Defining the origins of electron transfer at screen-printed graphene-like and graphite electrodes: MoO2 nanowire fabrication on edge plane sites reveals electrochemical insights.

PubMed

Rowley-Neale, Samuel J; Brownson, Dale A C; Banks, Craig E

2016-08-18

Molybdenum (di)oxide (MoO2) nanowires are fabricated onto graphene-like and graphite screen-printed electrodes (SPEs) for the first time, revealing crucial insights into the electrochemical properties of carbon/graphitic based materials. Distinctive patterns observed in the electrochemical process of nanowire decoration show that electron transfer occurs predominantly on edge plane sites when utilising SPEs fabricated/comprised of graphitic materials. Nanowire fabrication along the edge plane sites (and on edge plane like-sites/defects) of graphene/graphite is confirmed with Cyclic Voltammetry, Scanning Electron Microscopy (SEM) and Raman Spectroscopy. Comparison of the heterogeneous electron transfer (HET) rate constants (k°) at unmodified and nanowire coated SPEs show a reduction in the electrochemical reactivity of SPEs when the edge plane sites are effectively blocked/coated with MoO2. Throughout the process, the basal plane sites of the graphene/graphite electrodes remain relatively uncovered; except when the available edge plane sites have been utilised, in which case MoO2 deposition grows from the edge sites covering the entire surface of the electrode. This work clearly illustrates the distinct electron transfer properties of edge and basal plane sites on graphitic materials, indicating favourable electrochemical reactivity at the edge planes in contrast to limited reactivity at the basal plane sites. In addition to providing fundamental insights into the electron transfer properties of graphite and graphene-like SPEs, the reported simple, scalable, and cost effective formation of unique and intriguing MoO2 nanowires realised herein is of significant interest for use in both academic and commercial applications.

Effect of the universal acid-base indicator on the formation of the concentration-dependent diffusion instability

NASA Astrophysics Data System (ADS)

Mosheva, E. A.; Shmyrov, A. V.

2017-06-01

The effect of the universal acid-base indicator on the pattern formation and mass transfer in a two-layer system composed of two reactive miscible liquids in a vertical Hele-Shaw cell is studied experimentally. The reaction we study is a neutralization one. It turns out that the presence of the indicator leads to a change in the spatio-temporal characteristics of the system and even in the mass transfer mechanism near the reaction front—from diffusive to convective. The conditions, where the universal indicator does not affect the reaction and can be used as a visualizing mean, are reported.

Soft lithographic functionalization and patterning oxide-free silicon and germanium.

PubMed

Bowers, Carleen M; Toone, Eric J; Clark, Robert L; Shestopalov, Alexander A

2011-12-16

The development of hybrid electronic devices relies in large part on the integration of (bio)organic materials and inorganic semiconductors through a stable interface that permits efficient electron transport and protects underlying substrates from oxidative degradation. Group IV semiconductors can be effectively protected with highly-ordered self-assembled monolayers (SAMs) composed of simple alkyl chains that act as impervious barriers to both organic and aqueous solutions. Simple alkyl SAMs, however, are inert and not amenable to traditional patterning techniques. The motivation for immobilizing organic molecular systems on semiconductors is to impart new functionality to the surface that can provide optical, electronic, and mechanical function, as well as chemical and biological activity. Microcontact printing (μCP) is a soft-lithographic technique for patterning SAMs on myriad surfaces. Despite its simplicity and versatility, the approach has been largely limited to noble metal surfaces and has not been well developed for pattern transfer to technologically important substrates such as oxide-free silicon and germanium. Furthermore, because this technique relies on the ink diffusion to transfer pattern from the elastomer to substrate, the resolution of such traditional printing is essentially limited to near 1 μm. In contrast to traditional printing, inkless μCP patterning relies on a specific reaction between a surface-immobilized substrate and a stamp-bound catalyst. Because the technique does not rely on diffusive SAM formation, it significantly expands the diversity of patternable surfaces. In addition, the inkless technique obviates the feature size limitations imposed by molecular diffusion, facilitating replication of very small (<200 nm) features. However, up till now, inkless μCP has been mainly used for patterning relatively disordered molecular systems, which do not protect underlying surfaces from degradation. Here, we report a simple, reliable high-throughput method for patterning passivated silicon and germanium with reactive organic monolayers and demonstrate selective functionalization of the patterned substrates with both small molecules and proteins. The technique utilizes a preformed NHS-reactive bilayered system on oxide-free silicon and germanium. The NHS moiety is hydrolyzed in a pattern-specific manner with a sulfonic acid-modified acrylate stamp to produce chemically distinct patterns of NHS-activated and free carboxylic acids. A significant limitation to the resolution of many μCP techniques is the use of PDMS material which lacks the mechanical rigidity necessary for high fidelity transfer. To alleviate this limitation we utilized a polyurethane acrylate polymer, a relatively rigid material that can be easily functionalized with different organic moieties. Our patterning approach completely protects both silicon and germanium from chemical oxidation, provides precise control over the shape and size of the patterned features, and gives ready access to chemically discriminated patterns that can be further functionalized with both organic and biological molecules. The approach is general and applicable to other technologically-relevant surfaces.

Reactivity of propene, n-butene, and isobutene in the hydrogen transfer steps of n-hexane cracking over zeolites of different structure

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

Lukyanov, D.B.

The reaction of n-hexane cracking over HZSM-5, HY zeolite and mordenite (HM) was studied in accordance with the procedure of the [beta]-test recently proposed for quantitative characterization of zeolite hydrogen transfer activity. It is shown that this procedure allows one to obtain quantitative data on propene, n-butene, and isobutene reactivities in the hydrogen transfer steps of the reaction. The results demonstrate that in the absence of steric constraints (large pore HY and HM zeolites) isobutene is approximately 5 times more reactive in hydrogen transfer than n-butene. The latter, in turn, is about 1.3 times more reactive than propene. With mediummore » pore HZSM-5, steric inhibition of the hydrogen transfer between n-hexane and isobutene is observed. This results in a sharp decrease in the isobutene reactivity: over HZSM-5 zeolites isobutene is only 1.2 times more reactive in hydrogen transfer than n-butene. On the basis of these data it is concluded that the [beta]-test measures the [open quotes]real[close quotes] hydrogen transfer activity of zeolites, i.e., the activity that summarizes the effects of the acidic and structural properties of zeolites. An attempt is made to estimate the [open quotes]ideal[close quotes] zeolite hydrogen transfer activity, i.e., the activity determined by the zeolite acidic properties only. The estimations obtained show that this activity is approximately 1.8 and 1.6 times higher for HM zeolite in comparison with HZSM-5 and HY zeolites, respectively. 16 refs., 4 figs., 2 tabs.« less

Experimental investigation of piston heat transfer under conventional diesel and reactivity-controlled compression ignition combustion regimes

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

Splitter, Derek A; Hendricks, Terry Lee; Ghandhi, Jaal B

2014-01-01

The piston of a heavy-duty single-cylinder research engine was instrumented with 11 fast-response surface thermocouples, and a commercial wireless telemetry system was used to transmit the signals from the moving piston. The raw thermocouple data were processed using an inverse heat conduction method that included Tikhonov regularization to recover transient heat flux. By applying symmetry, the data were compiled to provide time-resolved spatial maps of the piston heat flux and surface temperature. A detailed comparison was made between conventional diesel combustion and reactivity-controlled compression ignition combustion operations at matched conditions of load, speed, boost pressure, and combustion phasing. The integratedmore » piston heat transfer was found to be 24% lower, and the mean surface temperature was 25 C lower for reactivity-controlled compression ignition operation as compared to conventional diesel combustion, in spite of the higher peak heat release rate. Lower integrated piston heat transfer for reactivity-controlled compression ignition was found over all the operating conditions tested. The results showed that increasing speed decreased the integrated heat transfer for conventional diesel combustion and reactivity-controlled compression ignition. The effect of the start of injection timing was found to strongly influence conventional diesel combustion heat flux, but had a negligible effect on reactivity-controlled compression ignition heat flux, even in the limit of near top dead center high-reactivity fuel injection timings. These results suggest that the role of the high-reactivity fuel injection does not significantly affect the thermal environment even though it is important for controlling the ignition timing and heat release rate shape. The integrated heat transfer and the dynamic surface heat flux were found to be insensitive to changes in boost pressure for both conventional diesel combustion and reactivity-controlled compression ignition. However, for reactivity-controlled compression ignition, the mean surface temperature increased with changes in boost suggesting that equivalence ratio affects steady-state heat transfer.« less

Atomically Traceable Nanostructure Fabrication

PubMed Central

Ballard, Josh B.; Dick, Don D.; McDonnell, Stephen J.; Bischof, Maia; Fu, Joseph; Owen, James H. G.; Owen, William R.; Alexander, Justin D.; Jaeger, David L.; Namboodiri, Pradeep; Fuchs, Ehud; Chabal, Yves J.; Wallace, Robert M.; Reidy, Richard; Silver, Richard M.; Randall, John N.; Von Ehr, James

2015-01-01

Reducing the scale of etched nanostructures below the 10 nm range eventually will require an atomic scale understanding of the entire fabrication process being used in order to maintain exquisite control over both feature size and feature density. Here, we demonstrate a method for tracking atomically resolved and controlled structures from initial template definition through final nanostructure metrology, opening up a pathway for top-down atomic control over nanofabrication. Hydrogen depassivation lithography is the first step of the nanoscale fabrication process followed by selective atomic layer deposition of up to 2.8 nm of titania to make a nanoscale etch mask. Contrast with the background is shown, indicating different mechanisms for growth on the desired patterns and on the H passivated background. The patterns are then transferred into the bulk using reactive ion etching to form 20 nm tall nanostructures with linewidths down to ~6 nm. To illustrate the limitations of this process, arrays of holes and lines are fabricated. The various nanofabrication process steps are performed at disparate locations, so process integration is discussed. Related issues are discussed including using fiducial marks for finding nanostructures on a macroscopic sample and protecting the chemically reactive patterned Si(100)-H surface against degradation due to atmospheric exposure. PMID:26274555

Atomically Traceable Nanostructure Fabrication.

PubMed

Ballard, Josh B; Dick, Don D; McDonnell, Stephen J; Bischof, Maia; Fu, Joseph; Owen, James H G; Owen, William R; Alexander, Justin D; Jaeger, David L; Namboodiri, Pradeep; Fuchs, Ehud; Chabal, Yves J; Wallace, Robert M; Reidy, Richard; Silver, Richard M; Randall, John N; Von Ehr, James

2015-07-17

Reducing the scale of etched nanostructures below the 10 nm range eventually will require an atomic scale understanding of the entire fabrication process being used in order to maintain exquisite control over both feature size and feature density. Here, we demonstrate a method for tracking atomically resolved and controlled structures from initial template definition through final nanostructure metrology, opening up a pathway for top-down atomic control over nanofabrication. Hydrogen depassivation lithography is the first step of the nanoscale fabrication process followed by selective atomic layer deposition of up to 2.8 nm of titania to make a nanoscale etch mask. Contrast with the background is shown, indicating different mechanisms for growth on the desired patterns and on the H passivated background. The patterns are then transferred into the bulk using reactive ion etching to form 20 nm tall nanostructures with linewidths down to ~6 nm. To illustrate the limitations of this process, arrays of holes and lines are fabricated. The various nanofabrication process steps are performed at disparate locations, so process integration is discussed. Related issues are discussed including using fiducial marks for finding nanostructures on a macroscopic sample and protecting the chemically reactive patterned Si(100)-H surface against degradation due to atmospheric exposure.

Linking Surface Topography Variations To Subsurface Mixing And Reaction Patterns

NASA Astrophysics Data System (ADS)

Le Borgne, T.; Bandopadhyay, A.; Davy, P.

2017-12-01

Fluctuations in surface topography generate nested streamline patterns in the subsurface over scales ranging from millimeters to kilometers. Because solute residence times can be very different for each streamlines, these patterns exert a strong control on biogeochemical reactions. While this effect has been quantified in reactive transport models, solute transfer across streamlines has been generally neglected. Yet, this process can lead to significant solute dilution and may trigger reactions by mixing water with different chemical compositions. Considering topography-driven subsurface flow cells of different sizes, we show that the resulting streamline structures act as shear flows, with shear rates that can vary over orders of magnitude depending on scale, permeability and hydraulic head gradient. This leads to the formation of localized layers of enhanced dilution and reaction, where mixing rates can be orders of magnitude larger than diffusion limited rates (Bandopadhyay et al. under review). We develop a theoretical model that predicts the depth and magnitude of these mixing hotspots and quantifies the resulting exports of conservative and reactive chemical species at discharge locations. We discuss consequences of these findings by applying this model at hyporheic zone, hillslope, and catchment scales.

Design and fabrication of inverted rib waveguide Bragg grating

NASA Astrophysics Data System (ADS)

Huang, Cheng-Sheng; Wang, Wei-Chih

2009-03-01

A polymeric SU8 rib waveguide Bragg grating filterfabricated using reactive ion etching (RIE) and solvent assisted microcontact molding (SAMIM) is presented. SAMIM is one kind of soft lithography. The technique is unique in which that a composite hPDMS/PDMS stamp was used to transfer the grating pattern onto an inverted SU8 rib waveguide system. The composite grating stamp can be used repeatedly several times with degradation. Using this stamp and inverter rib waveguide structure, the Bragg grating filter fabrication can be significantly simplified.

Fabrication of MEMS components using ultrafine-grained aluminium alloys

NASA Astrophysics Data System (ADS)

Qiao, Xiao Guang; Gao, Nong; Moktadir, Zakaria; Kraft, Michael; Starink, Marco J.

2010-04-01

A novel process for the fabrication of a microelectromechanical systems (MEMS) metallic component with features smaller than 10 µm and high thermal conductivity was investigated. This may be applied to new or improved microscale components, such as (micro-) heat exchangers. In the first stage of processing, equal channel angular pressing (ECAP) was employed to refine the grain size of commercial purity aluminium (Al-1050) to the ultrafine-grained (UFG) material. Embossing was conducted using a micro silicon mould fabricated by deep reactive ion etching (DRIE). Both cold embossing and hot embossing were performed on the coarse-grained and UFG Al-1050. Cold embossing on UFG Al-1050 led to a partially transferred pattern from the micro silicon mould and high failure rate of the mould. Hot embossing on UFG Al-1050 provided a smooth embossed surface with a fully transferred pattern and a low failure rate of the mould, while hot embossing on the coarse-grained Al-1050 resulted in a rougher surface with shear bands.

Transfer of Old ‘Reactivated’ Memory Retrieval Cues in Rats

PubMed Central

Briggs, James F.; Riccio, David C.

2008-01-01

The present studies examined whether the retrieval of an old ‘reactivated’ memory could be brought under the control of new contextual cues. In Experiment 1 rats trained in one context were exposed to different contextual cues either immediately, 60 min, or 120 min after a cued reactivation of the training memory. When tested in the shifted context, subjects exposed shortly after reactivation treated the shifted context as the original context. This transfer diminished with longer post-reactivation delays. Experiment 2 replicated the basic finding and demonstrated that the transfer of the old retrieval cues was specific to the contextual cues present during exposure. These findings are consistent with previous research (i.e., Briggs, Fitz, & Riccio, in press) showing the transfer of retrieval cues for a new memory, and demonstrating a similarity (in this case) between newly acquired and old reactivated memories. PMID:19190707

Mechanistic Insights into the Oxidation of Substituted Phenols via Hydrogen Atom Abstraction by a Cupric–Superoxo Complex

PubMed Central

2015-01-01

To obtain mechanistic insights into the inherent reactivity patterns for copper(I)–O2 adducts, a new cupric–superoxo complex [(DMM-tmpa)CuII(O2•–)]+ (2) [DMM-tmpa = tris((4-methoxy-3,5-dimethylpyridin-2-yl)methyl)amine] has been synthesized and studied in phenol oxidation–oxygenation reactions. Compound 2 is characterized by UV–vis, resonance Raman, and EPR spectroscopies. Its reactions with a series of para-substituted 2,6-di-tert-butylphenols (p-X-DTBPs) afford 2,6-di-tert-butyl-1,4-benzoquinone (DTBQ) in up to 50% yields. Significant deuterium kinetic isotope effects and a positive correlation of second-order rate constants (k2) compared to rate constants for p-X-DTBPs plus cumylperoxyl radical reactions indicate a mechanism that involves rate-limiting hydrogen atom transfer (HAT). A weak correlation of (kBT/e) ln k2 versus Eox of p-X-DTBP indicates that the HAT reactions proceed via a partial transfer of charge rather than a complete transfer of charge in the electron transfer/proton transfer pathway. Product analyses, 18O-labeling experiments, and separate reactivity employing the 2,4,6-tri-tert-butylphenoxyl radical provide further mechanistic insights. After initial HAT, a second molar equiv of 2 couples to the phenoxyl radical initially formed, giving a CuII–OO–(ArO′) intermediate, which proceeds in the case of p-OR-DTBP substrates via a two-electron oxidation reaction involving hydrolysis steps which liberate H2O2 and the corresponding alcohol. By contrast, four-electron oxygenation (O–O cleavage) mainly occurs for p-R-DTBP which gives 18O-labeled DTBQ and elimination of the R group. PMID:24953129

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

Kan, Jimmy J.; Gottwald, Matthias; Fullerton, Eric E.

We describe low-temperature characterization of magnetic tunnel junctions (MTJs) patterned by reactive ion etching for spin-transfer-torque magnetic random access memory. Magnetotransport measurements of typical MTJs show increasing tunneling magnetoresistance (TMR) and larger coercive fields as temperature is decreased down to 10 K. However, MTJs selected from the high-resistance population of an MTJ array exhibit stable intermediate magnetic states when measured at low temperature and show TMR roll-off below 100 K. These non-ideal low-temperature behaviors arise from edge damage during the etch process and can have negative impacts on thermal stability of the MTJs.

Hyper-reactive cloned mice generated by direct nuclear transfer of antigen-specific CD4+ T cells.

PubMed

Kaminuma, Osamu; Katayama, Kazufumi; Inoue, Kimiko; Saeki, Mayumi; Nishimura, Tomoe; Kitamura, Noriko; Shimo, Yusuke; Tofukuji, Soichi; Ishida, Satoru; Ogonuki, Narumi; Kamimura, Satoshi; Oikawa, Mami; Katoh, Shigeki; Mori, Akio; Shichijo, Michitaka; Hiroi, Takachika; Ogura, Atsuo

2017-06-01

T-cell receptor (TCR)-transgenic mice have been employed for evaluating antigen-response mechanisms, but their non-endogenous TCR might induce immune response differently than the physiologically expressed TCR Nuclear transfer cloning produces animals that retain the donor genotype in all tissues including germline and immune systems. Taking advantage of this feature, we generated cloned mice that carry endogenously rearranged TCR genes from antigen-specific CD4 + T cells. We show that T cells of the cloned mice display distinct developmental pattern and antigen reactivity because of their endogenously pre-rearranged TCRα (rTα) and TCRβ (rTβ) alleles. These alleles were transmitted to the offspring, allowing us to establish a set of mouse lines that show chronic-type allergic phenotypes, that is, bronchial and nasal inflammation, upon local administrations of the corresponding antigens. Intriguingly, the existence of either rTα or rTβ is sufficient to induce in vivo hypersensitivity. These cloned mice expressing intrinsic promoter-regulated antigen-specific TCR are a unique animal model with allergic predisposition for investigating CD4 + T-cell-mediated pathogenesis and cellular commitment in immune diseases. © 2017 The Authors.

Diverse Reactivity of ECp* (E = Al, Ga) toward Low-Coordinate Transition Metal Amides [TM(N(SiMe3)2)2] (TM = Fe, Co, Zn): Insertion, Cp* Transfer, and Orthometalation.

PubMed

Weßing, Jana; Göbel, Christoph; Weber, Birgit; Gemel, Christian; Fischer, Roland A

2017-03-20

The reactivity of the carbenoid group 13 metal ligands ECp* (E = Al, Ga) toward low valent transition metal complexes [TM(btsa) 2 ] (TM = Fe, Co, Zn; btsa = bis(trimethylsilyl)amide) was investigated, revealing entirely different reaction patterns for E = Al and Ga. Treatment of [Co(btsa) 2 ] with AlCp* yields [Cp*Co(μ-H)(Al(κ 2 -(CH 2 SiMe 2 )NSiMe 3 )(btsa))] (1) featuring an unusual heterometallic bicyclic structure that results from the insertion of AlCp* into the TM-N bond with concomitant ligand rearrangement including C-H activation at one amide ligand. For [Fe(btsa) 2 ], complete ligand exchange gives FeCp* 2 , irrespective of the employed stoichiometric ratio of the reactants. In contrast, treatment of [TM(btsa) 2 ] (TM = Fe, Co) with GaCp* forms the 1:1 and 1:2 adducts [(GaCp*)Co(btsa) 2 ] (2) and [(GaCp*) 2 Fe(btsa) 2 ] (3), respectively. The tendency of AlCp* to undergo Cp* transfer to the TM center appears to be dependent on the nature of the TM center: For [Zn(btsa) 2 ], no Cp* transfer is observed on reaction with AlCp*; instead, the insertion product [Zn(Al(η 2 -Cp*)(btsa)) 2 ] (4) is formed. In the reaction of [Co(btsa) 2 ] with the trivalent [Cp*AlH 2 ], transfer of the amide ligands without further ligand rearrangement is observed, leading to [Co(μ-H) 4 (Al(η 2 -Cp*)(btsa)) 2 ] (5).

Mathematical Modeling of the Heat Transfer and Conditions of Ignition of a Turbulent Flow of a Reactive Gas

NASA Astrophysics Data System (ADS)

Matvienko, O. V.

2016-01-01

Results of investigations into the heat transfer and conditions of ignition of a turbulent flow of a chemically reactive gas have been presented. Approximation formulas have been obtained for determining the critical conditions of ignition of the turbulent flow, the length of the preflame zone, and the criterion of heat transfer in subcritical and supercritical reaction regimes.

Transition of late-stage effector T cells to CD27+ CD28+ tumor-reactive effector memory T cells in humans after adoptive cell transfer therapy

PubMed Central

Powell, Daniel J.; Dudley, Mark E.; Robbins, Paul F.; Rosenberg, Steven A.

2007-01-01

In humans, the pathways of memory T-cell differentiation remain poorly defined. Recently, adoptive cell transfer (ACT) of tumor-reactive T lymphocytes to metastatic melanoma patients after nonmyeloablative chemotherapy has resulted in persistence of functional, tumor-reactive lymphocytes, regression of disease, and induction of melanocyte-directed autoimmunity in some responding patients. In the current study, longitudinal phenotypic analysis was performed on melanoma antigen–specific CD8+ T cells during their transition from in vitro cultured effector cells to long-term persistent memory cells following ACT to 6 responding patients. Tumor-reactive T cells used for therapy were generally late-stage effector cells with a CD27Lo CD28Lo CD45RA− CD62 ligand− (CD62L−) CC chemokine receptor 7− (CCR7−) interleukin-7 receptor αLo (IL-7RαLo) phenotype. After transfer, rapid up-regulation and continued expression of IL-7Rα in vivo suggested an important role for IL-7R in immediate and long-term T-cell survival. Although the tumor antigen–specific T-cell population contracted between 1 and 4 weeks after transfer, stable numbers of CD27+ CD28+ tumor-reactive T cells were maintained, demonstrating their contribution to the development of long-term, melanoma-reactive memory CD8+ T cells in vivo. At 2 months after transfer, melanoma-reactive T cells persisted at high levels and displayed an effector memory phenotype, including a CD27+ CD28+ CD62L− CCR7− profile, which may explain in part their ability to mediate tumor destruction. PMID:15345595

Behavioral Reactivity and Approach-Withdrawal Bias in Infancy

PubMed Central

Hane, Amie Ashley; Fox, Nathan A.; Henderson, Heather A.; Marshall, Peter J.

2008-01-01

Seven hundred and seventy nine infants were screened at 4 months of age for motor and emotional reactivity. At age 9 months, infants who showed extreme patterns of motor and negative (n = 75) or motor and positive (n = 73) reactivity and an unselected control group (n = 86) were administered the Laboratory Temperament Assessment Battery (Lab-TAB), and baseline electroencephalogram (EEG) data were collected. Negatively reactive infants showed significantly more avoidance than positively reactive infants and displayed a pattern of right frontal EEG asymmetry. Positively reactive infants exhibited significantly more approach behavior than controls and exhibited a pattern of left frontal asymmetry. Results support the notion that approach-withdrawal bias underlies reactivity in infancy. PMID:18793079

Identification and characterization of B cell precursors in rat lymphoid tissues. I. Adoptive transfer assays for precursors of TI-1, TI-2, and TD antigen-reactive B cells.

PubMed

Whalen, B J; Goldschneider, I

1993-10-01

Quantitative adoptive transfer assays were developed to detect the precursors of TI-1, TI-2, and TD antigen-reactive B cells in rat lymphoid tissues. Studies on the immune responses in normal and athymic nude rats validate the use of TNP-lipopolysaccharide as a TI-1 antigen, TNP-Ficoll as a TI-2 antigen, and SRBC as a TD antigen in rats. The precursors to these immunologically competent B cells are detected, following transfer into irradiated histocompatible recipients, by their ability to generate expanded populations of antigen-reactive B cells capable of mounting antibody responses (splenic IgM plaque-forming cells) to these antigens. Maximal numbers of antigen-reactive B cells emerge in antigenically naive rats after an interval of 7-12 days following transfer of donor lymphoid cells and decline rapidly thereafter. The delayed responses in adoptive recipients reconstituted with spleen cells are proportional to the numbers of spleen cells transferred and are shown to be primarily donor derived using histocompatible Ig kappa chain alloantigen disparate rat strain combinations. The precursors of TI-1, TI-2, and TD antigen-reactive B cells are present in both donor spleen and bone marrow. However, precursor cells to TI-1 and TD antigens are largely absent from donor lymph node cells, whereas precursors to the TI-2 antigen are as prevalent in donor lymph node as in donor spleen. These results support the hypothesis that newly formed virginal B cells represent transient populations of precursor cells that undergo further proliferation and differentiation in the spleen before acquiring immunological competence. The results also suggest that the precursors of TI-2 antigen-reactive B cells differ developmentally from those of TI-1 and TD antigen-reactive B cells, and that the antigen-reactive progeny of these precursors require additional stimulation in order to join the pool of long-lived peripheral B cells.

Aqueous two-phase system patterning of detection antibody solutions for cross-reaction-free multiplex ELISA

NASA Astrophysics Data System (ADS)

Frampton, John P.; White, Joshua B.; Simon, Arlyne B.; Tsuei, Michael; Paczesny, Sophie; Takayama, Shuichi

2014-05-01

Accurate disease diagnosis, patient stratification and biomarker validation require the analysis of multiple biomarkers. This paper describes cross-reactivity-free multiplexing of enzyme-linked immunosorbent assays (ELISAs) using aqueous two-phase systems (ATPSs) to confine detection antibodies at specific locations in fully aqueous environments. Antibody cross-reactions are eliminated because the detection antibody solutions are co-localized only to corresponding surface-immobilized capture antibody spots. This multiplexing technique is validated using plasma samples from allogeneic bone marrow recipients. Patients with acute graft versus host disease (GVHD), a common and serious condition associated with allogeneic bone marrow transplantation, display higher mean concentrations for four multiplexed biomarkers (HGF, elafin, ST2 and TNFR1) relative to healthy donors and transplant patients without GVHD. The antibody co-localization capability of this technology is particularly useful when using inherently cross-reactive reagents such as polyclonal antibodies, although monoclonal antibody cross-reactivity can also be reduced. Because ATPS-ELISA adapts readily available antibody reagents, plate materials and detection instruments, it should be easily transferable into other research and clinical settings.

Aqueous two-phase system patterning of detection antibody solutions for cross-reaction-free multiplex ELISA

PubMed Central

Frampton, John P.; White, Joshua B.; Simon, Arlyne B.; Tsuei, Michael; Paczesny, Sophie; Takayama, Shuichi

2014-01-01

Accurate disease diagnosis, patient stratification and biomarker validation require the analysis of multiple biomarkers. This paper describes cross-reactivity-free multiplexing of enzyme-linked immunosorbent assays (ELISAs) using aqueous two-phase systems (ATPSs) to confine detection antibodies at specific locations in fully aqueous environments. Antibody cross-reactions are eliminated because the detection antibody solutions are co-localized only to corresponding surface-immobilized capture antibody spots. This multiplexing technique is validated using plasma samples from allogeneic bone marrow recipients. Patients with acute graft versus host disease (GVHD), a common and serious condition associated with allogeneic bone marrow transplantation, display higher mean concentrations for four multiplexed biomarkers (HGF, elafin, ST2 and TNFR1) relative to healthy donors and transplant patients without GVHD. The antibody co-localization capability of this technology is particularly useful when using inherently cross-reactive reagents such as polyclonal antibodies, although monoclonal antibody cross-reactivity can also be reduced. Because ATPS-ELISA adapts readily available antibody reagents, plate materials and detection instruments, it should be easily transferable into other research and clinical settings. PMID:24786974

Physics and chemistry of complex oxide etching and redeposition control

NASA Astrophysics Data System (ADS)

Margot, Joëlle

2012-10-01

Since its introduction in the 1970s, plasma etching has become the universal method for fine-line pattern transfer onto thin films and is anticipated to remain so in foreseeable future. Despite many success stories, plasma etching processes fail to meet the needs for several of the newest materials involved in advanced devices for photonic, electronic and RF applications like ferroelectrics, electro-optic materials, high-k dielectrics, giant magnetoresistance materials and unconventional conductors. In this context, the work achieved over the last decade on the etching of multicomponent oxides thin films such as barium strontium titanate (BST), strontium titanate (STO) and niobate of calcium and barium (CBN) will be reviewed. These materials present a low reactivity with usual etching gases such as fluorinated and chlorinated gases, their etching is mainly governed by ion sputtering and reactive gases sometimes interact with surface materials to form compounds that inhibit etching. The etching of platinum will also be presented as an example of unconventional conductor materials for which severe redeposition limits the achievable etching quality. Finally, it will be shown how simulation can help to understand the etching mechanisms and to define avenues for higher quality patterning.

Nanostructured 2D cellular materials in silicon by sidewall transfer lithography NEMS

NASA Astrophysics Data System (ADS)

Syms, Richard R. A.; Liu, Dixi; Ahmad, Munir M.

2017-07-01

Sidewall transfer lithography (STL) is demonstrated as a method for parallel fabrication of 2D nanostructured cellular solids in single-crystal silicon. The linear mechanical properties of four lattices (perfect and defected diamond; singly and doubly periodic honeycomb) with low effective Young’s moduli and effective Poisson’s ratio ranging from positive to negative are modelled using analytic theory and the matrix stiffness method with an emphasis on boundary effects. The lattices are fabricated with a minimum feature size of 100 nm and an aspect ratio of 40:1 using single- and double-level STL and deep reactive ion etching of bonded silicon-on-insulator. Nanoelectromechanical systems (NEMS) containing cellular materials are used to demonstrate stretching, bending and brittle fracture. Predicted edge effects are observed, theoretical values of Poisson’s ratio are verified and failure patterns are described.

Directed assembly of nanomaterials for miniaturized sensors by dip-pen nanolithography using precursor inks

NASA Astrophysics Data System (ADS)

Su, Ming

The advent of nanomaterials with enhanced properties and the means to pattern them in a controlled fashion have paved the way to construct miniaturized sensors for improved detection. However it remains a challenge for the traditional methods to create such sensors and sensor arrays. Dip pen nanolithography (DPN) can form nanostructures on a substrate by controlling the transfer of molecule inks. However, previous DPN can not pattern solid materials on insulating surfaces, which are necessary to form functional electronic devices. In the dissertation, the concept of reactive precursor inks for DPN is developed for the generation of solid functional nanostructures of the following materials: organic molecule, sol-gel material, and conducting polymer. First, the covalent bonding is unnecessary for DPN as shown in the colored ink DPN; therefore the numbers of molecules that can be patterned is extended beyond thiol or thiolated molecules. Subsequently, a reactive precursor strategy (sol) is developed to pattern inorganic or organic/inorganic composite nanostructures on silicon based substrates. The method works by hydrolysis of metal precursors in the water meniscus and allows the preparation of solid structures with controlled geometry beyond the individual molecule level. Then the SnO 2 nanostructures patterned between the gaps of electrodes are tested as gas sensors. Proof-of-concept experiments are demonstrated on miniaturized sensors that show fast response and recovery to certain gases. Furthermore, an eight-unit sensor array is fabricated on a chip using SnO2 sols that are doped with different metals. The multiplexed device can recognize different gases by comparing the response patterns with the reference patterns of known gases generated on the same array. At last, the idea of precursor ink for DPN is extended to construct conducting polymer based devices. By using an acid promoted polymerization approach, conducting polymers are patterned on silicon dioxide substrates. The patterned organic solids response to light and behave as miniaturized photo-detectors. The microstructures are studied using microscopic and spectroscopic techniques.

Gas Phase Reactivity of Carboxylates with N-Hydroxysuccinimide Esters

PubMed Central

Peng, Zhou; McGee, William M.; Bu, Jiexun; Barefoot, Nathan Z.; McLuckey, Scott A.

2015-01-01

N-hydroxysuccinimide (NHS) esters have been used for gas phase conjugation reactions with peptides at nucleophilic sites, such as primary amines (N-terminus, ε-amine of lysine) or guanidines, by forming amide bonds through a nucleophilic attack on the carbonyl carbon. The carboxylate has recently been found to also be a reactive nucleophile capable of initiating a similar nucleophilic attack to form a labile anhydride bond. The fragile bond is easily cleaved, resulting in an oxygen transfer from the carboxylate-containing species to the reagent, nominally observed as a water transfer. This reactivity is shown for both peptides and non-peptidic species. Reagents isotopically labeled with O18 were used to confirm reactivity. This constitutes an example of distinct differences in reactivity of carboxylates between the gas-phase, where they are shown to be reactive, and the solution-phase, where they are not regarded as reactive with NHS esters. PMID:25338221

Infectious reactivation of cytomegalovirus explaining age- and sex-specific patterns of seroprevalence.

PubMed

van Boven, Michiel; van de Kassteele, Jan; Korndewal, Marjolein J; van Dorp, Christiaan H; Kretzschmar, Mirjam; van der Klis, Fiona; de Melker, Hester E; Vossen, Ann C; van Baarle, Debbie

2017-09-01

Human cytomegalovirus (CMV) is a herpes virus with poorly understood transmission dynamics. Person-to-person transmission is thought to occur primarily through transfer of saliva or urine, but no quantitative estimates are available for the contribution of different infection routes. Using data from a large population-based serological study (n = 5,179), we provide quantitative estimates of key epidemiological parameters, including the transmissibility of primary infection, reactivation, and re-infection. Mixture models are fitted to age- and sex-specific antibody response data from the Netherlands, showing that the data can be described by a model with three distributions of antibody measurements, i.e. uninfected, infected, and infected with increased antibody concentration. Estimates of seroprevalence increase gradually with age, such that at 80 years 73% (95%CrI: 64%-78%) of females and 62% (95%CrI: 55%-68%) of males are infected, while 57% (95%CrI: 47%-67%) of females and 37% (95%CrI: 28%-46%) of males have increased antibody concentration. Merging the statistical analyses with transmission models, we find that models with infectious reactivation (i.e. reactivation that can lead to the virus being transmitted to a novel host) fit the data significantly better than models without infectious reactivation. Estimated reactivation rates increase from low values in children to 2%-4% per year in women older than 50 years. The results advance a hypothesis in which transmission from adults after infectious reactivation is a key driver of transmission. We discuss the implications for control strategies aimed at reducing CMV infection in vulnerable groups.

Resistless lithography - selective etching of silicon with gallium doping regions

NASA Astrophysics Data System (ADS)

Abdullaev, D.; Milovanov, R.; Zubov, D.

2016-12-01

This paper presents the results for used of resistless lithography with a further reactive-ion etching (RIE) in various chemistry after local (Ga+) implantation of silicon with different doping dose and different size doped regions. We describe the different etching regimes for pattern transfer of FIB implanted Ga masks in silicon. The paper studied the influence of the implantation dose on the silicon surface, the masking effect and the mask resistance to erosion at dry etching. Based on these results we conclude about the possibility of using this method to create micro-and nanoscale silicon structures.

Oxygen anion (O- ) and hydroxide anion (HO- ) reactivity with a series of old and new refrigerants.

PubMed

Le Vot, Clotilde; Lemaire, Joël; Pernot, Pascal; Heninger, Michel; Mestdagh, Hélène; Louarn, Essyllt

2018-04-01

The reactivity of a series of commonly used halogenated compounds (trihalomethanes, chlorofluorocarbon, hydrochlorofluorocarbon, fluorocarbons, and hydrofluoroolefin) with hydroxide and oxygen anion is studied in a compact Fourier transform ion cyclotron resonance. O - is formed by dissociative electron attachment to N 2 O and HO - by a further ion-molecule reaction with ammonia. Kinetic experiments are performed by increasing duration of introduction of the studied molecule at a constant pressure. Hydroxide anion reactions mainly proceed by proton transfer for all the acidic compounds. However, nucleophilic substitution is observed for chlorinated and brominated compounds. For fluorinated compounds, a specific elimination of a neutral fluorinated alkene is observed in our results in parallel with the proton transfer reaction. Oxygen anion reacts rapidly and extensively with all compounds. Main reaction channels result from nucleophilic substitution, proton transfer, and formal H 2 + transfer. We highlight the importance of transfer processes (atom or ion) in the intermediate ion-neutral complex, explaining part of the observed reactivity and formed ions. In this paper, we present the first reactivity study of anions with HFO 1234yf. Finally, the potential of O - and HO - as chemical ionization reagents for trace analysis is discussed. Copyright © 2017 John Wiley & Sons, Ltd.

REDUCTIVE DEHALOGENATION OF HALOMETHANES IN IRON- AND SULFATE-REDUCING SEDIMENTS. 1. REACTIVITY PATTERN ANALYSIS

EPA Science Inventory

The incorporation of reductive transformations into environmental fate models requires the characterization of natural reductants in well-characterized sediments and aquifer materials. For this purpose, reactivity patterns (i.e., the range and relative order of reactivity) for a...

Child Maltreatment and Autonomic Nervous System Reactivity: Identifying Dysregulated Stress Reactivity Patterns using the Biopsychosocial Model of Challenge and Threat

PubMed Central

McLaughlin, Katie A.; Sheridan, Margaret A.; Alves, Sonia; Mendes, Wendy Berry

2014-01-01

OBJECTIVE Disruptions in stress response system development have been posited as mechanisms linking child maltreatment (CM) to psychopathology. Existing theories predict elevated sympathetic nervous system (SNS) reactivity following CM, but evidence for this is inconsistent. We present a novel framework for conceptualizing stress reactivity following CM using the biopsychosocial model of challenge and threat. We predicted that in the context of a social-evaluative stressor, maltreated adolescents would exhibit a threat pattern of reactivity, involving SNS activation paired with elevated vascular resistance and blunted cardiac output (CO) reactivity. METHODS A sample of 168 adolescents (mean age=14.9 years) participated. Recruitment targeted maltreated adolescents; 38.2% qualified as maltreated. Electrocardiogram, impedance cardiography, and blood pressure were acquired at rest and during an evaluated social stressor (Trier Social Stress Test). Pre-ejection period (PEP), CO, and total peripheral resistance (TPR) reactivity were computed during task preparation, speech-delivery, and verbal mental-arithmetic. Internalizing and externalizing symptoms were assessed. RESULTS Maltreatment was unrelated to PEP reactivity during preparation or speech, but maltreated adolescents had reduced PEP reactivity during math. Maltreatment exposure (F(1,145)=3.8-9.4, p=.053-<.001) and severity (β=−.10-.12, p=.030-.007) were associated with significantly reduced CO reactivity during all components of the stress-task and marginally associated with elevated TPR reactivity (F(1,145)=3.8-9.4, p=.053-<.001; β=.07-.11, p=.11-.009, respectively). Threat reactivity was negatively associated with externalizing symptoms. CONCLUSIONS Child maltreatment is associated with a dysregulated pattern of physiological reactivity consistent with theoretical conceptualizations of threat but not previously examined in relation to maltreatment, suggesting a more nuanced pattern of stress reactivity than predicted by current theoretical models. PMID:25170753

Does a higher metal oxidation state necessarily imply higher reactivity toward H-atom transfer? A computational study of C-H bond oxidation by high-valent iron-oxo and -nitrido complexes.

