warrant further exploration in selected populations of NSCLC.

Pemetrexed-carboplatin with intercalated icotinib in the treatment of patient with advanced EGFR wild-type lung adenocarcinoma

PubMed Central

Xu, Tongpeng; Wu, Hao; Jin, Shidai; Min, Huang; Zhang, Zhihong; Shu, Yongqian; Wen, Wei; Guo, Renhua

2017-01-01

Abstract Rationale: Tyrosine kinase inhibitors (TKIs) are known to have greater efficacy in epidermal growth factor receptor (EGFR) mutation nonsmall cell lung cancer (NSCLC). However, about 10% of EGFR wild-type (wt) patients respond to TKIs. Patient concerns: Several strategies to increase the efficacy of TKIs in wt NSCLC are the subjects of ongoing investigations. One of them is combining EGFR TKI with intercalated chemotherapy. Diagnoses: We describe a patient with EGFR wt NSCLC, who was found with ovarian and lung metastasis, was treated with pemetrexed and intercalated icotinib. Interventions: In this case, we reported the successful long-term maintenance treatment of a patient with EGFR wt NSCLC with pemetrexed and Icotinib. The patient (40-year-old female) was found with ovarian masses and lung masses. Pathological, immunohistochemical, and amplification refractory mutation system (ARMS) assay examinations of ovarian specimen suggested the expression of metastatic lung adenocarcinoma with wt EGFR. After failure treatment with paclitaxel-carboplatin, the patient received 4 cycles of pemetrexed plus platinum with intercalated icotinib and then remained on pemetrexed and icotinib. Outcomes: A partial response was achieved after the treatment. The patient's condition had remained stable on pemetrexed and icotinib for more than 20 months, with no evidence of progression. Lessons: To our knowledge, this is the first report using the long-term maintenance treatment with pemetrexed and intercalated icotinib in EGFR wt patient. The therapeutic strategies warrant further exploration in selected populations of NSCLC. PMID:28816950

Paul Trap Simulator Experiment (PTSX) to simulate intense beam propagation through a periodic focusing quadrupole field

NASA Astrophysics Data System (ADS)

Davidson, Ronald C.; Efthimion, Philip C.; Gilson, Erik; Majeski, Richard; Qin, Hong

2002-01-01

The Paul Trap Simulator Experiment (PTSX) is under construction at the Princeton Plasma Physics Laboratory to simulate intense beam propagation through a periodic quadrupole magnetic field. In the Paul trap configuration, a long nonneutral plasma column is confined axially by dc voltages on end cylinders at z=+L and z=-L, and transverse confinement is provided by segmented cylindrical electrodes with applied oscillatory voltages ±V0(t) over 90° segments. Because the transverse focusing force is similar in waveform to that produced by a discrete set of periodic quadrupole magnets in a frame moving with the beam, the Paul trap configuration offers the possibility of simulating intense beam propagation in a compact laboratory facility. The experimental layout is described, together with the planned experiments to study beam mismatch, envelope instabilities, halo particle production, and collective wave excitations.

Intercalation compounds and electrodes for batteries

DOEpatents

Chiang, Yet-Ming; Sadoway, Donald R.; Jang, Young-Il; Huang, Biyan

2004-09-07

This invention concerns intercalation compounds and in particular lithium intercalation compounds which have improved properties for use in batteries. Compositions of the invention include particulate metal oxide material having particles of multicomponent metal oxide, each including an oxide core of at least first and second metals in a first ratio, and each including a surface coating of metal oxide or hydroxide that does not include the first and second metals in the first ratio formed by segregation of at least one of the first and second metals from the core. The core may preferably comprise Li.sub.x M.sub.y N.sub.z O.sub.2 wherein M and N are metal atom or main group elements, x, y and z are numbers from about 0 to about 1 and y and z are such that a formal charge on M.sub.y N.sub.z portion of the compound is (4-x), and having a charging voltage of at least about 2.5V. The invention may also be characterized as a multicomponent oxide microstructure usable as a lithium intercalation material including a multiphase oxide core and a surface layer of one material, which is a component of the multiphase oxide core, that protects the underlying intercalation material from chemical dissolution or reaction. In a particular preferred example the multicomponent oxide may be an aluminum-doped lithium manganese oxide composition. Such aluminum-doped lithium manganese oxide compositions, having an orthorhombic structure, also form a part of the invention. In addition, the invention includes articles, particularly electrodes, for batteries formed from the compositions of the invention, and batteries including such electrodes. The invention further relates to a composite intercalation material comprising at least two compounds in which at least one compound has an orthorhombic structure Li.sub.x Al.sub.y Mn.sub.1-y O.sub.2, where y is nonzero, or a mixture of orthorhombic and monoclinic Li.sub.x Al.sub.y Mn.sub.1-y O.sub.2.

Selective sodium intercalation into sodium nickel-manganese sulfate for dual Na-Li-ion batteries.

PubMed

Marinova, Delyana M; Kukeva, Rosica R; Zhecheva, Ekaterina N; Stoyanova, Radostina K

2018-05-09

Double sodium transition metal sulfates combine in themselves unique intercalation properties with eco-compatible compositions - a specific feature that makes them attractive electrode materials for lithium and sodium ion batteries. Herein, we examine the intercalation properties of novel double sodium nickel-manganese sulfate, Na2Ni1/2Mn1/2(SO4)2, having a large monoclinic unit cell, through electrochemical and ex situ diffraction and spectroscopic methods. The sulfate salt Na2Ni1/2Mn1/2(SO4)2 is prepared by thermal dehydration of the corresponding hydrate salt Na2Ni1/2Mn1/2(SO4)2·4H2O having a blödite structure. The intercalation reactions on Na2Ni1-xMnx(SO4)2 are studied in two model cells: half-ion cell versus Li metal anode and full-ion cell versus Li4Ti5O12 anode by using lithium (LiPF6 dissolved in EC/DMC) and sodium electrolytes (NaPF6 dissolved in EC:DEC). Based on ex situ XRD and TEM analysis, it is found that sodium intercalation into Na2Ni1/2Mn1/2(SO4)2 takes place via phase separation into the Ni-rich monoclinic phase and Mn-rich alluaudite phase. The redox reactions involving participation of manganese and titanium ions are monitored by ex situ EPR spectroscopy. It has been demonstrated that manganese ions from the sulfate salt are participating in the electrochemical reaction, while the nickel ions remain intact. As a result, a reversible capacity of about 65 mA h g-1 is reached. The selective intercalation properties determine sodium nickel-manganese sulfate as a new electrode material for hybrid lithium-sodium ion batteries that is thought to combine the advantages of individual lithium and sodium batteries.

Composition driven monolayer to bilayer transformation in a surfactant intercalated Mg-Al layered double hydroxide.

PubMed

Naik, Vikrant V; Chalasani, Rajesh; Vasudevan, S

2011-03-15

The structure and organization of dodecyl sulfate (DDS) surfactant chains intercalated in an Mg-Al layered double hydroxide (LDH), Mg(1-x)Alx(OH)2, with differing Al/Mg ratios has been investigated. The Mg-Al LDHs can be prepared over a range of compositions with x varying from 0.167 to 0.37 and therefore provides a simple system to study how the organization of the alkyl chains of the intercalated DDS anions change with packing density; the Al/Mg ratio or x providing a convenient handle to do so. Powder X-ray diffraction measurements showed that at high packing densities (x ≥ 0.3) the alkyl chains of the intercalated dodecyl sulfate ions are anchored on opposing LDH sheets and arranged as bilayers with an interlayer spacing of ∼27 Å. At lower packing densities (x < 0.2) the surfactant chains form a monolayer with the alkyl chains oriented flat in the galleries with an interlayer spacing of ∼8 Å. For the in between compositions, 0.2 ≤ x < 0.3, the material is biphasic. MD simulations were performed to understand how the anchoring density of the intercalated surfactant chains in the Mg-Al LDH-DDS affects the organization of the chains and the interlayer spacing. The simulations are able to reproduce the composition driven monolayer to bilayer transformation in the arrangement of the intercalated surfactant chains and in addition provide insights into the factors that decide the arrangement of the surfactant chains in the two situations. In the bilayer arrangement, it is the dispersive van der Waals interactions between chains in opposing layers of the anchored bilayer that is responsible for the cohesive energy of the solid whereas at lower packing densities, where a monolayer arrangement is favored, Coulomb interactions between the positively charged Mg-Al LDH sheets and the negatively charged headgroup of the DDS anion dominate.

In Situ Multilength-Scale Tracking of Dimensional and Viscoelastic Changes in Composite Battery Electrodes.

PubMed

Dargel, Vadim; Jäckel, Nicolas; Shpigel, Netanel; Sigalov, Sergey; Levi, Mikhael D; Daikhin, Leonid; Presser, Volker; Aurbach, Doron

2017-08-23

Intercalation-induced dimensional changes in a composite battery electrode (comprising a polymeric binder) are one of the major factors limiting electrode cycling performance. Since electrode performance is expressed by the quantities averaged over its entire surface area (e.g., capacity retention, Faradaic efficiency, rate capability), significant efforts have been made to develop a methodology allowing its facile mechanical diagnostics at the same areal scale. Herein we introduce such a generic methodology for a highly sensitive in situ monitoring of intrinsic mechanical properties of composite battery electrodes. The gravimetric, dimensional, viscoelastic, and adhesive changes in the composite electrodes caused by Li-ions intercalation are assessed noninvasively and in real time by electrochemical quartz-crystal microbalance with dissipation monitoring (EQCM-D). Multiharmonic acoustic waves generated by EQCM-D penetrate into thin porous electrodes comprising either rigid or a soft binder resulting in frequency and dissipation changes quantified by analytical acoustic load impedance models. As a first demonstration, we used a composite LiFePO 4 (LFP) electrode containing either polyvinylidene dichloride (PVdF) or Na carboximethyl cellulose (NaCMC) as rigid and viscoelastic binders, respectively, in aqueous electrolytes. The intercalation-induced volume changes of LFP electrode were evaluated from a hydrodynamic correction to the mass effect of the intercalated ions for PVdF, and both components of the effective complex shear modulus (i.e., storage and loss moduli) in case of NaCMC binder have been extracted. The sliding friction coefficients for large particles bound at their bottom to the quartz crystal surface (a measure of the adhesion strength of binders) has also been evaluated. Tracking the mechanical properties of the composite electrodes in different environments and charging/cycling conditions in a self-consistent manner provides all necessary conditions for an optimal selection of the polymeric binders resistant to intercalation-induced volume changes of intercalation particles.

Distribution of cardiac sodium channels in clusters potentiates ephaptic interactions in the intercalated disc.

PubMed

Hichri, Echrak; Abriel, Hugues; Kucera, Jan P

2018-02-15

It has been proposed that ephaptic conduction, relying on interactions between the sodium (Na + ) current and the extracellular potential in intercalated discs, might contribute to cardiac conduction when gap junctional coupling is reduced, but this mechanism is still controversial. In intercalated discs, Na + channels form clusters near gap junction plaques, but the functional significance of these clusters has never been evaluated. In HEK cells expressing cardiac Na + channels, we show that restricting the extracellular space modulates the Na + current, as predicted by corresponding simulations accounting for ephaptic effects. In a high-resolution model of the intercalated disc, clusters of Na + channels that face each other across the intercellular cleft facilitate ephaptic impulse transmission when gap junctional coupling is reduced. Thus, our simulations reveal a functional role for the clustering of Na + channels in intercalated discs, and suggest that rearrangement of these clusters in disease may influence cardiac conduction. It has been proposed that ephaptic interactions in intercalated discs, mediated by extracellular potentials, contribute to cardiac impulse propagation when gap junctional coupling is reduced. However, experiments demonstrating ephaptic effects on the cardiac Na + current (I Na ) are scarce. Furthermore, Na + channels form clusters around gap junction plaques, but the electrophysiological significance of these clusters has never been investigated. In patch clamp experiments with HEK cells stably expressing human Na v 1.5 channels, we examined how restricting the extracellular space modulates I Na elicited by an activation protocol. In parallel, we developed a high-resolution computer model of the intercalated disc to investigate how the distribution of Na + channels influences ephaptic interactions. Approaching the HEK cells to a non-conducting obstacle always increased peak I Na at step potentials near the threshold of I Na activation and decreased peak I Na at step potentials far above threshold (7 cells, P = 0.0156, Wilcoxon signed rank test). These effects were consistent with corresponding control simulations with a uniform Na + channel distribution. In the intercalated disc computer model, redistributing the Na + channels into a central cluster of the disc potentiated ephaptic effects. Moreover, ephaptic impulse transmission from one cell to another was facilitated by clusters of Na + channels facing each other across the intercellular cleft when gap junctional coupling was reduced. In conclusion, our proof-of-principle experiments demonstrate that confining the extracellular space modulates cardiac I Na , and our simulations reveal the functional role of the aggregation of Na + channels in the perinexus. These findings highlight novel concepts in the physiology of cardiac excitation. © 2017 The Authors. The Journal of Physiology © 2017 The Physiological Society.

Sequence and onset of whole-body coordination when turning in response to a visual trigger: comparing people with Parkinson's disease and healthy adults.

PubMed

Ashburn, A; Kampshoff, C; Burnett, M; Stack, E; Pickering, R M; Verheyden, G

2014-01-01

Turning round is a routine everyday activity that can often lead to instability. The purpose of this study was to investigate abnormalities of turning among people with Parkinson's disease (PwPD) through the measurement of sequence of body segments and latency response. Participants were asked to turn 180° and whole-body movements were recorded using CODAmotion and Visio Fast eye tracking equipment. Thirty-one independently mobile PwPD and 15 age-matched healthy controls participated in the study. We found that contrary to common belief, the head preceded movement of all other body segments (eyes, shoulders, pelvis, first and second foot). We also found interaction between group and body segment (P=0.005), indicating that overall, PwPD took longer to move from head to second foot than age-matched healthy controls. For PwPD only, interactions were found between disease severity and body segment (P<0.0001), between age group and body segment (P<0.0001) and between gender and body segments (P<0.0001). For each interaction, longer time periods were noted between moving the first foot after the pelvis, and moving the second foot after the first, and this was noted for PwPD in Hoehn and Yahr stage III-IV (in comparison to Hoehn and Yahr stage I-II); for PwPD who were under 70 years (in comparison with 70 years or over); and for ladies (in comparison with men). Our results indicate that in PwPD and healthy elderly, turning-on-the-spot might not follow the top-to-bottom approach we know from previous research. Copyright © 2013. Published by Elsevier B.V.

Volcanic/Tectonic Characteristics of First and Second Order Segments and Ridge Discontinuities `Under the Hot-spot Influence' - TOBI Imagery from the Central Indian Ridge (CIR) Adjacent to the Rodriguez System.

NASA Astrophysics Data System (ADS)

Parson, L.; Murton, B.; Sauter, D.; Curewitz, D.; Okino, K.; German, C.; Leven, J.

2001-12-01

Deeptow sidescan sonar data (TOBI, 30kHz) acquired over more than 200 km of the Central Indian Ridge during RRS Charles Darwin cruise CD127 reveal an abundance of neovolcanic activity throughout both spreading segments and ridge non-transform discontinuities alike. Imagery of the previously unsurveyed northern section of the CIR immediately south of the Marie Celeste Fracture Zone confirms the presence of a shallow, magmatically inflated second order segment that is only recently rifted, with a rift floor surfaced throughout by virtually untectonised planar sheet flow units. First and second order segments exhibit a significant component of sheeted extrusives, ponded or in lake form, abutting or overstepped by hummocky and mounded pillow constructs. Non-transform discontinuities are commonly cut by fresh axial volcanic ridges oblique to both axial trend and offset. The depths of segment centers range from 2600m to more than 3700m, and segment forms include robust, hour-glass and rifted/starved end-members - but their overall extrusive pattern is strikingly invariant. Fracture Zone offsets of up to 65 kilometres are tectonically dominated, but their intersections with the axis are often mantled by multiple sheet flows rather than the relatively low proportions of sediment cover. The largest offsets are marked by outcrops of multiple, subparallel displacement surfaces, actively eroding transverse ridges, and ridge transform intersections with classic propagation/recession fabrics - each suggesting some instability in regional plate kinematics. While it is tempting to speculate that the Rodrigues hotspot appears to have a regional effect, enhancing magmatic delivery to the adjacent ridge and offset system, the apparent breadth of influence from what is assumed to be a rather feeble mantle anomaly is problematic.