PubMed

Geng, Caiyun; Ye, Shengfa; Neese, Frank

2014-04-28

In this work, the reactions of C-H bond activation by two series of iron-oxo ( (Fe(IV)), (Fe(V)), (Fe(VI))) and -nitrido model complexes ( (Fe(IV)), (Fe(V)), (Fe(VI))) with a nearly identical coordination geometry but varying iron oxidation states ranging from iv to vi were comprehensively investigated using density functional theory. We found that in a distorted octahedral coordination environment, the iron-oxo species and their isoelectronic nitrido analogues feature totally different intrinsic reactivities toward C-H bond cleavage. In the case of the iron-oxo complexes, the reaction barrier monotonically decreases as the iron oxidation state increases, consistent with the gradually enhanced electrophilicity across the series. The iron-nitrido complex is less reactive than its isoelectronic iron-oxo species, and more interestingly, a counterintuitive reactivity pattern was observed, i.e. the activation barriers essentially remain constant independent of the iron oxidation states. The detailed analysis using the Polanyi principle demonstrates that the different reactivities between these two series originate from the distinct thermodynamic driving forces, more specifically, the bond dissociation energies (BDEE-Hs, E = O, N) of the nascent E-H bonds in the FeE-H products. Further decomposition of the BDEE-Hs into the electron and proton affinity components shed light on how the oxidation states modulate the BDEE-Hs of the two series.

Reactive Behavior Patterns Go Online.

ERIC Educational Resources Information Center

Dziuban, Charles D.; Moskal, Patsy D.; Dziuban, Emily K.

2000-01-01

Surveys of all online students at the University of Central Florida during summer 1997 and spring 1998 provided 381 useable survey instruments assessing learner reactive behavior patterns with the Long-Dziuban Reactive Behavior Protocol. Results indicated that students in online courses tended not to be the independent learners. (PGS)

Asymmetry of flight and escape turning responses in horses.

PubMed

Austin, N P; Rogers, L J

2007-09-01

We investigated whether horses display greater reactivity to a novel stimulus presented in the left compared to the right monocular visual field, and whether a population bias exists for escape turning when the same stimulus was presented binocularly. Domestic horses (N=30) were tested on three occasions by a person opening an umbrella five metres away and then approaching. The distance each horse moved away before stopping was measured. Distance was greatest for approach on the left side, indicating right hemisphere control of flight behaviour, and thus followed the same pattern found previously in other species. When order of monocular presentation was considered, an asymmetry was detected. Horses tested initially on the left side exhibited greater reactivity for left approach, whereas horses tested on the right side first displayed no side difference in reactivity. Perhaps left hemisphere inhibition of flight response allowed horses to learn that the stimulus posed no threat and this information was transferred to the right hemisphere. No population bias existed for the direction of escape turning, but horses that turned to the right when approached from the front were found to exhibit longer flight distances than those that turned to the left.

Microheterogeneity of alpha 1-acid glycoprotein in healthy elderly subjects: patterns obtained by crossed affino-immunoelectrophoresis.

PubMed

Kawerk, N; Succari-Aderschlag, M; Foglietti, M J

1991-10-14

Total serum alpha 1-acid glycoprotein (AGP) concentration and concanavalin A-dependent microheterogeneity were studied in 31 healthy elderly subjects (18 men, 13 women, 71 to 76 yr old). Crossed affino-immunoelectrophoresis (CAIE) revealed three microheterogeneity variants of AGP: non-reactive, weakly reactive and strongly reactive with ConA. Two patterns were found in both elderly men and women, i.e. a normal pattern and one with an increase in the non-reactive form. Mean serum AGP levels in the elderly subjects with slightly higher than in a reference group of younger subjects. The Con A non-reactive form of AGP was increased in 42% of the elderly population. An increase in the non-reactive form of AGP in CAIE should be considered as general expression of chronic inflammation which is of no clinical relevance.

Panallergens and their impact on the allergic patient

PubMed Central

2010-01-01

The panallergen concept encompasses families of related proteins, which are involved in general vital processes and thus, widely distributed throughout nature. Plant panallergens share highly conserved sequence regions, structure, and function. They are responsible for many IgE cross-reactions even between unrelated pollen and plant food allergen sources. Although usually considered as minor allergens, sensitization to panallergens might be problematic as it bears the risk of developing multiple sensitizations. Clinical manifestations seem to be tightly connected with geographical and exposure factors. Future population- and disease-based screenings should provide new insights on panallergens and their contribution to disease manifestations. Such information requires molecule-based diagnostics and will be valuable for developing patient-tailored prophylactic and therapeutic approaches. In this article, we focus on profilins, non-specific lipid transfer proteins, polcalcins, and Bet v 1-related proteins and discuss possible consequences of panallergen sensitization for the allergic patient. Based on their pattern of IgE cross-reactivity, which is reflected by their distribution in the plant kingdom, we propose a novel classification of panallergens into ubiquitously spread "real panallergens" (e.g. profilins) and widespread "eurallergens" (e.g. polcalcins). "Stenallergens" display more limited distribution and cross-reactivity patterns, and "monallergens" are restricted to a single allergen source. PMID:20298513

Persistence of Multiple Tumor-Specific T-Cell Clones Is Associated with Complete Tumor Regression in a Melanoma Patient Receiving Adoptive Cell Transfer Therapy

PubMed Central

Zhou, Juhua; Dudley, Mark E.; Rosenberg, Steven A.; Robbins, Paul F.

2007-01-01

Summary The authors recently reported that adoptive immunotherapy with autologous tumor-reactive tumor infiltrating lymphocytes (TILs) immediately following a conditioning nonmyeloablative chemotherapy regimen resulted in an enhanced clinical response rate in patients with metastatic melanoma. These observations led to the current studies, which are focused on a detailed analysis of the T-cell antigen reactivity as well as the in vivo persistence of T cells in melanoma patient 2098, who experienced a complete regression of all metastatic lesions in lungs and soft tissues following therapy. Screening of an autologous tumor cell cDNA library using transferred TILs resulted in the identification of novel mutated growth arrest-specific gene 7 (GAS7) and glyceral-dehyde-3-phosphate dehydrogenase (GAPDH) gene transcripts. Direct sequence analysis of the expressed T-cell receptor beta chain variable regions showed that the transferred TILs contained multiple T-cell clonotypes, at least six of which persisted in peripheral blood for a month or more following transfer. The persistent T cells recognized both the mutated GAS7 and GAPDH. These persistent tumor-reactive T-cell clones were detected in tumor cell samples obtained from the patient following adoptive cell transfer and appeared to be represented at higher levels in the tumor sample obtained 1 month following transfer than in the peripheral blood obtained at the same time. Overall, these results indicate that multiple tumor-reactive T cells can persist in the peripheral blood and at the tumor site for prolonged times following adoptive transfer and thus may be responsible for the complete tumor regression in this patient. PMID:15614045

Reactive and anticipatory looking in 6-month-old infants during a visual expectation paradigm.

PubMed

Quan, Jeffry; Bureau, Jean-François; Abdul Malik, Adam B; Wong, Johnny; Rifkin-Graboi, Anne

2017-10-01

This article presents data from 278 six-month-old infants who completed a visual expectation paradigm in which audiovisual stimuli were first presented randomly (random phase), and then in a spatial pattern (pattern phase). Infants' eye gaze behaviour was tracked with a 60 Hz Tobii eye-tracker in order to measure two types of looking behaviour: reactive looking (i.e., latency to shift eye gaze in reaction to the appearance of stimuli) and anticipatory looking (i.e., percentage of time spent looking at the location where the next stimulus is about to appear during the inter-stimulus interval). Data pertaining to missing data and task order effects are presented. Further analyses show that infants' reactive looking was faster in the pattern phase, compared to the random phase, and their anticipatory looking increased from random to pattern phases. Within the pattern phase, infants' reactive looking showed a quadratic trend, with reactive looking time latencies peaking in the middle portion of the phase. Similarly, within the pattern phase, infants' anticipatory looking also showed a quadratic trend, with anticipatory looking peaking during the middle portion of the phase.

Distributed Patterns of Reactivation Predict Vividness of Recollection.

PubMed

St-Laurent, Marie; Abdi, Hervé; Buchsbaum, Bradley R

2015-10-01

According to the principle of reactivation, memory retrieval evokes patterns of brain activity that resemble those instantiated when an event was first experienced. Intuitively, one would expect neural reactivation to contribute to recollection (i.e., the vivid impression of reliving past events), but evidence of a direct relationship between the subjective quality of recollection and multiregional reactivation of item-specific neural patterns is lacking. The current study assessed this relationship using fMRI to measure brain activity as participants viewed and mentally replayed a set of short videos. We used multivoxel pattern analysis to train a classifier to identify individual videos based on brain activity evoked during perception and tested how accurately the classifier could distinguish among videos during mental replay. Classification accuracy correlated positively with memory vividness, indicating that the specificity of multivariate brain patterns observed during memory retrieval was related to the subjective quality of a memory. In addition, we identified a set of brain regions whose univariate activity during retrieval predicted both memory vividness and the strength of the classifier's prediction irrespective of the particular video that was retrieved. Our results establish distributed patterns of neural reactivation as a valid and objective marker of the quality of recollection.

Probing ‘Spin-Forbidden’ Oxygen Atom Transfer: Gas-Phase Reactions of Chromium-Porphyrin Complexes

PubMed Central

Fornarini, Simonetta; Lanucara, Francesco; Warren, Jeffrey J.

2010-01-01

Oxygen-atom transfer reactions of metalloporphyrin species play an important role in biochemical and synthetic oxidation reactions. An emerging theme in this chemistry is that spin-state changes can play important roles, and a ‘two-state’ reactivity model has been extensively applied especially in iron-porphyrin systems. Herein we explore the gas phase oxygen-atom transfer chemistry of meso-tetrakis(pentafluorophenyl)porphyrin (TPFPP) chromium complexes, as well as some other tetradentate macrocyclic ligands. Electrospray ionization in concert with Fourier transform ion cyclotron resonance (FT-ICR) spectrometry has been used to characterize and observe reactivity of the ionic species [(TPFPP)CrIII]+ (1) and [(TPFPP)CrVO]+ (2). These are an attractive system to examine the effects of spin state change on oxygen atom transfer because the d1 CrV species are doublets while the CrIII complexes have quartet ground states with high-lying doublet excited states. In the gas phase, [(TPFPP)CrIII]+ forms adducts with a variety of neutral donors but O-atom transfer is only observed for NO2. Pyridine N-oxide adducts of 1 do yield 2 upon collision induced dissociation (CID), but the ethylene oxide, DMSO, and TEMPO analogs do not. [(TPFPP)CrVO]+ is shown by its reactivity and by CID experiments to be a terminal metal-oxo with a single vacant coordination site. It also displays limited reaction chemistry, being deoxygenated only by the very potent reductant P(OMe)3. In general, [(TPFPP)CrVO]+ species are much less reactive than the Fe and Mn analogs. Thermochemical analysis of the reactions points towards the involvement of spin issues in the lower observed reactivity of the chromium complexes. PMID:20218631

PDF methods for turbulent reactive flows

NASA Technical Reports Server (NTRS)

Hsu, Andrew T.

1995-01-01

Viewgraphs are presented on computation of turbulent combustion, governing equations, closure problem, PDF modeling of turbulent reactive flows, validation cases, current projects, and collaboration with industry and technology transfer.

Correlation of structural properties with energy transfer of Eu-doped ZnO thin films prepared by sol-gel process and magnetron reactive sputtering

PubMed Central

Petersen, Julien; Brimont, Christelle; Gallart, Mathieu; Schmerber, Guy; Gilliot, Pierre; Ulhaq-Bouillet, Corinne; Rehspringer, Jean-Luc; Colis, Silviu; Becker, Claude; Slaoui, Abdelillah; Dinia, Aziz

2010-01-01

We investigated the structural and optical properties of Eu-doped ZnO thin films made by sol-gel technique and magnetron reactive sputtering on Si (100) substrate. The films elaborated by sol-gel process are polycrystalline while the films made by sputtering show a strongly textured growth along the c-axis. X-ray diffraction patterns and transmission electron microscopy analysis show that all samples are free of spurious phases. The presence of Eu2+ and Eu3+ into the ZnO matrix has been confirmed by x-ray photoemission spectroscopy. This means that a small fraction of Europium substitutes Zn2+ as Eu2+ into the ZnO matrix; the rest of Eu being in the trivalent state. This is probably due to the formation of Eu2O3 oxide at the surface of ZnO particles. This is at the origin of the strong photoluminescence band observed at 2 eV, which is characteristic of the 5D0→7F2 Eu3+ transition. In addition the photoluminescence excitonic spectra showed efficient energy transfer from the ZnO matrix to the Eu3+ ion, which is qualitatively similar for both films although the sputtered films have a better structural quality compared to the sol-gel process grown films. PMID:20644657

Differences in intersaccadic adaptation transfer between inward and outward adaptation.

PubMed

Schnier, Fabian; Lappe, Markus

2011-09-01

Saccadic adaptation is a mechanism to increase or decrease the amplitude gain of subsequent saccades, if a saccade is not on target. Recent research has shown that the mechanism of gain increasing, or outward adaptation, and the mechanism of gain decreasing, or inward adaptation, rely on partly different processes. We investigate how outward and inward adaptation of reactive saccades transfer to other types of saccades, namely scanning, overlap, memory-guided, and gap saccades. Previous research has shown that inward adaptation of reactive saccades transfers only partially to these other saccade types, suggesting differences in the control mechanisms between these saccade categories. We show that outward adaptation transfers stronger to scanning and overlap saccades than inward adaptation, and that the strength of transfer depends on the duration for which the saccade target is visible before saccade onset. Furthermore, we show that this transfer is mainly driven by an increase in saccade duration, which is apparent for all saccade categories. Inward adaptation, in contrast, is accompanied by a decrease in duration and in peak velocity, but only the peak velocity decrease transfers from reactive saccades to other saccade categories, i.e., saccadic duration remains constant or even increases for test saccades of the other categories. Our results, therefore, show that duration and peak velocity are independent parameters of saccadic adaptation and that they are differently involved in the transfer of adaptation between saccade categories. Furthermore, our results add evidence that inward and outward adaptation are different processes.

Reactive Pendant Mn═O in a Synthetic Structural Model of a Proposed S4 State in the Photosynthetic Oxygen Evolving Complex.

PubMed

Vaddypally, Shivaiah; Kondaveeti, Sandeep K; Karki, Santosh; Van Vliet, Megan M; Levis, Robert J; Zdilla, Michael J

2017-04-05

The molecular mechanism of the Oxygen Evolving Center of photosystem II has been under debate for decades. One frequently cited proposal is the nucleophilic attack by water hydroxide on a pendant Mn═O moiety, though no chemical example of this reactivity at a manganese cubane cluster has been reported. We describe here the preparation, characterization, and a reactivity study of a synthetic manganese cubane cluster with a pendant manganese-oxo moiety. Reaction of this cluster with alkenes results in oxygen and hydrogen atom transfer reactions to form alcohol- and ketone-based oxygen-containing products. Nitrene transfer from core imides is negligible. The inorganic product is a cluster identical to the precursor, but with the pendant Mn═O moiety replaced by a hydrogen abstracted from the organic substrate, and is isolated in quantitative yield. 18 O and 2 H isotopic labeling studies confirm the transfer of atoms between the cluster and the organic substrate. The results suggest that the core cubane structure of this model compound remains intact, and that the pendant Mn═O moiety is preferentially reactive.

Reactivation-Dependent Amnesia in Pavlovian Approach and Instrumental Transfer

ERIC Educational Resources Information Center

Lee, Jonathan L. C.; Everitt, Barry J.

2008-01-01

The theory of memory reconsolidation relates to the hypothesized restabilisation process that occurs following the reactivation of a memory through retrieval. Thus, the demonstration of reactivation-dependent amnesia for a previously acquired memory is a prerequisite for showing that such a memory undergoes reconsolidation. Here, we show that the…

Quenching of triplet-excited flavins by flavonoids. Structural assessment of antioxidative activity.

PubMed

Huvaere, Kevin; Olsen, Karsten; Skibsted, Leif H

2009-10-02

The mechanism of flavin-mediated photooxidation of flavonoids was investigated for aqueous solutions. Interaction of triplet-excited flavin mononucleotide with phenols, as determined by laser flash photolysis, occurred at nearly diffusion-controlled rates (k approximately 1.6 x 10(9) L mol(-1) s(-1) for phenol at pH 7, 293 K), but protection of the phenolic function by methylation inhibited reaction. Still, electron transfer was proposed as the dominating mechanism due to the lack of primary kinetic hydrogen/deuterium isotope effect and the low activation enthalpy (<20 kJ mol(-1)) for photooxidation. Activation entropy worked compensating in a series of phenolic derivatives, supporting a common oxidation mechanism. An ortho-hydroxymethoxy pattern was equally reactive (k approximately 2.3 x 10(9) L mol(-1) s(-1) for guaiacol at pH 7) as compounds with ortho-dihydroxy substitution (k approximately 2.4 x 10(9) L mol(-1) s(-1) for catechol at pH 7), which are generally referred to as good antioxidants. This refutes the common belief that stabilization of incipient phenoxyl radicals through intramolecular hydrogen bonding is the driving force behind the reducing activity of catechol-like compounds. Instead, such bonding improves ionization characteristics of the substrates, hence the differences in reactivity with (photo)oxidation of isolated phenols. Despite the similar reactivity, radicals from ortho-dihydroxy compounds are detected in high steady-state concentrations by electron paramagnetic resonance (EPR) spectroscopy, while those resulting from oxidation of ortho-hydroxymethoxy (or isolated phenolic) patterns were too reactive to be observed. The ability to deprotonate and form the corresponding radical anions at neutral pH was proposed as the decisive factor for stabilization and, consequently, for antioxidative action. Thus, substituting other ionizable functions for the ortho- or para-hydroxyl in phenolic compounds resulted in stable radical anion formation, as demonstrated for para-hydroxybenzoic acid, in contrast to its methyl ester.

Experimental Investigation of Piston Heat Transfer in a Light Duty Engine Under Conventional Diesel, Homogeneous Charge Compression Ignition, and Reactivity Controlled Compression Ignition Combustion Regimes

DTIC Science & Technology

2014-01-15

in a Light Duty Engine Under Conventional Diesel, Homogeneous Charge Compression Ignition , and Reactivity Controlled Compression Ignition ...Conventional Diesel (CDC), Homogeneous Charge Compression Ignition (HCCI), and Reactivity Controlled Compression Ignition (RCCI) combustion...LTC) regimes, including reactivity controlled compression ignition (RCCI), partially premixed combustion (PPC), and homogenous charge compression

First steps towards a gas-phase acidity ladder for derivatized fullerene dications

NASA Astrophysics Data System (ADS)

Petrie, Simon; Javahery, Gholamreza; Bohme, Diethard K.

1993-03-01

C2+60 can be derivatized by gas-phase ion/molecule reactions with polar hydrogen-bearing molecules. The adduct dications so produced may then undergo proton transfer to neutrals. The occurrence or absence of proton transfer as a secondary process gives information on the gas-phase acidity of the dicationic species C60·(XH)2+in. We have performed studies using a selected-ion flow tube at 294 ± 2 K and 0.35 ± 0.01 Torr, and have used observed reactivity of such dicationic fullerene adducts to determine upper or lower limits to their apparent and absolute gas-phase acidities. We present also a rationale for assessing the proton-transfer reactivity of dications via the apparent gas-phase acidity of these species, rather than the traditional use of gas-phase basicities or proton affinities. We propose that further studies of proton transfer from polycharged fullerene adducts may provide considerable useful information to model the reactivity of polyprotonated proteins and other large molecular polycatiions which can now be produced by techniques such as electrospray ionization.

Patterns of Children's Adrenocortical Reactivity to Interparental Conflict and Associations with Child Adjustment: A Growth Mixture Modeling Approach

ERIC Educational Resources Information Center

Koss, Kalsea J.; George, Melissa R. W.; Davies, Patrick T.; Cicchetti, Dante; Cummings, E. Mark; Sturge-Apple, Melissa L.

2013-01-01

Examining children's physiological functioning is an important direction for understanding the links between interparental conflict and child adjustment. Utilizing growth mixture modeling, the present study examined children's cortisol reactivity patterns in response to a marital dispute. Analyses revealed three different patterns of cortisol…

Gray scale x-ray mask

DOEpatents

Morales, Alfredo M [Livermore, CA; Gonzales, Marcela [Seattle, WA

2006-03-07

The present invention describes a method for fabricating an embossing tool or an x-ray mask tool, providing microstructures that smoothly vary in height from point-to-point in etched substrates, i.e., structure which can vary in all three dimensions. The process uses a lithographic technique to transfer an image pattern in the surface of a silicon wafer by exposing and developing the resist and then etching the silicon substrate. Importantly, the photoresist is variably exposed so that when developed some of the resist layer remains. The remaining undeveloped resist acts as an etchant barrier to the reactive plasma used to etch the silicon substrate and therefore provides the ability etch structures of variable depths.

Cardiovascular reactivity patterns and pathways to hypertension: a multivariate cluster analysis.

PubMed

Brindle, R C; Ginty, A T; Jones, A; Phillips, A C; Roseboom, T J; Carroll, D; Painter, R C; de Rooij, S R

2016-12-01

Substantial evidence links exaggerated mental stress induced blood pressure reactivity to future hypertension, but the results for heart rate reactivity are less clear. For this reason multivariate cluster analysis was carried out to examine the relationship between heart rate and blood pressure reactivity patterns and hypertension in a large prospective cohort (age range 55-60 years). Four clusters emerged with statistically different systolic and diastolic blood pressure and heart rate reactivity patterns. Cluster 1 was characterised by a relatively exaggerated blood pressure and heart rate response while the blood pressure and heart rate responses of cluster 2 were relatively modest and in line with the sample mean. Cluster 3 was characterised by blunted cardiovascular stress reactivity across all variables and cluster 4, by an exaggerated blood pressure response and modest heart rate response. Membership to cluster 4 conferred an increased risk of hypertension at 5-year follow-up (hazard ratio=2.98 (95% CI: 1.50-5.90), P<0.01) that survived adjustment for a host of potential confounding variables. These results suggest that the cardiac reactivity plays a potentially important role in the link between blood pressure reactivity and hypertension and support the use of multivariate approaches to stress psychophysiology.

Rapid Functional Decline of Activated and Memory Graft-vs-Host-Reactive T Cells Encountering Host Antigens in the Absence of Inflammation

PubMed Central

Li, Hao Wei; Andreola, Giovanna; Carlson, Alicia; Shao, Steven; Lin, Charles; Zhao, Guiling; Sykes, Megan

2015-01-01

Inflammation in the priming host environment has critical effects on the graft-vs-host (GVH) responses mediated by naïve donor T cells. However, it is unclear how a quiescent or inflammatory environment impacts the activity of GVH-reactive primed T and memory cells. We show here that GVH-reactive primed donor T cells generated in irradiated recipients had diminished ability compared to naïve T cells to increase donor chimerism when transferred to quiescent mixed allogeneic chimeras. GVH-reactive primed T cells showed marked loss of cytotoxic function and activation and delayed but not decreased proliferation or accumulation in lymphoid tissues when transferred to quiescent mixed chimeras compared to freshly irradiated secondary recipients. Primed CD4 and CD8 T cells provided mutual help to sustain these functions in both subsets. CD8 help for CD4 cells was largely IFN-γ-dependent. Toll-like receptor (TLR) stimulation following transfer of GVH-reactive primed T cells to mixed chimeras restored their cytotoxic effector function and permitted the generation of more effective T cell memory in association with reduced PD-1 expression on CD4 memory cells. Our data indicate that an inflammatory host environment is required for the maintenance of GVH-reactive primed T cell functions and the generation of memory T cells that can rapidly acquire effector functions. These findings have important implications for GVHD and T cell-mediated immunotherapies. PMID:26085679

Platinum transfer from hCTR1 to Atox1 is dependent on the type of platinum complex.

PubMed

Wu, Xuelei; Yuan, Siming; Wang, Erqiong; Tong, Yang; Ma, Guolin; Wei, Kaiju; Liu, Yangzhong

2017-05-24

In spite of their wide application, the cellular uptake of platinum based anticancer drugs is still unclear. The copper transport protein, hCTR1, is proposed to facilitate the cellular uptake of cisplatin, whereas organic cation transport (OCT) is more important for oxaliplatin. It has been reported that both N-terminal and C-terminal metal binding motifs of hCTR1 are highly reactive to cisplatin, which is the initial step of protein assisted cellular uptake of cisplatin. It is still unknown how the platinum drugs in hCTR1 transfer to cytoplasmic media, and whether various platinum complexes possess different activities in this process. Herein, we investigated the reaction of the platinated C-terminal metal binding motif of hCTR1 (C8) with the down-stream protein Atox1. Results show that Atox1 is highly reactive to the platinated C8 adducts of cisplatin and transplatin, whereas the oxaliplatin/C8 adduct is much less reactive. The platinum transfer from C8 to Atox1 occurs in the reaction, which results in the protein unfolding of Atox1. These results demonstrated that the platinated intracellular-domain of hCTR1 is reactive to Atox1, and the reactivity is dependent on the ligand and the coordination structure of platinum complexes. The different reactivity is consistent with the hypothesis that hCTR1 is more significant in the transport of cisplatin than that of oxaliplatin.

Ring-shaped stain patterns driven by solute reactive mesogens in liquid crystal solution

NASA Astrophysics Data System (ADS)

Cha, Tae Woon; Bulliard, Xavier; Choi, Sang Gun; Lee, Hyoung Sub; Kong, Hyang-Shik; Han, Sang Youn

2014-07-01

We report on the formation of ring-shaped stain patterns in a polymer-stabilized patterned vertical alignment mode liquid crystal display (LCD) during the cell filling process. Through the interpretation of the formation mechanism, an effective way to control its development is provided. Systematic trace of the reactive mesogens reveals that the formation of patterns is strongly related to the segregation of solute mesogens in the stain area. These undesirable patterns can be avoided or controlled by reducing the drop volume at each droplet using an inkjet printing technique, meaning that the printing technique could be a useful solution in display technology. For the formation of ring-shaped patterns, the dragging of reactive mesogens during the spreading of the liquid crystal solution plays a key role in the closed LCD cell.

Hydropersulfides: H-Atom Transfer Agents Par Excellence.

PubMed

Chauvin, Jean-Philippe R; Griesser, Markus; Pratt, Derek A

2017-05-10

Hydropersulfides (RSSH) are formed endogenously via the reaction of the gaseous biotransmitter hydrogen sulfide (H 2 S) and disulfides (RSSR) and/or sulfenic acids (RSOH). RSSH have been investigated for their ability to store H 2 S in vivo and as a line of defense against oxidative stress, from which it is clear that RSSH are much more reactive to two-electron oxidants than thiols. Herein we describe the results of our investigations into the H-atom transfer chemistry of RSSH, contrasting it with the well-known H-atom transfer chemistry of thiols. In fact, RSSH are excellent H-atom donors to alkyl (k ∼ 5 × 10 8 M -1 s -1 ), alkoxyl (k ∼ 1 × 10 9 M -1 s -1 ), peroxyl (k ∼ 2 × 10 6 M -1 s -1 ), and thiyl (k > 1 × 10 10 M -1 s -1 ) radicals, besting thiols by as little as 1 order and as much as 4 orders of magnitude. The inherently high reactivity of RSSH to H-atom transfer is based largely on thermodynamic factors; the weak RSS-H bond dissociation enthalpy (∼70 kcal/mol) and the associated high stability of the perthiyl radical make the foregoing reactions exothermic by 15-34 kcal/mol. Of particular relevance in the context of oxidative stress is the reactivity of RSSH to peroxyl radicals, where favorable thermodynamics are bolstered by a secondary orbital interaction in the transition state of the formal H-atom transfer that drives the inherent reactivity of RSSH to match that of α-tocopherol (α-TOH), nature's premier radical-trapping antioxidant. Significantly, the reactivity of RSSH eclipses that of α-TOH in H-bond-accepting media because of their low H-bond acidity (α 2 H ∼ 0.1). This affords RSSH a unique versatility compared to other highly reactive radical-trapping antioxidants (e.g., phenols, diarylamines, hydroxylamines, sulfenic acids), which tend to have high H-bond acidities. Moreover, the perthiyl radicals that result are highly persistent under autoxidation conditions and undergo very rapid dimerization (k = 5 × 10 9 M -1 s -1 ) in lieu of reacting with O 2 or autoxidizable substrates.

Transfer zones and fault reactivation in inverted rift basins: Insights from physical modelling

NASA Astrophysics Data System (ADS)

Konstantinovskaya, Elena A.; Harris, Lyal B.; Poulin, Jimmy; Ivanov, Gennady M.

2007-08-01

Lateral transfer zones of deformation and fault reactivation were investigated in multilayered silicone-sand models during extension and subsequent co-axial shortening. Model materials were selected to meet similarity criteria and to be distinguished on CT scans; this approach permitted non-destructive visualisation of the progressive evolution of structures. Transfer zones were initiated by an orthogonal offset in the geometry of a basal mobile aluminium sheet and/or by variations of layer thickness or material rheology in basal layers. Transfer zones affected rift propagation and fault kinematics in models. Propagation and overlapping rift culminations occurred in transfer zones during extension. During shortening, deviation in the orientation of frontal thrusts and fold axes occurred within transfer zones in brittle and ductile layers, respectively. CT scans showed that steep (58-67°) rift-margin normal faults were reactivated as reverse faults. The reactivated faults rotated to shallower dips (19-38°) with continuing shortening after 100% inversion. Rotation of rift phase faults appears to be due to deep level folding and uplift during the inversion phase. New thrust faults with shallow dips (20-34°) formed outside the inverted graben at late stages of shortening. Frontal ramps propagated laterally past the transfer structure during shortening. During inversion, the layers filling the rift structures underwent lateral compression at the depth, the graben fill was pushed up and outwards creating local extension near the surface. Sand marker layers in inverted graben have showed fold-like structures or rotation and tilting in the rifts and on the rift margins. The results of our experiments conform well to natural examples of inverted graben. Inverted rift basins are structurally complex and often difficult to interpret in seismic data. The models may help to unravel the structure and evolution of these systems, leading to improved hydrocarbon exploration assessments. Model results may also be used to help predict the location of basement discontinuities which may have focused hydrothermal fluids during basin formation and inversion.

Memory consolidation by replay of stimulus-specific neural activity.

PubMed

Deuker, Lorena; Olligs, Jan; Fell, Juergen; Kranz, Thorsten A; Mormann, Florian; Montag, Christian; Reuter, Martin; Elger, Christian E; Axmacher, Nikolai

2013-12-04

Memory consolidation transforms initially labile memory traces into more stable representations. One putative mechanism for consolidation is the reactivation of memory traces after their initial encoding during subsequent sleep or waking state. However, it is still unknown whether consolidation of individual memory contents relies on reactivation of stimulus-specific neural representations in humans. Investigating stimulus-specific representations in humans is particularly difficult, but potentially feasible using multivariate pattern classification analysis (MVPA). Here, we show in healthy human participants that stimulus-specific activation patterns can indeed be identified with MVPA, that these patterns reoccur spontaneously during postlearning resting periods and sleep, and that the frequency of reactivation predicts subsequent memory for individual items. We conducted a paired-associate learning task with items and spatial positions and extracted stimulus-specific activity patterns by MVPA in a simultaneous electroencephalography and functional magnetic resonance imaging (fMRI) study. As a first step, we investigated the amount of fMRI volumes during rest that resembled either one of the items shown before or one of the items shown as a control after the resting period. Reactivations during both awake resting state and sleep predicted subsequent memory. These data are first evidence that spontaneous reactivation of stimulus-specific activity patterns during resting state can be investigated using MVPA. They show that reactivation occurs in humans and is behaviorally relevant for stabilizing memory traces against interference. They move beyond previous studies because replay was investigated on the level of individual stimuli and because reactivations were not evoked by sensory cues but occurred spontaneously.

High Aspect Ratio Sub-15 nm Silicon Trenches From Block Copolymer Templates

NASA Astrophysics Data System (ADS)

Gu, Xiaodan; Liu, Zuwei; Gunkel, Ilja; Olynick, Deirdre; Russell, Thomas; University of Massachusetts Amherst Collaboration; Oxford Instrument Collaboration; Lawrence Berkeley National Lab Collaboration

2013-03-01

High-aspect-ratio sub-15 nm silicon trenches are fabricated directly from plasma etching of a block copolymer (BCP) mask. Polystyrene-b-poly(2-vinyl pyridine) (PS-b-P2VP) 40k-b-18k was spin coated and solvent annealed to form cylindrical structures parallel to the silicon substrate. The BCP thin film was reconstructed by immersion in ethanol and then subjected to an oxygen and argon reactive ion etching to fabricate the polymer mask. A low temperature ion coupled plasma with sulfur hexafluoride and oxygen was used to pattern transfer block copolymer structure to silicon with high selectivity (8:1) and fidelity. The silicon pattern was characterized by scanning electron microscopy and grazing incidence x-ray scattering. We also demonstrated fabrication of silicon nano-holes using polystyrene-b-polyethylene oxide (PS-b-PEO) using same methodology described above for PS-b-P2VP. Finally, we show such silicon nano-strucutre serves as excellent nano-imprint master template to pattern various functional materials like poly 3-hexylthiophene (P3HT).

Nanoscale Reactive Ion Etching of Silicon Nitride Thin Films for Embedded Nanomagnetic Device Fabrication

NASA Astrophysics Data System (ADS)

Hibbard-Lubow, David Luke

The demands of digital memory have increased exponentially in recent history, requiring faster, smaller and more accurate storage methods. Two promising solutions to this ever-present problem are Bit Patterned Media (BPM) and Spin-Transfer Torque Magnetic Random Access Memory (STT-MRAM). Producing these technologies requires difficult and expensive fabrication techniques. Thus, the production processes must be optimized to allow these storage methods to compete commercially while continuing to increase their information storage density and reliability. I developed a process for the production of nanomagnetic devices (which can take the form of several types of digital memory) embedded in thin silicon nitride films. My focus was on optimizing the reactive ion etching recipe required to embed the device in the film. Ultimately, I found that recipe 37 (Power: 250W, CF4 nominal/actual flow rate: 25/25.4 sccm, O2 nominal/actual flow rate: 3.1/5.2 sccm, which gave a maximum pressure around 400 mTorr) gave the most repeatable and anisotropic results. I successfully used processes described in this thesis to make embedded nanomagnets, which could be used as bit patterned media. Another promising application of this work is to make embedded magnetic tunneling junctions, which are the storage medium used in MRAM. Doing so will require still some tweaks to the fabrication methods. Techniques for making these changes and their potential effects are discussed.

Highly sensitive SnO2 sensor via reactive laser-induced transfer

PubMed Central

Palla Papavlu, Alexandra; Mattle, Thomas; Temmel, Sandra; Lehmann, Ulrike; Hintennach, Andreas; Grisel, Alain; Wokaun, Alexander; Lippert, Thomas

2016-01-01

Gas sensors based on tin oxide (SnO2) and palladium doped SnO2 (Pd:SnO2) active materials are fabricated by a laser printing method, i.e. reactive laser-induced forward transfer (rLIFT). Thin films from tin based metal-complex precursors are prepared by spin coating and then laser transferred with high resolution onto sensor structures. The devices fabricated by rLIFT exhibit low ppm sensitivity towards ethanol and methane as well as good stability with respect to air, moisture, and time. Promising results are obtained by applying rLIFT to transfer metal-complex precursors onto uncoated commercial gas sensors. We could show that rLIFT onto commercial sensors is possible if the sensor structures are reinforced prior to printing. The rLIFT fabricated sensors show up to 4 times higher sensitivities then the commercial sensors (with inkjet printed SnO2). In addition, the selectivity towards CH4 of the Pd:SnO2 sensors is significantly enhanced compared to the pure SnO2 sensors. Our results indicate that the reactive laser transfer technique applied here represents an important technical step for the realization of improved gas detection systems with wide-ranging applications in environmental and health monitoring control. PMID:27118531

Mixing-controlled reactive transport on travel times in heterogeneous media

NASA Astrophysics Data System (ADS)

Luo, J.; Cirpka, O.

2008-05-01

Modeling mixing-controlled reactive transport using traditional spatial discretization of the domain requires identifying the spatial distributions of hydraulic and reactive parameters including mixing-related quantities such as dispersivities and kinetic mass-transfer coefficients. In most applications, breakthrough curves of conservative and reactive compounds are measured at only a few locations and models are calibrated by matching these breakthrough curves, which is an ill posed inverse problem. By contrast, travel-time based transport models avoid costly aquifer characterization. By considering breakthrough curves measured on different scales, one can distinguish between mixing, which is a prerequisite for reactions, and spreading, which per se does not foster reactions. In the travel-time based framework, the breakthrough curve of a solute crossing an observation plane, or ending in a well, is interpreted as the weighted average of concentrations in an ensemble of non-interacting streamtubes, each of which is characterized by a distinct travel-time value. Mixing is described by longitudinal dispersion and/or kinetic mass transfer along individual streamtubes, whereas spreading is characterized by the distribution of travel times which also determines the weights associated to each stream tube. Key issues in using the travel-time based framework include the description of mixing mechanisms and the estimation of the travel-time distribution. In this work, we account for both apparent longitudinal dispersion and kinetic mass transfer as mixing mechanisms, thus generalizing the stochastic-convective model with or without inter-phase mass transfer and the advective-dispersive streamtube model. We present a nonparametric approach of determining the travel-time distribution, given a breakthrough curve integrated over an observation plane and estimated mixing parameters. The latter approach is superior to fitting parametric models in cases where the true travel-time distribution exhibits multiple peaks or long tails. It is demonstrated that there is freedom for the combinations of mixing parameters and travel-time distributions to fit conservative breakthrough curves and describe the tailing. Reactive transport cases with a bimolecular instantaneous irreversible reaction and a dual Michaelis-Menten problem demonstrate that the mixing introduced by local dispersion and mass transfer may be described by apparent mean mass transfer with coefficients evaluated by local breakthrough curves.

Oligosaccharide/silicon-containing block copolymers with 5 nm features for lithographic applications.

PubMed

Cushen, Julia D; Otsuka, Issei; Bates, Christopher M; Halila, Sami; Fort, Sébastien; Rochas, Cyrille; Easley, Jeffrey A; Rausch, Erica L; Thio, Anthony; Borsali, Redouane; Willson, C Grant; Ellison, Christopher J

2012-04-24

Block copolymers demonstrate potential for use in next-generation lithography due to their ability to self-assemble into well-ordered periodic arrays on the 3-100 nm length scale. The successful lithographic application of block copolymers relies on three critical conditions being met: high Flory-Huggins interaction parameters (χ), which enable formation of <10 nm features, etch selectivity between blocks for facile pattern transfer, and thin film self-assembly control. The present paper describes the synthesis and self-assembly of block copolymers composed of naturally derived oligosaccharides coupled to a silicon-containing polystyrene derivative synthesized by activators regenerated by electron transfer atom transfer radical polymerization. The block copolymers have a large χ and a low degree of polymerization (N) enabling formation of 5 nm feature diameters, incorporate silicon in one block for oxygen reactive ion etch contrast, and exhibit bulk and thin film self-assembly of hexagonally packed cylinders facilitated by a combination of spin coating and solvent annealing techniques. As observed by small angle X-ray scattering and atomic force microscopy, these materials exhibit some of the smallest block copolymer features in the bulk and in thin films reported to date.