[Surgical treatment of craniocervical instability. Review paper].

PubMed

Alpizar-Aguirre, Armando; Lara Cano, Jorge Giovanni; Rosales, Luis; Míramontes, Victor; Reyes-Sánchez, Alejandro Antonio

2007-01-01

The concept of spinal instability is still controversial. Anatomical, biomechanical, clinical and radiographic variants are involved and make the definition complicated. There are solid diagnostic bases in cases of fractures and degenerative disorders; however, pure spinal instability is still under study. The latter may be defined as increased mobility that goes beyond the physiological limits of one vertebra over another in at least one of the three spinal planes of motion. In the case of the craniocervical region, its understanding becomes even more challenging, since its anatomy and physiology are more complex and it is more mobile. Surgical treatment is possible with either an anterior or a posterior approach. Best results are obtained with occipitocervical or atlantoaxial stabilization through a posterior approach, since the anterior one has its limitations. For example, a transoral approach with a bone graft provides compression strength but does not enable immediate appropriate fixation and involves the risk of infection. The choice of the surgical approach must consider the patient's medical status, the specific spine levels involved, the extent of neurological compromise, the X-ray abnormalities and the individual pathology. The goals of surgery are achieved through an appropriate anatomical alignment, assuring the protection of the neural elements and achieving proper spine stabilization with as much preservation of the mobile vertebral segments as possible.

Highly Reversible Zinc-ion Intercalation with Chevrel Phase Mo6S8 Nanocubes and Applications for Advanced Zinc-ion Batteries

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

Cheng, Yingwen; Luo, Langli; Zhong, Li

We demonstrate the application of the Chevrel phase Mo6S8 nanocubes as the anode material for rechargeable Zn-ion batteries. Mo6S8 can host Zn2+ ions reversibility both in aqueous and nonaqueous electrolytes with specific capacities around 90 mAh/g and exhibited remarkable intercalation kinetics as well as stability. Furthermore, we assembled full cells by integrating Mo6S8 anode with zinc-polyiodide (I-/I3-) based catholytes, and demonstrated that such fuel cells was also able to deliver outstanding rate performance and cyclic stability. This first demonstration of zinc intercalating anode could inspire the design of advanced Zn ion batteries.

Synthesis and characterization of intercalated polyaniline-clay nanocomposite using supercritical CO2

NASA Astrophysics Data System (ADS)

Abdelraheem, A.; El-Shazly, A. H.; Elkady, M. F.

2018-05-01

Lately, supercritical CO2 (SCCO2) have been getting great interest. It can be used in numerous applications because it is environmentally friendly, safe, comparatively low cost, and nonflammable. One of its applications is being a solvent in the synthesis of polymeric-clay nanocomposite. In this paper, intercalated polyaniline-clay nanocomposite (PANC) was prepared using SCCO2. The intercalation structure of polyaniline chains between clay layers was verified by various characterization techniques. Scanning electron microscope and transmission electron microscope (SEM-TEM) were used to show the morphology of the synthesized nanocomposite. The molecular structure of PANC nanocomposite was confirmed using Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The BET surface area and the conductivity of the nanocomposite were determined.

Pulsed laser deposition of functionalized Mg-Al layered double hydroxide thin films

NASA Astrophysics Data System (ADS)

Vlad, A.; Birjega, R.; Tirca, I.; Matei, A.; Mardare, C. C.; Hassel, A. W.; Nedelcea, A.; Dinescu, M.; Zavoianu, R.

2018-02-01

In this paper, magnesium-aluminium layered double hydroxide (LDH) has been functionalized with sodium dodecyl sulfate (DS) and deposited as thin film by pulsed laser deposition (PLD). Mg, Al-LDH powders were prepared by co-precipitation and used as reference material. Intercalation of DS as an anionic surfactant into the LDHs host layers has been prepared in two ways: co-precipitation (P) and reconstruction (R). DS intercalation occurred in LDH powder via both preparation methods. The films deposited via PLD, in particular at 532 and 1064 nm, preserve the organic intercalated layered structure of the targets prepared from these powders. The results reveal the ability of proposed deposition technique to produce functional composite organo-modified LDHs thin films.

Intercalated graphite fiber composites as EMI shields in aerospace structures

NASA Technical Reports Server (NTRS)

Gaier, James R.

1990-01-01

The requirements for electromagnetic interference (EMI) shielding in aerospace structures are complicated over that of ground structures by their weight limitations. As a result, the best EMI shielding materials must blend low density, high strength, and high elastic modulus with high shielding ability. In addition, fabrication considerations including penetrations and joints play a major role. The EMI shielding properties are calculated for shields formed from pristine and intercalated graphite fiber/epoxy composites and compared to preliminary experimental results and to shields made from aluminum. Calculations indicate that EMI shields could be fabricated from intercalated graphite composites which would have less than 12 percent of the mass of conventional aluminum shields, based on mechanical properties and shielding properties alone.

Defect-mediated, thermally-activated encapsulation of metals at the surface of graphite

DOE PAGES

Zhou, Yinghui; Lii-Rosales, Ann; Kim, Minsung; ...

2017-11-04

Here, we show that 3 metals – Dy, Ru, and Cu – can form multilayer intercalated (encapsulated) islands at the graphite (0001) surface if 2 specific conditions are met: Defects are introduced on the graphite terraces to act as entry portals, and the metal deposition temperature is well above ambient. Focusing on Dy as a prototype, we show that surface encapsulation is much different than bulk intercalation, because the encapsulated metal takes the form of bulk-like rafts of multilayer Dy, rather than the dilute, single-layer structure known for the bulk compound. Carbon-covered metallic rafts even form for relatively unreactive metalsmore » (Ru and Cu) which have no known bulk intercalation compound.« less

Intercalation and controlled release of 2,4-dichlorophenoxyacetic acid using rhombohedral [LiAl2(OH)6]Cl·xH2O

NASA Astrophysics Data System (ADS)

Ragavan, Anusha; Khan, Aamir I.; O'Hare, Dermot

2006-05-01

2,4-Dichlorophenoxyacetic acid (2,4-D) has been fully intercalated into the rhombohedral polymorph of [LiAl2(OH)6]Cl·xH2O ([rhom-Li Al] LDH) by an ion exchange method. The controlled release of 2,4-D from the interlamellar spaces of [rhom-Li Al] LDH has been studied in a phosphate buffer, natural rainwater and deionised water. In buffer solution and rainwater, the intercalated herbicide is exchanged for anions in solution. In contrast, in deionised water the herbicide is released as part of the Li+/herbicide ion pair, leading to the formation of Al(OH)3 and the solvated ions.

Dynamic stability of maglev systems

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

Cai, Y.; Chen, S.S.; Mulcahy, T.M.

1992-04-01

Because dynamic instability is not acceptable for any commercial maglev systems, it is important to consider this phenomenon in the development of all maglev systems. This study considers the stability of maglev systems based on experimental data, scoping calculations, and simple mathematical models. Divergence and flutter are obtained for coupled vibration of a three-degree-of-freedom maglev vehicle on a guideway consisting of double L-shaped aluminum segments attached to a rotating wheel. The theory and analysis developed in this study identifies basic stability characteristics and future research needs of maglev systems.

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.

Early clinical effects of the Dynesys system plus transfacet decompression through the Wiltse approach for the treatment of lumbar degenerative diseases

PubMed Central

Liu, Chao; Wang, Lei; Tian, Ji-wei

2014-01-01

Background This study investigated early clinical effects of Dynesys system plus transfacet decompression through the Wiltse approach in treating lumbar degenerative diseases. Material/Methods 37 patients with lumbar degenerative disease were treated with the Dynesys system plus transfacet decompression through the Wiltse approach. Results Results showed that all patients healed from surgery without severe complications. The average follow-up time was 20 months (9–36 months). Visual Analogue Scale and Oswestry Disability Index scores decreased significantly after surgery and at the final follow-up. There was a significant difference in the height of the intervertebral space and intervertebral range of motion (ROM) at the stabilized segment, but no significant changes were seen at the adjacent segments. X-ray scans showed no instability, internal fixation loosening, breakage, or distortion in the follow-up. Conclusions The Dynesys system plus transfacet decompression through the Wiltse approach is a therapeutic option for mild lumbar degenerative disease. This method can retain the structure of the lumbar posterior complex and the motion of the fixed segment, reduce the incidence of low back pain, and decompress the nerve root. PMID:24859831

Transition Analysis for the HIFiRE-5 Vehicle

NASA Technical Reports Server (NTRS)

Choudhari, Meelan M.; Chang, Chau-Lyan; Li, Fei; Berger, Karen T.; Candler, Graham V.; Kimmel, Roger

2009-01-01

The Hypersonic International Flight Research and Experimentation (HIFiRE) 5 flight experiment by Air Force Research Laboratories and Australian Defense Science and Technology Organization is designed to provide in-flight boundary-layer transition data for a canonical 3D configuration at hypersonic Mach numbers. This paper outlines the progress, to date, on boundary layer stability analysis for the HIFiRE-5 flight configuration, as well as for selected test conditions from the wind tunnel experiments supporting the flight test. At flow conditions corresponding to the end of the test window, rather large values of linear amplification factor are predicted for both second mode (N>40) and crossflow (N>20) instabilities, strongly supporting the feasibility of first in-flight measurements of natural transition on a fully three-dimensional hypersonic configuration. Additional results highlight the rich mixture of instability mechanisms relevant to a large segment of the flight trajectory, as well as the effects of angle of attack and yaw angle on the predicted transition fronts for ground facility experiments at Mach 6.

A micromachined device describing over a hundred orders of parametric resonance

NASA Astrophysics Data System (ADS)

Jia, Yu; Du, Sijun; Arroyo, Emmanuelle; Seshia, Ashwin A.

2018-04-01

Parametric resonance in mechanical oscillators can onset from the periodic modulation of at least one of the system parameters, and the behaviour of the principal (1st order) parametric resonance has long been well established. However, the theoretically predicted higher orders of parametric resonance, in excess of the first few orders, have mostly been experimentally elusive due to the fast diminishing instability intervals. A recent paper experimentally reported up to 28 orders in a micromachined membrane oscillator. This paper reports the design and characterisation of a micromachined membrane oscillator with a segmented proof mass topology, in an attempt to amplify the inherent nonlinearities within the membrane layer. The resultant oscillator device exhibited up to over a hundred orders of parametric resonance, thus experimentally validating these ultra-high orders as well as overlapping instability transitions between these higher orders. This research introduces design possibilities for the transducer and dynamic communities, by exploiting the behaviour of these previously elusive higher order resonant regimes.

Noble-metal intercalation process leading to a protected adatom in a graphene hollow site

NASA Astrophysics Data System (ADS)

Narayanan Nair, M.; Cranney, M.; Jiang, T.; Hajjar-Garreau, S.; Aubel, D.; Vonau, F.; Florentin, A.; Denys, E.; Bocquet, M.-L.; Simon, L.

2016-08-01

In previous studies, we have shown that gold deposited on a monolayer (ML) of graphene on SiC(0001) is intercalated below the ML after an annealing procedure and affects the band structure of graphene. Here we prove experimentally and theoretically that some of the gold forms a dispersed phase composed of single adatoms, being intercalated between the ML and the buffer layer and in a hollow position with respect to C atoms of the ML on top. They are freestanding and negatively charged, due to the partial screening of the electron transfer between SiC and the ML, without changing the intrinsic n-type doping of the ML. As these single atoms decouple the ML from the buffer layer, the quasiparticles of graphene are less perturbed, thus increasing their Fermi velocity. Moreover, the hollow position of the intercalated single Au atoms might lead to spin-orbit coupling in the graphene layer covering IC domains. This effect of spin-orbit coupling has been recently observed experimentally in Au-intercalated graphene on SiC(0001) [D. Marchenko, A. Varykhalov, J. Sánchez-Barriga, Th. Seyller, and O. Rader, Appl. Phys. Lett. 108, 172405 (2016), 10.1063/1.4947286] and has been theoretically predicted for heavy atoms, like thallium, in a hollow position on graphene [C. Weeks, J. Hu, J. Alicea, M. Franz, and R. Wu, Phys. Rev. X 1, 021001 (2011), 10.1103/PhysRevX.1.021001; A. Cresti, D. V. Tuan, D. Soriano, A. W. Cummings, and S. Roche, Phys. Rev. Lett. 113, 246603 (2014), 10.1103/PhysRevLett.113.246603].

Interaction of curcumin with 1,2-dioctadecanoyl-sn-glycero-3-phosphocholine liposomes: Intercalation of rhamnolipids enhances membrane fluidity, permeability and stability of drug molecule.

PubMed

Moussa, Zeinab; Chebl, Mazhar; Patra, Digambara

2017-01-01

Stability of curcumin in neutral and alkaline buffer conditions has been a serious concern for its medicinal applications. We demonstrate that the stability of curucmin can be improved in 1,2-Dioctadecanoyl-sn-glycero-3-phosphocholine (DSPC) liposomes. Curcumin strongly partition into liquid crystalline phase compared to solid gel phase of DSPC liposomes. Variation of fluorescence intensity of curcumin associated with liposomes with temperature successfully determines phase transition temperature of DSPC liposomes. However, at higher molar ratio curcumin can influence phase transition temperature by intercalating into deep hydrophobic layer of liposomes and facilitating fusion of two membrane phases. Rhamnolipids (RLs) are recently being applied for various biomedical applications. Here, we have explored new insight on intercalation of rhamnolipids with DSPC liposomes. Intercalation of rhamnolipids exceptionally increases partition of curcumin into solid gel phase of DSPC liposomes, whereas this increase is moderate in liquid crystalline phase. Fluorescence quenching study establishes that permeability and fluidity of the DSPC liposomes are enhanced in the presence of RLs. Membrane permeability and fluidity can be improved further by increasing the percentage of RLs in DSPC liposomes. The phase transition temperature of DSPC liposomes decreases with increase in percentage of RLs in DSPC liposomes by encouraging fusion between solid gel and liquid crystalline phases. Intercalation of RLs is found to further boost stability of drug, curcumin, in DSPC liposomes. Thus, mixing RLs with DSPC liposomes could potentially serve as a good candidate for drug delivery application. Copyright © 2016 Elsevier B.V. All rights reserved.

Li Storage of Calcium Niobates for Lithium Ion Batteries.

PubMed

Yim, Haena; Yu, Seung-Ho; Yoo, So Yeon; Sung, Yung-Eun; Choi, Ji-Won

2015-10-01

New types of niobates negative electrode were studied for using in lithium-ion batteries in order to alternate metallic lithium anodes. The potassium intercalated compound KCa2Nb3O10 and proton intercalated compound HCa2Nb3O10 were studied, and the electrochemical results showed a reversible cyclic voltammetry profile with acceptable discharge capacity. The as-prepared KCa2Nb3O10 negative electrode had a low discharge capacity caused by high overpotential, but the reversible intercalation and deintercalation reaction of lithium ions was activated after exchanging H+ ions for intercalated K+ ions. The initial discharge capacity of HCa2Nb3O10 was 54.2 mAh/g with 92.1% of coulombic efficiency, compared with 10.4 mAh/g with 70.2% of coulombic efficiency for KCa2Nb3O10 at 1 C rate. The improved electrochemical performance of the HCa2Nb3O10 was related to the lower bonding energy between proton cation and perovskite layer, which facilitate Li+ ions intercalating into the cation site, unlike potassium cation and perovskite layer. Also, this negative material can be easily exfoliated to Ca2Nb3O10 layer by using cation exchange process. Then, obtained two-dimensional nanosheets layer, which recently expected to be an advanced electrode material because of its flexibility, chemical stable, and thin film fabricable, can allow Li+ ions to diffuse between the each perovskite layer. Therefore, this new type layered perovskite niobates can be used not only bulk-type lithium ion batteries but also thin film batteries as a negative material.