Transfer of Old "Reactivated" Memory Retrieval Cues in Rats

ERIC Educational Resources Information Center

Briggs, James F.; Riccio, David C.

2008-01-01

The present studies examined whether the retrieval of an old "reactivated" memory could be brought under the control of new contextual cues. In Experiment 1 rats trained in one context were exposed to different contextual cues either immediately, 60 or 120 min after a cued reactivation of the training memory. When tested in the shifted context,…

Transient heat and mass transfer analysis in a porous ceria structure of a novel solar redox reactor

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

Chandran, RB; Bader, R; Lipinski, W

2015-06-01

Thermal transport processes are numerically analyzed for a porous ceria structure undergoing reduction in a novel redox reactor for solar thermochemical fuel production. The cylindrical reactor cavity is formed by an array of annular reactive elements comprising the porous ceria monolith integrated with gas inlet and outlet channels. Two configurations are considered, with the reactor cavity consisting of 10 and 20 reactive elements, respectively. Temperature dependent boundary heat fluxes are obtained on the irradiated cavity wall by solving for the surface radiative exchange using the net radiation method coupled to the heat and mass transfer model of the reactive element.more » Predicted oxygen production rates are in the range 40-60 mu mol s(-1) for the geometries considered. After an initial rise, the average temperature of the reactive element levels off at 1660 and 1680 K for the two geometries, respectively. For the chosen reduction reaction rate model, oxygen release continues after the temperature has leveled off which indicates that the oxygen release reaction is limited by chemical kinetics and/or mass transfer rather than by the heating rate. For a fixed total mass of ceria, the peak oxygen release rate is doubled for the cavity with 20 reactive elements due to lower local oxygen partial pressure. (C) 2015 Elsevier Masson SAS. All rights reserved.« less

Heat transfer fluids containing nanoparticles

DOEpatents

Singh, Dileep; Routbort, Jules; Routbort, A.J.; Yu, Wenhua; Timofeeva, Elena; Smith, David S.; France, David M.

2016-05-17

A nanofluid of a base heat transfer fluid and a plurality of ceramic nanoparticles suspended throughout the base heat transfer fluid applicable to commercial and industrial heat transfer applications. The nanofluid is stable, non-reactive and exhibits enhanced heat transfer properties relative to the base heat transfer fluid, with only minimal increases in pumping power required relative to the base heat transfer fluid. In a particular embodiment, the plurality of ceramic nanoparticles comprise silicon carbide and the base heat transfer fluid comprises water and water and ethylene glycol mixtures.

A Novel Nano/Micro-Fluidic Reactor for Evaluation of Pore-Scale Reactive Transport

NASA Astrophysics Data System (ADS)

Werth, C. J.; Alcalde, R.; Ghazvini, S.; Sanford, R. A.; Fouke, B. W.; Valocchi, A. J.

2017-12-01

The reactive transport of pollutants in groundwater can be affected by the presence of stressor chemicals, which inhibit microbial functions. The stressor can be a primary reactant (e.g., trichloroethene), a reaction product (e.g., nitrite from nitrate), or some other chemical present in groundwater (e.g., antibiotic). In this work, a novel nano/microfluidic cell was developed to examine the effect of the antibiotic ciprofloxacin on nitrate reduction coupled to lactate oxidation. The reactor contains parallel boundary channels that deliver flow and solutes on either side of a pore network. The boundary channels are separated from the pore network by one centimeter-long, one micrometer-thick walls perforated by hundreds of nanoslits. The nanoslits allow solute mass transfer from the boundary channels to the pore network, but not microbial passage. The pore network was inoculated with a pure culture of Shewanella oneidensis MR-1, and this was allowed to grow on lactate and nitrate in the presence of ciprofloxacin, all delivered through the boundary channels. Microbial growth patterns suggest inhibition from ciprofloxacin and the nitrate reduction product nitrite, and a dependence on nitrate and lactate mass transfer rates from the boundary channels. A numerical model was developed to interpret the controlling mechanisms, and results indicate cell chemotaxis also affects nitrate reduction and microbial growth. The results are broadly relevant to bioremediation efforts where one or more chemicals that inhibit microbial growth are present and inhibit pollutant degradation rates.

CD8+ T cells produce a dialyzable antigen-specific activator of dendritic cells

PubMed Central

Myles, Ian A.; Zhao, Ming; Nardone, Glenn; Olano, Lisa R.; Reckhow, Jensen D.; Saleem, Danial; Break, Timothy J.; Lionakis, Michail S.; Myers, Timothy G.; Gardina, Paul J.; Kirkpatrick, Charles H.; Holland, Steven M.; Datta, Sandip K.

2017-01-01

Cellular lysates from PPD+ donors have been reported to transfer tuberculin reactivity to naïve recipients, but not diphtheria reactivity, and vice versa. A historically controversial topic, the terms "transfer factor" and "DLE" were used to characterize the reactivity-transferring properties of lysates. Intrigued by these reported phenomena, we found that the cellular extract derived from antigen-specific memory CD8+ T cells induces IL-6 from antigen-matched APCs. This ultimately elicits IL-17 from bystander memory CD8+ T cells. We have identified that dialyzable peptide sequences, S100a9, and the TCR β chain from CD8+ T cells contribute to the molecular nature of this activity. We further show that extracts from antigen-targeted T cells enhance immunity to Staphylococcus aureus and Candida albicans. These effects are sensitive to immunization protocols and extraction methodology in ways that may explain past discrepancies in the reproducibility of passive cellular immunity. PMID:27515950

Density functional study of the structural, electronic, and magnetic properties of Mo n and Mo n S ( n = 1 - 10) clusters

NASA Astrophysics Data System (ADS)

Ziane, M.; Amitouche, F.; Bouarab, S.; Vega, A.

2017-12-01

Structural and electronic properties of pure molybdenum Mo n and molybdenum-sulfide Mo n S ( n = 1 - 10) clusters were investigated in the framework of the density functional theory within the generalized gradient approximation to exchange and correlation with the aim of addressing how doping with a single S atom affects the geometries, magnetic properties, and reactivity of pure molybdenum clusters. These clusters exhibit a less marked tendency to dimerization than their isoelectronic Cr counterparts despite sharing their half-filled valence shell configuration. Doping with a single S impurity is enough to change the structure of the host molybdenum cluster to a large extent, as well as to modify the bonding pattern, the magnetic state and the magnetic moment distribution in the Mo host. Vertical ionization potentials and electron affinities are calculated to determine global reactivity indicators like the electronegativity and the chemical hardness. The results are discussed in terms of the thermodynamical and relative stabilities, charge transfer effects, and spin-polarized densities of electronic states.

Evaluation of an enzyme immunoassay system for measuring herpes simplex virus (HSV) type 1-specific and HSV type 2-specific IgG antibodies.

PubMed

Prince, H E; Ernst, C E; Hogrefe, W R

2000-01-01

MRL Diagnostics has developed a dual enzyme immunoassay (EIA) system that employs the recombinant Herpes Simplex Virus (HSV) type-specific glycoproteins G1 (HSV1) and G2 (HSV2) to detect HSV type-specific IgG antibodies. This system was evaluated using 155 consecutive sera previously tested in a conventional dual EIA system (Zeus) that employs multiple HSV1 and HSV2 proteins to detect type-common as well as type-specific antibodies. Sera were also analyzed by Western blot to determine the true HSV type-specific IgG reactivity pattern. Of 110 sera giving concordant reactivity patterns in the MRL and Zeus EIA systems, 108 (98%) also displayed concordant Western blot patterns; two sera gave false positive HSV2 reactivity in both EIA systems. Of 45 sera giving discordant MRL and Zeus EIA reactivity patterns, 41 (91%) displayed a Western blot reactivity pattern that matched the MRL reactivity pattern. Both the HSV1 IgG component and the HSV2 IgG component of the MRL EIA system were 100% sensitive and > 95% specific. In contrast, the Zeus HSV1 IgG EIA was 98% sensitive and 79% specific, and the Zeus HSV2 IgG EIA was 85% sensitive and 79% specific. An analysis of the distribution of index values in the MRL EIA system showed that low-positive values (1.0-3.0) were rare, but, when detected, often represented false positive results; only 11 MRL low-positive results were observed, but all 6 MRL false positive results were found within this low-positive subgroup. These findings show that the MRL dual EIA system effectively detects HSV type-specific IgG antibodies. Copyright 2000 Wiley-Liss, Inc.

Synthesis, Characterization and Reactivity of a Hexane-Soluble Silver Salt

ERIC Educational Resources Information Center

Stockland, Robert A. Jr.; Wilson, Brian D.; Goodman, Caton C.; Giese, Barret J.; Shrimp, Frederick L., II

2007-01-01

The connectivity of a hexane-soluble silver salt is established by using NMR spectroscopy to describe the synthesis, characterization and reactivity of the salt. The results found hexane-soluble silver to be an effective transfer agent.

Reactivity of hydropersulfides toward the hydroxyl radical unraveled: disulfide bond cleavage, hydrogen atom transfer, and proton-coupled electron transfer.

PubMed

Anglada, Josep M; Crehuet, Ramon; Adhikari, Sarju; Francisco, Joseph S; Xia, Yu

2018-02-14

Hydropersulfides (RSSH) are highly reactive as nucleophiles and hydrogen atom transfer reagents. These chemical properties are believed to be key for them to act as antioxidants in cells. The reaction involving the radical species and the disulfide bond (S-S) in RSSH, a known redox-active group, however, has been scarcely studied, resulting in an incomplete understanding of the chemical nature of RSSH. We have performed a high-level theoretical investigation on the reactions of the hydroxyl radical (˙OH) toward a set of RSSH (R = -H, -CH 3 , -NH 2 , -C(O)OH, -CN, and -NO 2 ). The results show that S-S cleavage and H-atom abstraction are the two competing channels. The electron inductive effect of R induces selective ˙OH substitution at one sulfur atom upon S-S cleavage, forming RSOH and ˙SH for the electron donating groups (EDGs), whereas producing HSOH and ˙SR for the electron withdrawing groups (EWGs). The H-Atom abstraction by ˙OH follows a classical hydrogen atom transfer (hat) mechanism, producing RSS˙ and H 2 O. Surprisingly, a proton-coupled electron transfer (pcet) process also occurs for R being an EDG. Although for RSSH having EWGs hat is the leading channel, S-S cleavage can be competitive or even dominant for the EDGs. The overall reactivity of RSSH toward ˙OH attack is greatly enhanced with the presence of an EDG, with CH 3 SSH being the most reactive species found in this study (overall rate constant: 4.55 × 10 12 M -1 s -1 ). Our results highlight the complexity in RSSH reaction chemistry, the extent of which is closely modulated by the inductive effect of the substituents in the case of the oxidation by hydroxyl radicals.

A comprehensive approach to reactive power scheduling in restructured power systems

NASA Astrophysics Data System (ADS)

Shukla, Meera

Financial constraints, regulatory pressure, and need for more economical power transfers have increased the loading of interconnected transmission systems. As a consequence, power systems have been operated close to their maximum power transfer capability limits, making the system more vulnerable to voltage instability events. The problem of voltage collapse characterized by a severe local voltage depression is generally believed to be associated with inadequate VAr support at key buses. The goal of reactive power planning is to maintain a high level of voltage security, through installation of properly sized and located reactive sources and their optimal scheduling. In case of vertically-operated power systems, the reactive requirement of the system is normally satisfied by using all of its reactive sources. But in case of different scenarios of restructured power systems, one may consider a fixed amount of exchange of reactive power through tie lines. Reviewed literature suggests a need for optimal scheduling of reactive power generation for fixed inter area reactive power exchange. The present work proposed a novel approach for reactive power source placement and a novel approach for its scheduling. The VAr source placement technique was based on the property of system connectivity. This is followed by development of optimal reactive power dispatch formulation which facilitated fixed inter area tie line reactive power exchange. This formulation used a Line Flow-Based (LFB) model of power flow analysis. The formulation determined the generation schedule for fixed inter area tie line reactive power exchange. Different operating scenarios were studied to analyze the impact of VAr management approach for vertically operated and restructured power systems. The system loadability, losses, generation and the cost of generation were the performance measures to study the impact of VAr management strategy. The novel approach was demonstrated on IEEE 30 bus system.

Miscible viscous fingering with chemical reaction involving precipitation.

NASA Astrophysics Data System (ADS)

Bae, Si-Kyun; Nagatsu, Yuichiro; Kato, Yoshihito; Tada, Yutaka

2007-11-01

When a reactive and miscible less-viscous liquid displaces a more-viscous liquid in a Hele-Shaw cell, reactive miscible viscous fingering takes place. The present study has experimentally examined how precipitation produced by chemical reaction affects miscible viscous fingering pattern. A 97 wt % glycerin solution containing iron(III) nitrate (yellow) and a solution containing potassium hexacyano ferrate(II) (colorless) were used as the more- and less-viscous liquids, respectively. In this case, the chemical reaction instantaneously takes place and produces the precipitation being dark blue in color. The experiments were done by varying reactant concentrations, the cell's gap width, and the displacement speed. We compared the patterns involving the precipitation reaction with those in the non-reactive cases. We have found fylfot-like pattern is observed, depending on the experimental condition, which has never been formed in the non-reactive experiments. As the reactant concentrations are increased or the displacement speed is decreased, the effects of the precipitation on the patterns are more pronounced.

Mechanism of superoxide and hydrogen peroxide generation by human electron-transfer flavoprotein and pathological variants.

PubMed

Rodrigues, João V; Gomes, Cláudio M

2012-07-01

Reactive oxygen species production by mitochondrial enzymes plays a fundamental role both in cellular signaling and in the progression of dysfunctional states. However, sources of reactive oxygen species and the mechanisms by which enzymes produce these reactive species still remain elusive. We characterized the generation of reactive oxygen species by purified human electron-transfer flavoprotein (ETF), a mitochondrial enzyme that has a central role in the metabolism of lipids, amino acids, and choline. The results showed that ETF produces significant amounts of both superoxide and hydrogen peroxide in the presence of its partner enzyme medium-chain acyl-CoA dehydrogenase (MCAD). ETF-mediated production of reactive oxygen species is partially inhibited at high MCAD/ETF ratios, whereas it is enhanced at high ionic strength. Determination of the reduction potentials of ETF showed that thermodynamic properties of the FAD cofactor are changed upon formation of a complex between ETF and MCAD, supporting the notion that protein:protein interactions modulate the reactivity of the protein with dioxygen. Two pathogenic ETF variants were also studied to determine which factors modulate the reactivity toward molecular oxygen and promote reactive oxygen species production. The results obtained show that destabilized conformations and defective protein:protein interactions increase the ability of ETF to generate reactive oxygen species. A possible role for these processes in mitochondrial dysfunction in metabolic disorders of fatty acid β-oxidation is discussed. Copyright © 2012 Elsevier Inc. All rights reserved.

Cardiovascular Reactivity in Patients With Major Depressive Disorder With High- or Low-Level Depressive Symptoms: A Cross-Sectional Comparison of Cardiovascular Reactivity to Laboratory-Induced Mental Stress.

PubMed

Wang, Mei-Yeh; Chiu, Chen-Huan; Lee, Hsin-Chien; Su, Chien-Tien; Tsai, Pei-Shan

2016-03-01

Depression increases the risk of adverse cardiac events. Cardiovascular reactivity is defined as the pattern of cardiovascular responses to mental stress. An altered pattern of cardiovascular reactivity is an indicator of subsequent cardiovascular disease. Because depression and adverse cardiac events may have a dose-dependent association, this study examined the differences in cardiovascular reactivity to mental stress between patients with major depressive disorder (MDD) with high depression levels and those with low depression levels. Moreover, autonomic nervous system regulation is a highly plausible biological mechanism for the pattern of cardiovascular reactivity to mental stress. The association between cardiovascular reactivity and parameters of heart rate variability (HRV), an index for quantifying autonomic nervous system activity modulation, was thus examined. This study included 88 patients with MDD. HRV was measured before stress induction. The Stroop Color and Word Test and mirror star-tracing task were used to induce mental stress. We observed no significant association between depressive symptom level and any of the cardiovascular reactivity parameters. Cardiovascular reactivity to mental stress was comparable between patients with MDD with high-level depressive symptoms and those with low-level depressive symptoms. After adjusting for confounding variables, the high-frequency domain of HRV was found to be an independent predictor of the magnitude of heart rate reactivity (β = -.33, p = .002). In conclusion, the magnitude of cardiovascular reactivity may be independent of depression severity in patients with MDD. The autonomic regulation of cardiovascular responses to mental stress primarily influences heart rate reactivity in patients with MDD. © The Author(s) 2015.

2013 MOLECULAR ENERGY TRANSFER GORDON RESEARCH CONFERENCE (JANUARY 13-18, 2013 - VENTURA BEACH MARRIOTT, VENTURA CA

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

Reid, Scott A.

2012-10-18

Sessions covered all areas of molecular energy transfer, with 10 sessions of talks and poster sessions covering the areas of :  Energy Transfer in Inelastic and Reactive Scattering  Energy Transfer in Photoinitiated and Unimolecular Reactions  Non-adiabatic Effects in Energy Transfer  Energy Transfer at Surfaces and Interfaces  Energy Transfer in Clusters, Droplets, and Aerosols  Energy Transfer in Solution and Solid  Energy Transfer in Complex Systems  Energy Transfer: New vistas and horizons  Molecular Energy Transfer: Where Have We Been and Where are We Going?

Method for providing an arbitrary three-dimensional microstructure in silicon using an anisotropic deep etch

DOEpatents

Morales, Alfredo M.; Gonzales, Marcela

2004-06-15

The present invention describes a method for fabricating an embossing tool or an x-ray mask tool, providing microstructures that smoothly vary in height from point-to-point in etched substrates, i.e., structure which can vary in all three dimensions. The process uses a lithographic technique to transfer an image pattern in the surface of a silicon wafer by exposing and developing the resist and then etching the silicon substrate. Importantly, the photoresist is variably exposed so that when developed some of the resist layer remains. The remaining undeveloped resist acts as an etchant barrier to the reactive plasma used to etch the silicon substrate and therefore provides the ability etch structures of variable depths.

First OH reactivity measurements in Harvard Forest

NASA Astrophysics Data System (ADS)

Herdlinger-Blatt, I. S.; Martin, S. T.; Hansel, A.; McKinney, K. A.

2013-12-01

The OH reactivity provides critical insight into the HOx budget under actual atmospheric conditions, and has implications for the production of ozone and the formation of secondary organic material. Previous studies have indicated that the OH reactivity measured at field sites often exceeds model estimations, but current experiments remain inconclusive about the origin of the discrepancy between the modeled and measured OH reactivity (Lou et al., 2010). As of now there are only a limited number of atmospheric studies of total OH reactivity available, so to improve understanding of the OH reactivity more studies are needed. The first OH reactivity measurements in the northeastern United States are being performed during the summer of 2013 at Harvard Forest. Harvard forest, is located about 100 km west of the Boston metropolitan area, is one of the most intensively studied forests in North America. The main biogenic VOC emitted from Harvard Forest is isoprene followed by monoterpenes and methanol. Sampling for the OH reactivity measurements will be conducted from a 30m tall meteorological tower at the Harvard Forest site. The air is drawn into a reaction cell where the OH reactivity is determined using the Comparative Reactivity Method (Sinha et al., 2008) employing a High-Sensitivity Proton Transfer Reaction Mass Spectrometer (Lindinger et al., 1998, Hansel et al., 1998). In addition to the OH reactivity measurements, the most abundant compounds present in the air sample will be quantified using PTR-MS. The quantification of these compounds is needed to compare the theoretical calculated OH reactivity with the measured OH reactivity data. The measurements will be used to evaluate our understanding of the OH budget at Harvard Forest. References: A. Hansel, A. Jordan, C. Warneke, R. Holzinger, and W. Lindinger.: Improved Detection Limit of the Proton-transfer Reaction Mass Spectrometer: On-line Monitoring of Volatile Organic Compounds at Mixing Ratios of a Few PPTV, Rapid Commun. Mass Spectrom., 12, 871-875, (1998). W. Lindinger, A. Hansel, and A. Jordan: Proton-transfer-reaction mass spectrometry (PTR-MS): on-line monitoring of volatile organic compounds at pptv levels. Chemical Society Reviews , 27, 1998. S. Lou, F. Holland, F. Rohrer, K. Lu, B. Bohn, T. Brauers, C. C. Chang, H. Fuchs, R. Häseler, K. Kita, Y. Kondo, X. Li, M. Shao, L. Zeng, A. Wahner, Y. Zhang, W. Wang, and A. Hofzumahaus, Atmospheric OH reactivities in the Pearl River Delta - China in summer 2006: measurement and model results, Atmos. Chem. Phys., 10, 11243-11260, (2010). V. Sinha, J. Williams, J.N. Crowley, and J. Lelieveld., The Comparaptive Reactivity Methode - a new tool to measure total OH Reactivity in ambient air, Atmos. Env., 38, 2511-2522, (2008).

Converging evidence for control of color-word Stroop interference at the item level.

PubMed

Bugg, Julie M; Hutchison, Keith A

2013-04-01

Prior studies have shown that cognitive control is implemented at the list and context levels in the color-word Stroop task. At first blush, the finding that Stroop interference is reduced for mostly incongruent items as compared with mostly congruent items (i.e., the item-specific proportion congruence [ISPC] effect) appears to provide evidence for yet a third level of control, which modulates word reading at the item level. However, evidence to date favors the view that ISPC effects reflect the rapid prediction of high-contingency responses and not item-specific control. In Experiment 1, we first show that an ISPC effect is obtained when the relevant dimension (i.e., color) signals proportion congruency, a problematic pattern for theories based on differential response contingencies. In Experiment 2, we replicate and extend this pattern by showing that item-specific control settings transfer to new stimuli, ruling out alternative frequency-based accounts. In Experiment 3, we revert to the traditional design in which the irrelevant dimension (i.e., word) signals proportion congruency. Evidence for item-specific control, including transfer of the ISPC effect to new stimuli, is apparent when 4-item sets are employed but not when 2-item sets are employed. We attribute this pattern to the absence of high-contingency responses on incongruent trials in the 4-item set. These novel findings provide converging evidence for reactive control of color-word Stroop interference at the item level, reveal theoretically important factors that modulate reliance on item-specific control versus contingency learning, and suggest an update to the item-specific control account (Bugg, Jacoby, & Chanani, 2011).

Patterns produced when soil is transferred to bras by placing and dragging actions: The application of digital photography and image processing to support visible observations.

PubMed

Murray, Kathleen R; Fitzpatrick, Robert W; Bottrill, Ralph; Kobus, Hilton

2017-07-01

A series of soil transference experiments (STEs) were undertaken to determine whether patterns identified in laboratory experiments could also be recognised at a simulated crime scene in the field. A clothed 55kg human rescue dummy dressed in a padded bra was either dragged or merely placed on a soil surface at sites with natural and anthropogenic soil types under both wet and dry soil conditions. Transfer patterns produced by dragging compared favourably with those of laboratory experiments. Twelve patterns were identified when a clothed human rescue dummy was dragged across the two soil types in the field. This expanded the original set of eight soil transfer patterns identified from dragging weighted fabric across soil samples in the laboratory. Soil transferred by placing the human rescue dummy resulted in a set of six transfer patterns that were different to those produced by dragging. By comparing trace soil patterns transferred to bras using each transfer method, it was revealed that certain transfer patterns on bras could indicate how the fabric had made contact with a soil surface. A photographic method was developed for crime scene examiners to capture this often subtle soil evidence before a body is transported or the clothing removed. This improved understanding of the dynamics of soil transference to bras and related clothing fabric may assist forensic investigators reconstruct the circumstances of a variety of forensic events. Copyright © 2017 Elsevier B.V. All rights reserved.

MODULAR APPLICATION OF COMPUTATIONAL MODELS OF INHALED REACTIVE GAS DOSIMETRY FOR RISK ASSESSMENT OF RESPIRATORY TRACT TOXICITY: CHLORINE

EPA Science Inventory

Inhaled reactive gases typically cause respiratory tract toxicity with a prominent proximal to distal lesion pattern. This pattern is largely driven by airflow and interspecies differences between rodents and humans result from factors such as airway architecture, ventilation ra...

Charge transfer from TiO2 into adsorbed benzene diazonium compounds

NASA Astrophysics Data System (ADS)

Merson, A.; Dittrich, Th.; Zidon, Y.; Rappich, J.; Shapira, Yoram

2004-08-01

Electron transfer from sol-gel-prepared TiO2 into adsorbed benzene diazonium compounds has been investigated using cyclic voltammetry, x-ray photoelectron spectroscopy, contact potential difference, and surface photovoltage spectroscopy. The results show that the potential of maximum electron transfer depends strongly on the dipole moment of the benzene compound. Two reactive surface sites at which electron transfer occurs have been identified.

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe 3Mn-Iodosobenzene Adducts

DOE PAGES

de Ruiter, Graham; Carsch, Kurtis M.; Gul, Sheraz; ...

2017-03-24

In this paper, we report the synthesis, characterization, and reactivity of [LFe 3(PhPz) 3OMn( sPhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2Fe IIMn II vs. Fe III 3Mn II) influence oxygen atom transfer in tetranuclear Fe 3Mn clusters. Finally, in particular, a one-electron redox change atmore » a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.« less

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

PubMed

de Ruiter, Graham; Carsch, Kurtis M; Gul, Sheraz; Chatterjee, Ruchira; Thompson, Niklas B; Takase, Michael K; Yano, Junko; Agapie, Theodor

2017-04-18

We report the synthesis, characterization, and reactivity of [LFe 3 (PhPz) 3 OMn( s PhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57 Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2 Fe II Mn II vs. Fe III 3 Mn II ) influence oxygen atom transfer in tetranuclear Fe 3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanism of pyrogallol red oxidation induced by free radicals and reactive oxidant species. A kinetic and spectroelectrochemistry study.

PubMed

Atala, E; Velásquez, G; Vergara, C; Mardones, C; Reyes, J; Tapia, R A; Quina, F; Mendes, M A; Speisky, H; Lissi, E; Ureta-Zañartu, M S; Aspée, A; López-Alarcón, C

2013-05-02

Pyrogallol red (PGR) presents high reactivity toward reactive (radical and nonradical) species (RS). This property of PGR, together with its characteristic spectroscopic absorption in the visible region, has allowed developing methodologies aimed at evaluating the antioxidant capacity of foods, beverages, and human fluids. These methods are based on the evaluation of the consumption of PGR induced by RS and its inhibition by antioxidants. However, at present, there are no reports regarding the degradation mechanism of PGR, limiting the extrapolation to how antioxidants behave in different systems comprising different RS. In the present study, we evaluate the kinetics of PGR consumption promoted by different RS (peroxyl radicals, peroxynitrite, nitrogen dioxide, and hypochlorite) using spectroscopic techniques and detection of product by HPLC mass spectrometry. The same pattern of oxidation and spectroscopic properties of the products is observed, independently of the RS employed. Mass analysis indicates the formation of only one product identified as a quinone derivative, excluding the formation of peroxides or hydroperoxides and/or chlorinated compounds, in agreement with FOX's assays and oxygen consumption experiments. Cyclic voltammetry, carried out at different pH's, shows an irreversible oxidation of PGR, indicating the initial formation of a phenoxy radical and a second charge transfer reaction generating an ortho-quinone derivative. Spectroelectrochemical oxidation of PGR shows oxidation products with identical UV-visible absorption properties to those observed in RS-induced oxidation.

Reversing Conventional Reactivity of Mixed Oxo/Alkyl Rare-Earth Complexes: Non-Redox Oxygen Atom Transfer.

PubMed

Hong, Jianquan; Tian, Haiwen; Zhang, Lixin; Zhou, Xigeng; Del Rosal, Iker; Weng, Linhong; Maron, Laurent

2018-01-22

The preferential substitution of oxo ligands over alkyl ones of rare-earth complexes is commonly considered as "impossible" due to the high oxophilicity of metal centers. Now, it has been shown that simply assembling mixed methyl/oxo rare-earth complexes to a rigid trinuclear cluster framework cannot only enhance the activity of the Ln-oxo bond, but also protect the highly reactive Ln-alkyl bond, thus providing a previously unrecognized opportunity to selectively manipulate the oxo ligand in the presence of numerous reactive functionalities. Such trimetallic cluster has proved to be a suitable platform for developing the unprecedented non-redox rare-earth-mediated oxygen atom transfer from ketones to CS 2 and PhNCS. Controlled experiments and computational studies shed light on the driving force for these reactions, emphasizing the importance of the sterical accessibility and multimetallic effect of the cluster framework in promoting reversal of reactivity of rare-earth oxo complexes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nitrogen reactive ion etch processes for the selective removal of poly-(4-vinylpyridine) in block copolymer films.

PubMed

Flynn, Shauna P; Bogan, Justin; Lundy, Ross; Khalafalla, Khalafalla E; Shaw, Matthew; Rodriguez, Brian J; Swift, Paul; Daniels, Stephen; O'Connor, Robert; Hughes, Greg; Kelleher, Susan M

2018-08-31

Self-assembling block copolymer (BCP) patterns are one of the main contenders for the fabrication of nanopattern templates in next generation lithography technology. Transforming these templates to hard mark materials is key for pattern transfer and in some cases, involves selectively removing one block from the nanopattern. For poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP), a high χ BCP system which could be potentially incorporated into semiconductor nanofabrication, this selective removal is predominantly done by a wet etch/activation process. Conversely, this process has numerous disadvantages including lack of control and high generation of waste leading to high cost. For these reasons, our motivation was to move away from the wet etch process and optimise a dry etch which would overcome the limitations associated with the activation process. The work presented herein shows the development of a selective plasma etch process for the removal of P4VP cores from PS-b-P4VP nanopatterned film. Results have shown that a nitrogen reactive ion etch plasma has a selectivity for P4VP of 2.2:1 and suggest that the position of the nitrogen in the aromatic ring of P4VP plays a key role in this selectivity. In situ plasma etching and x-ray photoelectron spectrometry measurements were made without breaking vacuum, confirming that the nitrogen plasma has selectivity for removal of P4VP over PS.

Convergent Evolution of Pathogen Effectors toward Reactive Oxygen Species Signaling Networks in Plants.

PubMed

Jwa, Nam-Soo; Hwang, Byung Kook

2017-01-01

Microbial pathogens have evolved protein effectors to promote virulence and cause disease in host plants. Pathogen effectors delivered into plant cells suppress plant immune responses and modulate host metabolism to support the infection processes of pathogens. Reactive oxygen species (ROS) act as cellular signaling molecules to trigger plant immune responses, such as pathogen-associated molecular pattern (PAMP)-triggered immunity (PTI) and effector-triggered immunity. In this review, we discuss recent insights into the molecular functions of pathogen effectors that target multiple steps in the ROS signaling pathway in plants. The perception of PAMPs by pattern recognition receptors leads to the rapid and strong production of ROS through activation of NADPH oxidase Respiratory Burst Oxidase Homologs (RBOHs) as well as peroxidases. Specific pathogen effectors directly or indirectly interact with plant nucleotide-binding leucine-rich repeat receptors to induce ROS production and the hypersensitive response in plant cells. By contrast, virulent pathogens possess effectors capable of suppressing plant ROS bursts in different ways during infection. PAMP-triggered ROS bursts are suppressed by pathogen effectors that target mitogen-activated protein kinase cascades. Moreover, pathogen effectors target vesicle trafficking or metabolic priming, leading to the suppression of ROS production. Secreted pathogen effectors block the metabolic coenzyme NADP-malic enzyme, inhibiting the transfer of electrons to the NADPH oxidases (RBOHs) responsible for ROS generation. Collectively, pathogen effectors may have evolved to converge on a common host protein network to suppress the common plant immune system, including the ROS burst and cell death response in plants.

Formation of infectious dengue virus-antibody immune complex in vivo in marmosets (Callithrix jacchus) after passive transfer of anti-dengue virus monoclonal antibodies and infection with dengue virus.

PubMed

Moi, Meng Ling; Ami, Yasushi; Shirai, Kenji; Lim, Chang-Kweng; Suzaki, Yuriko; Saito, Yuka; Kitaura, Kazutaka; Saijo, Masayuki; Suzuki, Ryuji; Kurane, Ichiro; Takasaki, Tomohiko

2015-02-01

Infection with a dengue virus (DENV) serotype induces cross-reactive, weakly neutralizing antibodies to different dengue serotypes. It has been postulated that cross-reactive antibodies form a virus-antibody immune complex and enhance DENV infection of Fc gamma receptor (FcγR)-bearing cells. We determined whether infectious DENV-antibody immune complex is formed in vivo in marmosets after passive transfer of DENV-specific monoclonal antibody (mAb) and DENV inoculation and whether infectious DENV-antibody immune complex is detectable using FcγR-expressing cells. Marmosets showed that DENV-antibody immune complex was exclusively infectious to FcγR-expressing cells on days 2, 4, and 7 after passive transfer of each of the mAbs (mAb 4G2 and mAb 6B6C) and DENV inoculation. Although DENV-antibody immune complex was detected, contribution of the passively transferred antibody to overall viremia levels was limited in this study. The results indicate that DENV cross-reactive antibodies form DENV-antibody immune complex in vivo, which is infectious to FcγR-bearing cells but not FcγR-negative cells. © The American Society of Tropical Medicine and Hygiene.

Physiological correlates of emotional reactivity and regulation in early adolescents.

PubMed

Latham, Melissa D; Cook, Nina; Simmons, Julian G; Byrne, Michelle L; Kettle, Jonathan W L; Schwartz, Orli; Vijayakumar, Nandita; Whittle, Sarah; Allen, Nicholas B

2017-07-01

Few studies have examined physiological correlates of emotional reactivity and regulation in adolescents, despite the occurrence in this group of significant developmental changes in emotional functioning. The current study employed multiple physiological measures (i.e., startle-elicited eyeblink and ERP, skin conductance, facial EMG) to assess the emotional reactivity and regulation of 113 early adolescents in response to valenced images. Reactivity was measured while participants viewed images, and regulation was measured when they were asked to discontinue or maintain their emotional reactions to the images. Adolescent participants did not exhibit fear-potentiated startle blink. However, they did display affect-consistent zygomatic and corrugator activity during reactivity, as well as inhibition of some of these facial patterns during regulation. Skin conductance demonstrated arousal dependent activity during reactivity, and overall decreases during regulation. These findings suggest that early adolescents display reactivity to valenced pictures, but not to startle probes. Psychophysiological patterns during emotion regulation indicate additional effort and/or attention during the regulation process. Copyright © 2017 Elsevier B.V. All rights reserved.

Punicalagin and catechins contain polyphenolic substructures that influence cell viability and can be monitored by radical chemosensors sensitive to electron transfer.

PubMed

Carreras, Anna; Mateos-Martín, María Luisa; Velázquez-Palenzuela, Amado; Brillas, Enric; Sánchez-Tena, Susana; Cascante, Marta; Juliá, Luis; Torres, Josep Lluís

2012-02-22

Plant polyphenols may be free radical scavengers or generators, depending on their nature and concentration. This dual effect, mediated by electron transfer reactions, may contribute to their influence on cell viability. This study used two stable radicals (tris(2,3,5,6-tetrachloro-4-nitrophenyl)methyl (TNPTM) and tris(2,4,6-trichloro-3,5-dinitrophenyl)methyl (HNTTM)) sensitive only to electron transfer reduction reactions to monitor the redox properties of polyphenols (punicalagin and catechins) that contain phenolic hydroxyls with different reducing capacities. The use of the two radicals reveals that punicalagin's substructures consisting of gallate esters linked together by carbon-carbon (C-C) bonds are more reactive than simple gallates and less reactive than the pyrogallol moiety of green tea catechins. The most reactive hydroxyls, detected by TNPTM, are present in the compounds that affect HT-29 cell viability the most. TNPTM reacts with C-C-linked gallates and pyrogallol and provides a convenient way to detect potentially beneficial polyphenols from natural sources.

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

de Ruiter, Graham; Carsch, Kurtis M.; Gul, Sheraz

In this paper, we report the synthesis, characterization, and reactivity of [LFe 3(PhPz) 3OMn( sPhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2Fe IIMn II vs. Fe III 3Mn II) influence oxygen atom transfer in tetranuclear Fe 3Mn clusters. Finally, in particular, a one-electron redox change atmore » a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.« less

Formation of Au nano-patterns on various substrates using simplified nano-transfer printing method

NASA Astrophysics Data System (ADS)

Kim, Jong-Woo; Yang, Ki-Yeon; Hong, Sung-Hoon; Lee, Heon

2008-06-01

For future device applications, fabrication of the metal nano-patterns on various substrates, such as Si wafer, non-planar glass lens and flexible plastic films become important. Among various nano-patterning technologies, nano-transfer print method is one of the simplest techniques to fabricate metal nano-patterns. In nano-transfer printing process, thin Au layer is deposited on flexible PDMS mold, containing surface protrusion patterns, and the Au layer is transferred from PDMS mold to various substrates due to the difference of bonding strength of Au layer to PDMS mold and to the substrate. For effective transfer of Au layer, self-assembled monolayer, which has strong bonding to Au, is deposited on the substrate as a glue layer. In this study, complicated SAM layer coating process was replaced to simple UV/ozone treatment, which can activates the surface and form the -OH radicals. Using simple UV/ozone treatments on both Au and substrate, Au nano-pattern can be successfully transferred to as large as 6 in. diameter Si wafer, without SAM coating process. High fidelity transfer of Au nano-patterns to non-planar glass lens and flexible PET film was also demonstrated.

Traveltime-based descriptions of transport and mixing in heterogeneous domains

NASA Astrophysics Data System (ADS)

Luo, Jian; Cirpka, Olaf A.

2008-09-01

Modeling mixing-controlled reactive transport using traditional spatial discretization of the domain requires identifying the spatial distributions of hydraulic and reactive parameters including mixing-related quantities such as dispersivities and kinetic mass transfer coefficients. In most applications, breakthrough curves (BTCs) of conservative and reactive compounds are measured at only a few locations and spatially explicit models are calibrated by matching these BTCs. A common difficulty in such applications is that the individual BTCs differ too strongly to justify the assumption of spatial homogeneity, whereas the number of observation points is too small to identify the spatial distribution of the decisive parameters. The key objective of the current study is to characterize physical transport by the analysis of conservative tracer BTCs and predict the macroscopic BTCs of compounds that react upon mixing from the interpretation of conservative tracer BTCs and reactive parameters determined in the laboratory. We do this in the framework of traveltime-based transport models which do not require spatially explicit, costly aquifer characterization. By considering BTCs of a conservative tracer measured on different scales, one can distinguish between mixing, which is a prerequisite for reactions, and spreading, which per se does not foster reactions. In the traveltime-based framework, the BTC of a solute crossing an observation plane, or ending in a well, is interpreted as the weighted average of concentrations in an ensemble of non-interacting streamtubes, each of which is characterized by a distinct traveltime value. Mixing is described by longitudinal dispersion and/or kinetic mass transfer along individual streamtubes, whereas spreading is characterized by the distribution of traveltimes, which also determines the weights associated with each stream tube. Key issues in using the traveltime-based framework include the description of mixing mechanisms and the estimation of the traveltime distribution. In this work, we account for both apparent longitudinal dispersion and kinetic mass transfer as mixing mechanisms, thus generalizing the stochastic-convective model with or without inter-phase mass transfer and the advective-dispersive streamtube model. We present a nonparametric approach of determining the traveltime distribution, given a BTC integrated over an observation plane and estimated mixing parameters. The latter approach is superior to fitting parametric models in cases wherein the true traveltime distribution exhibits multiple peaks or long tails. It is demonstrated that there is freedom for the combinations of mixing parameters and traveltime distributions to fit conservative BTCs and describe the tailing. A reactive transport case of a dual Michaelis-Menten problem demonstrates that the reactive mixing introduced by local dispersion and mass transfer may be described by apparent mean mass transfer with coefficients evaluated by local BTCs.