Spermine Attenuates the Action of the DNA Intercalator, Actinomycin D, on DNA Binding and the Inhibition of Transcription and DNA Replication

PubMed Central

Chen, Jeremy J. W.; Wu, Wen-Lin; Yuann, Jeu-Ming P.; Su, Wang-Lin; Chuang, Show-Mei; Hou, Ming-Hon

2012-01-01

The anticancer activity of DNA intercalators is related to their ability to intercalate into the DNA duplex with high affinity, thereby interfering with DNA replication and transcription. Polyamines (spermine in particular) are almost exclusively bound to nucleic acids and are involved in many cellular processes that require nucleic acids. Until now, the effects of polyamines on DNA intercalator activities have remained unclear because intercalation is the most important mechanism employed by DNA-binding drugs. Herein, using actinomycin D (ACTD) as a model, we have attempted to elucidate the effects of spermine on the action of ACTD, including its DNA-binding ability, RNA and DNA polymerase interference, and its role in the transcription and replication inhibition of ACTD within cells. We found that spermine interfered with the binding and stabilization of ACTD to DNA. The presence of increasing concentrations of spermine enhanced the transcriptional and replication activities of RNA and DNA polymerases, respectively, in vitro treated with ActD. Moreover, a decrease in intracellular polyamine concentrations stimulated by methylglyoxal-bis(guanylhydrazone) (MGBG) enhanced the ACTD-induced inhibition of c-myc transcription and DNA replication in several cancer cell lines. The results indicated that spermine attenuates ACTD binding to DNA and its inhibition of transcription and DNA replication both in vitro and within cells. Finally, a synergistic antiproliferative effect of MGBG and ACTD was observed in a cell viability assay. Our findings will be of significant relevance to future developments in combination with cancer therapy by enhancing the anticancer activity of DNA interactors through polyamine depletion. PMID:23144800

Spermine attenuates the action of the DNA intercalator, actinomycin D, on DNA binding and the inhibition of transcription and DNA replication.

PubMed

Wang, Sheng-Yu; Lee, Alan Yueh-Luen; Lee, Yueh-Luen; Lai, Yi-Hua; Chen, Jeremy J W; Wu, Wen-Lin; Yuann, Jeu-Ming P; Su, Wang-Lin; Chuang, Show-Mei; Hou, Ming-Hon

2012-01-01

The anticancer activity of DNA intercalators is related to their ability to intercalate into the DNA duplex with high affinity, thereby interfering with DNA replication and transcription. Polyamines (spermine in particular) are almost exclusively bound to nucleic acids and are involved in many cellular processes that require nucleic acids. Until now, the effects of polyamines on DNA intercalator activities have remained unclear because intercalation is the most important mechanism employed by DNA-binding drugs. Herein, using actinomycin D (ACTD) as a model, we have attempted to elucidate the effects of spermine on the action of ACTD, including its DNA-binding ability, RNA and DNA polymerase interference, and its role in the transcription and replication inhibition of ACTD within cells. We found that spermine interfered with the binding and stabilization of ACTD to DNA. The presence of increasing concentrations of spermine enhanced the transcriptional and replication activities of RNA and DNA polymerases, respectively, in vitro treated with ActD. Moreover, a decrease in intracellular polyamine concentrations stimulated by methylglyoxal-bis(guanylhydrazone) (MGBG) enhanced the ACTD-induced inhibition of c-myc transcription and DNA replication in several cancer cell lines. The results indicated that spermine attenuates ACTD binding to DNA and its inhibition of transcription and DNA replication both in vitro and within cells. Finally, a synergistic antiproliferative effect of MGBG and ACTD was observed in a cell viability assay. Our findings will be of significant relevance to future developments in combination with cancer therapy by enhancing the anticancer activity of DNA interactors through polyamine depletion.

Charging YOYO-1 on Capillary Wall for Online DNA Intercalation and Integrating This Approach with Multiplex PCR and Bare Narrow Capillary–Hydrodynamic Chromatography for Online DNA Analysis

PubMed Central

2016-01-01

Multiplex polymerase chain reaction (PCR) has been widely utilized for high-throughput pathogen identification. Often, a dye is used to intercalate the amplified DNA fragments, and identifications of the pathogens are carried out by DNA melting curve analysis or gel electrophoresis. Integrating DNA amplification and identification is a logic path toward maximizing the benefit of multiplex PCR. Although PCR and gel electrophoresis have been integrated, replenishing the gels after each run is tedious and time-consuming. In this technical note, we develop an approach to address this issue. We perform multiplex PCR inside a capillary, transfer the amplified fragments to a bare narrow capillary, and measure their lengths online using bare narrow capillary–hydrodynamic chromatography (BaNC-HDC), a new technique recently developed in our laboratory for free-solution DNA separation. To intercalate the DNA with YOYO-1 (a fluorescent dye) for BaNC-HDC, we flush the capillary column with a YOYO-1 solution; positively charged YOYO-1 is adsorbed (or charged) onto the negatively charged capillary wall. As DNA molecules are driven down the column for separation, they react with the YOYO-1 stored on the capillary wall and are online-intercalated with the dye. With a single YOYO-1 charging, the column can be used for more than 40 runs, although the fluorescence signal intensities of the DNA peaks decrease gradually. Although the dye-DNA intercalation occurs during the separation, it does not affect the retention times, separation efficiencies, or resolutions. PMID:25555111

A study on plastic wrinkling in thin-walled tube bending via an energy-based wrinkling prediction model

NASA Astrophysics Data System (ADS)

Li, H; Yang, H; Zhan, M

2009-04-01

Thin-walled tube bending is an advanced technology for producing precision bent tube parts in aerospace, aviation and automobiles, etc. With increasing demands of bending tubes with a larger tube diameter and a smaller bending radius, wrinkling instability is a critical issue to be solved urgently for improving the bending limit and forming quality in this process. In this study, by using the energy principle, combined with analytical and finite element (FE) numerical methods, an energy-based wrinkling prediction model for thin-walled tube bending is developed. A segment shell model is proposed to consider the critical wrinkling region, which captures the deformation features of the tube bending process. The dissipation energy created by the reaction forces at the tube-dies interface for restraining the compressive instability is also included in the prediction model, which can be numerically calculated via FE simulation. The validation of the model is performed and its physical significance is evaluated from various aspects. Then the plastic wrinkling behaviors in thin-walled tube bending are addressed. From the energy viewpoint, the effect of the basic parameters including the geometrical and material parameters on the onset of wrinkling is identified. In particular, the influence of multi-tools constraints such as clearance and friction at various interfaces on the wrinkling instability is obtained. The study provides instructive understanding of the plastic wrinkling instability and the model may be suitable for the wrinkling prediction of a doubly-curved shell in the complex forming process with contact conditions.

Late Complication of Surgically Treated Atlantoaxial Instability: Occipital Bone Erosion Induced by Protruded Fixed Titanium Rod: A Case Report

PubMed Central

Nakao, Yaoki; Shimokawa, Nobuyuki; Morisako, Hiroki; Tsukazaki, Yuji; Terada, Aiko; Nakajo, Kosuke; Fu, Yoshihiko

2014-01-01

Objective Polyaxial screw-rod fixation of C1-C2 is a relatively new technique to treat atlantoaxial instability, and there have been few reports in the literature outlining all possible complications. The purpose of this case report is to present the occurrence and management of occipital bone erosion induced by the protruded rostral part of a posterior atlantoaxial screw-rod construct causing headache. Clinical Features A 70-year-old Asian man with rheumatoid arthritis initially presented to our institution with atlantoaxial instability causing progressive quadraparesis and neck pain. Intervention and Outcome Posterior atlantoaxial instrumented fixation using C1 lateral mass screws in conjunction with C2 pedicle screws was performed to stabilize these segments. Postoperatively, the patient regained the ability to independently walk and had no radiographic evidence of instrumentation hardware failure and excellent sagittal alignment. However, despite a well-stabilized fusion, the patient began to complain of headache during neck extension. Follow-up imaging studies revealed left occipital bone erosion induced by a protruded titanium rod fixed with setscrews. During revision surgery, the rod protrusion was modified and the headaches diminished. Conclusion This case demonstrates that occipital bone erosion after posterior atlantoaxial fixation causing headache may occur. The principal cause of bone erosion in this case was rod protrusion. Although posterior atlantoaxial fixation using the screw-rod system was selected to manage atlantoaxial instability because it has less complications than other procedures, surgeons should pay attention that the length of the rod protrusion should not exceed 2 mm. PMID:25435842

1,8-Naphthalimide: A Potent DNA Intercalator and Target for Cancer Therapy.

PubMed

Tandon, Runjhun; Luxami, Vijay; Kaur, Harsovin; Tandon, Nitin; Paul, Kamaldeep

2017-10-01

The poor pharmacokinetics, side effects and particularly the rapid emergence of drug resistance compromise the efficiency of clinically used anticancer drugs. Therefore, the discovery of novel and effective drugs is still an extremely primary mission. Naphthalimide family is one of the highly active anticancer drug based upon effective intercalator with DNA. In this article, we review the discovery and development of 1,8-naphthalimide moiety, and, especially, pay much attention to the structural modifications and structure activity relationships. The review demonstrates how modulation of the moiety affecting naphthalimide compound for DNA binding that is achieved to afford a profile of antitumor activity. The DNA binding of imide and ring substitution at naphthalimide, bisnaphthalimide, naphthalimide-metal complexes is achieved by molecular recognition through intercalation mode. Thus, this synthetic/natural small molecule can act as a drug when activation or inhibition of DNA function, is required to cure or control the cancer disease. The present study is a review of the advances in 1,8-naphthalimide-related research, with a focus on how such derivatives are intercalated into DNA for their anticancer activities. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-rate capability of three-dimensionally ordered macroporous T-Nb2O5 through Li+ intercalation pseudocapacitance

NASA Astrophysics Data System (ADS)

Lou, Shuaifeng; Cheng, Xinqun; Wang, Long; Gao, Jinlong; Li, Qin; Ma, Yulin; Gao, Yunzhi; Zuo, Pengjian; Du, Chunyu; Yin, Geping

2017-09-01

Orthorhombic Niobium oxide (T-Nb2O5) has been regarded as a promising anode material for high-rate lithium ion batteries (LIBs) due to its potential to operate at high rates with improved safety and high theoretical capacity of 200 mA h g-1. Herein, three-dimensionally ordered macroporous (3DOM) T-Nb2O5, with mesoporous hierarchical structure, was firstly prepared by a simple approach employing self-assembly polystyrene (PS) microspheres as hard templates. The obtained T-Nb2O5 anode material presents obvious and highly-efficiency pseudocapacitive Li+ intercalation behaviour, which plays a dominant role in the kinetics of electrode process. As a result, rapid Li+ intercalation/de-intercalation are achieved, leading to excellent rate capability and long cycle life. The 3DOM T-Nb2O5 shows a remarkable high capacity of 106 and 77 mA h g-1 at the rate of 20C and 50C. The work presented herein holds great promise for future design of material structure, and demonstrates the great potential of T-Nb2O5 as a practical high-rate anode material for LIBs.

Theoretical Investigation of oxides for batteries and fuel cell applications

NASA Astrophysics Data System (ADS)

Ganesh, Panchapakesan; Lubimtsev, Andrew A.; Balachandran, Janakiraman

I will present theoretical studies of Li-ion and proton-conducting oxides using a combination of theory and computations that involve Density Functional Theory based atomistic modeling, cluster-expansion based studies, global optimization, high-throughput computations and machine learning based investigation of ionic transport in oxide materials. In Li-ion intercalated oxides, we explain the experimentally observed (Nature Materials 12, 518-522 (2013)) 'intercalation pseudocapacitance' phenomenon, and explain why Nb2O5 is special to show this behavior when Li-ions are intercalated (J. Mater. Chem. A, 2013,1, 14951-14956), but not when Na-ions are used. In addition, we explore Li-ion intercalation theoretically in VO2 (B) phase, which is somewhat structurally similar to Nb2O5 and predict an interesting role of site-trapping on the voltage and capacity of the material, validated by ongoing experiments. Computations of proton conducting oxides explain why Y-doped BaZrO3 , one of the fastest proton conducting oxide, shows a decrease in conductivity above 20% Y-doping. Further, using high throughput computations and machine learning tools we discover general principles to improve proton conductivity. Acknowledgements: LDRD at ORNL and CNMS at ORNL

Anthraquinones quinizarin and danthron unwind negatively supercoiled DNA and lengthen linear DNA

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

Verebová, Valéria; Adamcik, Jozef; Danko, Patrik

2014-01-31

Highlights: • Anthraquinones quinizarin and danthron unwind negatively supercoiled DNA. • Anthraquinones quinizarin and danthron lengthen linear DNA. • Anthraquinones quinizarin and danthron possess middle binding affinity to DNA. • Anthraquinones quinizarin and danthron interact with DNA by intercalating mode. - Abstract: The intercalating drugs possess a planar aromatic chromophore unit by which they insert between DNA bases causing the distortion of classical B-DNA form. The planar tricyclic structure of anthraquinones belongs to the group of chromophore units and enables anthraquinones to bind to DNA by intercalating mode. The interactions of simple derivatives of anthraquinone, quinizarin (1,4-dihydroxyanthraquinone) and danthron (1,8-dihydroxyanthraquinone),more » with negatively supercoiled and linear DNA were investigated using a combination of the electrophoretic methods, fluorescence spectrophotometry and single molecule technique an atomic force microscopy. The detection of the topological change of negatively supercoiled plasmid DNA, unwinding of negatively supercoiled DNA, corresponding to appearance of DNA topoisomers with the low superhelicity and an increase of the contour length of linear DNA in the presence of quinizarin and danthron indicate the binding of both anthraquinones to DNA by intercalating mode.« less

Interplay between intercalated oxygen superstructures and monolayer h -BN on Cu(100)

DOE PAGES

Ma, Chuanxu; Park, Jewook; Liu, Lei; ...

2016-08-18

The confinement effect of intercalated atoms in van der Waals heterostructures can lead to interesting interactions between the confined atoms or molecules and the overlaying two-dimensional (2D) materials. In this paper, we report the formation of ordered Cu(100) p(2×2) oxygen superstructures by oxygen intercalation under the monolayer hexagonal boron nitride (h-BN) on Cu after annealing. By using scanning tunneling microscopy and x-ray photoelectron spectroscopy, we identify the superstructure and reveal its roles in passivating the exposed Cu surfaces, decoupling h-BN and Cu, and disintegrating h-BN monolayers. The oxygen superstructure appears as a 2D pattern on the exposed Cu surface ormore » quasi-1D stripes of paired oxygen intercalated in the interface of h-BN and Cu predominantly oriented along the moiré modulations. The oxygen superstructure is shown to etch the overlaying h-BN monolayer in a thermal annealing process. After extended annealing, the h-BN monolayer disintegrates into nanoislands with zigzag edges. Finally, we discuss the implications of these findings on the stability and oxidation resistance of h-BN and relate them to challenges in process integration and 2D heterostructures.« less

An Inexpensive Co-Intercalated Layered Double Hydroxide Composite with Electron Donor-Acceptor Character for Photoelectrochemical Water Splitting

PubMed Central

Zheng, Shufang; Lu, Jun; Yan, Dongpeng; Qin, Yumei; Li, Hailong; Evans, David G.; Duan, Xue

2015-01-01

In this paper, the inexpensive 4,4-diaminostilbene-2,2-disulfonate (DAS) and 4,4-dinitro-stilbene-2,2- disulfonate (DNS) anions with arbitrary molar ratios were successfully co-intercalated into Zn2Al-layered double hydroxides (LDHs). The DAS(50%)-DNS/LDHs composite exhibited the broad UV-visible light absorption and fluorescence quenching, which was a direct indication of photo-induced electron transfer (PET) process between the intercalated DAS (donor) and DNS (acceptor) anions. This was confirmed by the matched HOMO/LUMO energy levels alignment of the intercalated DAS and DNS anions, which was also compatible for water splitting. The DAS(50%)-DNS/LDHs composite was fabricated as the photoanode and Pt as the cathode. Under the UV-visible light illumination, the enhanced photo-generated current (4.67 mA/cm2 at 0.8 V vs. SCE) was generated in the external circuit, and the photoelectrochemical water split was realized. Furthermore, this photoelectrochemical water splitting performance had excellent crystalline, electrochemical and optical stability. Therefore, this novel inorganic/organic hybrid photoanode exhibited potential application prospect in photoelectrochemical water splitting. PMID:26174201

Anion-intercalated layered double hydroxides modified test strips for detection of heavy metal ions.