SU8 inverted-rib waveguide Bragg grating filter.

PubMed

Huang, Cheng-Sheng; Wang, Wei-Chih

2013-08-01

A polymeric SU8 inverted-rib waveguide Bragg grating filter fabricated using reactive ion etching (RIE) and solvent assisted microcontact molding (SAMIM) is presented. SAMIM is one kind of soft lithography. The technique is unique in that a composite hard-polydimethysiloxane/polydimethysiloxane stamp is used to transfer the grating pattern onto an inverted SU8 rib waveguide system. The composite grating stamp can be used repeatedly several times without degradation. Using this stamp and inverter-rib waveguide structure, the Bragg grating filter fabrication can be significantly simplified. The experiment result shows an attenuation dip in the transmission spectra, with a value of -7 dBm at 1550 nm for a grating with a period of 0.492 μm on an inverted-rib waveguide with 6.6 μm width and 4 μm height.

Combinations of resting RSA and RSA reactivity impact maladaptive mood repair and depression symptoms

PubMed Central

Yaroslavsky, Ilya; Bylsma, Lauren M.; Rottenberg, Jonathan; Kovacs, Maria

2013-01-01

We examined whether the combined indices of respiratory sinus arrhythmia at rest (resting RSA) and in response to a sad film (RSA reactivity) predict effective and ineffective responses to reduce sadness (adaptive vs. maladaptive mood repair) in women with histories of juvenile-onset depression (n = 74) and no history of major mental disorders (n = 75). Structural equation models were used to estimate latent resting RSA, depression, and adaptive and maladaptive mood repair and to test the study hypotheses. Results indicated that combinations of resting RSA+RSA reactivity (RSA patterns) predicted maladaptive mood repair, which in turn, mediated the effects of RSA pattern on depression. Further, RSA patterns moderated the depressogenic effects of maladaptive mood repair. RSA patterns were unrelated to adaptive mood repair. Our findings suggest that mood repair is one mechanism through which physiological vulnerabilities adversely affect mental health. PMID:23827087

Combinations of resting RSA and RSA reactivity impact maladaptive mood repair and depression symptoms.

PubMed

Yaroslavsky, Ilya; Bylsma, Lauren M; Rottenberg, Jonathan; Kovacs, Maria

2013-10-01

We examined whether the combined indices of respiratory sinus arrhythmia at rest (resting RSA) and in response to a sad film (RSA reactivity) predict effective and ineffective responses to reduce sadness (adaptive vs. maladaptive mood repair) in women with histories of juvenile-onset depression (n=74) and no history of major mental disorders (n=75). Structural equation models were used to estimate latent resting RSA, depression, and adaptive and maladaptive mood repair and to test the study hypotheses. Results indicated that combinations of resting RSA+RSA reactivity (RSA patterns) predicted maladaptive mood repair, which in turn, mediated the effects of RSA pattern on depression. Further, RSA patterns moderated the depressogenic effects of maladaptive mood repair. RSA patterns were unrelated to adaptive mood repair. Our findings suggest that mood repair is one mechanism through which physiological vulnerabilities adversely affect mental health. Copyright © 2013 Elsevier B.V. All rights reserved.

On Pedagogy

ERIC Educational Resources Information Center

Gergely, Gyorgy; Egyed, Katalin; Kiraly, Ildiko

2007-01-01

Humans are adapted to spontaneously transfer relevant cultural knowledge to conspecifics and to fast-learn the contents of such teaching through a human-specific social learning system called "pedagogy" ( Csibra & Gergely, 2006). Pedagogical knowledge transfer is triggered by specific communicative cues (such as eye-contact, contingent reactivity,…

Morphogenesis of polycrystalline dendritic patterns from evaporation of a reactive nanofluid sessile drop

NASA Astrophysics Data System (ADS)

Wu, Hua; Briscoe, Wuge H.

2018-04-01

We report polycrystalline residual patterns with dendritic micromorphologies upon fast evaporation of a mixed-solvent sessile drop containing reactive ZnO nanoparticles. The molecular and particulate species generated in situ upon evaporative drying collude with and modify the Marangoni solvent flows and Bénard-Marangoni instabilities, as they undergo self-assembly and self-organization under conditions far from equilibrium, leading to the ultimate hierarchical central cellular patterns surrounded by a peripheral coffee ring upon drying.

T-cell Responses in the Microenvironment of Primary Renal Cell Carcinoma-Implications for Adoptive Cell Therapy.

PubMed

Andersen, Rikke; Westergaard, Marie Christine Wulff; Kjeldsen, Julie Westerlin; Müller, Anja; Pedersen, Natasja Wulff; Hadrup, Sine Reker; Met, Özcan; Seliger, Barbara; Kromann-Andersen, Bjarne; Hasselager, Thomas; Donia, Marco; Svane, Inge Marie

2018-02-01

In vitro expansion of large numbers of highly potent tumor-reactive T cells appears a prerequisite for effective adoptive cell therapy (ACT) with autologous tumor-infiltrating lymphocytes (TIL) as shown in metastatic melanoma (MM). We therefore sought to determine whether renal cell carcinomas (RCC) are infiltrated with tumor-reactive T cells that could be efficiently employed for adoptive transfer immunotherapy. TILs and autologous tumor cell lines (TCL) were successfully generated from 22 (92%) and 17 (77%) of 24 consecutive primary RCC specimens and compared with those generated from metastatic melanoma. Immune recognition of autologous TCLs or fresh tumor digests was observed in CD8 + TILs from 82% of patients (18/22). Cytotoxicity assays confirmed the tumoricidal capacity of RCC-TILs. The overall expansion capacity of RCC-TILs was similar to MM-TILs. However, the magnitude, polyfunctionality, and ability to expand in classical expansion protocols of CD8 + T-cell responses was lower compared with MM-TILs. The RCC-TILs that did react to the tumor were functional, and antigen presentation and processing of RCC tumors was similar to MM-TILs. Direct recognition of tumors with cytokine-induced overexpression of human leukocyte antigen class II was observed from CD4 + T cells (6/12; 50%). Thus, TILs from primary RCC specimens could be isolated, expanded, and could recognize tumors. However, immune responses of expanded CD8 + RCC-TILs were typically weaker than MM-TILs and displayed a mono-/oligofunctional pattern. The ability to select, enrich, and expand tumor-reactive polyfunctional T cells may be critical in developing effective ACT with TILs for RCC. In summary, TILs isolated from primary RCC specimens could recognize tumors. However, their immune responses were weaker than MM-TILs and displayed a mono-/oligofunctional pattern. The ability to select and expand polyfunctional T cells may improve cell therapy for RCC. Cancer Immunol Res; 6(2); 222-35. ©2018 AACR . ©2018 American Association for Cancer Research.

Pile transfer function

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

Franz, J.P.

The purpose of this memo is to present a detailed derivation of the transfer function of a critical pile and to relate this steady-state description and the transient response to a step function change of reactivity. Reference to G.E. report JIO-1 - Revised is implied throughout this discussion.

Optimization of T-cell Reactivity by Exploiting TCR Chain Centricity for the Purpose of Safe and Effective Antitumor TCR Gene Therapy.

PubMed

Ochi, Toshiki; Nakatsugawa, Munehide; Chamoto, Kenji; Tanaka, Shinya; Yamashita, Yuki; Guo, Tingxi; Fujiwara, Hiroshi; Yasukawa, Masaki; Butler, Marcus O; Hirano, Naoto

2015-09-01

Adoptive transfer of T cells redirected by a high-affinity antitumor T-cell receptor (TCR) is a promising treatment modality for cancer patients. Safety and efficacy depend on the selection of a TCR that induces minimal toxicity and elicits sufficient antitumor reactivity. Many, if not all, TCRs possess cross-reactivity to unrelated MHC molecules in addition to reactivity to target self-MHC/peptide complexes. Some TCRs display chain centricity, in which recognition of MHC/peptide complexes is dominated by one of the TCR hemi-chains. In this study, we comprehensively studied how TCR chain centricity affects reactivity to target self-MHC/peptide complexes and alloreactivity using the TCR, clone TAK1, which is specific for human leukocyte antigen-A*24:02/Wilms tumor 1(235-243) (A24/WT1(235)) and cross-reactive with B*57:01 (B57). The TAK1β, but not the TAK1α, hemi-chain possessed chain centricity. When paired with multiple clonotypic TCRα counter-chains encoding TRAV12-2, 20, 36, or 38-2, the de novo TAK1β-containing TCRs showed enhanced, weakened, or absent reactivity to A24/WT1(235) and/or to B57. T cells reconstituted with these TCRα genes along with TAK1β possessed a very broad range (>3 log orders) of functional and structural avidities. These results suggest that TCR chain centricity can be exploited to enhance desired antitumor TCR reactivity and eliminate unwanted TCR cross-reactivity. TCR reactivity to target MHC/peptide complexes and cross-reactivity to unrelated MHC molecules are not inextricably linked and are separable at the TCR sequence level. However, it is still mandatory to carefully monitor for possible harmful toxicities caused by adoptive transfer of T cells redirected by thymically unselected TCRs. ©2015 American Association for Cancer Research.

Watson-Crick base pairing controls excited-state decay in natural DNA.

PubMed

Bucher, Dominik B; Schlueter, Alexander; Carell, Thomas; Zinth, Wolfgang

2014-10-13

Excited-state dynamics are essential to understanding the formation of DNA lesions induced by UV light. By using femtosecond IR spectroscopy, it was possible to determine the lifetimes of the excited states of all four bases in the double-stranded environment of natural DNA. After UV excitation of the DNA duplex, we detected a concerted decay of base pairs connected by Watson-Crick hydrogen bonds. A comparison of single- and double-stranded DNA showed that the reactive charge-transfer states formed in the single strands are suppressed by base pairing in the duplex. The strong influence of the Watson-Crick hydrogen bonds indicates that proton transfer opens an efficient decay path in the duplex that prohibits the formation or reduces the lifetime of reactive charge-transfer states. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactive trajectories of the Ru2+/3+ self-exchange reaction and the connection to Marcus' theory.

PubMed

Tiwari, Ambuj; Ensing, Bernd

2016-12-22

Outer sphere electron transfer between two ions in aqueous solution is a rare event on the time scale of first principles molecular dynamics simulations. We have used transition path sampling to generate an ensemble of reactive trajectories of the self-exchange reaction between a pair of Ru 2+ and Ru 3+ ions in water. To distinguish between the reactant and product states, we use as an order parameter the position of the maximally localised Wannier center associated with the transferring electron. This allows us to align the trajectories with respect to the moment of barrier crossing and compute statistical averages over the path ensemble. We compare our order parameter with two typical reaction coordinates used in applications of Marcus theory of electron transfer: the vertical gap energy and the solvent electrostatic potential at the ions.

Reactivity III: An Advanced Course in Integrated Organic, Inorganic, and Biochemistry

ERIC Educational Resources Information Center

Schaller, Chris P.; Graham, Kate J.; Jakubowski, Henry V.

2017-01-01

Reactivity III is a new course that presents chemical reactions from the domains of organic, inorganic, and biochemistry that are not readily categorized by electrophile-nucleophile interactions. Many of these reactions involve the transfer of a single electron, in either an intermolecular fashion in the case of oxidation/reduction reactions or an…

Cross-reactivity among non-specific lipid-transfer proteins from food and pollen allergenic sources.

PubMed

Morales, María; López-Matas, M Ángeles; Moya, Raquel; Carnés, Jerónimo

2014-12-15

Non-specific lipid-transfer proteins (nsLTPs) are a family of pan-allergens present in foods and pollen. However, sequence homology among them is limited. The objective of this study was to evaluate the IgE-mediated cross-reactivity between nsLTPs from different sources and evaluate the allergenic properties of LTPs from peach (Pru p 3) and pellitory (Par j 1/Par j 2), major fruit and pollen allergens. Both proteins were purified and characterised. Cross-reactivity studies among nsLTPs from different foods and pollens were performed by immunoblot inhibition using sera specific to peach or pellitory pollen. Cross-reactivity with Pru p 3 was observed in hazelnut, onion, corn, peanut and apple while in pollens, none of the extracts was inhibited with Par j 1/2. In conclusion, Pru p 3 did not inhibit LTPs from most fruits. Therefore, although Pru p 3 covers the largest number of epitopes, diagnosis with only this allergen may not detect all LTP sensitivities. Copyright © 2014 Elsevier Ltd. All rights reserved.

Roles of oxyanions in promoting the partial oxidation of styrene on Ag(110): nitrate, carbonate, sulfite, and sulfate.

PubMed

Zhou, Ling; Madix, Robert J

2010-11-02

The promotion roles of nitrate, carbonate, sulfite, and sulfate in oxidation of styrene on Ag(110) have been studied by means of temperature-programmed reaction spectroscopy (TPRS) and X-ray photoelectron spectroscopy (XPS). While isolated nitrate leads only to the secondary oxidation of styrene, a surface co-covered by nitrate, oxygen, and 0.1 ML cesium promotes a low-temperature epoxidation pathway. XPS indicates that adsorbed surface oxygen is the oxidant in this selective reaction pathway, and, though it affects the reactivity of the surface oxygen, nitrate is a spectator. Carbonate acts as an oxygen transfer agent and exhibits similar reactivity and selectivity as an oxidant for styrene as does atomic oxygen on Ag(110). The reactivities of sulfite and sulfate are strongly dependent on their surface structures, the c(6 × 2) sulfite showing the capacity to transfer oxygen to styrene.

Development and manufacture of reactive-transfer-printed CIGS photovoltaic modules

NASA Astrophysics Data System (ADS)

Eldada, Louay; Sang, Baosheng; Lu, Dingyuan; Stanbery, Billy J.

2010-09-01

In recent years, thin-film photovoltaic (PV) companies started realizing their low manufacturing cost potential, and grabbing an increasingly larger market share from multicrystalline silicon companies. Copper Indium Gallium Selenide (CIGS) is the most promising thin-film PV material, having demonstrated the highest energy conversion efficiency in both cells and modules. However, most CIGS manufacturers still face the challenge of delivering a reliable and rapid manufacturing process that can scale effectively and deliver on the promise of this material system. HelioVolt has developed a reactive transfer process for CIGS absorber formation that has the benefits of good compositional control, high-quality CIGS grains, and a fast reaction. The reactive transfer process is a two stage CIGS fabrication method. Precursor films are deposited onto substrates and reusable print plates in the first stage, while in the second stage, the CIGS layer is formed by rapid heating with Se confinement. High quality CIGS films with large grains were produced on a full-scale manufacturing line, and resulted in high-efficiency large-form-factor modules. With 14% cell efficiency and 12% module efficiency, HelioVolt started to commercialize the process on its first production line with 20 MW nameplate capacity.

Oxoiron(IV) Tetramethylcyclam Complexes with Axial Carboxylate Ligands: Effect of Tethering the Carboxylate on Reactivity.

PubMed

Bigelow, Jennifer O; England, Jason; Klein, Johannes E M N; Farquhar, Erik R; Frisch, Jonathan R; Martinho, Marlène; Mandal, Debasish; Münck, Eckard; Shaik, Sason; Que, Lawrence

2017-03-20

Oxoiron(IV) species are implicated as reactive intermediates in nonheme monoiron oxygenases, often acting as the agent for hydrogen-atom transfer from substrate. A histidine is the most likely ligand trans to the oxo unit in most enzymes characterized thus far but is replaced by a carboxylate in the case of isopenicillin N synthase. As the effect of a trans carboxylate ligand on the properties of the oxoiron(IV) unit has not been systematically studied, we have synthesized and characterized four oxoiron(IV) complexes supported by the tetramethylcyclam (TMC) macrocycle and having a carboxylate ligand trans to the oxo unit. Two complexes have acetate or propionate axial ligands, while the other two have the carboxylate functionality tethered to the macrocyclic ligand framework by one or two methylene units. Interestingly, these four complexes exhibit substrate oxidation rates that differ by more than 100-fold, despite having E p,c values for the reduction of the Fe═O unit that span a range of only 130 mV. Eyring parameters for 1,4-cyclohexadiene oxidation show that reactivity differences originate from differences in activation enthalpy between complexes with tethered carboxylates and those with untethered carboxylates, in agreement with computational results. As noted previously for the initial subset of four complexes, the logarithms of the oxygen atom transfer rates of 11 complexes of the Fe IV (O)TMC(X) series increase linearly with the observed E p,c values, reflecting the electrophilicity of the Fe═O unit. In contrast, no correlation with E p,c values is observed for the corresponding hydrogen atom transfer (HAT) reaction rates; instead, the HAT rates increase as the computed triplet-quintet spin state gap narrows, consistent with Shaik's two-state-reactivity model. In fact, the two complexes with untethered carboxylates are among the most reactive HAT agents in this series, demonstrating that the axial ligand can play a key role in tuning the HAT reactivity in a nonheme iron enzyme active site.

A comparative study of the hydrogen-bonding patterns and prototropism in solid 2-thiocytosine (potential antileukemic agent) and cytosine, as studied by 1H-14N NQDR and QTAIM/ DFT.

PubMed

Latosińska, Jolanta N; Seliger, Janez; Zagar, Veselko; Burchardt, Dorota V

2012-01-01

A potential antileukemic and anticancer agent, 2-thiocytosine (2-TC), has been studied experimentally in the solid state by (1)H-(14)N NMR-NQR double resonance (NQDR) and theoretically by the quantum theory of atoms in molecules (QTAIM)/density functional theory (DFT). Eighteen resonance frequencies on (14)N were detected at 180 K and assigned to particular nitrogen sites (-NH(2), -N=, and -NH-) in 2-thiocytosine. Factors such as the nonequivalence of molecules (connected to the duplication of sites) and possible prototropic tautomerism (capable of modifying the type of site due to proton transfer) were taken into account during frequency assignment. The result of replacing oxygen with sulfur, which leads to changes in the intermolecular interaction pattern and molecular aggregation, is discussed. This study demonstrates the advantages of combining NQDR and DFT to extract detailed information on the H-bonding properties of crystals with complex H-bonding networks. Solid-state properties were found to have a profound impact on the stabilities and reactivities of both compounds.

Electronic structure and reactivity of three-coordinate iron complexes.

PubMed

Holland, Patrick L

2008-08-01

[Reaction: see text]. The identity and oxidation state of the metal in a coordination compound are typically thought to be the most important determinants of its reactivity. However, the coordination number (the number of bonds to the metal) can be equally influential. This Account describes iron complexes with a coordination number of only three, which differ greatly from iron complexes with octahedral (six-coordinate) geometries with respect to their magnetism, electronic structure, preference for ligands, and reactivity. Three-coordinate complexes with a trigonal-planar geometry are accessible using bulky, anionic, bidentate ligands (beta-diketiminates) that steer a monodentate ligand into the plane of their two nitrogen donors. This strategy has led to a variety of three-coordinate iron complexes in which iron is in the +1, +2, and +3 oxidation states. Systematic studies on the electronic structures of these complexes have been useful in interpreting their properties. The iron ions are generally high spin, with singly occupied orbitals available for pi interactions with ligands. Trends in sigma-bonding show that iron(II) complexes favor electronegative ligands (O, N donors) over electropositive ligands (hydride). The combination of electrostatic sigma-bonding and the availability of pi-interactions stabilizes iron(II) fluoride and oxo complexes. The same factors destabilize iron(II) hydride complexes, which are reactive enough to add the hydrogen atom to unsaturated organic molecules and to take part in radical reactions. Iron(I) complexes use strong pi-backbonding to transfer charge from iron into coordinated alkynes and N 2, whereas iron(III) accepts charge from a pi-donating imido ligand. Though the imidoiron(III) complex is stabilized by pi-bonding in the trigonal-planar geometry, addition of pyridine as a fourth donor weakens the pi-bonding, which enables abstraction of H atoms from hydrocarbons. The unusual bonding and reactivity patterns of three-coordinate iron compounds may lead to new catalysts for oxidation and reduction reactions and may be used by nature in transient intermediates of nitrogenase enzymes.

Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions.

PubMed

Rice, Derek B; Massie, Allyssa A; Jackson, Timothy A

2017-11-21

Biological systems capitalize on the redox versatility of manganese to perform reactions involving dioxygen and its derivatives superoxide, hydrogen peroxide, and water. The reactions of manganese enzymes influence both human health and the global energy cycle. Important examples include the detoxification of reactive oxygen species by manganese superoxide dismutase, biosynthesis by manganese ribonucleotide reductase and manganese lipoxygenase, and water splitting by the oxygen-evolving complex of photosystem II. Although these enzymes perform very different reactions and employ structurally distinct active sites, manganese intermediates with peroxo, hydroxo, and oxo ligation are commonly proposed in catalytic mechanisms. These intermediates are also postulated in mechanisms of synthetic manganese oxidation catalysts, which are of interest due to the earth abundance of manganese. In this Account, we describe our recent efforts toward understanding O-O bond activation pathways of Mn III -peroxo adducts and hydrogen-atom transfer reactivity of Mn IV -oxo and Mn III -hydroxo complexes. In biological and synthetic catalysts, peroxomanganese intermediates are commonly proposed to decay by either Mn-O or O-O cleavage pathways, although it is often unclear how the local coordination environment influences the decay mechanism. To address this matter, we generated a variety of Mn III -peroxo adducts with varied ligand environments. Using parallel-mode EPR and Mn K-edge X-ray absorption techniques, the decay pathway of one Mn III -peroxo complex bearing a bulky macrocylic ligand was investigated. Unlike many Mn III -peroxo model complexes that decay to oxo-bridged-Mn III Mn IV dimers, decay of this Mn III -peroxo adduct yielded mononuclear Mn III -hydroxo and Mn IV -oxo products, potentially resulting from O-O bond activation of the Mn III -peroxo unit. These results highlight the role of ligand sterics in promoting the formation of mononuclear products and mark an important step in designing Mn III -peroxo complexes that convert cleanly to high-valent Mn-oxo species. Although some synthetic Mn IV -oxo complexes show great potential for oxidizing substrates with strong C-H bonds, most Mn IV -oxo species are sluggish oxidants. Both two-state reactivity and thermodynamic arguments have been put forth to explain these observations. To address these issues, we generated a series of Mn IV -oxo complexes supported by neutral, pentadentate ligands with systematically perturbed equatorial donation. Kinetic investigations of these complexes revealed a correlation between equatorial ligand-field strength and hydrogen-atom and oxygen-atom transfer reactivity. While this trend can be understood on the basis of the two-state reactivity model, the reactivity trend also correlates with variations in Mn III/IV reduction potential caused by changes in the ligand field. This work demonstrates the dramatic influence simple ligand perturbations can have on reactivity but also illustrates the difficulties in understanding the precise basis for a change in reactivity. In the enzyme manganese lipoxygenase, an active-site Mn III -hydroxo adduct initiates substrate oxidation by abstracting a hydrogen atom from a C-H bond. Precedent for this chemistry from synthetic Mn III -hydroxo centers is rare. To better understand hydrogen-atom transfer by Mn III centers, we developed a pair of Mn III -hydroxo complexes, formed in high yield from dioxygen oxidation of Mn II precursors, capable of attacking weak O-H and C-H bonds. Kinetic and computational studies show a delicate interplay between thermodynamic and steric influences in hydrogen-atom transfer reactivity, underscoring the potential of Mn III -hydroxo units as mild oxidants.

Convergent Evolution of Pathogen Effectors toward Reactive Oxygen Species Signaling Networks in Plants

PubMed Central

Jwa, Nam-Soo; Hwang, Byung Kook

2017-01-01

Microbial pathogens have evolved protein effectors to promote virulence and cause disease in host plants. Pathogen effectors delivered into plant cells suppress plant immune responses and modulate host metabolism to support the infection processes of pathogens. Reactive oxygen species (ROS) act as cellular signaling molecules to trigger plant immune responses, such as pathogen-associated molecular pattern (PAMP)-triggered immunity (PTI) and effector-triggered immunity. In this review, we discuss recent insights into the molecular functions of pathogen effectors that target multiple steps in the ROS signaling pathway in plants. The perception of PAMPs by pattern recognition receptors leads to the rapid and strong production of ROS through activation of NADPH oxidase Respiratory Burst Oxidase Homologs (RBOHs) as well as peroxidases. Specific pathogen effectors directly or indirectly interact with plant nucleotide-binding leucine-rich repeat receptors to induce ROS production and the hypersensitive response in plant cells. By contrast, virulent pathogens possess effectors capable of suppressing plant ROS bursts in different ways during infection. PAMP-triggered ROS bursts are suppressed by pathogen effectors that target mitogen-activated protein kinase cascades. Moreover, pathogen effectors target vesicle trafficking or metabolic priming, leading to the suppression of ROS production. Secreted pathogen effectors block the metabolic coenzyme NADP-malic enzyme, inhibiting the transfer of electrons to the NADPH oxidases (RBOHs) responsible for ROS generation. Collectively, pathogen effectors may have evolved to converge on a common host protein network to suppress the common plant immune system, including the ROS burst and cell death response in plants. PMID:29033963

Reactivity of the cadmium ion in concentrated phosphoric acid solutions.

PubMed

De Gyves, J; Gonzales, J; Louis, C; Bessiere, J

1989-07-01

The solvation transfer coefficients which characterize the changes of ion reactivity with phosphoric acid concentration have been calculated for cadmium from the constants of the successive chloride complexes, and for silver and diethyldithiophosphate from potentiometric measurements. They evidence the strong desolvation of the cadmium species in concentrated phosphoric acid media, causing a remarkable increase of its reactivity. They allow the results of liquid-liquid extraction, precipitation and flotation reactions to be correctly interpreted and their changes to be foreseen when the reagents are modified.

Stress Reactivity and Corticolimbic Response to Emotional Faces in Adolescents

ERIC Educational Resources Information Center

Liu, Jie; Chaplin, Tara M.; Wang, Fei; Sinha, Rajita; Mayes, Linda C.; Blumberg, Hilary P.

2012-01-01

Objective: Adolescence is a critical period in the development of lifelong patterns of responding to stress. Understanding underpinnings of variations in stress reactivity in adolescents is important, as adolescents with altered stress reactivity are vulnerable to negative risk-taking behaviors including substance use, and have increased lifelong…

Patterns of Children’s Adrenocortical Reactivity to Interparental Conflict and Associations with Child Adjustment: A Growth Mixture Modeling Approach

PubMed Central

Koss, Kalsea J.; George, Melissa R. W.; Davies, Patrick T.; Cicchetti, Dante; Cummings, E. Mark; Sturge-Apple, Melissa L.

2013-01-01

Examining children’s physiological functioning is an important direction for understanding the links between interparental conflict and child adjustment. Utilizing growth mixture modeling, the present study examined children’s cortisol reactivity patterns in response to a marital dispute. Analyses revealed three different patterns of cortisol responses, consistent with both a sensitization and an attenuation hypothesis. Child-rearing disagreements and perceived threat were associated with children exhibiting a rising cortisol pattern whereas destructive conflict was related to children displaying a flat pattern. Physiologically rising patterns were also linked with emotional insecurity and internalizing and externalizing behaviors. Results supported a sensitization pattern of responses as maladaptive for children in response to marital conflict with evidence also linking an attenuation pattern with risk. The present study supports children’s adrenocortical functioning as one mechanism through which interparental conflict is related to children’s coping responses and psychological adjustment. PMID:22545835

ELUCIDATING THE ROLE OF ELECTRON TRANSFER MEDIATORS IN REDUCTIVE TRANSFORMATIONS IN NATURAL SEDIMENTS

EPA Science Inventory

To study the identity and reactivity of electron transfer mediators (ETMs) in natural sediments, the reduction kinetics of a glass bead-azo dye complex were measured in abiotic and biotic model systems, as well as in natural sediments. In abiotic model systems, the bead-dye comp...

Transfer molding processes for nanoscale patterning of poly-L-lactic acid (PLLA) films

NASA Astrophysics Data System (ADS)

Dhakal, Rabin; Peer, Akshit; Biswas, Rana; Kim, Jaeyoun

2016-03-01

Nanoscale patterned structures composed of biomaterials exhibit great potential for the fabrication of functional biostructures. In this paper, we report cost-effective, rapid, and highly reproducible soft lithographic transfer-molding techniques for creating periodic micro- and nano-scale textures on poly (L-lactic acid) (PLLA) surface. These artificial textures can increase the overall surface area and change the release dynamics of the therapeutic agents coated on it. Specifically, we use the double replication technique in which the master pattern is first transferred to the PDMS mold and the pattern on PDMS is then transferred to the PLLA films through drop-casting as well as nano-imprinting. The ensuing comparison studies reveal that the drop-cast PLLA allows pattern transfer at higher levels of fidelity, enabling the realization of nano-hole and nano-cone arrays with pitch down to ~700 nm. The nano-patterned PLLA film was then coated with rapamycin to make it drug-eluting.

Coal desulfurization

NASA Technical Reports Server (NTRS)

Corcoran, William H. (Inventor); Vasilakos, Nicholas P. (Inventor); Lawson, Daniel D. (Inventor)

1982-01-01

A method for enhancing solubilizing mass transport of reactive agents into and out of carbonaceous materials, such as coal. Solubility parameters of mass transfer and solvent media are matched to individual peaks in the solubility parameter spectrum of coals to enhance swelling and/or dissolution. Methanol containing reactive agent carriers are found particularly effective for removing organic sulfur from coals by chlorinolysis.

Dynamics of Electron Transfer for a Nonsuperexchange Coherent Mechanism. I

DTIC Science & Technology

1989-10-13

observation. In the treatment three collective nuclear coordinates are introduced, permitting independent reorganization energies for each reactive center... nuclear coordinates are introduced, permitting independent reorganization energies for each reactive center. With certain approximations, namely, equal...numerically. One rough but simple analytical result for the latter is also given. tPresent address: Departmento de Quimica , Facultad de Ciencias

Transferable Reactive Force Fields: Extensions of ReaxFF-lg to Nitromethane.

PubMed

Larentzos, James P; Rice, Betsy M

2017-03-09

Transferable ReaxFF-lg models of nitromethane that predict a variety of material properties over a wide range of thermodynamic states are obtained by screening a library of ∼6600 potentials that were previously optimized through the Multiple Objective Evolutionary Strategies (MOES) approach using a training set that included information for other energetic materials composed of carbon, hydrogen, nitrogen, and oxygen. Models that best match experimental nitromethane lattice constants at 4.2 K and 1 atm are evaluated for transferability to high-pressure states at room temperature and are shown to better predict various liquid- and solid-phase structural, thermodynamic, and transport properties as compared to the existing ReaxFF and ReaxFF-lg parametrizations. Although demonstrated for an energetic material, the library of ReaxFF-lg models is supplied to the scientific community to enable new research explorations of complex reactive phenomena in a variety of materials research applications.

Scriptaid and 5-aza-2'deoxycytidine enhanced expression of pluripotent genes and in vitro developmental competence in interspecies Black-footed cat cloned embryos

USGS Publications Warehouse

Gómez, M. C.; Biancardi, M.N.; Jenkins, J.A.; Dumas, C.; Galiguis, J.; Wang, G.; Earle Pope, C.

2012-01-01

Somatic cell nuclear transfer offers the possibility of preserving endangered species including the black-footed cat, which is threatened with extinction. The effectiveness and efficiency of somatic cell nuclear transfer (SCNT) depends on a variety of factors, but 'inappropriate epigenetic reprogramming of the transplanted nucleus is the primary cause of the developmental failure of cloned embryos. Abnormal epigenetic events such as DNA methylation and histone modifications during SCNT perturb the expression of imprinted and pluripotent-related genes that, consequently, may result in foetal and neonatal abnormalities. We have demonstrated that pregnancies can be established after transfer of black-footed cat cloned embryos into domestic cat recipients, but none of the implanted embryos developed to term and the foetal failure has been associated to aberrant reprogramming in cloned embryos. There is growing evidence that modifying the epigenetic pattern of the chromatin template of both donor cells and reconstructed embryos with a combination of inhibitors of histone deacetylases and DNA methyltransferases results in enhanced gene reactivation and improved in vitro and in vivo developmental competence. Epigenetic modifications of the chromatin template of black-footed cat donor cells and reconstructed embryos with epigenetic-modifying compounds enhanced in vitro development, and regulated the expression of pluripotent genes, but these epigenetic modifications did not improve in vivo developmental competence.

Soil transference patterns on bras: Image processing and laboratory dragging experiments.

PubMed

Murray, Kathleen R; Fitzpatrick, Robert W; Bottrill, Ralph S; Berry, Ron; Kobus, Hilton

2016-01-01

In a recent Australian homicide, trace soil on the victim's clothing suggested she was initially attacked in her front yard and not the park where her body was buried. However the important issue that emerged during the trial was how soil was transferred to her clothing. This became the catalyst for designing a range of soil transference experiments (STEs) to study, recognise and classify soil patterns transferred onto fabric when a body is dragged across a soil surface. Soil deposits of interest in this murder were on the victim's bra and this paper reports the results of anthropogenic soil transfer to bra-cups and straps caused by dragging. Transfer patterns were recorded by digital photography and photomicroscopy. Eight soil transfer patterns on fabric, specific to dragging as the transfer method, appeared consistently throughout the STEs. The distinctive soil patterns were largely dependent on a wide range of soil features that were measured and identified for each soil tested using X-ray Diffraction and Non-Dispersive Infra-Red analysis. Digital photographs of soil transfer patterns on fabric were analysed using image processing software to provide a soil object-oriented classification of all soil objects with a diameter of 2 pixels and above transferred. Although soil transfer patterns were easily identifiable by naked-eye alone, image processing software provided objective numerical data to support this traditional (but subjective) interpretation. Image software soil colour analysis assigned a range of Munsell colours to identify and compare trace soil on fabric to other trace soil evidence from the same location; without requiring a spectrophotometer. Trace soil from the same location was identified by linking soils with similar dominant and sub-dominant Munsell colour peaks. Image processing numerical data on the quantity of soil transferred to fabric, enabled a relationship to be discovered between soil type, clay mineralogy (smectite), particle size and soil moisture content that would not have been possible otherwise. Soil type (e.g. Anthropogenic, gravelly sandy loam soil or Natural, organic-rich soil), clay mineralogy (smectite) and soil moisture content were the greatest influencing factors in all the dragging soil transference tests (both naked eye and measured properties) to explain the eight categories of soil transference patterns recorded. This study was intended to develop a method for dragging soil transference laboratory experiments and create a baseline of preliminary soil type/property knowledge. Results confirm the need to better understand soil behaviour and properties of clothing fabrics by further testing of a wider range of soil types and clay mineral properties. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Visualization of natural convection heat transfer on a sphere

NASA Astrophysics Data System (ADS)

Lee, Dong-Young; Chung, Bum-Jin

2017-12-01

Natural convection heat transfer phenomena on spheres were investigated by adopting mass transfer experiments based on analogy concept. The diameters of spheres were varied from 0.01 m to 0.12 m, which correspond to the Rayleigh numbers of 1.69×108-2.91×1011. The measured mass transfer coefficients agreed well with the existing correlations. The copper electroplating patterns on the spheres visualized the local heat transfer depending on angular distance. The streak plating patterns were observed on the upper part of the sphere, resulting from the wavy flow patterns caused by the instability.

Mass transfer in thin films under counter-current gas: experiments and numerical study

NASA Astrophysics Data System (ADS)

Lucquiaud, Mathieu; Lavalle, Gianluca; Schmidt, Patrick; Ausner, Ilja; Wehrli, Marc; O Naraigh, Lennon; Valluri, Prashant

2016-11-01

Mass transfer in liquid-gas stratified flows is strongly affected by the waviness of the interface. For reactive flows, the chemical reactions occurring at the liquid-gas interface also influence the mass transfer rate. This is encountered in several technological applications, such as absorption units for carbon capture. We investigate the absorption rate of carbon dioxide in a liquid solution. The experimental set-up consists of a vertical channel where a falling film is sheared by a counter-current gas flow. We measure the absorption occurring at different flow conditions, by changing the liquid solution, the liquid flow rate and the gas composition. With the aim to support the experimental results with numerical simulations, we implement in our level-set flow solver a novel module for mass transfer taking into account a variant of the ghost-fluid formalism. We firstly validate the pure mass transfer case with and without hydrodynamics by comparing the species concentration in the bulk flow to the analytical solution. In a final stage, we analyse the absorption rate in reactive flows, and try to reproduce the experimental results by means of numerical simulations to explore the active role of the waves at the interface.

A mouse model of fragile X syndrome exhibits heightened arousal and/or emotion following errors or reversal of contingencies.

PubMed

Moon, J; Ota, K T; Driscoll, L L; Levitsky, D A; Strupp, B J

2008-07-01

This study was designed to further assess cognitive and affective functioning in a mouse model of Fragile X syndrome (FXS), the Fmr1(tm1Cgr) or Fmr1 "knockout" (KO) mouse. Male KO mice and wild-type littermate controls were tested on learning set and reversal learning tasks. The KO mice were not impaired in associative learning, transfer of learning, or reversal learning, based on measures of learning rate. Analyses of videotapes of the reversal learning task revealed that both groups of mice exhibited higher levels of activity and wall-climbing during the initial sessions of the task than during the final sessions, a pattern also seen for trials following an error relative to those following a correct response. Notably, the increase in both behavioral measures seen early in the task was significantly more pronounced for the KO mice than for controls, as was the error-induced increase in activity level. This pattern of effects suggests that the KO mice reacted more strongly than controls to the reversal of contingencies and pronounced drop in reinforcement rate, and to errors in general. This pattern of effects is consistent with the heightened emotional reactivity frequently described for humans with FXS. (c) 2008 Wiley Periodicals, Inc.

Decal transfer microfabrication

DOEpatents

Nuzzo, Ralph G.; Childs, William Robert

2004-10-19

A method of making a microstructure includes forming a pattern in a surface of a silicon-containing elastomer, oxidizing the pattern, contacting the pattern with a substrate; and bonding the oxidized pattern and the substrate such that the pattern and the substrate are irreversibly attached. The silicon-containing elastomer may be removably attached to a transfer pad.

Largely overlapping neuronal substrates of reactivity to drug, gambling, food and sexual cues: A comprehensive meta-analysis.

PubMed

Noori, Hamid R; Cosa Linan, Alejandro; Spanagel, Rainer

2016-09-01

Cue reactivity to natural and social rewards is essential for motivational behavior. However, cue reactivity to drug rewards can also elicit craving in addicted subjects. The degree to which drug and natural rewards share neural substrates is not known. The objective of this study is to conduct a comprehensive meta-analysis of neuroimaging studies on drug, gambling and natural stimuli (food and sex) to identify the common and distinct neural substrates of cue reactivity to drug and natural rewards. Neural cue reactivity studies were selected for the meta-analysis by means of activation likelihood estimations, followed by sensitivity and clustering analyses of averaged neuronal response patterns. Data from 176 studies (5573 individuals) suggests largely overlapping neural response patterns towards all tested reward modalities. Common cue reactivity to natural and drug rewards was expressed by bilateral neural responses within anterior cingulate gyrus, insula, caudate head, inferior frontal gyrus, middle frontal gyrus and cerebellum. However, drug cues also generated distinct activation patterns in medial frontal gyrus, middle temporal gyrus, posterior cingulate gyrus, caudate body and putamen. Natural (sexual) reward cues induced unique activation of the pulvinar in thalamus. Neural substrates of cue reactivity to alcohol, drugs of abuse, food, sex and gambling are largely overlapping and comprise a network that processes reward, emotional responses and habit formation. This suggests that cue-mediated craving involves mechanisms that are not exclusive for addictive disorders but rather resemble the intersection of information pathways for processing reward, emotional responses, non-declarative memory and obsessive-compulsive behavior. Copyright © 2016 Elsevier B.V. and ECNP. All rights reserved.

Insights into the reactivation of cobalamin-dependent methionine synthase

PubMed Central

Koutmos, Markos; Datta, Supratim; Pattridge, Katherine A.; Smith, Janet L.; Matthews, Rowena G.

2009-01-01

Cobalamin-dependent methionine synthase (MetH) is a modular protein that catalyzes the transfer of a methyl group from methyltetrahydrofolate to homocysteine to produce methionine and tetrahydrofolate. The cobalamin cofactor, which serves as both acceptor and donor of the methyl group, is oxidized once every ≈2,000 catalytic cycles and must be reactivated by the uptake of an electron from reduced flavodoxin and a methyl group from S-adenosyl-L-methionine (AdoMet). Previous structures of a C-terminal fragment of MetH (MetHCT) revealed a reactivation conformation that juxtaposes the cobalamin- and AdoMet-binding domains. Here we describe 2 structures of a disulfide stabilized MetHCT (s-sMetHCT) that offer further insight into the reactivation of MetH. The structure of s-sMetHCT with cob(II)alamin and S-adenosyl-L-homocysteine represents the enzyme in the reactivation step preceding electron transfer from flavodoxin. The structure supports earlier suggestions that the enzyme acts to lower the reduction potential of the Co(II)/Co(I) couple by elongating the bond between the cobalt and its upper axial water ligand, effectively making the cobalt 4-coordinate, and illuminates the role of Tyr-1139 in the stabilization of this 4-coordinate state. The structure of s-sMetHCT with aquocobalamin may represent a transient state at the end of reactivation as the newly remethylated 5-coordinate methylcobalamin returns to the 6-coordinate state, triggering the rearrangement to a catalytic conformation. PMID:19846791

Formation mechanism and mechanics of dip-pen nanolithography using molecular dynamics.

PubMed

Wu, Cheng-Da; Fang, Te-Hua; Lin, Jen-Fin

2010-03-02

Molecular dynamics simulations are used to investigate the mechanisms of molecular transference, pattern formation, and mechanical behavior in the dip-pen nanolithography (DPN) process. The effects of deposition temperature were studied using molecular trajectories, the meniscus characteristic, surface absorbed energy, and pattern formation analysis. At the first transferred stage (at the initial indentation depth), the conformation of SAM molecules lies almost on the substrate surface. The molecules start to stand on the substrate due to the pull and drag forces at the second transferred stage (after the tip is pulled up). According to the absorbed energy behavior, the second transferred stage has larger transferred amounts and the transfer rate is strongly related to temperature. When molecules were deposited at low temperature (e.g., room temperature), the pattern shape was more highly concentrated. The pattern shape at high temperatures expanded and the area increased because of good molecular diffusion.

A method to transfer speckle patterns for digital image correlation

NASA Astrophysics Data System (ADS)

Chen, Zhenning; Quan, Chenggen; Zhu, Feipeng; He, Xiaoyuan

2015-09-01

A simple and repeatable speckle creation method based on water transfer printing (WTP) is proposed to reduce artificial measurement error for digital image correlation (DIC). This technique requires water, brush, and a piece of transfer paper that is made of prefabricated decal paper, a protected sheet, and printed speckle patterns. The speckle patterns are generated and optimized via computer simulations, and then printed on the decal paper. During the experiments, operators can moisten the basement with water and the brush, so that digital patterns can be simply transferred to the carriers’ surfaces. Tensile experiments with an extended three-dimensional (3D) DIC system are performed to test and verify the validity of WTP patterns. It is shown that by comparing with a strain gage, the strain error is less than 50μɛ in a uniform tensile test. From five carbon steel tensile experiments, Lüders bands in both WTP patterns and spray paint patterns are demonstrated to propagate symmetrically. In the necking part where the strain is up to 66%, WTP patterns are proved to adhere to the specimens well. Hence, WTP patterns are capable of maintaining coherence and adherence to the specimen surface. The transfer paper, working as the role of strain gage in the electrometric method, will contribute to speckle creation.

Cross-reactivity between pollen extracts from six artemisia species.

PubMed

Brandys, J; Grimsøen, A; Nilsen, B M; Paulsen, B S; Park, H S; Hong, C S

1993-06-01

Pollen extracts of six different ARTEMISIA species, A. VULGARIS, A. SCOPARIA, A. PRINCEPS, A. TRIDENTATA, A. ANNUA, and A. CAMPESTRIS were compared using SDS-PAGE, IEF, immunoblotting, and immunoelectrophoretic methods. The band patterns obtained after SDS-PAGE and IEF showed a large degree of similarity between the extracts. Immunoblotting of these gels using a pool of sera from patients allergic to A. VULGARIS gave essentially the same IgE-binding band pattern with all the extracts, demonstrating an extensive degree of cross-reactivity between A. VULGARIS and the other ARTEMISIA species. FRIE using a polyspecific antiserum against A. VULGARIS showed that all the extracts contained several antigens that were immunologically identical to antigens in A. VULGARIS extract. Antigens showing immunological identity to the important A. VULGARIS allergens Ag 12 and ART V II were present in all the extracts. The cross-reactivity between A. VULGARIS and A. PRINCEPS was further verified by screening of ten Korean and nine Norwegian individual patient sera against extracts of both species in SDS-PAGE or IEF immunoblotting. Both groups of patients had essentially the same pattern of reactivity towards both pollen extracts.

Emotional reactivity and the association between psychopathy-linked narcissism and aggression in detained adolescent boys.

PubMed

Muñoz Centifanti, Luna C; Kimonis, Eva R; Frick, Paul J; Aucoin, Katherine J

2013-05-01

Different patterns of emotional reactivity characterize proactive and reactive functions of aggressive behavior, and theory also suggests a link of both types with narcissism. How people with narcissistic traits respond emotionally to competitive scenarios could influence their aggressiveness. Participants were 85 adolescent boys from a detention center. Several indices of emotional functioning were assessed, including attentional bias to negative emotional stimuli and psychophysiological responding. In addition, we included self-report and laboratory measures of aggression and measures of psychopathy-linked narcissism, callous-unemotional traits, and impulsivity. Psychopathy-linked narcissism was uniquely related to unprovoked aggression (i.e., proactive aggression) and to heightened attention to pictures depicting others' distress. Compared with those scoring low on narcissism, those high on narcissism, who were the least physiologically reactive group, evinced greater proactive aggression, whereas those showing a pattern of coactivation (i.e., sympathetic and parasympathetic autonomic reactivity) evinced greater reactive aggression. Results are consistent with descriptions of narcissistic individuals as being hypervigilant to negative cues and exhibiting poor emotion regulation. These characteristics may lead to aggressive and violent behavior aimed at maintaining dominance over others.

Dissolved CO2 Increases Breakthrough Porosity in Natural Porous Materials.

PubMed

Yang, Y; Bruns, S; Stipp, S L S; Sørensen, H O

2017-07-18

When reactive fluids flow through a dissolving porous medium, conductive channels form, leading to fluid breakthrough. This phenomenon is caused by the reactive infiltration instability and is important in geologic carbon storage where the dissolution of CO 2 in flowing water increases fluid acidity. Using numerical simulations with high resolution digital models of North Sea chalk, we show that the breakthrough porosity is an important indicator of dissolution pattern. Dissolution patterns reflect the balance between the demand and supply of cumulative surface. The demand is determined by the reactive fluid composition while the supply relies on the flow field and the rock's microstructure. We tested three model scenarios and found that aqueous CO 2 dissolves porous media homogeneously, leading to large breakthrough porosity. In contrast, solutions without CO 2 develop elongated convective channels known as wormholes, with low breakthrough porosity. These different patterns are explained by the different apparent solubility of calcite in free drift systems. Our results indicate that CO 2 increases the reactive subvolume of porous media and reduces the amount of solid residual before reactive fluid can be fully channelized. Consequently, dissolved CO 2 may enhance contaminant mobilization near injection wellbores, undermine the mechanical sustainability of formation rocks and increase the likelihood of buoyance driven leakage through carbonate rich caprocks.

Pulse wave velocity in patients with severe head injury a pilot study.

PubMed

Shahsavari, S; McKelvey, T; Rydenhag, B; Ritzén, C Eriksson

2010-01-01

The study aimed to determine the potential of pulse wave velocity measurements to reflect changes in compliant cerebral arteries/arterioles in head injured patients. The approach utilizes the electrocardiogram and intracranial pressure signals to measure the wave transit time between heart and cranial cavity. Thirty five clinical records of nineteen head injured patients, with different levels of cerebrovascular pressure-reactivity response, were investigated through the study. Results were compared with magnitude of normalized transfer function at the fundamental cardiac frequency. In patients with intact cerebrovascular pressure-reactivity, magnitude of normalized transfer function at the fundamental cardiac component was found to be highly correlated with pulse wave transit time.

Cardiovascular reactivity as a mechanism linking child trauma to adolescent psychopathology.

PubMed

Heleniak, Charlotte; McLaughlin, Katie A; Ormel, Johan; Riese, Harriette

2016-10-01

Alterations in physiological reactivity to stress are argued to be central mechanisms linking adverse childhood environmental experiences to internalizing and externalizing psychopathology. Childhood trauma exposure may influence physiological reactivity to stress in distinct ways from other forms of childhood adversity. This study applied a novel theoretical model to investigate the impact of childhood trauma on cardiovascular stress reactivity - the biopsychosocial model of challenge and threat. This model suggests that inefficient cardiovascular responses to stress - a threat as opposed to challenge profile - are characterized by blunted cardiac output (CO) reactivity and increased vascular resistance. We examined whether childhood trauma exposure predicted an indicator of the threat profile of cardiovascular reactivity and whether such a pattern was associated with adolescent psychopathology in a population-representative sample of 488 adolescents (M=16.17years old, 49.2% boys) in the TRacking Adolescents' Individual Lives Survey (TRAILS). Exposure to trauma was associated with both internalizing and externalizing symptoms and a pattern of cardiovascular reactivity consistent with the threat profile, including blunted CO reactivity during a social stress task. Blunted CO reactivity, in turn, was positively associated with externalizing, but not internalizing symptoms and mediated the link between trauma and externalizing psychopathology. None of these associations varied by gender. The biopsychosocial model of challenge and threat provides a novel theoretical framework for understanding disruptions in physiological reactivity to stress following childhood trauma exposure, revealing a potential pathway linking such exposure with externalizing problems in adolescents. Copyright © 2016 Elsevier B.V. All rights reserved.

Cardiovascular reactivity as a mechanism linking child trauma to adolescent psychopathology

PubMed Central

Heleniak, Charlotte; McLaughlin, Katie A.; Ormel, Johan; Riese, Harriette

2016-01-01

Alterations in physiological reactivity to stress are argued to be central mechanisms linking adverse childhood environmental experiences to internalizing and externalizing psychopathology. Childhood trauma exposure may influence physiological reactivity to stress in distinct ways from other forms of childhood adversity. This study applied a novel theoretical model to investigate the impact of childhood trauma on cardiovascular stress reactivity – the biopsychosocial model of challenge and threat. This model suggests that inefficient cardiovascular responses to stress – a threat as opposed to challenge profile – are characterized by blunted cardiac output (CO) reactivity and increased vascular resistance. We examined whether childhood trauma exposure predicted an indicator of the threat profile of cardiovascular reactivity and whether such a pattern was associated with adolescent psychopathology in a population-representative sample of 488 adolescents (M = 16.17 years old, 49.2% boys) in the TRacking Adolescents’ Individual Lives Survey (TRAILS). Exposure to trauma was associated with both internalizing and externalizing symptoms and a pattern of cardiovascular reactivity consistent with the threat profile, including blunted CO reactivity during a social stress task. Blunted CO reactivity, in turn, was positively associated with externalizing, but not internalizing symptoms and mediated the link between trauma and externalizing psychopathology. None of these associations varied by gender. The biopsychosocial model of challenge and threat provides a novel theoretical framework for understanding disruptions in physiological reactivity to stress following childhood trauma exposure, revealing a potential pathway linking such exposure with externalizing problems in adolescents. PMID:27568327

The number and growth pattern of plasmacytoid dendritic cells vary in different types of reactive lymph nodes: an immunohistochemical study.

PubMed

Rollins-Raval, Marian A; Marafioti, Teresa; Swerdlow, Steven H; Roth, Christine G

2013-06-01

Plasmacytoid dendritic cells, which play a fundamental role in the innate immune response, are best known for their presence in hyaline-vascular Castleman disease and histiocytic necrotizing lymphadenitis. The relative number and distribution in many reactive entities as detected using more sensitive methods are uncertain, and their diagnostic implications are unknown. Immunohistochemical studies for plasmacytoid dendritic cell-associated markers CD123 and CD2AP were performed on 42 lymph nodes with hyaline-vascular Castleman disease, histiocytic necrotizing lymphadenitis, sarcoidosis, necrotizing granulomatous inflammation, viral infection, dermatopathic lymphadenopathy, autoimmune disease, and a histologic pattern compatible with toxoplasmosis. The overall plasmacytoid dendritic cell numbers and growth patterns (tight aggregates, loose aggregates/clusters, scattered single cells) were assessed. Plasmacytoid dendritic cells were present in all cases and were predominantly distributed in loose aggregates/clusters or singly. They were most numerous in granulomatous inflammation and histiocytic necrotizing lymphadenitis, whereas viral infections showed the fewest overall numbers and a predominant pattern of scattered single cells. Tight aggregates of plasmacytoid dendritic cells were most numerous in hyaline-vascular Castleman disease (100% sensitive, 68% specific). Plasmacytoid dendritic cells are not limited to a small number of reactive lymphadenopathies but are found in many reactive processes, often with a predominant pattern of loose aggregates/clusters and scattered single cells. However, tight aggregates were a characteristic feature of hyaline-vascular Castleman disease, and viral infections typically showed only few scattered cells distributed singly. Copyright © 2013 Elsevier Inc. All rights reserved.

Occupational Rhinoconjunctivitis due to Maize in a Snack Processor: A Cross-Reactivity Study Between Lipid Transfer Proteins From Different Cereals and Peach.

PubMed

Guillen, Daiana; Barranco, Pilar; Palacín, Arantxa; Quirce, Santiago

2014-09-01

We report the case of a snack processor who developed occupational rhinoconjunctivitis due to maize brand exposure during the extrusion process, and who experienced abdominal pain upon drinking beer. The allergens implicated and the cross-reactivity between non-specific lipid transfer proteins (LTPs) from different cereals and peach were investigated. Skin prick tests and specific IgE to cereal flours, pulmonary functions tests and specific conjunctival and inhalation challenges to maize extract were performed. In vitro studies included IgE immunoblotting and ELISA inhibition assays. Skin prick tests with maize flour, maize brand and wheat flour extracts were positive, whereas serum specific IgE was positive only to maize flour. Specific inhalation challenge (SIC) to maize flour did not elicit an asthmatic reaction; however, conjunctival challenge test with the same extract was positive. Patient's serum recognized IgE-binding bands in the maize and beer extracts corresponding to LTPs. In the ELISA inhibition assays, a significant degree of allergenic cross-reactivity was found between maize and beer LTPs, whereas no cross-reactivity was observed between maize LTP and wheat and peach LTPs.

Roll-to-roll continuous patterning and transfer of graphene via dispersive adhesion

NASA Astrophysics Data System (ADS)

Choi, Taejun; Kim, Sang Jin; Park, Subeom; Hwang, Taek Yong; Jeon, Youngro; Hong, Byung Hee

2015-04-01

We present a roll-to-roll, continuous patterning and transfer of graphene sheets capable of residue-free and fast patterning. The graphene sheet is supported with dispersive adhesion. Graphene is continuously patterned by the difference in adhesion forces with a pre-defined embossed roller. The patterned graphene sheet adheres to the polyethylene terephthalate (PET)/silicone with very low strength and can be easily transferred to various substrates without the aid of any heating mechanism. The width of the patterned film was 120 mm and a production rate of 15 m min-1 for patterning was achieved. Large-area uniformity was confirmed by observing the optical images on 4 inch Si wafer and Raman mapping spectra for 50 × 50 mm2.We present a roll-to-roll, continuous patterning and transfer of graphene sheets capable of residue-free and fast patterning. The graphene sheet is supported with dispersive adhesion. Graphene is continuously patterned by the difference in adhesion forces with a pre-defined embossed roller. The patterned graphene sheet adheres to the polyethylene terephthalate (PET)/silicone with very low strength and can be easily transferred to various substrates without the aid of any heating mechanism. The width of the patterned film was 120 mm and a production rate of 15 m min-1 for patterning was achieved. Large-area uniformity was confirmed by observing the optical images on 4 inch Si wafer and Raman mapping spectra for 50 × 50 mm2. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr06991a

Laser-assisted simultaneous transfer and patterning of vertically aligned carbon nanotube arrays on polymer substrates for flexible devices.

PubMed

In, Jung Bin; Lee, Daeho; Fornasiero, Francesco; Noy, Aleksandr; Grigoropoulos, Costas P

2012-09-25

We demonstrate a laser-assisted dry transfer technique for assembling patterns of vertically aligned carbon nanotube arrays on a flexible polymeric substrate. A laser beam is applied to the interface of a nanotube array and a polycarbonate sheet in contact with one another. The absorbed laser heat promotes nanotube adhesion to the polymer in the irradiated regions and enables selective pattern transfer. A combination of the thermal transfer mechanism with rapid direct writing capability of focused laser beam irradiation allows us to achieve simultaneous material transfer and direct micropatterning in a single processing step. Furthermore, we demonstrate that malleability of the nanotube arrays transferred onto a flexible substrate enables post-transfer tailoring of electric conductance by collapsing the aligned nanotubes in different directions. This work suggests that the laser-assisted transfer technique provides an efficient route to using vertically aligned nanotubes as conductive elements in flexible device applications.

Effects of reservoir heterogeneity on scaling of effective mass transfer coefficient for solute transport

NASA Astrophysics Data System (ADS)

Leung, Juliana Y.; Srinivasan, Sanjay

2016-09-01

Modeling transport process at large scale requires proper scale-up of subsurface heterogeneity and an understanding of its interaction with the underlying transport mechanisms. A technique based on volume averaging is applied to quantitatively assess the scaling characteristics of effective mass transfer coefficient in heterogeneous reservoir models. The effective mass transfer coefficient represents the combined contribution from diffusion and dispersion to the transport of non-reactive solute particles within a fluid phase. Although treatment of transport problems with the volume averaging technique has been published in the past, application to geological systems exhibiting realistic spatial variability remains a challenge. Previously, the authors developed a new procedure where results from a fine-scale numerical flow simulation reflecting the full physics of the transport process albeit over a sub-volume of the reservoir are integrated with the volume averaging technique to provide effective description of transport properties. The procedure is extended such that spatial averaging is performed at the local-heterogeneity scale. In this paper, the transport of a passive (non-reactive) solute is simulated on multiple reservoir models exhibiting different patterns of heterogeneities, and the scaling behavior of effective mass transfer coefficient (Keff) is examined and compared. One such set of models exhibit power-law (fractal) characteristics, and the variability of dispersion and Keff with scale is in good agreement with analytical expressions described in the literature. This work offers an insight into the impacts of heterogeneity on the scaling of effective transport parameters. A key finding is that spatial heterogeneity models with similar univariate and bivariate statistics may exhibit different scaling characteristics because of the influence of higher order statistics. More mixing is observed in the channelized models with higher-order continuity. It reinforces the notion that the flow response is influenced by the higher-order statistical description of heterogeneity. An important implication is that when scaling-up transport response from lab-scale results to the field scale, it is necessary to account for the scale-up of heterogeneity. Since the characteristics of higher-order multivariate distributions and large-scale heterogeneity are typically not captured in small-scale experiments, a reservoir modeling framework that captures the uncertainty in heterogeneity description should be adopted.

Glimpses of East Antarctica: Aeromagnetic and satellite magnetic view from the central Transantarctic Mountains of East Antarctica

USGS Publications Warehouse

Finn, Carol A.; Goodge, John W.

2010-01-01

Aeromagnetic and satellite magnetic data provide glimpses of the crustal architecture within the Ross Sea sector of the enigmatic, ice-covered East Antarctic shield critical for understanding both global tectonic and climate history. In the central Transantarctic Mountains (CTAM), exposures of Precambrian basement, coupled with new high-resolution magnetic data, other recent aeromagnetic transects, and satellite magnetic and seismic tomography data, show that the shield in this region comprises an Archean craton modified both by Proterozoic magmatism and early Paleozoic orogenic basement reactivation. CTAM basement structures linked to the Ross Orogeny are imaged 50–100 km farther west than previously mapped, bounded by inboard upper crustal Proterozoic granites of the Nimrod igneous province. Magnetic contrasts between craton and rift margin sediments define the Neoproterozoic rift margin, likely reactivated during Ross orogenesis and Jurassic extension. Interpretation of satellite magnetic and aeromagnetic patterns suggests that the Neoproterozoic rift margin of East Antarctica is offset by transfer zones to form a stepwise series of salients tracing from the CTAM northward through the western margin of the Wilkes Subglacial Basin to the coast at Terre Adélie. Thinned Precambrian crust inferred to lie east of the rift margin cannot be imaged magnetically because of modification by Neoproterozoic and younger tectonic events.

Cyt c6-3: A New Isoform of Photosynthetic Cyt c6 Exclusive to Heterocyst-Forming Cyanobacteria.

PubMed

Torrado, Alejandro; Valladares, Ana; Puerto-Galán, Leonor; Hervás, Manuel; Navarro, José A; Molina-Heredia, Fernando P

2017-02-01

All known cyanobacteria contain Cyt c6, a small soluble electron carrier protein whose main function is to transfer electrons from the Cyt b6f complex to PSI, although it is also involved in respiration. We have previously described a second isoform of this protein, the Cyt c6-like, whose function remains unknown. Here we describe a third isoform of Cyt c6 (here called Cytc6-3), which is only found in heterocyst-forming filamentous cyanobacteria. Cyt c6-3 is expressed in vegetative cells but is specifically repressed in heterocysts cells under diazotrophic growth conditions. Although there is a close structural similarity between Cyt c6-3 and Cyt c6 related to the general protein folding, Cyt c6-3 presents differential electrostatic surface features as compared with Cyt c6, its expression is not copper dependent and has a low reactivity towards PSI. According to the different expression pattern, functional reactivity and structural properties, Cyt c6-3 has to play an as yet to be defined regulatory role related to heterocyst differentiation. © The Author 2016. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Influence of Proton Acceptors on the Proton-Coupled Electron Transfer Reaction Kinetics of a Ruthenium-Tyrosine Complex.

PubMed

Lennox, J Christian; Dempsey, Jillian L

2017-11-22

A polypyridyl ruthenium complex with fluorinated bipyridine ligands and a covalently bound tyrosine moiety was synthesized, and its photo-induced proton-coupled electron transfer (PCET) reactivity in acetonitrile was investigated with transient absorption spectroscopy. Using flash-quench methodology with methyl viologen as an oxidative quencher, a Ru 3+ species is generated that is capable of initiating the intramolecular PCET oxidation of the tyrosine moiety. Using a series of substituted pyridine bases, the reaction kinetics were found to vary as a function of proton acceptor concentration and identity, with no significant H/D kinetic isotope effect. Through analysis of the kinetics traces and comparison to a control complex without the tyrosine moiety, PCET reactivity was found to proceed through an equilibrium electron transfer followed by proton transfer (ET-PT) pathway in which irreversible deprotonation of the tyrosine radical cation shifts the ET equilibrium, conferring a base dependence on the reaction. Comprehensive kinetics modeling allowed for deconvolution of complex kinetics and determination of rate constants for each elementary step. Across the five pyridine bases explored, spanning a range of 4.2 pK a units, a linear free-energy relationship was found for the proton transfer rate constant with a slope of 0.32. These findings highlight the influence that proton transfer driving force exerts on PCET reaction kinetics.

Acyl transfer from membrane lipids to peptides is a generic process.

PubMed

Dods, Robert H; Bechinger, Burkhard; Mosely, Jackie A; Sanderson, John M

2013-11-15

The generality of acyl transfer from phospholipids to membrane-active peptides has been probed using liquid chromatography-mass spectrometry analysis of peptide-lipid mixtures. The peptides examined include melittin, magainin II, PGLa, LAK1, LAK3 and penetratin. Peptides were added to liposomes with membrane lipid compositions ranging from pure phosphatidylcholine (PC) to mixtures of PC with phosphatidylethanolamine, phosphatidylserine or phosphatidylglycerol. Experiments were typically conducted at pH7.4 at modest salt concentrations (90 mM NaCl). In favorable cases, lipidated peptides were further characterized by tandem mass spectrometry methods to determine the sites of acylation. Melittin and magainin II were the most reactive peptides, with significant acyl transfer detected under all conditions and membrane compositions. Both peptides were lipidated at the N-terminus by transfer from PC, phosphatidylethanolamine, phosphatidylserine or phosphatidylglycerol, as well as at internal sites: lysine for melittin; serine and lysine for magainin II. Acyl transfer could be detected within 3h of melittin addition to negatively charged membranes. The other peptides were less reactive, but for each peptide, acylation was found to occur in at least one of the conditions examined. The data demonstrate that acyl transfer is a generic process for peptides bound to membranes composed of diacylglycerophospholipids. Phospholipid membranes cannot therefore be considered as chemically inert toward peptides and by extension proteins. © 2013. Published by Elsevier Ltd. All rights reserved.

Pre-existing oblique transfer zones and transfer/transform relationships in continental margins: New insights from the southeastern Gulf of Aden, Socotra Island, Yemen

NASA Astrophysics Data System (ADS)

Bellahsen, N.; Leroy, S.; Autin, J.; Razin, P.; d'Acremont, E.; Sloan, H.; Pik, R.; Ahmed, A.; Khanbari, K.

2013-11-01

Transfer zones are ubiquitous features in continental rifts and margins, as are transform faults in oceanic lithosphere. Here, we present a structural study of the Hadibo Transfer Zone (HTZ), located in Socotra Island (Yemen) in the southeastern Gulf of Aden. There, we interpret this continental transfer fault zone to represent a reactivated pre-existing structure. Its trend is oblique to the direction of divergence and it has been active from the early up to the latest stages of rifting. One of the main oceanic fracture zones (FZ), the Hadibo-Sharbithat FZ, is aligned with and appears to be an extension of the HTZ and is probably genetically linked to it. Comparing this setting with observations from other Afro-Arabian rifts as well as with passive margins worldwide, it appears that many continental transfer zones are reactivated pre-existing structures, oblique to divergence. We therefore establish a classification system for oceanic FZ based upon their relationship with syn-rift structures. Type 1 FZ form at syn-rift structures and are late syn-rift to early syn-OCT. Type 2 FZ form during the OCT formation and Type 3 FZ form within the oceanic domain, after the oceanic spreading onset. The latter are controlled by far-field forces, magmatic processes, spreading rates, and oceanic crust rheology.

Complex auditory behaviour emerges from simple reactive steering

NASA Astrophysics Data System (ADS)

Hedwig, Berthold; Poulet, James F. A.

2004-08-01

The recognition and localization of sound signals is fundamental to acoustic communication. Complex neural mechanisms are thought to underlie the processing of species-specific sound patterns even in animals with simple auditory pathways. In female crickets, which orient towards the male's calling song, current models propose pattern recognition mechanisms based on the temporal structure of the song. Furthermore, it is thought that localization is achieved by comparing the output of the left and right recognition networks, which then directs the female to the pattern that most closely resembles the species-specific song. Here we show, using a highly sensitive method for measuring the movements of female crickets, that when walking and flying each sound pulse of the communication signal releases a rapid steering response. Thus auditory orientation emerges from reactive motor responses to individual sound pulses. Although the reactive motor responses are not based on the song structure, a pattern recognition process may modulate the gain of the responses on a longer timescale. These findings are relevant to concepts of insect auditory behaviour and to the development of biologically inspired robots performing cricket-like auditory orientation.

The symphonic structure of childhood stress reactivity: Patterns of sympathetic, parasympathetic, and adrenocortical responses to psychological challenge

PubMed Central

Quas, Jodi A.; Yim, Ilona S.; Oberlander, Tim F.; Nordstokke, David; Essex, Marilyn J.; Armstrong, Jeffrey M.; Bush, Nicole; Obradović, Jelena; Boyce, W. Thomas

2015-01-01

Despite widespread recognition that the physiological systems underlying stress reactivity are well coordinated at a neurobiological level, surprisingly little empirical attention has been given to delineating precisely how the systems actually interact with one another when confronted with stress. We examined cross-system response proclivities in anticipation of and following standardized laboratory challenges in 664 4- to 14-year-olds from four independent studies. In each study, measures of stress reactivity within both the locus coeruleus-norepinephrine system (i.e., the sympathetic and parasympathetic branches of the autonomic nervous system) and the corticotrophin releasing hormone system (i.e., the hypothalamic-pituitary-adrenal axis) were collected. Latent profile analyses revealed six distinctive patterns that recurred across the samples: moderate reactivity (average cross-system activation; 52%-80% of children across samples), parasympathetic-specific reactivity (2%-36%), anticipatory arousal (4%-9%), multisystem reactivity (7%—14%), hypothalamic-pituitary-adrenal axis specific reactivity (6%-7%), and underarousal (0%-2%). Groups meaningfully differed in socioeconomic status, family adversity, and age. Results highlight the sample-level reliability of children’s neuroendocrine responses to stress and suggest important cross-system regularities that are linked to development and prior experiences and may have implications for subsequent physical and mental morbidity. PMID:24909883

Depression and emotional reactivity: variation among Asian Americans of East Asian descent and European Americans.

PubMed

Chentsova-Dutton, Yulia E; Chu, Joyce P; Tsai, Jeanne L; Rottenberg, Jonathan; Gross, James J; Gotlib, Ian H

2007-11-01

Studies of Western samples (e.g., European Americans [EAs]) suggest that depressed individuals tend to show diminished emotional reactivity (J. G. Gehricke & A. J. Fridlund, 2002; G. E. Schwartz, P. L. Fair, P. Salt, M. R. Mandel, & G. L. Klerman, 1976a, 1976b). Do these findings generalize to individuals oriented to other cultures (e.g., East Asian cultures)? The authors compared the emotional reactions (i.e., reports of emotional experience, facial behavior, and physiological reactivity) of depressed and nondepressed EAs and Asian Americans of East Asian descent (AAs) to sad and amusing films. Their results were consistent with previous findings: Depressed EAs showed a pattern of diminished reactivity to the sad film (less crying, less intense reports of sadness) compared with nondepressed participants. In contrast, depressed AAs showed a pattern of heightened emotional reactivity (greater crying) compared with nondepressed participants. Across cultural groups, depressed and nondepressed participants did not differ in their reports of amusement or facial behavior during the amusing film. Physiological reactivity to the film clips did not differ between depressed and control participants for either cultural group. Thus, although depression may influence particular aspects of emotional reactivity across cultures (e.g., crying), the specific direction of this influence may depend on prevailing cultural norms regarding emotional expression. (c) 2007 APA

Catalytic transfer hydrogenation for stabilization of bio-oil oxygenates: reduction of p-cresol and furfural over bimetallic Ni-Cu catalysts using isopropanol

USDA-ARS?s Scientific Manuscript database

Transfer hydrogenation and hydrodeoxygenation of model bio-oil compounds (p-cresol and furfural) and bio-oils derived from biomass via traditional pyrolysis and tail-gas reactive pyrolysis (TGRP) were conducted. Mild batch reaction conditions were employed, using isopropanol as a hydrogen donor over...

Analysis of Coolant Options for Advanced Metal Cooled Nuclear Reactors

DTIC Science & Technology

2006-12-01

24 Table 3.3 Hazards of Sodium Reaction Products, Hydride And Oxide...........................26 Table 3.4 Chemical Reactivity Of Selected...Liquid Metal Fast Breeder Reactor ORIGEN Oak Ridge Isotope Generator ORIGENARP Oak Ridge Isotope Generator Automated Rapid Processing PWR ...nuclear reactors, both because of the possibility of increased reactivity due to boiling and the potential loss of effectiveness of coolant heat transfer

Strong Inhibition of O-Atom Transfer Reactivity for Mn(IV)(O)(π-Radical-Cation)(Lewis Acid) versus Mn(V)(O) Porphyrinoid Complexes.

PubMed

Zaragoza, Jan Paulo T; Baglia, Regina A; Siegler, Maxime A; Goldberg, David P

2015-05-27

The oxygen atom transfer (OAT) reactivity of two valence tautomers of a Mn(V)(O) porphyrinoid complex was compared. The OAT kinetics of Mn(V)(O)(TBP8Cz) (TBP8Cz = octakis(p-tert-butylphenyl)corrolazinato(3-)) reacting with a series of triarylphosphine (PAr3) substrates were monitored by stopped-flow UV-vis spectroscopy, and revealed second-order rate constants ranging from 16(1) to 1.43(6) × 10(4) M(-1) s(-1). Characterization of the OAT transition state analogues Mn(III)(OPPh3)(TBP8Cz) and Mn(III)(OP(o-tolyl)3)(TBP8Cz) was carried out by single-crystal X-ray diffraction (XRD). A valence tautomer of the closed-shell Mn(V)(O)(TBP8Cz) can be stabilized by the addition of Lewis and Brønsted acids, resulting in the open-shell Mn(IV)(O)(TBP8Cz(•+)):LA (LA = Zn(II), B(C6F5)3, H(+)) complexes. These Mn(IV)(O)(π-radical-cation) derivatives exhibit dramatically inhibited rates of OAT with the PAr3 substrates (k = 8.5(2) × 10(-3) - 8.7 M(-1) s(-1)), contrasting the previously observed rate increase of H-atom transfer (HAT) for Mn(IV)(O)(TBP8Cz(•+)):LA with phenols. A Hammett analysis showed that the OAT reactivity for Mn(IV)(O)(TBP8Cz(•+)):LA is influenced by the Lewis acid strength. Spectral redox titration of Mn(IV)(O)(TBP8Cz(•+)):Zn(II) gives Ered = 0.69 V vs SCE, which is nearly +700 mV above its valence tautomer Mn(V)(O)(TBP8Cz) (Ered = -0.05 V). These data suggest that the two-electron electrophilicity of the Mn(O) valence tautomers dominate OAT reactivity and do not follow the trend in one-electron redox potentials, which appear to dominate HAT reactivity. This study provides new fundamental insights regarding the relative OAT and HAT reactivity of valence tautomers such as M(V)(O)(porph) versus M(IV)(O)(porph(•+)) (M = Mn or Fe) found in heme enzymes.

Insights into the reactivation of cobalamin-dependent methionine synthase

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

Koutmos, Markos; Datta, Supratim; Pattridge, Katherine A.

2009-12-10

Cobalamin-dependent methionine synthase (MetH) is a modular protein that catalyzes the transfer of a methyl group from methyltetrahydrofolate to homocysteine to produce methionine and tetrahydrofolate. The cobalamin cofactor, which serves as both acceptor and donor of the methyl group, is oxidized once every {approx}2,000 catalytic cycles and must be reactivated by the uptake of an electron from reduced flavodoxin and a methyl group from S-adenosyl-L-methionine (AdoMet). Previous structures of a C-terminal fragment of MetH (MetH{sup CT}) revealed a reactivation conformation that juxtaposes the cobalamin- and AdoMet-binding domains. Here we describe 2 structures of a disulfide stabilized MetH{sup CT} ({sub s-s}MetH{supmore » CT}) that offer further insight into the reactivation of MetH. The structure of {sub s-s}MetH{sup CT} with cob(II)alamin and S-adenosyl-L-homocysteine represents the enzyme in the reactivation step preceding electron transfer from flavodoxin. The structure supports earlier suggestions that the enzyme acts to lower the reduction potential of the Co(II)/Co(I) couple by elongating the bond between the cobalt and its upper axial water ligand, effectively making the cobalt 4-coordinate, and illuminates the role of Tyr-1139 in the stabilization of this 4-coordinate state. The structure of {sub s-s}MetH{sub CT} with aquocobalamin may represent a transient state at the end of reactivation as the newly remethylated 5-coordinate methylcobalamin returns to the 6-coordinate state, triggering the rearrangement to a catalytic conformation.« less

A theory for bioinorganic chemical reactivity of oxometal complexes and analogous oxidants: the exchange and orbital-selection rules.

PubMed

Usharani, Dandamudi; Janardanan, Deepa; Li, Chunsen; Shaik, Sason

2013-02-19

Over the past decades metalloenzymes and their synthetic models have emerged as an area of increasing research interest. The metalloenzymes and their synthetic models oxidize organic molecules using oxometal complexes (OMCs), especially oxoiron(IV)-based ones. Theoretical studies have helped researchers to characterize the active species and to resolve mechanistic issues. This activity has generated massive amounts of data on the relationship between the reactivity of OMCs and the transition metal's identity, oxidation state, ligand sphere, and spin state. Theoretical studies have also produced information on transition state (TS) structures, reaction intermediates, barriers, and rate-equilibrium relationships. For example, the experimental-theoretical interplay has revealed that nonheme enzymes carry out H-abstraction from strong C-H bonds using high-spin (S = 2) oxoiron(IV) species with four unpaired electrons on the iron center. However, other reagents with higher spin states and more unpaired electrons on the metal are not as reactive. Still other reagents carry out these transformations using lower spin states with fewer unpaired electrons on the metal. The TS structures for these reactions exhibit structural selectivity depending on the reactive spin states. The barriers and thermodynamic driving forces of the reactions also depend on the spin state. H-Abstraction is preferred over the thermodynamically more favorable concerted insertion into C-H bonds. Currently, there is no unified theoretical framework that explains the totality of these fascinating trends. This Account aims to unify this rich chemistry and understand the role of unpaired electrons on chemical reactivity. We show that during an oxidative step the d-orbital block of the transition metal is enriched by one electron through proton-coupled electron transfer (PCET). That single electron elicits variable exchange interactions on the metal, which in turn depend critically on the number of unpaired electrons on the metal center. Thus, we introduce the exchange-enhanced reactivity (EER) principle, which predicts the preferred spin state during oxidation reactions, the dependence of the barrier on the number of unpaired electrons in the TS, and the dependence of the deformation energy of the reactants on the spin state. We complement EER with orbital-selection rules, which predict the structure of the preferred TS and provide a handy theory of bioinorganic oxidative reactions. These rules show how EER provides a Hund's Rule for chemical reactivity: EER controls the reactivity landscape for a great variety of transition-metal complexes and substrates. Among many reactivity patterns explained, EER rationalizes the abundance of high-spin oxoiron(IV) complexes in enzymes that carry out bond activation of the strongest bonds. The concepts used in this Account might also be applicable in other areas such as in f-block chemistry and excited-state reactivity of 4d and 5d OMCs.

Retraction Note: Catalytic living ring-opening metathesis polymerization

NASA Astrophysics Data System (ADS)

Nagarkar, Amit A.; Kilbinger, Andreas F. M.