PubMed

Wang, Nan; Sun, Jianchao; Fan, Hai; Ai, Shiyun

2016-01-01

In this work, a novel approach for facile and rapid detection of heavy metal ions using anion-intercalated layered double hydroxides (LDHs) modified test strips is demonstrated. By intercalating Fe(CN)6(4-) or S(2-) anions into the interlayers of LDHs on the filter paper, various heavy metal ions can be easily detected based on the color change before and after reaction between the anions and the heavy metal ions. Upon the dropping of heavy metal ions solutions to the test strips, the colors of the test strips changed instantly, which can be easily observed by naked eyes. With the decrease of the concentration, the color depth changed obviously. The lowest detection concentration can be up to 1×10(-6) mol L(-1). Due to the easily intercalation of anions into the interlayer of the LDHs on test trips, this procedure provides a general method for the construction of LDHs modified test strips for detection of heavy metal ions. The stability of the prepared test strips is investigated. Furthermore, all the results were highly reproducible. The test strips may have potential applications in environmental monitoring fields. Copyright © 2015 Elsevier B.V. All rights reserved.

Nucleation and growth kinetics for intercalated islands during deposition on layered materials with isolated pointlike surface defects

DOE PAGES

Han, Yong; Lii-Rosales, A.; Zhou, Y.; ...

2017-10-13

Theory and stochastic lattice-gas modeling is developed for the formation of intercalated metal islands in the gallery between the top layer and the underlying layer at the surface of layered materials. Our model for this process involves deposition of atoms, some fraction of which then enter the gallery through well-separated pointlike defects in the top layer. Subsequently, these atoms diffuse within the subsurface gallery leading to nucleation and growth of intercalated islands nearby the defect point source. For the case of a single point defect, continuum diffusion equation analysis provides insight into the nucleation kinetics. However, complementary tailored lattice-gas modelingmore » produces a more comprehensive and quantitative characterization. We analyze the large spread in nucleation times and positions relative to the defect for the first nucleated island. We also consider the formation of subsequent islands and the evolution of island growth shapes. The shapes reflect in part our natural adoption of a hexagonal close-packed island structure. As a result, motivation and support for the model is provided by scanning tunneling microscopy observations of the formation of intercalated metal islands in highly-ordered pyrolytic graphite at higher temperatures.« less

Radiation Protection of New Lightweight Electromagnetic Interference Shielding Materials Determined

NASA Technical Reports Server (NTRS)

1996-01-01

Weight savings as high as 80 percent could be achieved by simply switching from aluminum electromagnetic interference (EMI) shielding covers for spacecraft power systems to EMI covers made from intercalated graphite fiber composites. Because EMI covers typically make up about one-fifth of the power system mass, this change would decrease the mass of a spacecraft power system by more than 15 percent. Intercalated graphite fibers are made by diffusing guest atoms or molecules, such as bromine, between the carbon planes of the graphite fibers. The resulting bromine-intercalated fibers have mechanical and thermal properties nearly identical to pristine graphite fibers, but their resistivity is lower by a factor of 5, giving them better electrical conductivity than stainless steel and making these composites suitable for EMI shielding.

Technological hurdles to the application of intercalated graphite fibers

NASA Technical Reports Server (NTRS)

Gaier, James R.

1988-01-01

Before intercalated graphite fibers can be developed as an effective power material, there are several technological hurdles which must be overcome. These include the environmental stability, homogeneity and bulk properties, connection procedures, and costs. Strides were made within the last several years in stability and homogeneity of intercalated graphite fibers. Bulk properties and connection procedures are areas of active research now. Costs are still prohibitive for all but the most demanding applications. None of these problems, however, appear to be unsolvable, and their solution may result in wide spread GOC application. The development of a relatively simple technology application, such as EMI shielding, would stimulate the solution of scale-up problems. Once this technology is developed, then more demanding applications, such as power bus bars, may be possible.

Indirect measurement of N-14 quadrupolar coupling for NH3 intercalated in potassium graphite

NASA Technical Reports Server (NTRS)

Tsang, T.; Fronko, R. M.; Resing, H. A.

1987-01-01

A method for indirect measurement of the nuclear quadrupolar coupling was developed and applied to NH3 molecules in the graphite intercalation compound K(NH3)4.3C24, which has a layered structure with alternating carbon and intercalant layers. Three triplets were observed in the H-1 NMR spectra of the compound. The value of the N-14 quadrupolar coupling constant of NH3 (3.7 MHz), determined indirectly from the H-1 NMR spectra, was intermediate between the gas value of 4.1 MHz and the solid-state value of 3.2 MHz. The method was also used to deduce the (H-1)-(H-1) and (N-14)-(H-1) dipolar interactions, the H-1 chemical shifts, and the molecular orientations and motions of NH3.

Modification and intercalation of layered zirconium phosphates: a solid-state NMR monitoring.

PubMed

Bakhmutov, Vladimir I; Kan, Yuwei; Sheikh, Javeed Ahmad; González-Villegas, Julissa; Colón, Jorge L; Clearfield, Abraham

2017-07-01

Several layered zirconium phosphates treated with Zr(IV) ions, modified by monomethoxy-polyethyleneglycol-monophosphate and intercalated with doxorubicin hydrochloride have been studied by solid-state MAS NMR techniques. The organic components of the phosphates have been characterized by the 13 C{ 1 H} CP MAS NMR spectra compared with those of initial compounds. The multinuclear NMR monitoring has provided to establish structure and covalent attachment of organic/inorganic moieties to the surface and interlayer spaces of the phosphates. The MAS NMR experiments including kinetics of proton-phosphorus cross polarization have resulted in an unusual structure of zirconium phosphate 6 combining decoration of the phosphate surface by polymer units and their partial intercalation into the interlayer space. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Flattening and manipulation of the electronic structure of h-BN/Rh(111) nanomesh upon Sn intercalation

NASA Astrophysics Data System (ADS)

Sugiyama, Yuya; Bernard, Carlo; Okuyama, Yuma; Ideta, Shin-ichiro; Tanaka, Kiyohisa; Greber, Thomas; Hirahara, Toru

2018-06-01

We have deposited Sn on corrugated hexagonal boron nitride (h-BN) nanomeshs formed on Rh(111) and found that Sn atoms are intercalated between h-BN and Rh, flattening the h-BN. Our reflection high-energy electron diffraction (RHEED) analysis showed that the average in-plane lattice constant of h-BN increases due to the loss of the corrugation. Furthermore, electronic structure measurements based on angle-resolved photoemission spectroscopy (ARPES) showed that the h-BN π band width increases significantly while the σ band width does not change as much. These behaviors were partly different from previous reports on the intercalation of h-BN/Rh system. Our results offer a novel, simple method to control the electronic structure of h-BN.

Electrostatic Estimation of Intercalant Jump-Diffusion Barriers Using Finite-Size Ion Models.

PubMed

Zimmermann, Nils E R; Hannah, Daniel C; Rong, Ziqin; Liu, Miao; Ceder, Gerbrand; Haranczyk, Maciej; Persson, Kristin A

2018-02-01

We report on a scheme for estimating intercalant jump-diffusion barriers that are typically obtained from demanding density functional theory-nudged elastic band calculations. The key idea is to relax a chain of states in the field of the electrostatic potential that is averaged over a spherical volume using different finite-size ion models. For magnesium migrating in typical intercalation materials such as transition-metal oxides, we find that the optimal model is a relatively large shell. This data-driven result parallels typical assumptions made in models based on Onsager's reaction field theory to quantitatively estimate electrostatic solvent effects. Because of its efficiency, our potential of electrostatics-finite ion size (PfEFIS) barrier estimation scheme will enable rapid identification of materials with good ionic mobility.