2018-05-01

We the authors are retracting this Article because of our failure to reproduce the molecular weight dispersities (PDI) shown in Fig. 4 using the chain-transfer agent described in the paper (CTA1). While the degenerate chain-transfer mechanism described in Fig. 3 is correct, the best molecular weight dispersities that could be reproduced with the chain-transfer agent shown in the Article are much larger (PDI > 2.0) than reported.We have since studied the kinetics of CTA1 in comparison with several other chain-transfer agents we are currently investigating and we now understand that the reactivity of CTA1 towards propagating ruthenium alkylidene complexes is very low. Very long monomer addition times would therefore have been necessary to gain control over the molecular weight distribution. Such long addition times would exceed the lifetime of the Grubbs catalyst in solution. Faster addition of the monomer has since repeatedly been shown to broaden the molecular weight dispersity.Additionally, the best chain-transfer agents we are currently investigating are orders of magnitude more reactive than CTA1 but give broader molecular weight dispersities than reported in Fig. 4. Molecular weight and dispersity control as shown in Fig. 4 is therefore an inappropriate claim for CTA1.The authors deeply regret these errors and apologize to the community.

Computer simulation of data on chromosome aberrations produced by X rays or alpha particles and detected by fluorescence in situ hybridization.

PubMed

Chen, A M; Lucas, J N; Simpson, P J; Griffin, C S; Savage, J R; Brenner, D J; Hlatky, L R; Sachs, R K

1997-11-01

With fluorescence in situ hybridization (FISH), many different categories of chromosome aberrations can be recognized-dicentrics, translocations, rings and various complex aberrations such as insertions or three-way interchanges. Relative frequencies for the various aberration categories indicate mechanisms of radiation-induced damage and reflect radiation quality. Data obtained with FISH support a proximity version of the classic random breakage-and-reunion model for the formation of aberrations. A Monte Carlo computer implementation of the model, called the CAS (chromosome aberration simulator), is generalized here to high linear energy transfer (LET) and compared to published data for human cells irradiated with X rays or 238Pu alpha particles. For each kind of radiation, the CAS has two adjustable parameters: the number of interaction sites per cell nucleus and the number of reactive double-strand breaks (DSBs) per gray. Aberration frequencies for various painted chromosomes, of varying lengths, and for 11 different categories of simple or complex aberrations were simulated and compared to the data. The optimal number of interaction sites was found to be approximately 13 for X irradiation and approximately 25 for alpha-particle irradiation. The relative biological effectiveness (RBE) of alpha particles for the induction of reactive DSBs (which are a minority of all DSBs) was found to be approximately 4. The two-parameter CAS model adequately matches data for many different categories of aberrations. It can use data obtained with FISH for any one painting pattern to predict results for any other kind of painting pattern or whole-genome staining, and to estimate a suggested overall numerical damage indicator for chromosome aberration studies, the total misrejoining number.

Subsurface to substrate: dual-scale micro/nanofluidic networks for investigating transport anomalies in tight porous media.

PubMed

Kelly, Shaina A; Torres-Verdín, Carlos; Balhoff, Matthew T

2016-08-07

Micro/nanofluidic experiments in synthetic representations of tight porous media, often referred to as "reservoir-on-a-chip" devices, are an emerging approach to researching anomalous fluid transport trends in energy-bearing and fluid-sequestering geologic porous media. We detail, for the first time, the construction of dual-scale micro/nanofluidic devices that are relatively large-scale, two-dimensional network representations of granular and fractured nanoporous media. The fabrication scheme used in the development of the networks on quartz substrates (master patterns) is facile and replicable: transmission electron microscopy (TEM) grids with lacey carbon support film were used as shadow masks in thermal evaporation/deposition and reactive ion etch (RIE) was used for hardmask pattern transfer. The reported nanoscale network geometries are heterogeneous and composed of hydraulically resistive paths (throats) meeting at junctures (pores) to mimic the low topological connectivity of nanoporous sedimentary rocks such as shale. The geometry also includes homogenous microscale grid patterns that border the nanoscale networks and represent microfracture pathways. Master patterns were successfully replicated with a sequence of polydimethylsiloxane (PDMS) and Norland Optical Adhesive (NOA) 63 polymers. The functionality of the fabricated quartz and polymer nanofluidic devices was validated with aqueous imbibition experiments and differential interference contrast microscopy. These dual-scale fluidic devices are promising predictive tools for hypothesis testing and calibration against bulk fluid measurements in tight geologic, biologic, and synthetic porous material of similar dual-scale pore structure. Applications to shale/mudrock transport studies in particular are focused on herein.

Do pattern recognition skills transfer across sports? A preliminary analysis.

PubMed

Smeeton, Nicholas J; Ward, Paul; Williams, A Mark

2004-02-01

The ability to recognize patterns of play is fundamental to performance in team sports. While typically assumed to be domain-specific, pattern recognition skills may transfer from one sport to another if similarities exist in the perceptual features and their relations and/or the strategies used to encode and retrieve relevant information. A transfer paradigm was employed to compare skilled and less skilled soccer, field hockey and volleyball players' pattern recognition skills. Participants viewed structured and unstructured action sequences from each sport, half of which were randomly represented with clips not previously seen. The task was to identify previously viewed action sequences quickly and accurately. Transfer of pattern recognition skill was dependent on the participant's skill, sport practised, nature of the task and degree of structure. The skilled soccer and hockey players were quicker than the skilled volleyball players at recognizing structured soccer and hockey action sequences. Performance differences were not observed on the structured volleyball trials between the skilled soccer, field hockey and volleyball players. The skilled field hockey and soccer players were able to transfer perceptual information or strategies between their respective sports. The less skilled participants' results were less clear. Implications for domain-specific expertise, transfer and diversity across domains are discussed.

Neurobehavioral foundation of environmental reactivity.

PubMed

Moore, Sarah R; Depue, Richard A

2016-02-01

Sensitivity to environmental context has been of interest for many years, but the nature of individual differences in environmental sensitivity has become of particular focus over the past 2 decades. What is particularly uncertain are the neural variables and processes that mediate the effects of environment on developmental outcomes. Accordingly, we provide a neurobehavioral foundation of reactivity to the environment in several steps. First, the different patterns of environmental sensitivity are defined to identify the significant factors involved in the manifestation of these patterns. Second, we focus on neurobiological reactivity as the construct underlying variation in sensitivity to the environment by (a) providing an organizing threshold model of elicitation of neurobiology by environmental context; and (b) integrating the literature on 2 sets of neuromodulators in terms of each modulator's (a) contribution to neural and behavioral reactivity to stimulation, and (b) relation to emotional-motivational systems (dopamine, opiates and oxytocin, corticotropin-releasing hormone) or the general modulation of those systems (serotonin, norepinephrine, and GABA). Discussion concludes with (a) a comprehensive neurobehavioral framework of environmental reactivity based on a combinatorial model of a supertrait, (b) methodological implications of the model, and (c) a developmental perspective on environmental reactivity. (c) 2016 APA, all rights reserved).

Wafer-scale layer transfer of GaAs and Ge onto Si wafers using patterned epitaxial lift-off

NASA Astrophysics Data System (ADS)

Mieda, Eiko; Maeda, Tatsuro; Miyata, Noriyuki; Yasuda, Tetsuji; Kurashima, Yuichi; Maeda, Atsuhiko; Takagi, Hideki; Aoki, Takeshi; Yamamoto, Taketsugu; Ichikawa, Osamu; Osada, Takenori; Hata, Masahiko; Ogawa, Arito; Kikuchi, Toshiyuki; Kunii, Yasuo

2015-03-01

We have developed a wafer-scale layer-transfer technique for transferring GaAs and Ge onto Si wafers of up to 300 mm in diameter. Lattice-matched GaAs or Ge layers were epitaxially grown on GaAs wafers using an AlAs release layer, which can subsequently be transferred onto a Si handle wafer via direct wafer bonding and patterned epitaxial lift-off (ELO). The crystal properties of the transferred GaAs layers were characterized by X-ray diffraction (XRD), photoluminescence, and the quality of the transferred Ge layers was characterized using Raman spectroscopy. We find that, after bonding and the wet ELO processes, the quality of the transferred GaAs and Ge layers remained the same compared to that of the as-grown epitaxial layers. Furthermore, we realized Ge-on-insulator and GaAs-on-insulator wafers by wafer-scale pattern ELO technique.

Numerical investigation of coupled density-driven flow and hydrogeochemical processes below playas

NASA Astrophysics Data System (ADS)

Hamann, Enrico; Post, Vincent; Kohfahl, Claus; Prommer, Henning; Simmons, Craig T.

2015-11-01

Numerical modeling approaches with varying complexity were explored to investigate coupled groundwater flow and geochemical processes in saline basins. Long-term model simulations of a playa system gain insights into the complex feedback mechanisms between density-driven flow and the spatiotemporal patterns of precipitating evaporites and evolving brines. Using a reactive multicomponent transport model approach, the simulations reproduced, for the first time in a numerical study, the evaporite precipitation sequences frequently observed in saline basins ("bull's eyes"). Playa-specific flow, evapoconcentration, and chemical divides were found to be the primary controls for the location of evaporites formed, and the resulting brine chemistry. Comparative simulations with the computationally far less demanding surrogate single-species transport models showed that these were still able to replicate the major flow patterns obtained by the more complex reactive transport simulations. However, the simulated degree of salinization was clearly lower than in reactive multicomponent transport simulations. For example, in the late stages of the simulations, when the brine becomes halite-saturated, the nonreactive simulation overestimated the solute mass by almost 20%. The simulations highlight the importance of the consideration of reactive transport processes for understanding and quantifying geochemical patterns, concentrations of individual dissolved solutes, and evaporite evolution.

Embryo-endometrial interactions during early development after embryonic diapause in the marsupial tammar wallaby.

PubMed

Renfree, Marilyn B; Shaw, Geoff

2014-01-01

The marsupial tammar wallaby has the longest period of embryonic diapause of any mammal. Reproduction in the tammar is seasonal, regulated by photoperiod and also lactation. Reactivation is triggered by falling daylength after the austral summer solstice in December. Young are born late January and commence a 9-10-month lactation. Females mate immediately after birth. The resulting conceptus develops over 6- 7 days to form a unilaminar blastocyst of 80-100 cells and enters lactationally, and later seasonally, controlled diapause. The proximate endocrine signal for reactivation is an increase in progesterone which alters uterine secretions. Since the diapausing blastocyst is surrounded by the zona and 2 other acellular coats, the mucoid layer and shell coat, the uterine signals that maintain or terminate diapause must involve soluble factors in the secretions rather than any direct cellular interaction between uterus and embryo. Our studies suggest involvement of a number of cytokines in the regulation of diapause in tammars. The endometrium secretes platelet activating factor (PAF) and leukaemia inhibitory factor, which increase after reactivation. Receptors for PAF are low on the blastocyst during diapause but are upregulated at reactivation. Conversely, there is endometrial expression of the muscle segment homeobox gene MSX2 throughout diapause, but it is rapidly downregulated at reactivation. These patterns are consistent with those observed in diapausing mice and mink after reactivation, despite the very different patterns of endocrine control of diapause in these 3 divergent species. These common patterns suggest a similar underlying mechanism for diapause, perhaps common to all mammals, but which is activated in only a few.

Dry etched SiO2 Mask for HgCdTe Etching Process

NASA Astrophysics Data System (ADS)

Chen, Y. Y.; Ye, Z. H.; Sun, C. H.; Deng, L. G.; Zhang, S.; Xing, W.; Hu, X. N.; Ding, R. J.; He, L.

2016-09-01

A highly anisotropic etching process with low etch-induced damage is indispensable for advanced HgCdTe (MCT) infrared focal plane array (IRFPA) detectors. The inductively coupled plasma (ICP) enhanced reactive ion etching technique has been widely adopted in manufacturing HgCdTe IRFPA devices. An accurately patterned mask with sharp edges is decisive to accomplish pattern duplication. It has been reported by our group that the SiO2 mask functions well in etching HgCdTe with high selectivity. However, the wet process in defining the SiO2 mask is limited by ambiguous edges and nonuniform patterns. In this report, we patterned SiO2 with a mature ICP etching technique, prior to which a thin ZnS film was deposited by thermal evaporation. The SiO2 film etching can be terminated at the auto-stopping point of the ZnS layer thanks to the high selectivity of SiO2/ZnS in SF6 based etchant. Consequently, MCT etching was directly performed without any other treatment. This mask showed acceptable profile due to the maturity of the SiO2 etching process. The well-defined SiO2 pattern and the etched smooth surfaces were investigated with scanning electron microscopy and atomic force microscope. This new mask process could transfer the patterns exactly with very small etch-bias. A cavity with aspect-ratio (AR) of 1.2 and root mean square roughness of 1.77 nm was achieved first, slightly higher AR of 1.67 was also get with better mask profile. This masking process ensures good uniformity and surely benefits the delineation of shrinking pixels with its high resolution.

New approach for producing chemical templates over large area by Molecular Transfer Printing

NASA Astrophysics Data System (ADS)

Inoue, Takejiro; Janes, Dustin; Ren, Jiaxing; Willson, Grant; Ellison, Christopher; Nealey, Paul

2014-03-01

Fabrication of well-defined chemically patterned surfaces is crucially important to the development of next generation microprocessors, hard disk memory devices, photonic/plasmonic devices, separation membranes, and biological microarrays. One promising patterning method in these fields is Molecular Transfer Printing (MTP), which replicates chemical patterns with feature dimensions of the order of 10nm utilizing a master template defined by the microphase separated domains of a block copolymer thin film. The total transfer printing area achievable by MTP has so far been limited by the contact area between two rigid substrates. Therefore, strategies to make conformal contact between substrates could be practically useful because a single lithographically-defined starting pattern could be used to fabricate many replicates by a low-cost process. Here we show a new approach that utilizes a chemically deposited SiN layer and a liquid conformal layer to enable transfer printing of chemical patterns upon thermal annealing over large, continuous areas. We anticipate that our process could be integrated into Step and Flash Imprint Lithography (SFIL) tools to achieve conformal layer thicknesses thin and uniform enough to permit pattern transfer through a dry-etch protocol.

A spectroscopist's view of energy states, energy transfers, and chemical reactions.

PubMed

Moore, C Bradley

2007-01-01

This chapter describes a research career beginning at Berkeley in 1960, shortly after Sputnik and the invention of the laser. Following thesis work on vibrational spectroscopy and the chemical reactivity of small molecules, we studied vibrational energy transfers in my own lab. Collision-induced transfers among vibrations of a single molecule, from one molecule to another, and from vibration to rotation and translation were elucidated. My research group also studied the competition between vibrational relaxation and chemical reaction for potentially reactive collisions with one molecule vibrationally excited. Lasers were used to enrich isotopes by the excitation of a predissociative transition of a selected isotopomer. We also tested the hypotheses of transition-state theory for unimolecular reactions of ketene, formaldehyde, and formyl fluoride by (a) resolving individual molecular eigenstates above a dissociation threshold, (b) locating vibrational levels at the transition state, (c) observing quantum resonances in the barrier region for motion along a reaction coordinate, and (d) studying energy release to fragments.

Memory Reactivation Predicts Resistance to Retroactive Interference: Evidence from Multivariate Classification and Pattern Similarity Analyses

PubMed Central

Rugg, Michael D.

2016-01-01

Memory reactivation—the reinstatement of processes and representations engaged when an event is initially experienced—is believed to play an important role in strengthening and updating episodic memory. The present study examines how memory reactivation during a potentially interfering event influences memory for a previously experienced event. Participants underwent fMRI during the encoding phase of an AB/AC interference task in which some words were presented twice in association with two different encoding tasks (AB and AC trials) and other words were presented once (DE trials). The later memory test required retrieval of the encoding tasks associated with each of the study words. Retroactive interference was evident for the AB encoding task and was particularly strong when the AC encoding task was remembered rather than forgotten. We used multivariate classification and pattern similarity analysis (PSA) to measure reactivation of the AB encoding task during AC trials. The results demonstrated that reactivation of generic task information measured with multivariate classification predicted subsequent memory for the AB encoding task regardless of whether interference was strong and weak (trials for which the AC encoding task was remembered or forgotten, respectively). In contrast, reactivation of neural patterns idiosyncratic to a given AB trial measured with PSA only predicted memory when the strength of interference was low. These results suggest that reactivation of features of an initial experience shared across numerous events in the same category, but not features idiosyncratic to a particular event, are important in resisting retroactive interference caused by new learning. SIGNIFICANCE STATEMENT Reactivating a previously encoded memory is believed to provide an opportunity to strengthen the memory, but also to return the memory to a labile state, making it susceptible to interference. However, there is debate as to how memory reactivation elicited by a potentially interfering event influences subsequent retrieval of the memory. The findings of the current study indicate that reactivating features idiosyncratic to a particular experience during interference only influences subsequent memory when interference is relatively weak. Critically, reactivation of generic contextual information predicts subsequent source memory when retroactive interference is either strong and weak. The results indicate that reactivation of generic information about a prior episode mitigates forgetting due to retroactive interference. PMID:27076433

Development of template and mask replication using jet and flash imprint lithography

NASA Astrophysics Data System (ADS)

Brooks, Cynthia; Selinidis, Kosta; Doyle, Gary; Brown, Laura; LaBrake, Dwayne; Resnick, Douglas J.; Sreenivasan, S. V.

2010-09-01

The Jet and Flash Imprint Lithography (J-FILTM)1-7 process uses drop dispensing of UV curable resists to assist high resolution patterning for subsequent dry etch pattern transfer. The technology is actively being used to develop solutions for memory markets including Flash memory and patterned media for hard disk drives. It is anticipated that the lifetime of a single template (for patterned media) or mask (for semiconductor) will be on the order of 104 - 105 imprints. This suggests that tens of thousands of templates/masks will be required. It is not feasible to employ electronbeam patterning directly to deliver these volumes. Instead, a "master" template - created by directly patterning with an electron-beam tool - will be replicated many times with an imprint lithography tool to produce the required supply of "working" templates/masks. In this paper, we review the development of the pattern transfer process for both template and mask replicas. Pattern transfer of resolutions down to 25nm has been demonstrated for bit patterned media replication. In addition, final resolution on a semiconductor mask of 28nm has been confirmed. The early results on both etch depth and CD uniformity are promising, but more extensive work is required to characterize the pattern transfer process.

Mapping the Relationship between Glycosyl Acceptor Reactivity and Glycosylation Stereoselectivity.

PubMed

van der Vorm, Stefan; van Hengst, Jacob M A; Bakker, Marloes; Overkleeft, Herman S; van der Marel, Gijsbert A; Codée, Jeroen D C

2018-03-30

The reactivity of both coupling partners-the glycosyl donor and acceptor-is decisive for the outcome of a glycosylation reaction, in terms of both yield and stereoselectivity. Where the reactivity of glycosyl donors is well understood and can be controlled through manipulation of the functional/protecting-group pattern, the reactivity of glycosyl acceptor alcohols is poorly understood. We here present an operationally simple system to gauge glycosyl acceptor reactivity, which employs two conformationally locked donors with stereoselectivity that critically depends on the reactivity of the nucleophile. A wide array of acceptors was screened and their structure-reactivity/stereoselectivity relationships established. By systematically varying the protecting groups, the reactivity of glycosyl acceptors can be adjusted to attain stereoselective cis-glucosylations. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Enhanced electron transfer kinetics through hybrid graphene-carbon nanotube films.

PubMed

Henry, Philémon A; Raut, Akshay S; Ubnoske, Stephen M; Parker, Charles B; Glass, Jeffrey T

2014-11-01

We report the first study of the electrochemical reactivity of a graphenated carbon nanotube (g-CNT) film. The electron transfer kinetics of the ferri-ferrocyanide couple were examined for a g-CNT film and compared to the kinetics to standard carbon nanotubes (CNTs). The g-CNT film exhibited much higher catalytic activity, with a heterogeneous electron-transfer rate constant, k 0 , approximately two orders of magnitude higher than for standard CNTs. Scanning electron microscopy and Raman spectroscopy were used to correlate the higher electron transfer kinetics with the higher edge-density of the g-CNT film.

Identification and Optimization of Short Helical Peptides with Novel Reactive Functionality as Catalysts for Acyl Transfer by Reactive Tagging

DTIC Science & Technology

2014-01-21

269–278. 4 M. H. Fonseca and B. List, Curr. Opin. Chem. Biol., 2004, 8, 319–326. 5 P. Krattiger, C. McCarthy, A. Pfaltz and H. Wennemers, Angew. Chem...Benedetti, Trends Biochem. Sci., 1991, 16, 350–353. 33 C. Toniolo, A. Polese, F. Formaggio, M. Crisma and J. Kamphuis, J. Am. Chem. Soc., 1996 , 118, 2744

Hampering Effect of Cholesterol on the Permeation of Reactive Oxygen Species through Phospholipids Bilayer: Possible Explanation for Plasma Cancer Selectivity

NASA Astrophysics Data System (ADS)

van der Paal, Jonas; Verheyen, Claudia; Neyts, Erik C.; Bogaerts, Annemie

2017-01-01

In recent years, the ability of cold atmospheric pressure plasmas (CAPS) to selectively induce cell death in cancer cells has been widely established. This selectivity has been assigned to the reactive oxygen and nitrogen species (RONS) created in CAPs. To provide new insights in the search for an explanation for the observed selectivity, we calculate the transfer free energy of multiple ROS across membranes containing a varying amount of cholesterol. The cholesterol fraction is investigated as a selectivity parameter because membranes of cancer cells are known to contain lower fractions of cholesterol compared to healthy cells. We find that cholesterol has a significant effect on the permeation of reactive species across a membrane. Indeed, depending on the specific reactive species, an increasing cholesterol fraction can lead to (i) an increase of the transfer free energy barrier height and width, (ii) the formation of a local free energy minimum in the center of the membrane and (iii) the creation of extra free energy barriers due to the bulky sterol rings. In the context of plasma oncology, these observations suggest that the increased ingress of RONS in cancer cells can be explained by the decreased cholesterol fraction of their cell membrane.

Typology of emergent eating patterns in early childhood.

PubMed

Hittner, James B; Faith, Myles S

2011-12-01

The stability of eating patterns from infancy through childhood is largely unknown. This study identified subgroups of children based on emergent eating patterns from ages 1 to 3 years and examined differences between groups in demographic, anthropometric and temperamental variables. We conducted secondary analyses of 262 boys and 225 girls from the Colorado Adoption Project. Three eating styles (Reactivity to Food, Predictable Appetite, Distractibility at Mealtime) and five temperaments were assessed at ages 1 and 3 years. Weight and height (length) were assessed on children and mothers. Correlations examined the stability of eating patterns, cluster analysis identified subgroups of emergent eating styles, and analysis of variance identified variables differentiating the derived subgroups. Eating styles were moderately stable over time, although all increased on average. Four subgroups were identified: Diet Expanding and Preference Establishing Eaters (37%), Emerging Reactive Tendency Eaters (23%), Emerging Food-Indifferent and Non-Fussy Eaters (31%), and Emerging High-Reactive and Fussy Eaters (9%). The subgroups differed in year 1 Wt/L and Reaction to Food, and year 1-to-3 changes in Emotionality and Reaction to Food. Four emergent eating patterns were identified. How these subgroups of children differ in later weight and health trajectories warrants research. Copyright © 2011 Elsevier Ltd. All rights reserved.

Divergent T-Cell Cytokine Patterns in Inflammatory Arthritis

NASA Astrophysics Data System (ADS)

Simon, A. K.; Seipelt, E.; Sieper, J.

1994-08-01

A major immunoregulatory mechanism in inflammatory infections and allergic diseases is the control of the balance of cytokines secreted by Th1/Th2 subsets of T helper (Th) cells. This might also be true in autoimmune diseases; a Th2 pattern that prevents an effective immune response in infections with intracellular bacteria may favor immunosuppression in autoimmune diseases. The pattern of cytokine expression was compared in the synovial tissue from patients with a typical autoimmune disease, rheumatoid arthritis, and with a disorder with similar synovial pathology but driven by persisting exogenous antigen, reactive arthritis. We screened 12 rheumatoid and 9 reactive arthritis synovial tissues by PCR and in situ hybridization for their expression of T-cell cytokines. The cytokine pattern differs significantly between the two diseases; rheumatoid arthritis samples express a Th1-like pattern whereas in reactive arthritis interferon γ expression is accompanied by that of interleukin 4. Studying the expression of cytokines by in situ hybridization confirmed the results found by PCR; they also show an extremely low frequency of cytokine-transcribing cells. In a double-staining experiment, it was demonstrated that interleukin 4 is made by CD4 cells. These experiments favor the possibility of therapeutic intervention in inflammatory rheumatic diseases by means of inhibitory cytokines.

Thermodynamic Hydricity of Transition Metal Hydrides

DOE PAGES

Wiedner, Eric S.; Chambers, Matthew B.; Pitman, Catherine L.; ...

2016-08-02

Transition metal hydrides play a critical role in stoichiometric and catalytic transformations. Knowledge of free energies for cleaving metal hydride bonds enables the prediction of chemical reactivity, such as for the bond-forming and bondbreaking events that occur in a catalytic reaction. Thermodynamic hydricity is the free energy required to cleave an M-H bond to generate a hydride ion (H -). Three primary methods have been developed for hydricity determination: the hydride transfer method establishes hydride transfer equilibrium with a hydride donor/acceptor pair of known hydricity, the H 2 heterolysis method involves measuring the equilibrium of heterolytic cleavage of H 2more » in the presence of a base, and the potential-pK a method considers stepwise transfer of a proton and two electrons to give a net hydride transfer. Using these methods, over 100 thermodynamic hydricity values for transition metal hydrides have been determined in acetonitrile or water. In acetonitrile, the hydricity of metal hydrides spans a range of more than 50 kcal/mol. Finally, methods for using hydricity values to predict chemical reactivity are also discussed, including organic transformations, the reduction of CO 2, and the production and oxidation of hydrogen.« less

A new insight into the oxidative mechanism of caffeine and related methylxanthines in aprotic medium: May caffeine be really considered as an antioxidant?

PubMed

Petrucci, Rita; Zollo, Giuseppe; Curulli, Antonella; Marrosu, Giancarlo

2018-05-12

Antioxidant properties have been recently suggested for caffeine that seems showing protective effects against damages caused by oxidative stress. In particular, a HO scavenging activity has been ascribed to caffeine. Even if the oxidation of caffeine has been widely studied, the antioxidant mechanism is still far to be understood. The electrochemical behavior of caffeine, theobromine and theophylline was studied in aprotic medium by cyclic voltammetry and electrolysis in UV-vis cell; a computational analysis of the molecular structures based on the Density Functional Theory was performed; the reactivity of all substrates towards lead dioxide, superoxide and galvinoxyl radical was followed by UV-vis spectrophotometry. Results supported the mono-electronic oxidation of the C 4 C 5 bond for all substrates at high oxidation potentials, the electron-transfer process leading to a radical cation or a neutral radical according to the starting methylxanthine N 7 -substituted (caffeine and theobromine) or N 7 -unsubstituted (theophylline), respectively. A different following chemical fate might be predicted for the radical cation or the neutral radical. No interaction was evidenced towards the tested reactive oxygen species. No reactivity via H-atom transfer was evidenced for all studied compounds, suggesting that an antiradical activity should be excluded. Some reactivity only with strong oxidants could be predicted via electron-transfer. The acclaimed HO scavenging activity should be interpreted in these terms. The study suggested that CAF might be hardly considered an antioxidant. Beyond the experimental methods used, the discussion of the present results might provide food for thought to the wide audience working on antioxidants. Copyright © 2018. Published by Elsevier B.V.

Electrostatic redesign of the [myoglobin, cytochrome b5] interface to create a well-defined docked complex with rapid interprotein electron transfer.

PubMed

Xiong, Peng; Nocek, Judith M; Griffin, Amanda K K; Wang, Jingyun; Hoffman, Brian M

2009-05-27

Cyt b(5) is the electron-carrier "repair" protein that reduces met-Mb and met-Hb to their O(2)-carrying ferroheme forms. Studies of electron transfer (ET) between Mb and cyt b(5) revealed that they react on a "Dynamic Docking" (DD) energy landscape on which binding and reactivity are uncoupled: binding is weak and involves an ensemble of nearly isoenergetic configurations, only a few of which are reactive; those few contribute negligibly to binding. We set the task of redesigning the surface of Mb so that its reaction with cyt b(5) instead would occur on a conventional "simple docking" (SD) energy landscape, on which a complex exhibits a well-defined (set of) reactive binding configuration(s), with binding and reactivity thus no longer being decoupled. We prepared a myoglobin (Mb) triple mutant (D44K/D60K/E85K; Mb(+6)) substituted with Zn-deuteroporphyrin and monitored cytochrome b(5) (cyt b(5)) binding and electron transfer (ET) quenching of the (3)ZnMb(+6) triplet state. In contrast, to Mb(WT), the three charge reversals around the "front-face" heme edge of Mb(+6) have directed cyt b(5) to a surface area of Mb adjacent to its heme, created a well-defined, most-stable structure that supports good ET pathways, and apparently coupled binding and ET: both K(a) and k(et) are increased by the same factor of approximately 2 x 10(2), creating a complex that exhibits a large ET rate constant, k(et) = 10(6 1) s(-1), and is in slow exchange (k(off) < k(et)). In short, these mutations indeed appear to have created the sought-for conversion from DD to simple docking (SD) energy landscapes.

Wavelet assessment of cerebrospinal compensatory reserve and cerebrovascular reactivity.

PubMed

Latka, M; Kolodziej, W; Turalska, M; Latka, D; Zub, W; West, B J

2007-05-01

We introduce a wavelet transfer model to relate spontaneous arterial blood pressure (ABP) fluctuations to intracranial pressure (ICP) fluctuations. We employ a complex continuous wavelet transform to develop a consistent mathematical framework capable of parametrizing both cerebral compensatory reserve and cerebrovascular reactivity. The frequency-dependent gain and phase of the wavelet transfer function are introduced because of the non-stationary character of the ICP and ABP time series. The gain characterizes the dampening of spontaneous ABP fluctuations and is interpreted as a novel measure of cerebrospinal compensatory reserve. For a group of 12 patients who died as a result of cerebral lesions (Glasgow Outcome Scale (GOS) = 1) the average gain in the low-frequency (0.02- 0.07 Hz) range was 0.51 +/- 0.13 and significantly exceeded that of 17 patients with GOS = 2 having an average gain of 0.26 +/- 0.11 with p = 1x10(-4) (Kruskal-Wallis test). A time-averaged synchronization index (which may vary from 0 to 1) defined in terms of the wavelet transfer function phase yields information about the stability of the phase difference of the ABP and ICP signals and is used as a cerebrovascular reactivity index. A low value of synchronization index reflects a normally reactive vascular bed, while a high value indicates pathological entrainment of ABP and ICP fluctuations. Such entrainment is strongly pronounced in patients with fatal outcome (for this group the low-frequency synchronization index was 0.69 +/- 0.17). The gain and synchronization parameters define a cerebral hemodynamic state space (CHS) in which the patients with GOS = 1 are to large extent partitioned away from those with GOS = 2. The concept of CHS elucidates the interplay of vascular and compensatory mechanisms.

Adoptive cell therapy using PD-1+ myeloma-reactive T cells eliminates established myeloma in mice.

PubMed

Jing, Weiqing; Gershan, Jill A; Blitzer, Grace C; Palen, Katie; Weber, James; McOlash, Laura; Riese, Matthew; Johnson, Bryon D

2017-01-01

Adoptive cellular therapy (ACT) with cancer antigen-reactive T cells following lymphodepletive pre-conditioning has emerged as a potentially curative therapy for patients with advanced cancers. However, identification and enrichment of appropriate T cell subsets for cancer eradication remains a major challenge for hematologic cancers. PD-1 + and PD-1 - T cell subsets from myeloma-bearing mice were sorted and analyzed for myeloma reactivity in vitro. In addition, the T cells were activated and expanded in culture and given to syngeneic myeloma-bearing mice as ACT. Myeloma-reactive T cells were enriched in the PD-1 + cell subset. Similar results were also observed in a mouse AML model. PD-1 + T cells from myeloma-bearing mice were found to be functional, they could be activated and expanded ex vivo, and they maintained their anti-myeloma reactivity after expansion. Adoptive transfer of ex vivo-expanded PD-1 + T cells together with a PD-L1 blocking antibody eliminated established myeloma in Rag-deficient mice. Both CD8 and CD4 T cell subsets were important for eradicating myeloma. Adoptively transferred PD-1 + T cells persisted in recipient mice and were able to mount an adaptive memory immune response. These results demonstrate that PD-1 is a biomarker for functional myeloma-specific T cells, and that activated and expanded PD-1 + T cells can be effective as ACT for myeloma. Furthermore, this strategy could be useful for treating other hematologic cancers.

A mobile-mobile transport model for simulating reactive transport in connected heterogeneous fields

NASA Astrophysics Data System (ADS)

Lu, Chunhui; Wang, Zhiyuan; Zhao, Yue; Rathore, Saubhagya Singh; Huo, Jinge; Tang, Yuening; Liu, Ming; Gong, Rulan; Cirpka, Olaf A.; Luo, Jian

2018-05-01

Mobile-immobile transport models can be effective in reproducing heavily tailed breakthrough curves of concentration. However, such models may not adequately describe transport along multiple flow paths with intermediate velocity contrasts in connected fields. We propose using the mobile-mobile model for simulating subsurface flow and associated mixing-controlled reactive transport in connected fields. This model includes two local concentrations, one in the fast- and the other in the slow-flow domain, which predict both the concentration mean and variance. The normalized total concentration variance within the flux is found to be a non-monotonic function of the discharge ratio with a maximum concentration variance at intermediate values of the discharge ratio. We test the mobile-mobile model for mixing-controlled reactive transport with an instantaneous, irreversible bimolecular reaction in structured and connected random heterogeneous domains, and compare the performance of the mobile-mobile to the mobile-immobile model. The results indicate that the mobile-mobile model generally predicts the concentration breakthrough curves (BTCs) of the reactive compound better. Particularly, for cases of an elliptical inclusion with intermediate hydraulic-conductivity contrasts, where the travel-time distribution shows bimodal behavior, the prediction of both the BTCs and maximum product concentration is significantly improved. Our results exemplify that the conceptual model of two mobile domains with diffusive mass transfer in between is in general good for predicting mixing-controlled reactive transport, and particularly so in cases where the transfer in the low-conductivity zones is by slow advection rather than diffusion.

Patterns of Adolescent Regulatory Responses during Family Conflict and Mental Health Trajectories

PubMed Central

Koss, Kalsea J.; Cummings, E. Mark; Davies, Patrick T.; Cicchetti, Dante

2016-01-01

Four distinct patterns of adolescents’ behavioral, emotional, and physiological responses to family conflict were identified during mother-father-adolescent (M=13.08 years) interactions. Most youth displayed adaptively-regulated patterns comprised of low overt and subjective distress. Under-controlled adolescents exhibited elevated observable and subjective anger. Over-controlled adolescents were withdrawn and reported heightened subjective distress. Physiologically reactive adolescents had elevated cortisol coupled with low overt and subjective distress. Regulation patterns were associated with unique mental health trajectories. Under-controlled adolescents had elevated conduct and peer problems whereas over-controlled adolescents had higher anxiety and depressive symptoms. Physiologically reactive adolescents had low concurrent, but increasing levels of depressive, anxiety, and peer problem symptoms. Findings underscore the importance of examining organizations of regulatory strategies in contributing to adolescent mental health. PMID:28498540

Interparental Aggression and Infant Patterns of Adrenocortical and Behavioral Stress Responses

PubMed Central

Towe-Goodman, Nissa R.; Stifter, Cynthia A.; Mills-Koonce, W. Roger; Granger, Douglas A.

2011-01-01

Drawing on emotional security theory, this study examined linkages between interparental aggression, infant self-regulatory behaviors, and patterns of physiological and behavioral stress responses in a diverse sample of 735 infants residing in predominately low-income, nonmetropolitan communities. Latent profile analysis revealed four classes of adrenocortical and behavioral stress response patterns at 7-months of age, using assessments of behavioral and cortisol reactivity to an emotion eliciting challenge, as well as global ratings of the child’s negative affect and basal cortisol levels. The addition of covariates within the latent profile model suggested that children with more violence in the home and who used less caregiver-oriented regulation strategies were more likely to exhibit a pattern of high cortisol reactivity with moderate signs of distress rather than the average stress response, suggesting possible patterns of adaptation in violent households. PMID:22127795

Mitochondrial reactive oxygen species accelerate gastric cancer cell invasion

PubMed Central

Tamura, Masato; Matsui, Hirofumi; Tomita, Tsutomu; Sadakata, Hisato; Indo, Hiroko P.; Majima, Hideyuki J.; Kaneko, Tsuyoshi; Hyodo, Ichinosuke

2014-01-01

Tumor invasion is the most important factor to decide patient’s prognosis. The relation between reactive oxygen species and tumor invasion is mainly reported that nicotinamide adenine dinucleotide phosphate oxidase in the cell membrane is a reactive oxygen species producer for formulating an invadopodia. On the other hand, mitochondrion was known as one of the most important reactive oxygen species-producer in the cell via an energy transfer system. However, the relation between mitochondrial reactive oxygen species and the tumor invasion was not well clarified. In this study, we evaluated the relation between mitochondrial reactive oxygen species and tumor invasion using a normal gastric mucosal cell-line (RGM-1) and a cancerous mutant RGM-1 cell-line (RGK-1). Manganese superoxide dismutase-expressing RGK-1 cell-lines were used for a scavenging mitochondrial reactive oxygen species. The cells have been evaluated their movement ability as follows; cellular ruffling frequencies, wound healing assay to evaluate horizontal cellular migration, and invasion assay using matrigel to analyze vertical cellular migration. All cellular movement abilities were inhibited by scavenging mitochondrial reactive oxygen species with manganese superoxide dismutase. Therefore mitochondrial reactive oxygen species was one of factors enhancing the tumor invasion in gastric cancer. PMID:24426185

Tectonic inheritance, reactivation and long term fault weakening processes

NASA Astrophysics Data System (ADS)

Holdsworth, Bob

2017-04-01

This talk gives a geological review of weakening processes in faults and their long-term effect on reactivation and tectonic inheritance during crustal deformation. Examples will be drawn from the Atlantic margins, N America, Japan and the Alps. Tectonic inheritance and reactivation are fundamentally controlled by the processes of stress concentration and shear localisation manifested at all scales in the continental lithosphere. Lithosphere-scale controls include crustal thickness, thermal age and the boundary conditions imposed by the causative plate tectonic processes during extension. At the other end of the scale range, grain-scale controls include local environmental controls (depth, stress, strain rate), rock composition, grainsize, fabric intensity and the presence of fluids or melt. Intermediate-scale geometric controls are largely related to the size, orientation and interconnectivity of pre-existing anisotropies. If reactivation of pre-existing structures occurs, it likely requires a combination of processes across all three scale ranges to be favourable. This can make the unequivocal recognition of inheritance and reactivation difficult. Large (e.g. crustal-scale) pre-existing structures are especially important due to their ability to efficiently concentrate stress and localise strain. For big faults (San Andreas, Great Glen, Median Tectonic Line), detailed studies of the associated exposed fault rocks indicate that reactivation is linked to the development of strongly anisotropic phyllosilicate-rich fault rocks that are weak (e.g. friction coefficients as low as 0.2 or less) under a broad range of deformation conditions. In the case of pre-existing regional dyke swarms (S Atlantic, NW Scotland) - which may themselves track deep mantle fabrics at depth - multiple reactivation of dyke margins is widespread and may preclude reactivation of favourably oriented local basement fabrics. In a majority of cases, pre-existing structures in the crust are significantly oblique (<70°) to far field stress orientations. As a result, even quite modest amounts of reactivation will inevitably lead to transtensional/transpressional strains involving variable components of strike-slip and extension or shortening. The occurrence of bulk non-coaxial, non-plane strain leads to strain partitioning and/or (non-Andersonian) multimodal fracturing where the deformation cannot be described or reconstructed in single 2D cross-sectional or map view. Further complications can arise due to repeated seismogenic rupturing of larger offset faults leading to local stress transfer and reactivation of widely distributed smaller pre-existing structures in the wall rocks (e.g. Adamello Massif, Alps). The Atlantic margins demonstrate that pre-existing structures can influence deformation patterns across a range of scales, but such reactivation should never be assumed to be the norm. In many cases, the scales of faulting and displacement magnitudes associated with these reactivation events are modest compared to the regional-scale deformation of the margin. However, reactivation most certainly does influence the kilometre and smaller-scale complexity of faults, fractures and folds. It will therefore impact significantly on the development of geological architectures and their economic importance, e.g. location and nature of fluid channelways, trap geometries, reservoir performance, etc.