Ion-driven photoluminescence modulation of quasi-two-dimensional MoS2 nanoflakes for applications in biological systems.

PubMed

Ou, Jian Zhen; Chrimes, Adam F; Wang, Yichao; Tang, Shi-yang; Strano, Michael S; Kalantar-zadeh, Kourosh

2014-02-12

Quasi-two-dimensional (quasi-2D) molybdenum disulfide (MoS2) is a photoluminescence (PL) material with unique properties. The recent demonstration of its PL, controlled by the intercalation of positive ions, can lead to many opportunities for employing this quasi-2D material in ion-related biological applications. Here, we present two representative models of biological systems that incorporate the ion-controlled PL of quasi-2D MoS2 nanoflakes. The ion exchange behaviors of these two models are investigated to reveal enzymatic activities and cell viabilities. While the ion intercalation of MoS2 in enzymatic activities is enabled via an external applied voltage, the intercalation of ions in cell viability investigations occurs in the presence of the intrinsic cell membrane potential.

Crackles and instabilities during lung inflation

NASA Astrophysics Data System (ADS)

Alencar, Adriano M.; Majumdar, Arnab; Hantos, Zoltan; Buldyrev, Sergey V.; Eugene Stanley, H.; Suki, Béla

2005-11-01

In a variety of physico-chemical reactions, the actual process takes place in a reactive zone, called the “active surface”. We define the active surface of the lung as the set of airway segments that are closed but connected to the trachea through an open pathway, which is the interface between closed and open regions in a collapsed lung. To study the active surface and the time interval between consecutive openings, we measured the sound pressure of crackles, associated with the opening of collapsed airway segments in isolated dog lungs, inflating from the collapsed state in 120 s. We analyzed the sequence of crackle amplitudes, inter-crackle intervals, and low frequency energy from acoustic data. The series of spike amplitudes spans two orders of magnitude and the inter-crackle intervals spans over five orders of magnitude. The distribution of spike amplitudes follows a power law for nearly two decades, while the distribution of time intervals between consecutive crackles shows two regimes of power law behavior, where the first region represents crackles coming from avalanches of openings whereas the second region is due to the time intervals between separate avalanches. Using the time interval between measured crackles, we estimated the time evolution of the active surface during lung inflation. In addition, we show that recruitment and instabilities along the pressure-volume curve are associated with airway opening and recruitment. We find a good agreement between the theory of the dynamics of lung inflation and the experimental data which combined with numerical results may prove useful in the clinical diagnosis of lung diseases.

Orthodontic treatment stability predictors: A retrospective longitudinal study.

PubMed

de Bernabé, Paloma González-Gil; Montiel-Company, José María; Paredes-Gallardo, Vanessa; Gandía-Franco, Jose Luis; Bellot-Arcís, Carlos

2017-03-01

To examine medium- to long-term orthodontic treatment stability and its possible association with certain variables. In a retrospective longitudinal study of 70 postretention patients, the Peer Assessment Rating (PAR) index was measured at the start (T1) and end (T2) of treatment and between 4 and 10 years afterwards (T3). The stability was considered absolute when the T2 and T3 values were identical and relative when the difference was within the ±5 range. Among the 70 patients, 65.8% were female and 34.2% were male. Their mean age was 14.5 years. The mean treatment length was 2.4 years. The mean retention phase was 3.3 years. The mean pre- and posttreatment PAR scores were 29.8 (T1) and 6.3 (T2). The mean T1-T2 difference was 23.6. The mean T2-T3 difference was -0.39. Within the study, 7.1% presented absolute stability and 68.6% presented relative stability. Lower anterior segment alignment and overbite were the most unstable occlusal features and tended to worsen. Fixed retainer (odds ratio [OR] 0.31; 95% confidence interval [CI] 0.10-0.98) as a protective factor and years without retention (OR 1.32; 95% CI 1.03-1.68) as a risk factor are predictor variables of instability in the case of lower anterior segment alignment. The PAR value at the end of treatment (OR 1.29; 95% CI 1.08-1.54) and extractions (OR 4.76; 95% CI 1.05-21.6) before treatment are predictors for midline instability.

Impact of treatment delay on mortality in ST-segment elevation myocardial infarction (STEMI) patients presenting with and without haemodynamic instability: results from the German prospective, multicentre FITT-STEMI trial.

PubMed

Scholz, Karl Heinrich; Maier, Sebastian K G; Maier, Lars S; Lengenfelder, Björn; Jacobshagen, Claudius; Jung, Jens; Fleischmann, Claus; Werner, Gerald S; Olbrich, Hans G; Ott, Rainer; Mudra, Harald; Seidl, Karlheinz; Schulze, P Christian; Weiss, Christian; Haimerl, Josef; Friede, Tim; Meyer, Thomas

2018-04-01

The aim of this study was to investigate the effect of contact-to-balloon time on mortality in ST-segment elevation myocardial infarction (STEMI) patients with and without haemodynamic instability. Using data from the prospective, multicentre Feedback Intervention and Treatment Times in ST-Elevation Myocardial Infarction (FITT-STEMI) trial, we assessed the prognostic relevance of first medical contact-to-balloon time in n = 12 675 STEMI patients who used emergency medical service transportation and were treated with primary percutaneous coronary intervention (PCI). Patients were stratified by cardiogenic shock (CS) and out-of-hospital cardiac arrest (OHCA). For patients treated within 60 to 180 min from the first medical contact, we found a nearly linear relationship between contact-to-balloon times and mortality in all four STEMI groups. In CS patients with no OHCA, every 10-min treatment delay resulted in 3.31 additional deaths in 100 PCI-treated patients. This treatment delay-related increase in mortality was significantly higher as compared to the two groups of OHCA patients with shock (2.09) and without shock (1.34), as well as to haemodynamically stable patients (0.34, P < 0.0001). In patients with CS, the time elapsing from the first medical contact to primary PCI is a strong predictor of an adverse outcome. This patient group benefitted most from immediate PCI treatment, hence special efforts to shorten contact-to-balloon time should be applied in particular to these high-risk STEMI patients. NCT00794001.

Structural basis of DNA folding and recognition in an AMP-DNA aptamer complex: distinct architectures but common recognition motifs for DNA and RNA aptamers complexed to AMP.

PubMed

Lin, C H; Patel, D J

1997-11-01

Structural studies by nuclear magnetic resonance (NMR) of RNA and DNA aptamer complexes identified through in vitro selection and amplification have provided a wealth of information on RNA and DNA tertiary structure and molecular recognition in solution. The RNA and DNA aptamers that target ATP (and AMP) with micromolar affinity exhibit distinct binding site sequences and secondary structures. We report below on the tertiary structure of the AMP-DNA aptamer complex in solution and compare it with the previously reported tertiary structure of the AMP-RNA aptamer complex in solution. The solution structure of the AMP-DNA aptamer complex shows, surprisingly, that two AMP molecules are intercalated at adjacent sites within a rectangular widened minor groove. Complex formation involves adaptive binding where the asymmetric internal bubble of the free DNA aptamer zippers up through formation of a continuous six-base mismatch segment which includes a pair of adjacent three-base platforms. The AMP molecules pair through their Watson-Crick edges with the minor groove edges of guanine residues. These recognition G.A mismatches are flanked by sheared G.A and reversed Hoogsteen G.G mismatch pairs. The AMP-DNA aptamer and AMP-RNA aptamer complexes have distinct tertiary structures and binding stoichiometries. Nevertheless, both complexes have similar structural features and recognition alignments in their binding pockets. Specifically, AMP targets both DNA and RNA aptamers by intercalating between purine bases and through identical G.A mismatch formation. The recognition G.A mismatch stacks with a reversed Hoogsteen G.G mismatch in one direction and with an adenine base in the other direction in both complexes. It is striking that DNA and RNA aptamers selected independently from libraries of 10(14) molecules in each case utilize identical mismatch alignments for molecular recognition with micromolar affinity within binding-site pockets containing common structural elements.