Nanoparticle augmented radiation treatment decreases cancer cell proliferation.

PubMed

Townley, Helen E; Rapa, Elizabeth; Wakefield, Gareth; Dobson, Peter J

2012-05-01

We report significant and controlled cell death using novel x-ray-activatable titania nanoparticles (NPs) doped with lanthanides. Preferential incorporation of such materials into tumor tissue can enhance the effect of radiation therapy. Herein, the incorporation of gadolinium into the NPs is designed to optimize localized energy absorption from a conventional medical x-ray. This result is further optimized by the addition of other rare earth elements. Upon irradiation, energy is transferred to the titania crystal structure, resulting in the generation of reactive oxygen species (ROS). The authors report significant and controlled cell death using x-ray-activated titania nanoparticles doped with lanthanides as enhancers. Upon irradiation X-ray energy is transferred to the titania crystal structure, resulting in the generation of reactive oxygen species. Copyright © 2012 Elsevier Inc. All rights reserved.

Ocular sensitization of mice by live (but not irradiated) Chlamydia trachomatis serovar A

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

Colley, D.G.; Goodman, T.G.; Barsoum, I.S.

1986-10-01

Ocular exposure of mice to live elementary bodies of Chlamydia trachomatis serovar A results in immunological sensitization of the mice. This reactivity is manifested by the development of early (5 h) and delayed-type (24 h) dermal reactivity and serovar-specific antibody formation against either live or irradiated (100 kilorads) elementary bodies. Parallel ocular exposure of mice to irradiated elementary bodies does not result in this sensitization. The early and late dermal immune responses induced by ocular exposure to live organisms can be transferred to unexposed mice by serum and lymphoid cell transfers, respectively. It appears that successful murine ocular sensitization bymore » human C. trachomatis serovar A elementary bodies is an ability manifested by live organisms and not by inactivated but antigenic organisms.« less

Chirality Transfer in Gold(I)-Catalysed Direct Allylic Etherifications of Unactivated Alcohols: Experimental and Computational Study

PubMed Central

Barker, Graeme; Johnson, David G; Young, Paul C; Macgregor, Stuart A; Lee, Ai-Lan

2015-01-01

Gold(I)-catalysed direct allylic etherifications have been successfully carried out with chirality transfer to yield enantioenriched, γ-substituted secondary allylic ethers. Our investigations include a full substrate-scope screen to ascertain substituent effects on the regioselectivity, stereoselectivity and efficiency of chirality transfer, as well as control experiments to elucidate the mechanistic subtleties of the chirality-transfer process. Crucially, addition of molecular sieves was found to be necessary to ensure efficient and general chirality transfer. Computational studies suggest that the efficiency of chirality transfer is linked to the aggregation of the alcohol nucleophile around the reactive π-bound Au–allylic ether complex. With a single alcohol nucleophile, a high degree of chirality transfer is predicted. However, if three alcohols are present, alternative proton transfer chain mechanisms that erode the efficiency of chirality transfer become competitive. PMID:26248980

Reactivation of Reward-Related Patterns from Single Past Episodes Supports Memory-Based Decision Making.

PubMed

Wimmer, G Elliott; Büchel, Christian

2016-03-09

Rewarding experiences exert a strong influence on later decision making. While decades of neuroscience research have shown how reinforcement gradually shapes preferences, decisions are often influenced by single past experiences. Surprisingly, relatively little is known about the influence of single learning episodes. Although recent work has proposed a role for episodes in decision making, it is largely unknown whether and how episodic experiences contribute to value-based decision making and how the values of single episodes are represented in the brain. In multiple behavioral experiments and an fMRI experiment, we tested whether and how rewarding episodes could support later decision making. Participants experienced episodes of high reward or low reward in conjunction with incidental, trial-unique neutral pictures. In a surprise test phase, we found that participants could indeed remember the associated level of reward, as evidenced by accurate source memory for value and preferences to re-engage with rewarded objects. Further, in a separate experiment, we found that high-reward objects shown as primes before a gambling task increased financial risk taking. Neurally, re-exposure to objects in the test phase led to significant reactivation of reward-related patterns. Importantly, individual variability in the strength of reactivation predicted value memory performance. Our results provide a novel demonstration that affect-related neural patterns are reactivated during later experience. Reactivation of value information represents a mechanism by which memory can guide decision making. Copyright © 2016 the authors 0270-6474/16/362868-13$15.00/0.

Pru p 3, a marker allergen for lipid transfer protein sensitization also in Central Europe.

PubMed

Mothes-Luksch, N; Raith, M; Stingl, G; Focke-Tejkl, M; Razzazi-Fazeli, E; Zieglmayer, R; Wöhrl, S; Swoboda, I

2017-09-01

In the Mediterranean area, lipid transfer proteins (LTPs) are important causes of plant-food allergies often associated with severe allergic reactions. There, peach LTP (Pru p 3) seems to be the primary sensitizer, whereas in Central Europe, little is known about the importance of LTP sensitization. In this region, allergen extract-based diagnosis is often complicated by co-sensitization to Bet v 1, the major birch pollen allergen, its cross-reactive food allergens, and profilins. We investigated the role of LTP sensitization in Central European patients displaying strong allergic reactions to plant-derived food. Analysis of IgE reactivity revealed that ten of thirteen patients were sensitized to Pru p 3, nine to Bet v 1, and two to profilin. Our results showed that LTP sensitization represents a risk factor for severe allergic symptoms in Central Europe. Furthermore, the strong IgE reactivity detected in immunoblots of plant-food extracts indicated that Pru p 3 can be used as a marker allergen for LTP sensitization also in Central European patients. © 2017 The Authors Allergy Published by John Wiley & Sons Ltd.

Work-related allergy and asthma in spice mill workers - The impact of processing dried spices on IgE reactivity patterns.

PubMed

van der Walt, Anita; Lopata, Andreas L; Nieuwenhuizen, Natalie E; Jeebhay, Mohamed F

2010-01-01

Three spice mill workers developed work-related allergy and asthma after prolonged exposure to high levels (>10 mg/m(3)) of inhalable spice dust. Patterns of sensitization to a variety of spices and putative allergens were identified. Work-related allergy and asthma were assessed on history, clinical evaluation, pulmonary function and fractional exhaled nitric oxide. Specific IgE reactivity to a range of common inhalant, food and spice allergens was evaluated using ImmunoCAP and allergen microarray. The presence of non-IgE-mediated reactions was determined by basophil stimulation (CAST-ELISA). Specific allergens were identified by immunoblotting to extracts of raw and dried processed garlic, onion and chili pepper. Asthma was confirmed in all 3 subjects, with work-related patterns prominent in worker 1 and 3. Sensitization to multiple spices and pollen was observed in both atopic workers 1 and 2, whereas garlic and chili pepper sensitization featured in all 3 workers. Microarray analysis demonstrated prominent profilin reactivity in atopic worker 2. Immunoblotting demonstrated a 50-kDa cross-reactive allergen in garlic and onion, and allergens of approximately 40 and 52 kDa in chili pepper. Dry powdered garlic and onion demonstrated greater IgE binding. This study demonstrated IgE reactivity to multiple spice allergens in workers exposed to high levels of inhalable spice dust. Processed garlic and onion powder demonstrated stronger IgE reactivity than the raw plant. Atopy and polysensitization to various plant profilins, suggesting pollen-food syndrome, represent additional risk factors for sensitizer-induced work-related asthma in spice mill workers. 2010 S. Karger AG, Basel.

Resist surface crosslinking using amine-based reactive rinses to mitagate pattern collapse in thin film lithography

NASA Astrophysics Data System (ADS)

Yeh, Wei-Ming; Lawson, Richard A.; Tolbert, Laren M.; Henderson, Clifford L.

2012-03-01

As the semiconductor industry continues to push to smaller critical dimensions, pattern collapse during lithographic processing caused by unbalanced capillary forces during the final rinse and drying process has become an important problem that can limit the practical resolution of a resist material to feature sizes larger than its intrinsic resolution limit. One of the primary modes of pattern collapse is via elastoplastic pattern deformation which is strongly related to the mechanical properties of the resist. One approach to mitigating such collapse problems is to enhance the mechanical properties of the resist features. Since such modification of resist physical properties for pattern collapse purposes is difficult to achieve through modified formulation of the resist itself (i.e. due to the complex set of requirements that a resist must satisfy and the complex set of physical and chemical phenomena that underlie the imaging processing itself), we have pursued an alternative strategy for improving the resist mechanical properties after features are developed in the film but before they are rinsed and dried. The family of techniques being developed in this work function through the use of aqueous compatible reactive rinse solutions that can be applied to developed resist features while they are wet during normal rinse processing on a track system. By applying these techniques during the rinse process, the resist features can be strengthened before they are subjected to significant capillary forces during the final drying step. In this work, the use of diamine compounds to reactively crosslink the surface of resists containing carboxylic acid groups through formation of amide bonds using carbodiimide chemistry has been explored. One advantage of this approach is that it is an aqueous process that should be easily compatible with high volume, track-based lithographic processes. Contact angle studies and x-ray photoelectron spectroscopy (XPS) were used to characterize the surface crosslinking reaction using such diamine surface rinse treatments. Pattern collapse test structures were fabricated and analyzed to measure the amount of mechanical property improvement imparted by such treatments. Application of such amine reactive rinses was found to clearly result in an improvement in the resistance of resists to pattern collapse as observed by SEM. A comparison of the critical stress at the point of pattern collapse as a function of resist feature size also clearly shows a significant improvement in mechanical resilience of resist samples processed with the reactive rinse treatment.

Preliminary evidence of attenuated blood pressure reactivity to acute stress in adults following a recent marital separation.

PubMed

Grinberg, Austin M; O'Hara, Karey L; Sbarra, David A

2018-03-01

This study explores cardiovascular reactivity during an acute-stress task in a sample of recently separated adults. In a cross-sectional design, we examined the association between adults' subjective separation-related distress and changes in heart rate and blood pressure across the acute-stress laboratory paradigm in a sample of 133 (n = 49 men) recently separated adults. Heart rate (HR) and Blood pressure (BP) were recorded across a resting baseline period, a math stressor task, and a recovery period. Multilevel analyses revealed that adults who reported greater separation-related distress exhibited higher initial BP and a slower linear increase in BP across the study period. In addition, adults reporting greater separation-related distress evidenced significantly slower declines in diastolic blood pressure (DBP) following the acute-stress task. HR reactivity was not moderated by separation-related distress. In recently separated adults, preliminary evidence suggests that the context of the stressors may reveal differential patterns of problematic reactivity (exaggerated or blunted responding). Greater emotional intrusion and hyperactivity symptoms may index increased risk for blunted cardiovascular reactivity to general stressors. This pattern of reactivity is consistent with models of allostatic load that emphasise the deleterious effect of hyporesponsivity to environmental demands.

Preparation for a Clinical Trial Using Adoptive Transfer of Tumor-Reactive TGF_Beta-Insensitive CD8+ T Cells for Treatment of Prostate Cancer

DTIC Science & Technology

2006-07-01

TumorCells Qiang Zhang,1 Thomas L. Jang,1 Ximing Yang,2 Irwin Park,1 Robert E. Meyer,2 Shilajit Kundu,1 Michael Pins,2 Borko Javonovic,3 Timothy Kuzel,4...reactive CD8+ T cells activates the antitumor immune response cycle Qiang Zhang,1 Ximing Yang,2,5 Shilajit D. Kundu,1 Michael Pins,2,5 Borko Javonovic

Beyond Born-Oppenheimer theory for ab initio constructed diabatic potential energy surfaces of singlet H3+ to study reaction dynamics using coupled 3D time-dependent wave-packet approach.

PubMed

Ghosh, Sandip; Mukherjee, Saikat; Mukherjee, Bijit; Mandal, Souvik; Sharma, Rahul; Chaudhury, Pinaki; Adhikari, Satrajit

2017-08-21

The workability of beyond Born-Oppenheimer theory to construct diabatic potential energy surfaces (PESs) of a charge transfer atom-diatom collision process has been explored by performing scattering calculations to extract accurate integral cross sections (ICSs) and rate constants for comparison with most recent experimental quantities. We calculate non-adiabatic coupling terms among the lowest three singlet states of H 3 + system (1 1 A ' , 2 1 A ' , and 3 1 A ' ) using MRCI level of calculation and solve the adiabatic-diabatic transformation equation to formulate the diabatic Hamiltonian matrix of the same process [S. Mukherjee et al., J. Chem. Phys. 141, 204306 (2014)] for the entire region of nuclear configuration space. The nonadiabatic effects in the D + + H 2 reaction has been studied by implementing the coupled 3D time-dependent wave packet formalism in hyperspherical coordinates [S. Adhikari and A. J. C. Varandas, Comput. Phys. Commun. 184, 270 (2013)] with zero and non-zero total angular momentum (J) on such newly constructed accurate (ab initio) diabatic PESs of H 3 + . We have depicted the convergence profiles of reaction probabilities for the reactive non-charge transfer, non-reactive charge transfer, and reactive charge transfer processes for different collisional energies with respect to the helicity (K) and total angular momentum (J) quantum numbers. Finally, total and state-to-state ICSs are calculated as a function of collision energy for the initial rovibrational state (v = 0, j = 0) of the H 2 molecule, and consequently, those quantities are compared with previous theoretical and experimental results.

Optimized plasma etch window of block copolymers and neutral brush layers for enhanced direct self-assembly pattern transfer into a hardmask layer

NASA Astrophysics Data System (ADS)

Brakensiek, Nickolas; Xu, Kui; Sweat, Daniel; Hockey, Mary Ann

2018-03-01

Directed self-assembly (DSA) of block copolymers (BCPs) is one of the most promising patterning technologies for future lithography nodes. However, one of the biggest challenges to DSA is the pattern transfer by plasma etching from BCP to hardmask (HM) because the etch selectivity between BCP and neutral brush layer underneath is usually not high enough to enable robust pattern transfer. This paper will explore the plasma etch conditions of both BCPs and neutral brush layers that may improve selectivity and allow a more robust pattern transfer of DSA patterns into the hardmask layer. The plasma etching parameters that are under investigation include the selection of oxidative or reductive etch chemistries, as well as plasma gas pressure, power, and gas mixture fractions. Investigation into the relationship between BCP/neutral brush layer materials with varying chemical compositions and the plasma etching conditions will be highlighted. The culmination of this work will demonstrate important etch parameters that allow BCPs and neutral brush layers to be etched into the underlying hardmask layer with a large process window.

Diastereoselective Synthesis of Seven-Membered Ring trans-Alkenes from Dienes and Aldehydes by Silylene Transfer

PubMed Central

Greene, Margaret A.; Prévost, Michel; Tolopilo, Joshua; Woerpel, K. A.

2012-01-01

Silver-catalyzed silylene transfer to alkenes formed vinylsilacyclopropanes regioselectively. These allylic silanes underwent additions to aldehydes to form seven-membered ring trans-alkenes with high diastereoselectivity. The high reactivity of the trans alkenes is evidenced by their formal [1,3]-sigmatropic rearrangement reactions and their rapid additions of oxygen–hydrogen bonds across the carbon–carbon double bonds. PMID:22780578

Reaction Dynamics at Liquid Interfaces

NASA Astrophysics Data System (ADS)

Benjamin, Ilan

2015-04-01

The liquid interface is a narrow, highly anisotropic region, characterized by rapidly varying density, polarity, and molecular structure. I review several aspects of interfacial solvation and show how these affect reactivity at liquid/liquid interfaces. I specifically consider ion transfer, electron transfer, and SN2 reactions, showing that solvent effects on these reactions can be understood by examining the unique structure and dynamics of the liquid interface region.

Reactivity and Air Composition at Taehwa Research Forest During KORUS-AQ 2016

NASA Astrophysics Data System (ADS)

Sanchez, D.; Seco, R.; Gu, D.; Jeong, D.; Blake, D. R.; Herndon, S. C.; Lee, Y.; Mak, J. E.; McGee, T. J.; Guenther, A. B.; Kim, S.

2017-12-01

The existence of unmeasured volatile organic compounds (VOCs) has been strongly suggested by past studies. Combining OH reactivity (inverse OH lifetime) observations, or total reactivity of ambient air, with VOC and other trace gas observations allows us to examine reactive gas budgets. Previous studies at various field sites have shown that significant amounts of OH reactivity cannot be accounted for, especially in areas influenced by biogenic VOCs and their oxidation products. Thus, we will present the improvements in completing the OH reactivity budget at the Taehwa research forest using the OH reactivity, VOC, and other trace gas observations conducted from May to June during the KORUS-AQ 2016 campaign in South Korea. OH reactivity was measured using the comparative reactivity method with chemical ionization mass spectrometry (CRM-CIMS). The VOCs were measured using a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). A preliminary assessment of the OH reactivity budget at the Taehwa research using only conventionally measured trace gases and VOCs demonstrated that 54% of OH reactivity remained unaccounted. However, the improved mass resolution and sensitivity towards higher mass compounds (m/z > 100) of the PTR-ToF-MS allowed us to observe typically unmeasured VOCs. Identification of these VOCs may help account for the remaining missing OH reactivity observed at the Taehwa research forest.

Graphene-based electrodes for enhanced organic thin film transistors based on pentacene.

PubMed

Basu, Sarbani; Lee, Mu Chen; Wang, Yeong-Her

2014-08-21

This paper presents 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) and pentacene-based organic thin film transistors (OTFTs) with monolayer graphene source-drain (S-D) electrodes. The electrodes are patterned using conventional photolithographic techniques combined with reactive ion etching. The monolayer graphene film grown by chemical vapor deposition on Cu foil was transferred on a Si dioxide surface using a polymer-supported transfer method to fabricate bottom-gate, bottom-contact OTFTs. The pentacene OTFTs with graphene S-D contacts exhibited superior performance with a mobility of 0.1 cm(2) V(-1) s(-1) and an on-off ratio of 10(5) compared with OTFTs with Au-based S-D contacts, which had a mobility of 0.01 cm(2) V(-1) s(-1) and an on-off ratio of 10(3). The crystallinity, grain size, and microscopic defects (or the number of layers of graphene films) of the TIPS-pentacene/pentacene films were analyzed by X-ray diffraction spectroscopy, atomic force microscopy, and Raman spectroscopy, respectively. The feasibility of using graphene as an S-D electrode in OTFTs provides an alternative material with high carrier injection efficiency, chemical stability, and excellent interface properties with organic semiconductors, thus exhibiting improved device performance of C-based electronic OTFTs at a reduced cost.

Reduced graphene oxide-mediated Z-scheme BiVO4/CdS nanocomposites for boosted photocatalytic decomposition of harmful organic pollutants.

PubMed

Clament Sagaya Selvam, N; Kim, Yeong Gyeong; Kim, Dong Jin; Hong, Won-Hwa; Kim, Woong; Park, Sung Hyuk; Jo, Wan-Kuen

2018-09-01

The efficient photocatalytic degradation of harmful organic pollutants (isoniazid (ISN) and 1,4-dioxane (DX)) via the Z-scheme electron transfer mechanism was accomplished using a photostable composite photocatalyst consisting of BiVO 4 , CdS, and reduced graphene oxide (RGO). Compared to their pristine counterparts, the RGO-mediated Z-scheme CdS/BiVO 4 (CdS/RGO-BiVO 4 ) nanocomposites exhibited superior degradation activities, mainly attributed to the prolonged charge separation. RGO was found to be involved in visible-light harvesting and acted as a solid-state electron mediator at the CdS/BiVO 4 interface to realize an effective Z-scheme electron transfer pathway, avoid photocatalyst self-oxidation, and lengthen the life span of charge carriers. The results of reactive species scavenging experiments, photoluminescence measurements, and transient photocurrent measurements, as well as the calculated band potentials of the synthesized photocatalysts, supported the Z-scheme electron/hole pair separation mechanism. Additionally, the intermediates formed during the degradation of ISN and DX were identified, and a possible fragmentation pattern was proposed. This systematic work aims to develop photostable Z-scheme composites as unique photocatalytic systems for the efficient removal of harmful organic pollutants. Copyright © 2018 Elsevier B.V. All rights reserved.

Nitric Oxide Homeostasis in Neurodegenerative Diseases.

PubMed

Hannibal, Luciana

2016-01-01

The role of nitric oxide in the pathogenesis and progression of neurodegenerative illnesses such as Parkinson's and Alzheimer's diseases has become prominent over the years. Increased activity of the enzymes that produce reactive oxygen species, decreased activity of antioxidant enzymes and imbalances in glutathione pools mediate and mark the neurodegenerative process. Much of the oxidative damage of proteins is brought about by the overproduction of nitric oxide by nitric oxide synthases (NOS) and its subsequent reactivity with reactive oxygen species. Proteomic methods have advanced the field tremendously, by facilitating the quantitative assessment of differential expression patterns and oxidative modifications of proteins and alongside, mapping their non-canonical functions. As a signaling molecule involved in multiple biochemical pathways, the level of nitric oxide is subject to tight regulation. All three NOS isoforms display aberrant patterns of expression in Alzheimer's disease, altering intracellular signaling and routing oxidative stress in directions that are uncompounded. This review discusses the prime factors that control nitric oxide biosynthesis, reactivity footprints and ensuing effects in the development of neurodegenerative diseases.

EEG classification of emotions using emotion-specific brain functional network.

PubMed

Gonuguntla, V; Shafiq, G; Wang, Y; Veluvolu, K C

2015-08-01

The brain functional network perspective forms the basis to relate mechanisms of brain functions. This work analyzes the network mechanisms related to human emotion based on synchronization measure - phase-locking value in EEG to formulate the emotion specific brain functional network. Based on network dissimilarities between emotion and rest tasks, most reactive channel pairs and the reactive band corresponding to emotions are identified. With the identified most reactive pairs, the subject-specific functional network is formed. The identified subject-specific and emotion-specific dynamic network pattern show significant synchrony variation in line with the experiment protocol. The same network pattern are then employed for classification of emotions. With the study conducted on the 4 subjects, an average classification accuracy of 62 % was obtained with the proposed technique.

Phase behavior of block copolymers in compressed carbon dioxide and as single domain-layer, nanolithographic etch resists for sub-10 nm pattern transfer

NASA Astrophysics Data System (ADS)

Chandler, Curran Matthew

Diblock copolymers have many interesting properties, which first and foremost include their ability to self-assemble into various ordered, regularly spaced domains with nanometer-scale feature sizes. The work in this dissertation can be logically divided into two parts -- the first and the majority of this work describes the phase behavior of certain block copolymer systems, and the second discusses real applications possible with block copolymer templates. Many compressible fluids have solvent-like properties dependent on fluid pressure and can be used as processing aids similar to liquid solvents. Here, compressed CO2 was shown to swell several thin homopolymer films, including polystyrene and polyisoprene, as measured by high pressure ellipsometry at elevated temperatures and pressures. The ellipsometric technique was modified to produce accurate data at these conditions through a custom pressure vessel design. The order-disorder transition (ODT) temperatures of several poly(styrene-bisoprene) diblock copolymers were also investigated by static birefringence when dilated with compressed CO2. Sorption of CO2 in each copolymer resulted in significant depressions of the ODT temperature as a function of fluid pressure, and the data above was used to estimate the quantitative amount of solvent in each of the diblock copolymers. These depressions were not shown to follow dilution approximation, and showed interesting, exaggerated scaling of the ODT at near-bulk polymer concentrations. The phase behavior of block copolymer surfactants was studied when blended with polymer or small molecule additives capable of selective hydrogen bonds. This work used small angle X-ray scattering (SAXS) to identify several low molecular weight systems with strong phase separation and ordered domains as small as 2--3 nanometers upon blending. One blend of a commercially-available surfactant with a small molecule additive was further developed and showed promise as a thin-film pattern transfer template. In this scenario, block copolymer thin films on domain thick with self-assembled feature sizes of only 6--7 nm were used as plasma etch resists. Here the block copolymer's pattern was successfully transferred into the underlying SiO2 substrate using CF4--based reactive ion etching. The result was a parallel, cylindrical nanostructure etched into SiO2.

Oblique patterned etching of vertical silicon sidewalls

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

Burckel, D. Bruce; Finnegan, Patrick S.; Henry, M. David

A method for patterning on vertical silicon surfaces in high aspect ratio silicontopography is presented. A Faraday cage is used to direct energetic reactive ions obliquely through a patterned suspended membrane positioned over the topography. The technique is capable of forming high-fidelity pattern (100 nm) features, adding an additional fabrication capability to standard top-down fabrication approaches.

Oblique patterned etching of vertical silicon sidewalls

NASA Astrophysics Data System (ADS)

Bruce Burckel, D.; Finnegan, Patrick S.; David Henry, M.; Resnick, Paul J.; Jarecki, Robert L.

2016-04-01

A method for patterning on vertical silicon surfaces in high aspect ratio silicon topography is presented. A Faraday cage is used to direct energetic reactive ions obliquely through a patterned suspended membrane positioned over the topography. The technique is capable of forming high-fidelity pattern (100 nm) features, adding an additional fabrication capability to standard top-down fabrication approaches.

Oblique patterned etching of vertical silicon sidewalls

DOE PAGES

Burckel, D. Bruce; Finnegan, Patrick S.; Henry, M. David; ...

2016-04-05

A method for patterning on vertical silicon surfaces in high aspect ratio silicontopography is presented. A Faraday cage is used to direct energetic reactive ions obliquely through a patterned suspended membrane positioned over the topography. The technique is capable of forming high-fidelity pattern (100 nm) features, adding an additional fabrication capability to standard top-down fabrication approaches.

Multiconfiguration Molecular Mechanics Based on Combined Quantum Mechanical and Molecular Mechanical Calculations.

PubMed

Lin, Hai; Zhao, Yan; Tishchenko, Oksana; Truhlar, Donald G

2006-09-01

The multiconfiguration molecular mechanics (MCMM) method is a general algorithm for generating potential energy surfaces for chemical reactions by fitting high-level electronic structure data with the help of molecular mechanical (MM) potentials. It was previously developed as an extension of standard MM to reactive systems by inclusion of multidimensional resonance interactions between MM configurations corresponding to specific valence bonding patterns, with the resonance matrix element obtained from quantum mechanical (QM) electronic structure calculations. In particular, the resonance matrix element is obtained by multidimensional interpolation employing a finite number of geometries at which electronic-structure calculations of the energy, gradient, and Hessian are carried out. In this paper, we present a strategy for combining MCMM with hybrid quantum mechanical molecular mechanical (QM/MM) methods. In the new scheme, electronic-structure information for obtaining the resonance integral is obtained by means of hybrid QM/MM calculations instead of fully QM calculations. As such, the new strategy can be applied to the studies of very large reactive systems. The new MCMM scheme is tested for two hydrogen-transfer reactions. Very encouraging convergence is obtained for rate constants including tunneling, suggesting that the new MCMM method, called QM/MM-MCMM, is a very general, stable, and efficient procedure for generating potential energy surfaces for large reactive systems. The results are found to converge well with respect to the number of Hessians. The results are also compared to calculations in which the resonance integral data are obtained by pure QM, and this illustrates the sensitivity of reaction rate calculations to the treatment of the QM-MM border. For the smaller of the two systems, comparison is also made to direct dynamics calculations in which the potential energies are computed quantum mechanically on the fly.

Histologic Grading of Prostatic Adenocarcinoma Can Be Further Optimized: Analysis of the Relative Prognostic Strength of Individual Architectural Patterns in 1275 Patients From the Canary Retrospective Cohort.

PubMed

McKenney, Jesse K; Wei, Wei; Hawley, Sarah; Auman, Heidi; Newcomb, Lisa F; Boyer, Hilary D; Fazli, Ladan; Simko, Jeff; Hurtado-Coll, Antonio; Troyer, Dean A; Tretiakova, Maria S; Vakar-Lopez, Funda; Carroll, Peter R; Cooperberg, Matthew R; Gleave, Martin E; Lance, Raymond S; Lin, Dan W; Nelson, Peter S; Thompson, Ian M; True, Lawrence D; Feng, Ziding; Brooks, James D

2016-11-01

Histologic grading remains the gold standard for prognosis in prostate cancer, and assessment of Gleason score plays a critical role in active surveillance management. We sought to optimize the prognostic stratification of grading and developed a method of recording and studying individual architectural patterns by light microscopic evaluation that is independent of standard Gleason grade. Some of the evaluated patterns are not assessed by current Gleason grading (eg, reactive stromal response). Individual histologic patterns were correlated with recurrence-free survival in a retrospective postradical prostatectomy cohort of 1275 patients represented by the highest-grade foci of carcinoma in tissue microarrays. In univariable analysis, fibromucinous rupture with varied epithelial complexity had a significantly lower relative risk of recurrence-free survival in cases graded as 3+4=7. Cases having focal "poorly formed glands," which could be designated as pattern 3+4=7, had lower risk than cribriform patterns with either small cribriform glands or expansile cribriform growth. In separate multivariable Cox proportional hazard analyses of both Gleason score 3+3=6 and 3+4=7 carcinomas, reactive stromal patterns were associated with worse recurrence-free survival. Decision tree models demonstrate potential regrouping of architectural patterns into categories with similar risk. In summary, we argue that Gleason score assignment by current consensus guidelines are not entirely optimized for clinical use, including active surveillance. Our data suggest that focal poorly formed gland and cribriform patterns, currently classified as Gleason pattern 4, should be in separate prognostic groups, as the latter is associated with worse outcome. Patterns with extravasated mucin are likely overgraded in a subset of cases with more complex epithelial bridges, whereas stromogenic cancers have a worse outcome than conveyed by Gleason grade alone. These findings serve as a foundation to facilitate optimization of histologic grading and strongly support incorporating reactive stroma into routine assessment.

Dual Catalysis Strategies in Photochemical Synthesis

PubMed Central

2016-01-01

The interaction between an electronically excited photocatalyst and an organic molecule can result in the genertion of a diverse array of reactive intermediates that can be manipulated in a variety of ways to result in synthetically useful bond constructions. This Review summarizes dual-catalyst strategies that have been applied to synthetic photochemistry. Mechanistically distinct modes of photocatalysis are discussed, including photoinduced electron transfer, hydrogen atom transfer, and energy transfer. We focus upon the cooperative interactions of photocatalysts with redox mediators, Lewis and Brønsted acids, organocatalysts, enzymes, and transition metal complexes. PMID:27109441

Recent advances in transition metal-catalyzed N -atom transfer reactions of azides

PubMed Central

Driver, Tom G.

2011-01-01

Transition metal-catalyzed N-atom transfer reactions of azides provide efficient ways to construct new carbon–nitrogen and sulfur–nitrogen bonds. These reactions are inherently green: no additive besides catalyst is needed to form the nitrenoid reactive intermediate, and the by-product of the reaction is environmentally benign N2 gas. As such, azides can be useful precursors for transition metal-catalyzed N-atom transfer to sulfides, olefins and C–H bonds. These methods offer competitive selectivities and comparable substrate scope as alternative processes to generate metal nitrenoids. PMID:20617243

Dual Catalysis Strategies in Photochemical Synthesis.

PubMed

Skubi, Kazimer L; Blum, Travis R; Yoon, Tehshik P

2016-09-14

The interaction between an electronically excited photocatalyst and an organic molecule can result in the genertion of a diverse array of reactive intermediates that can be manipulated in a variety of ways to result in synthetically useful bond constructions. This Review summarizes dual-catalyst strategies that have been applied to synthetic photochemistry. Mechanistically distinct modes of photocatalysis are discussed, including photoinduced electron transfer, hydrogen atom transfer, and energy transfer. We focus upon the cooperative interactions of photocatalysts with redox mediators, Lewis and Brønsted acids, organocatalysts, enzymes, and transition metal complexes.

Reactivation of Rate Remapping in CA3.

PubMed

Schwindel, C Daniela; Navratilova, Zaneta; Ali, Karim; Tatsuno, Masami; McNaughton, Bruce L

2016-09-07

The hippocampus is thought to contribute to episodic memory by creating, storing, and reactivating patterns that are unique to each experience, including different experiences that happen at the same location. Hippocampus can combine spatial and contextual/episodic information using a dual coding scheme known as "global" and "rate" remapping. Global remapping selects which set of neurons can activate at a given location. Rate remapping readjusts the firing rates of this set depending on current experience, thus expressing experience-unique patterns at each location. But can the experience-unique component be retrieved spontaneously? Whereas reactivation of recent, spatially selective patterns in hippocampus is well established, it is never perfect, raising the issue of whether the experiential component might be absent. This question is key to the hypothesis that hippocampus can assist memory consolidation by reactivating and broadcasting experience-specific "index codes" to neocortex. In CA3, global remapping exhibits attractor-like dynamics, whereas rate remapping apparently does not, leading to the hypothesis that only the former can be retrieved associatively and casting doubt on the general consolidation hypothesis. Therefore, we studied whether the rate component is reactivated spontaneously during sleep. We conducted neural ensemble recordings from CA3 while rats ran on a circular track in different directions (in different sessions) and while they slept. It was shown previously that the two directions of running result in strong rate remapping. During sleep, the most recent rate distribution was reactivated preferentially. Therefore, CA3 can retrieve patterns spontaneously that are unique to both the location and the content of recent experience. The hippocampus is required for memory of events and their spatial contexts. The primary correlate of hippocampal activity is location in space, but multiple memories can occur in the same location. To be useful for distinguishing these memories, the hippocampus must be able, not only to express, but also to retrieve both spatial and nonspatial information about events. Whether it can retrieve nonspatial information has been challenged recently. We exposed rats to two different experiences (running in different directions) in the same locations and showed that even the nonspatial components of hippocampal cell firing are reactivated spontaneously during sleep, supporting the conclusion that both types of information about a recent experience can be retrieved. Copyright © 2016 the authors 0270-6474/16/369342-09$15.00/0.

A phenotype of early infancy predicts reactivity of the amygdala in male adults.

PubMed

Schwartz, C E; Kunwar, P S; Greve, D N; Kagan, J; Snidman, N C; Bloch, R B

2012-10-01

One of the central questions that has occupied those disciplines concerned with human development is the nature of continuities and discontinuities from birth to maturity. The amygdala has a central role in the processing of novelty and emotion in the brain. Although there is considerable variability among individuals in the reactivity of the amygdala to novel and emotional stimuli, the origin of these individual differences is not well understood. Four-month old infants called high reactive (HR) demonstrate a distinctive pattern of vigorous motor activity and crying to specific unfamiliar visual, auditory and olfactory stimuli in the laboratory. Low-reactive infants show the complementary pattern. Here, we demonstrate that the HR infant phenotype predicts greater amygdalar reactivity to novel faces almost two decades later in adults. A prediction of individual differences in brain function at maturity can be made on the basis of a single behavioral assessment made in the laboratory at 4 months of age. This is the earliest known human behavioral phenotype that predicts individual differences in patterns of neural activity at maturity. These temperamental differences rooted in infancy may be relevant to understanding individual differences in vulnerability and resilience to clinical psychiatric disorder. Males who were HR infants showed particularly high levels of reactivity to novel faces in the amygdala that distinguished them as adults from all other sex/temperament subgroups, suggesting that their amygdala is particularly prone to engagement by unfamiliar faces. These findings underline the importance of taking gender into account when studying the developmental neurobiology of human temperament and anxiety disorders. The genetic study of behavioral and biologic intermediate phenotypes (or 'endophenotypes') indexing anxiety-proneness offers an important alternative to examining phenotypes based on clinically defined disorder. As the HR phenotype is characterized by specific patterns of reactivity to elemental visual, olfactory and auditory stimuli, well before complex social behaviors such as shyness or fearful interaction with strangers can be observed, it may be closer to underlying neurobiological mechanisms than behavioral profiles observed later in life. This possibility, together with the fact that environmental factors have less time to impact the 4-month phenotype, suggests that this temperamental profile may be a fruitful target for high-risk genetic studies.

Reactivity of a Cobalt(III)–Hydroperoxo Complex in Electrophilic Reactions

DOE PAGES

Shin, Bongki; Sutherlin, Kyle D.; Ohta, Takehiro; ...

2016-11-15

The reactivity of mononuclear metal-hydroperoxo adducts has fascinated researchers in many areas due to their diverse biological and catalytic processes. In this study, a mononuclear cobalt(III)-peroxo complex bearing a tetradentate macrocyclic ligand, [Co III(Me 3-TPADP)(O 2)] + (Me 3-TPADP = 3,6,9-trimethyl-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane), was prepared by reacting [Co II(Me 3-TPADP)(CH 3CN) 2] 2+ with H 2O 2 in the presence of triethylamine. Upon protonation, the cobalt(III)- peroxo intermediate was converted into a cobalt(III)-hydroperoxo complex, [Co III(Me 3-TPADP)(O 2H)(CH 3CN)] 2+. The mononuclear cobalt(III)-peroxo and -hydroperoxo intermediates were characterized by a variety of physicochemical methods. Results of electrospray ionization mass spectrometry clearly showmore » the transformation of the intermediates: the peak at m/z 339.2 assignable to the cobalt(III)-peroxo species disappears with concomitant growth of the peak at m/z 190.7 corresponding to the cobalt(III)-hydroperoxo complex (with bound CH 3CN). Isotope labeling experiments further support the existence of the cobalt(III)-peroxo and -hydroperoxo complexes. In particular, the O-O bond stretching frequency of the cobalt(III)-hydroperoxo complex was determined to be 851 cm -1 for 16O 2H samples (803 cm -1 for 18O 2H samples) and its Co-O vibrational energy was observed at 571 cm -1 for 16O 2H samples (551 cm -1 for 18O 2H samples; 568 cm -1 for 16O 2 2H samples) by resonance Raman spectroscopy. Reactivity studies performed with the cobalt(III)-peroxo and -hydroperoxo complexes in organic functionalizations reveal that the latter is capable of conducting oxygen atom transfer with an electrophilic character, whereas the former exhibits no oxygen atom transfer reactivity under the same reaction conditions. Alternatively, the cobalt(III)-hydroperoxo complex does not perform hydrogen atom transfer reactions, while analogous low-spin Fe(III)-hydroperoxo complexes are capable of this reactivity. Density function theory calculations indicate that this lack of reactivity is due to the high free energy cost of O-O bond homolysis that would be required to produce the hypothetical Co(IV)-oxo product.« less

Reactivity of a Cobalt(III)–Hydroperoxo Complex in Electrophilic Reactions

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

Shin, Bongki; Sutherlin, Kyle D.; Ohta, Takehiro

The reactivity of mononuclear metal-hydroperoxo adducts has fascinated researchers in many areas due to their diverse biological and catalytic processes. In this study, a mononuclear cobalt(III)-peroxo complex bearing a tetradentate macrocyclic ligand, [Co III(Me 3-TPADP)(O 2)] + (Me 3-TPADP = 3,6,9-trimethyl-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane), was prepared by reacting [Co II(Me 3-TPADP)(CH 3CN) 2] 2+ with H 2O 2 in the presence of triethylamine. Upon protonation, the cobalt(III)- peroxo intermediate was converted into a cobalt(III)-hydroperoxo complex, [Co III(Me 3-TPADP)(O 2H)(CH 3CN)] 2+. The mononuclear cobalt(III)-peroxo and -hydroperoxo intermediates were characterized by a variety of physicochemical methods. Results of electrospray ionization mass spectrometry clearly showmore » the transformation of the intermediates: the peak at m/z 339.2 assignable to the cobalt(III)-peroxo species disappears with concomitant growth of the peak at m/z 190.7 corresponding to the cobalt(III)-hydroperoxo complex (with bound CH 3CN). Isotope labeling experiments further support the existence of the cobalt(III)-peroxo and -hydroperoxo complexes. In particular, the O-O bond stretching frequency of the cobalt(III)-hydroperoxo complex was determined to be 851 cm -1 for 16O 2H samples (803 cm -1 for 18O 2H samples) and its Co-O vibrational energy was observed at 571 cm -1 for 16O 2H samples (551 cm -1 for 18O 2H samples; 568 cm -1 for 16O 2 2H samples) by resonance Raman spectroscopy. Reactivity studies performed with the cobalt(III)-peroxo and -hydroperoxo complexes in organic functionalizations reveal that the latter is capable of conducting oxygen atom transfer with an electrophilic character, whereas the former exhibits no oxygen atom transfer reactivity under the same reaction conditions. Alternatively, the cobalt(III)-hydroperoxo complex does not perform hydrogen atom transfer reactions, while analogous low-spin Fe(III)-hydroperoxo complexes are capable of this reactivity. Density function theory calculations indicate that this lack of reactivity is due to the high free energy cost of O-O bond homolysis that would be required to produce the hypothetical Co(IV)-oxo product.« less

Training on Working Memory and Inhibitory Control in Young Adults

PubMed Central

Maraver, Maria J.; Bajo, M. Teresa; Gomez-Ariza, Carlos J.

2016-01-01

Different types of interventions have focused on trying to improve Executive Functions (EFs) due to their essential role in human cognition and behavior regulation. Although EFs are thought to be diverse, most training studies have targeted cognitive processes related to working memory (WM), and fewer have focused on training other control mechanisms, such as inhibitory control (IC). In the present study, we aimed to investigate the differential impact of training WM and IC as compared with control conditions performing non-executive control activities. Young adults were divided into two training (WM/IC) and two (active/passive) control conditions. Over six sessions, the training groups engaged in three different computer-based adaptive activities (WM or IC), whereas the active control group completed a program with low control-demanding activities that mainly involved processing speed. In addition, motivation and engagement were monitored through the training. The WM-training activities required maintenance, updating and memory search processes, while those from the IC group engaged response inhibition and interference control. All participants were pre- and post-tested in criterion tasks (n-back and Stroop), near transfer measures of WM (Operation Span) and IC (Stop-Signal). Non-trained far transfer outcome measures included an abstract reasoning test (Raven’s Advanced Progressive Matrices) and a well-validated experimental task (AX-CPT) that provides indices of cognitive flexibility considering proactive/reactive control. Training results revealed that strongly motivated participants reached higher levels of training improvements. Regarding transfer effects, results showed specific patterns of near transfer effects depending on the type of training. Interestingly, it was only the IC training group that showed far transfer to reasoning. Finally, all trained participants showed a shift toward a more proactive mode of cognitive control, highlighting a general effect of training on cognitive flexibility. The present results reveal specific and general modulations of executive control mechanisms after brief training intervention targeting either WM or IC. PMID:27917117

Intergenerational transfers in the era of HIV/AIDS: Evidence from rural Malawi.

PubMed

Kohler, Iliana V; Kohler, Hans-Peter; Anglewicz, Philip; Behrman, Jere R

2012-12-13

Intergenerational transfer patterns in sub-Saharan Africa are poorly understood, despite the alleged importance of support networks to ameliorate the complex implications of the HIV/AIDS epidemic for families. There is a considerable need for research on intergenerational support networks and transfers to better understand the mechanisms through which extended families cope with the HIV/AIDS epidemic and potentially alleviate some of its consequences in sub-Saharan Africa, and to comprehend how transfers respond-or not-to perceptions about own and other family members' health. Using the 2008 round of the Malawi Longitudinal Study of Families and Health (MLSFH), we estimate the age patterns and the multiple directions of financial and non-financial transfer flows in rural Malawi-from prime-aged respondents to their elderly parents and adult children age 15 and up. We also estimate the social, demographic and economic correlates of financial and non-financial transfers of financial intergenerational transfers in this context. Our findings are that: (1) intergenerational financial and non-financial transfers are widespread and a key characteristic of family relationships in rural Malawi; (2) downward and upward transfers are importantly constrained and determined by the availability of transfer partners (parents or adult children); (3) financial net transfers are strongly age-patterned and the middle generations are net-providers of transfers; (4) non-financial transfers are based on mutual assistance rather than reallocation of resources; and (5) intergenerational transfers are generally not related to health status, including HIV positive status.

Competitive FRET-aptamer-based detection of methylphosphonic acid, a common nerve agent metabolite.

PubMed

Bruno, John G; Carrillo, Maria P; Phillips, Taylor; Vail, Neal K; Hanson, Douglas

2008-09-01

Competitive fluorescence resonance energy transfer (FRET)-aptamer-based assay formats are described for one-step detection of methylphosphonic acid (MPA; a metabolite of several organophosphorus (OP) nerve agents). AminoMPA was attached to tosyl-magnetic beads and used for DNA aptamer selection from which one dominant aptamer sequence emerged. Two different FRET approaches were attempted. In one approach, the complementary DNA sequence was used as a template for labeling the aptamer with Alexa Fluor 546 (AF 546)-14-dUTP by asymmetric PCR. Following 3-dimensional (3-D), molecular modeling of the aptamer-MPA complex, a series of three fluoresceinated aptamers labeled at positions 50, 51, and 52 in the putative optimal binding pocket were synthesized. In both FRET formats, aminoMPA was linked to Black Hole Quencher (BHQ-1 or BHQ-2)-succinimides and allowed to bind the fluorescein or AF 546-labeled MPA aptamer. Following gel filtration to purify the labeled MPA aptamer-BHQ-aminoMPA FRET complexes, the complexes were competed against various concentrations of unlabeled MPA, MPA derivatives, and unrelated compounds in titration and cross-reactivity studies. Both approaches yielded low microgram per milliliter detection limits for MPA with generally low levels of cross-reactivity for unrelated compounds. However, the data suggest a pattern of traits that may effect the direction (lights on or off) and intensity of the FRET.

Relation between alternating open/closed-conduit conditions and deformation patterns: An example from the Somma-Vesuvius volcano (southern Italy)

NASA Astrophysics Data System (ADS)

Tramparulo, F. D. A.; Vitale, S.; Isaia, R.; Tadini, A.; Bisson, M.; Prinzi, E. P.

2018-07-01

We present the results of a meso-scale systematic structural analysis of fractures, faults and dykes exposed at the Somma-Vesuvius volcano (southern Italy). Observed fractures include: (i) radial and tangential (with respect the caldera axis), sub-metric to metric joints associated with the edifice load and volcano-tectonic activity (i.e. inflation, deflation and caldera collapse stages) and (ii) decameter-scale fractures related to volcano flank instabilities. For the Somma-Vesuvius volcano, preexisting radial joints were commonly reactivated as transfer faults during the caldera formation, allowing different blocks to move toward the center of the collapsing area. Dykes occur with different geometries, including en-echelon structures bounding structural depressions. The orientation analysis of all structures indicates that they are preferentially oriented. Furthermore, we provide a morphological lineament analysis using high-resolution Digital Terrain Models of Somma-Vesuvius. Azimuth and spatial distribution of dykes and morphological lineaments were analyzed for comparison with the old Somma Crater and Gran Cono axes, respectively. Results highlight the overprinting of radial and clustered strain patterns recorded in different volcano-tectonic evolution stages. We suggest a possible deformation evolution model in which structures develop along either radial or preferential trends, highlighting different volcanic conditions: (i) where radial patterns occur, the structures developed during volcanic inflation cycles with a closed magmatic conduit condition whereas (ii) clustered patterns are probably associated with a regional strain field that overcomes the local deformation field, a situation typical in the case of open-conduit activity.

CD4+ T Cells Reactive to Enteric Bacterial Antigens in Spontaneously Colitic C3H/HeJBir Mice: Increased T Helper Cell Type 1 Response and Ability to Transfer Disease

PubMed Central

Cong, Yingzi; Brandwein, Steven L.; McCabe, Robert P.; Lazenby, A.; Birkenmeier, Edward H.; Sundberg, John P.; Elson, Charles O.

1998-01-01

C3H/HeJBir mice are a new substrain that spontaneously develop colitis early in life. This study was done to determine the T cell reactivity of C3H/HeJBir mice to candidate antigens that might be involved in their disease. C3H/HeJBir CD4+ T cells were strongly reactive to antigens of the enteric bacterial flora, but not to epithelial or food antigens. The stimulatory material in the enteric bacteria was trypsin sensitive and restricted by class II major histocompatibility complex molecules, but did not have the properties of a superantigen. The precursor frequency of interleuken (IL)-2–producing, bacterial-reactive CD4+ T cells in colitic mice was 1 out of 2,000 compared to 1 out of 20,000–25,000 in noncolitic control mice. These T cells produced predominately IL-2 and interferon γ, consistent with a T helper type 1 cell response and were present at 3–4 wk, the age of onset of the colitis. Adoptive transfer of bacterial-antigen–activated CD4+ T cells from colitic C3H/HeJBir but not from control C3H/HeJ mice into C3H/HeSnJ scid/scid recipients induced colitis. These data represent a direct demonstration that T cells reactive with conventional antigens of the enteric bacterial flora can mediate chronic inflammatory bowel disease. PMID:9500788

Experimental investigation on the heat transfer characteristics and flow pattern in vertical narrow channels heated from one side

NASA Astrophysics Data System (ADS)

Huang, Lihao; Li, Gang; Tao, Leren

2016-07-01

Experimental investigation for the flow boiling of water in a vertical rectangular channel was conducted to reveal the boiling heat transfer mechanism and flow patterns map aspects. The onset of nucleate boiling went upward with the increasing of the working fluid mass flow rate or the decreasing of the inlet working fluid temperature. As the vapour quality was increased, the local heat transfer coefficient increased first, then decreased, followed by various flow patterns. The test data from other researchers had a similar pattern transition for the bubble-slug flow and the slug-annular flow. Flow pattern transition model analysis was performed to make the comparison with current test data. The slug-annular and churn-annular transition models showed a close trend with current data except that the vapor phase superficial velocity of flow pattern transition was much higher than that of experimental data.

Relative role of transfer zones in controlling sequence stacking patterns and facies distribution: insights from the Fushan Depression, South China Sea

NASA Astrophysics Data System (ADS)

Liu, Entao; Wang, Hua; Li, Yuan; Huang, Chuanyan

2015-04-01

In sedimentary basins, a transfer zone can be defined as a coordinated system of deformational features which has good prospects for hydrocarbon exploration. Although the term 'transfer zone' has been widely applied to the study of extensional basins, little attention has been paid to its controlling effect on sequence tracking pattern and depositional facies distribution. Fushan Depression is a half-graben rift sub-basin, located in the southeast of the Beibuwan Basin, South China Sea. In this study, comparative analysis of seismic reflection, palaeogeomorphology, fault activity and depositional facies distribution in the southern slope indicates that three different types of sequence stacking patterns (i.e. multi-level step-fault belt in the western area, flexure slope belt in the central area, gentle slope belt in the eastern area) were developed along the southern slope, together with a large-scale transfer zone in the central area, at the intersection of the western and eastern fault systems. Further analysis shows that the transfer zone played an important role in the diversity of sequence stacking patterns in the southern slope by dividing the Fushan Depression into two non-interfering tectonic systems forming different sequence patterns, and leading to the formation of the flexure slope belt in the central area. The transfer zone had an important controlling effect on not only the diversity of sequence tracking patterns, but also the facies distribution on the relay ramp. During the high-stand stage, under the controlling effect of the transfer zone, the sediments contain a significant proportion of coarser material accumulated and distributed along the ramp axis. By contrast, during the low-stand stage, the transfer zone did not seem to contribute significantly to the low-stand fan distribution which was mainly controlled by the slope gradient (palaeogeomorphology). Therefore, analysis of the transfer zone can provide a new perspective for basin analysis. In addition, the transfer zone area demonstrated unique hydrocarbon accumulation models different from the western and eastern areas. It was not only a structural high combined with sufficient coarse-grained reservoir quality sands, but was also associated with large-scale sublacustrine fan deposits with high quality reservoirs, indicating that the recognition of transfer zones can improve the prediction of hydrocarbon occurrences in similar settings.

Control of Cytomegalovirus Viremia after Allogeneic Stem Cell Transplantation: A Review on CMV-Specific T Cell Reconstitution.

PubMed

van der Heiden, Pim; Marijt, Erik; Falkenburg, Fred; Jedema, Inge

2018-04-04

Recipients of allogeneic stem cell transplantation (alloSCT) are at risk for reactivation of endogenous herpesviruses due to profound and prolonged T cell deficiency following conditions such as graft-versus-host disease, immunosuppression, and/or T cell depletion. Reactivation of endogenous cytomegalovirus (CMV) is the most frequently occurring herpesvirus reactivation following alloSCT. Antiviral medication is often used in pre-emptive treatment strategies initiated when increases in CMV viral loads are detected as a result of active reactivation of the virus. Despite pre-emptive antiviral treatment, the incidence of CMV disease in CMV-seropositive alloSCT patients is still 10% at 1 year following alloSCT. This illustrates the necessity for adequate CMV-specific T cell immunity for long-term control of CMV and prevention of CMV disease. In this review, we analyzed the available studies on the influence of donor CMV status on CMV-specific T cell reconstitution and CMV disease. Furthermore, we reviewed the available studies on the safety and efficacy of adoptive transfer of donor CMV-specific T cells for the prevention and treatment of CMV disease following alloSCT, including studies on adoptive transfer of third-party CMV-specific T cells as a possible alternative when donor T cells are not available. Copyright © 2018 The American Society for Blood and Marrow Transplantation. Published by Elsevier Inc. All rights reserved.

Effect of multiple slip on a chemically reactive MHD non-Newtonian nanofluid power law fluid flow over a stretching sheet with microorganism

NASA Astrophysics Data System (ADS)

Basir, Mohammad Faisal Mohd; Ismail, Fazreen Amira; Amirsom, Nur Ardiana; Latiff, Nur Amalina Abdul; Ismail, Ahmad Izani Md.

2017-04-01

The effect of multiple slip on a chemically reactive magnetohydrodynamic (MHD) non-Newtonian power law fluid flow over a stretching sheet with microorganism was numerically investigated. The governing partial differential equations were transformed into nonlinear ordinary differential equations using the similarity transformations developed by Lie group analysis. The reduced governing nonlinear ordinary differential equations were then numerically solved using the Runge-Kutta-Fehlberg fourth-fifth order method. Good agreement was found between the present numerical solutions with the existing published results to support the validity and the accuracy of the numerical computations. The influences of the velocity, thermal, mass and microorganism slips, the magnetic field parameter and the chemical reaction parameter on the dimensionless velocity, temperature, nanoparticle volume fraction, microorganism concentration, the distribution of the density of motile microorganisms have been illustrated graphically. The effects of the governing parameters on the physical quantities, namely, the local heat transfer rate, the local mass transfer rate and the local microorganism transfer rate were analyzed and discussed.

Attrition and performance of community college transfers

PubMed Central

Aulck, Lovenoor; West, Jevin

2017-01-01

Community colleges are an important part of the US higher education landscape, yet the aptitude and preparedness of student transfers to baccalaureate institutions is often called into question. Examining transcript records and demographic information of nearly 70,000 students across over 15 years of registrar records at a public university, this study performed a descriptive analysis of the persistence, performance, and academic migration patterns of community college transfers, transfers from four-year institutions, and freshmen entrants. We found little difference between community college transfers and freshmen entrants in terms of post-transfer grades and persistence. Transfers from four-year institutions had higher grades but also had higher attrition rates than their peers. This study also found no strong evidence of transfer shock on students’ post-transfer grades. When examining the tendencies of students to shift fields of study during their educational pursuits, the academic migration patterns of transfer students were more concentrated than those of freshmen entrants. PMID:28407002

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

Huang, Chuanfu; Kresin, Vitaly V., E-mail: kresin@usc.edu

This note describes a system for transferring a load of high purity lithium metal into a molecular or cluster beam source. A hot loading vessel is thoroughly baked out while empty and overpressured with argon. A clean Li rod is then dropped in through a long narrow tube. The thoroughly degassed interior of the vessel and the rapid melting of the inserted rod facilitate contamination-free transfer of the highly reactive liquid metal into the source oven.

Theoretical Studies of Gas Phase Elementary and Carbon Nanostructure Growth Reactions

DTIC Science & Technology

2013-09-19

time dynamics of electron transfer in a prototype redox reaction that occurs in reactive collisions between neutral and ionic fullerenes is discussed...The LvNMD show that the electron transfer occurs within 60 fs directly preceding the collision of the fullerenes , followed by structural changes...collisions between neutral and multiply charged fullerenes . 2 B. Collaboration with the AFRL. Collaboration with the VIggiano group at AFRL at

Highly galloylated tannin fractions from witch hazel (Hamamelis virginiana) bark: electron transfer capacity, in vitro antioxidant activity, and effects on skin-related cells.

PubMed

Touriño, Sonia; Lizárraga, Daneida; Carreras, Anna; Lorenzo, Sonia; Ugartondo, Vanessa; Mitjans, Montserrat; Vinardell, María Pilar; Juliá, Luis; Cascante, Marta; Torres, Josep Lluís

2008-03-01

Witch hazel ( Hammamelis virginiana) bark is a rich source of both condensed and hydrolizable oligomeric tannins. From a polyphenolic extract soluble in both ethyl acetate and water, we have generated fractions rich in pyrogallol-containing polyphenols (proanthocyanidins, gallotannins, and gallates). The mixtures were highly active as free radical scavengers against ABTS, DPPH (hydrogen donation and electron transfer), and HNTTM (electron transfer). They were also able to reduce the newly introduced TNPTM radical, meaning that they included some highly reactive components. Witch hazel phenolics protected red blood cells from free radical-induced hemolysis and were mildly cytotoxic to 3T3 fibroblasts and HaCat keratinocytes. They also inhibited the proliferation of tumoral SK-Mel 28 melanoma cells at lower concentrations than grape and pine procyanidins. The high content in pyrogallol moieties may be behind the effect of witch hazel phenolics on skin cells. Because the most cytotoxic and antiproliferative mixtures were also the most efficient as electron transfer agents, we hypothesize that the final putative antioxidant effect of polyphenols may be in part attributed to the stimulation of defense systems by mild prooxidant challenges provided by reactive oxygen species generated through redox cycling.

Effects of Experimenter Surveillance on Reactive Self-Monitoring.

ERIC Educational Resources Information Center

Belfiore, Phillip J.; And Others

1989-01-01

Worker reactivity patterns were examined in a study of two women with mild and moderate mental retardation who self-monitored their work productivity with and without external surveillance. Findings suggest that surveillance is a setting event that may be important in achieving and maintaining self-management program benefits. (MSE)

Situational Determinants of Social Anxiety in Clinic and Nonclinic Samples: Physiological and Cognitive Correlates.

ERIC Educational Resources Information Center

Turner, Samuel M.; And Others

1986-01-01

Nonclinic socially anxious individuals, clinic socially anxious patients, and nonsocially anxious subjects were assessed for changes in patterns of physiological reactivity and cognition across three interpersonal tasks. Results indicated that both thoughts and physiological reactivity were influenced by situational parameters. (Author/ABB)

How reactive fluids alter fracture walls and affect shale-matrix accessibility

NASA Astrophysics Data System (ADS)

Fitts, J. P.; Deng, H.; Peters, C. A.

2014-12-01

Predictions of mass transfer across fracture boundaries and fluid flow in fracture networks provide fundamental inputs into risk and life cycle assessments of geologic energy technologies including oil and gas extraction, geothermal energy systems and geologic CO2 storage. However, major knowledge gaps exist due to the lack of experimental observations of how reactive fluids alter the pore structures and accessible surface area within fracture boundaries that control the mass transfer of organics, metals and salts, and influence fluid flow within the fracture. To investigate the fracture and rock matrix properties governing fracture boundary alteration, we developed a new flow-through cell that enables time-dependent 2D x-ray imaging of mineral dissolution and/or precipitation at a fracture surface. The parallel plate design provides an idealized fracture geometry to investigate the relationship between flow rate, reaction rate, and mineral spatial heterogeneity and variation. In the flow-cell, a carbonate-rich sample of Eagle Ford shale was reacted with acidified brine. The extent and rate of mineral dissolution were correlated with calcite abundance relative to less soluble silicate minerals. Three-dimensional x-ray tomography of the reacted fracture wall shows how calcite dissolution left behind a porous network of silicate minerals. And while this silicate network essentially preserved the location of the initial fracture wall, the pore network structures within the fracture boundary were dramatically altered, such that the accessible surface area of matrix components increased significantly. In a second set of experiments with a limestone specimen, however, the extent of dissolution and retreat of the fracture wall was not strictly correlated with the occurrence of calcite. Instead, the pattern and extent of dissolution suggested secondary causes such as calcite morphology, the presence of argillaceous minerals and other diagenetic features. Our experiments show that while calcite dissolution is the primary geochemical driver of fracture wall alterations, hydrodynamic properties and matrix accessibility within fracture boundaries evolve based on a complex relationship between mineral spatial heterogeneity and variation, fluid chemistry and flow rate.

Reinstatement of Individual Past Events Revealed by the Similarity of Distributed Activation Patterns during Encoding and Retrieval

PubMed Central

Wing, Erik A.; Ritchey, Maureen; Cabeza, Roberto

2015-01-01

Neurobiological memory models assume memory traces are stored in neocortex, with pointers in the hippocampus, and are then reactivated during retrieval, yielding the experience of remembering. Whereas most prior neuroimaging studies on reactivation have focused on the reactivation of sets or categories of items, the current study sought to identify cortical patterns pertaining to memory for individual scenes. During encoding, participants viewed pictures of scenes paired with matching labels (e.g., “barn,” “tunnel”), and, during retrieval, they recalled the scenes in response to the labels and rated the quality of their visual memories. Using representational similarity analyses, we interrogated the similarity between activation patterns during encoding and retrieval both at the item level (individual scenes) and the set level (all scenes). The study yielded four main findings. First, in occipitotemporal cortex, memory success increased with encoding-retrieval similarity (ERS) at the item level but not at the set level, indicating the reactivation of individual scenes. Second, in ventrolateral pFC, memory increased with ERS for both item and set levels, indicating the recapitulation of memory processes that benefit encoding and retrieval of all scenes. Third, in retrosplenial/posterior cingulate cortex, ERS was sensitive to individual scene information irrespective of memory success, suggesting automatic activation of scene contexts. Finally, consistent with neurobiological models, hippocampal activity during encoding predicted the subsequent reactivation of individual items. These findings show the promise of studying memory with greater specificity by isolating individual mnemonic representations and determining their relationship to factors like the detail with which past events are remembered. PMID:25313659

The effect of the number of transferred embryos, the interval between nuclear transfer and embryo transfer, and the transfer pattern on pig cloning efficiency.

PubMed

Rim, Chol Ho; Fu, Zhixin; Bao, Lei; Chen, Haide; Zhang, Dan; Luo, Qiong; Ri, Hak Chol; Huang, Hefeng; Luan, Zhidong; Zhang, Yan; Cui, Chun; Xiao, Lei; Jong, Ui Myong

2013-12-01

To improve the efficiency of producing cloned pigs, we investigated the influence of the number of transferred embryos, the culturing interval between nuclear transfer (NT) and embryo transfer, and the transfer pattern (single oviduct or double oviduct) on cloning efficiency. The results demonstrated that transfer of either 150-200 or more than 200NT embryos compared to transfer of 100-150 embryos resulted in a significantly higher pregnancy rate (48 ± 16, 50 ± 16 vs. 29 ± 5%, p<0.05) and average litter size (4.1 ± 2.3, 7 ± 3.6 vs. 2.5 ± 0.5). In vitro culture of reconstructed embryos for a longer time (40 h vs. 20 h) resulted in higher (p<0.05) pregnancy rate (44 ± 9 vs. 31 ± 3%) and delivery rate (44 ± 9 vs. 25 ± 9%). Furthermore, double oviductal transfer dramatically increased pregnancy rate (83 ± 6 vs. 27+8%, p<0.05), delivery rate (75 ± 2 vs. 27+8%, p<0.05) and average litter size (6.5 ± 2.8 vs. 2.6 ± 1.2) compared to single oviductal transfer. Our study demonstrated that an improvement in pig cloning efficiency is achieved by adjusting the number and in vitro culture time of reconstructed embryos as well as the embryo transfer pattern. Copyright © 2013 Elsevier B.V. All rights reserved.

Thermo-mechanical toner transfer for high-quality digital image correlation speckle patterns

NASA Astrophysics Data System (ADS)

Mazzoleni, Paolo; Zappa, Emanuele; Matta, Fabio; Sutton, Michael A.

2015-12-01

The accuracy and spatial resolution of full-field deformation measurements performed through digital image correlation are greatly affected by the frequency content of the speckle pattern, which can be effectively controlled using particles with well-defined and consistent shape, size and spacing. This paper introduces a novel toner-transfer technique to impress a well-defined and repeatable speckle pattern on plane and curved surfaces of metallic and cement composite specimens. The speckle pattern is numerically designed, printed on paper using a standard laser printer, and transferred onto the measurement surface via a thermo-mechanical process. The tuning procedure to compensate for the difference between designed and toner-transferred actual speckle size is presented. Based on this evidence, the applicability of the technique is discussed with respect to surface material, dimensions and geometry. Proof of concept of the proposed toner-transfer technique is then demonstrated for the case of a quenched and partitioned welded steel plate subjected to uniaxial tensile loading, and for an aluminum plate exposed to temperatures up to 70% of the melting point of aluminum and past the melting point of typical printer toner powder.

Adoptive transfer of gene-engineered CD4+ helper T cells induces potent primary and secondary tumor rejection.

PubMed

Moeller, Maria; Haynes, Nicole M; Kershaw, Michael H; Jackson, Jacob T; Teng, Michele W L; Street, Shayna E; Cerutti, Loretta; Jane, Stephen M; Trapani, Joseph A; Smyth, Mark J; Darcy, Phillip K

2005-11-01

Because CD4+ T cells play a key role in aiding cellular immune responses, we wanted to assess whether increasing numbers of gene-engineered antigen-restricted CD4+ T cells could enhance an antitumor response mediated by similarly gene-engineered CD8+ T cells. In this study, we have used retroviral transduction to generate erbB2-reactive mouse T-cell populations composed of various proportions of CD4+ and CD8+ cells and then determined the antitumor reactivity of these mixtures. Gene-modified CD4+ and CD8+ T cells were shown to specifically secrete Tc1 (T cytotoxic-1) or Tc2 cytokines, proliferate, and lyse erbB2+ tumor targets following antigen ligation in vitro. In adoptive transfer experiments using severe combined immunodeficient (scid) mice, we demonstrated that injection of equivalent numbers of antigen-specific engineered CD8+ and CD4+ T cells led to significant improvement in survival of mice bearing established lung metastases compared with transfer of unfractionated (largely CD8+) engineered T cells. Transferred CD4+ T cells had to be antigen-specific (not just activated) and secrete interferon gamma (IFN-gamma) to potentiate the antitumor effect. Importantly, antitumor responses in these mice correlated with localization and persistence of gene-engineered T cells at the tumor site. Strikingly, mice that survived primary tumor challenge could reject a subsequent rechallenge. Overall, this study has highlighted the therapeutic potential of using combined transfer of antigen-specific gene-modified CD8+ and CD4+ T cells to significantly enhance T-cell adoptive transfer strategies for cancer therapy.

Foundations for Streaming Model Transformations by Complex Event Processing.

PubMed

Dávid, István; Ráth, István; Varró, Dániel

2018-01-01

Streaming model transformations represent a novel class of transformations to manipulate models whose elements are continuously produced or modified in high volume and with rapid rate of change. Executing streaming transformations requires efficient techniques to recognize activated transformation rules over a live model and a potentially infinite stream of events. In this paper, we propose foundations of streaming model transformations by innovatively integrating incremental model query, complex event processing (CEP) and reactive (event-driven) transformation techniques. Complex event processing allows to identify relevant patterns and sequences of events over an event stream. Our approach enables event streams to include model change events which are automatically and continuously populated by incremental model queries. Furthermore, a reactive rule engine carries out transformations on identified complex event patterns. We provide an integrated domain-specific language with precise semantics for capturing complex event patterns and streaming transformations together with an execution engine, all of which is now part of the Viatra reactive transformation framework. We demonstrate the feasibility of our approach with two case studies: one in an advanced model engineering workflow; and one in the context of on-the-fly gesture recognition.

Course-Taking Patterns of Community College Students Beginning in STEM: Using Data Mining Techniques to Reveal Viable STEM Transfer Pathways

ERIC Educational Resources Information Center

Wang, Xueli

2016-01-01

This research focuses on course-taking patterns of beginning community college students enrolled in one or more non-remedial science, technology, engineering, and mathematics (STEM) courses during their first year of college, and how these patterns are mapped against upward transfer in STEM fields of study. Drawing upon postsecondary transcript…

IgG and IgM anti-snRNP reactivity in sequentially obtained serum samples from patients with connective tissue diseases.

PubMed Central

Nyman, U; Lundberg, I; Hedfors, E; Wahren, M; Pettersson, I

1992-01-01

Sequentially obtained serum samples from 30 patients with connective tissue disease positive for antibody to ribonucleoprotein (RNP) were examined to determine the specificities of IgG and IgM antibodies to snRNP during the disease course using immunoblotting of nuclear extracts. The antibody patterns were correlated with disease activity. The patterns of antibody to snRNP of individual patients were mainly stable during the study but changes in levels of antibody to snRNP were seen corresponding to changes in clinical activity. These results indicate that increased reactivity of serum IgM antibodies against the B/B' proteins seems to precede a clinically evident exacerbation of disease whereas IgG antibody reactivity to the 70 K protein peaks at the time of a disease flare. Images PMID:1485812

Testing promotes effector transfer.

PubMed

Boutin, Arnaud; Panzer, Stefan; Salesse, Robin N; Blandin, Yannick

2012-11-01

The retrieval of information from memory during testing has recently been shown to promote transfer in the verbal domain. Motor-related research, however, has ignored testing as a relevant method to enhance motor transfer. We thus investigated whether testing has the potential to induce generalised motor memories by favouring effector transfer. Participants were required to reproduce a spatial-temporal pattern of elbow extensions and flexions with their dominant right arm. We tested the ability of participants to transfer the original pattern (extrinsic transformation; i.e., goal-based configuration) or the mirrored pattern (intrinsic transformation; i.e., movement-based configuration) to the unpractised non-dominant left arm. To evaluate how testing affects motor transfer at 24-h testing, participants were either administered an initial testing session during early practice (early testing group) or shortly after the end of practice (late testing group; i.e., no alternation between practice and testing sessions). No initial testing session was completed for the control group. We found better effector transfer at 24-h testing for the early testing group for both extrinsic and intrinsic transformations of the movement pattern when compared with the control group, while no testing benefit was observed for the late testing group. This indicates that testing positively affects motor learning, yielding enhanced long-term transfer capabilities. We thus demonstrate the critical role of retrieval practice via testing during the process of motor memory encoding, and provide the conditions under which testing effectively contributes to the generalisation of motor memories. Copyright © 2012 Elsevier B.V. All rights reserved.

Evidence for Consolidation of Neuronal Assemblies after Seizures in Humans

PubMed Central

Stead, Matt; Bower, Regina S.; Kucewicz, Michal T.; Sulc, Vlastimil; Cimbalnik, Jan; Brinkmann, Benjamin H.; Vasoli, Vincent M.; St. Louis, Erik K.; Meyer, Fredric B.; Marsh, W. Richard; Worrell, Gregory A.

2015-01-01

The establishment of memories involves reactivation of waking neuronal activity patterns and strengthening of associated neural circuits during slow-wave sleep (SWS), a process known as “cellular consolidation” (Dudai and Morris, 2013). Reactivation of neural activity patterns during waking behaviors that occurs on a timescale of seconds to minutes is thought to constitute memory recall (O'Keefe and Nadel, 1978), whereas consolidation of memory traces may be revealed and served by correlated firing (reactivation) that appears during sleep under conditions suitable for synaptic modification (Buhry et al., 2011). Although reactivation has been observed in human neuronal recordings (Gelbard-Sagiv et al., 2008; Miller et al., 2013), reactivation during sleep has not, likely because data are difficult to obtain and the effect is subtle. Seizures, however, provide intense and synchronous, yet sparse activation (Bower et al., 2012) that could produce a stronger consolidation effect if seizures activate learning-related mechanisms similar to those activated by learned tasks. Continuous wide-bandwidth recordings from patients undergoing intracranial monitoring for drug-resistant epilepsy revealed reactivation of seizure-related neuronal activity during subsequent SWS, but not wakefulness. Those neuronal assemblies that were most strongly activated during seizures showed the largest correlation changes, suggesting that consolidation selectively strengthened neuronal circuits activated by seizures. These results suggest that seizures “hijack” physiological learning mechanisms and also suggest a novel epilepsy therapy targeting neuronal dynamics during post-seizure sleep. PMID:25609617

Total OH reactivity study from VOC photochemical oxidation in the SAPHIR chamber

NASA Astrophysics Data System (ADS)

Yu, Z.; Tillmann, R.; Hohaus, T.; Fuchs, H.; Novelli, A.; Wegener, R.; Kaminski, M.; Schmitt, S. H.; Wahner, A.; Kiendler-Scharr, A.

2015-12-01

It is well known that hydroxyl radicals (OH) act as a dominant reactive species in the degradation of VOCs in the atmosphere. In recent field studies, directly measured total OH reactivity often showed poor agreement with OH reactivity calculated from VOC measurements (e.g. Nölscher et al., 2013; Lu et al., 2012a). This "missing OH reactivity" is attributed to unaccounted biogenic VOC emissions and/or oxidation products. The comparison of total OH reactivity being directly measured and calculated from single component measurements of VOCs and their oxidation products gives us a further understanding on the source of unmeasured reactive species in the atmosphere. This allows also the determination of the magnitude of the contribution of primary VOC emissions and their oxidation products to the missing OH reactivity. A series of experiments was carried out in the atmosphere simulation chamber SAPHIR in Jülich, Germany, to explore in detail the photochemical degradation of VOCs (isoprene, ß-pinene, limonene, and D6-benzene) by OH. The total OH reactivity was determined from the measurement of VOCs and their oxidation products by a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS) with a GC/MS/FID system, and directly measured by a laser-induced fluorescence (LIF) at the same time. The comparison between these two total OH reactivity measurements showed an increase of missing OH reactivity in the presence of oxidation products of VOCs, indicating a strong contribution to missing OH reactivity from uncharacterized oxidation products.

Hippocampal memory consolidation during sleep: a comparison of mammals and birds

PubMed Central

Rattenborg, Niels C.; Martinez-Gonzalez, Dolores; Roth, Timothy C.; Pravosudov, Vladimir V.

2010-01-01

The transition from wakefulness to sleep is marked by pronounced changes in brain activity. The brain rhythms that characterize the two main types of mammalian sleep, slow-wave sleep (SWS) and rapid eye movement (REM) sleep, are thought to be involved in the functions of sleep. In particular, recent theories suggest that the synchronous slow-oscillation of neocortical neuronal membrane potentials, the defining feature of SWS, is involved in processing information acquired during wakefulness. According to the Standard Model of memory consolidation, during wakefulness the hippocampus receives input from neocortical regions involved in the initial encoding of an experience and binds this information into a coherent memory trace that is then transferred to the neocortex during SWS where it is stored and integrated within preexisting memory traces. Evidence suggests that this process selectively involves direct connections from the hippocampus to the prefrontal cortex (PFC), a multimodal, high-order association region implicated in coordinating the storage and recall of remote memories in the neocortex. The slow-oscillation is thought to orchestrate the transfer of information from the hippocampus by temporally coupling hippocampal sharp-wave/ripples (SWRs) and thalamocortical spindles. SWRs are synchronous bursts of hippocampal activity, during which waking neuronal firing patterns are reactivated in the hippocampus and neocortex in a coordinated manner. Thalamocortical spindles are brief 7–14 Hz oscillations that may facilitate the encoding of information reactivated during SWRs. By temporally coupling the readout of information from the hippocampus with conditions conducive to encoding in the neocortex, the slow-oscillation is thought to mediate the transfer of information from the hippocampus to the neocortex. Although several lines of evidence are consistent with this function for mammalian SWS, it is unclear whether SWS serves a similar function in birds, the only taxonomic group other than mammals to exhibit SWS and REM sleep. Based on our review of research on avian sleep, neuroanatomy, and memory, although involved in some forms of memory consolidation, avian sleep does not appear to be involved in transferring hippocampal memories to other brain regions. Despite exhibiting the slow-oscillation, SWRs and spindles have not been found in birds. Moreover, although birds independently evolved a brain region – the caudolateral nidopallium (NCL) – involved in performing high-order cognitive functions similar to those performed by the PFC, direct connections between the NCL and hippocampus have not been found in birds, and evidence for the transfer of information from the hippocampus to the NCL or other extra-hippocampal regions is lacking. Although based on the absence of evidence for various traits, collectively, these findings suggest that unlike mammalian SWS, avian SWS may not be involved in transferring memories from the hippocampus. Furthermore, it suggests that the slow-oscillation, the defining feature of mammalian and avian SWS, may serve a more general function independent of that related to coordinating the transfer of information from the hippocampus to the PFC in mammals. Given that SWS is homeostatically regulated (a process intimately related to the slow-oscillation) in mammals and birds, functional hypotheses linked to this process may apply to both taxonomic groups. PMID:21070585

Hippocampal memory consolidation during sleep: a comparison of mammals and birds.

PubMed

Rattenborg, Niels C; Martinez-Gonzalez, Dolores; Roth, Timothy C; Pravosudov, Vladimir V

2011-08-01

The transition from wakefulness to sleep is marked by pronounced changes in brain activity. The brain rhythms that characterize the two main types of mammalian sleep, slow-wave sleep (SWS) and rapid eye movement (REM) sleep, are thought to be involved in the functions of sleep. In particular, recent theories suggest that the synchronous slow-oscillation of neocortical neuronal membrane potentials, the defining feature of SWS, is involved in processing information acquired during wakefulness. According to the Standard Model of memory consolidation, during wakefulness the hippocampus receives input from neocortical regions involved in the initial encoding of an experience and binds this information into a coherent memory trace that is then transferred to the neocortex during SWS where it is stored and integrated within preexisting memory traces. Evidence suggests that this process selectively involves direct connections from the hippocampus to the prefrontal cortex (PFC), a multimodal, high-order association region implicated in coordinating the storage and recall of remote memories in the neocortex. The slow-oscillation is thought to orchestrate the transfer of information from the hippocampus by temporally coupling hippocampal sharp-wave/ripples (SWRs) and thalamocortical spindles. SWRs are synchronous bursts of hippocampal activity, during which waking neuronal firing patterns are reactivated in the hippocampus and neocortex in a coordinated manner. Thalamocortical spindles are brief 7-14 Hz oscillations that may facilitate the encoding of information reactivated during SWRs. By temporally coupling the readout of information from the hippocampus with conditions conducive to encoding in the neocortex, the slow-oscillation is thought to mediate the transfer of information from the hippocampus to the neocortex. Although several lines of evidence are consistent with this function for mammalian SWS, it is unclear whether SWS serves a similar function in birds, the only taxonomic group other than mammals to exhibit SWS and REM sleep. Based on our review of research on avian sleep, neuroanatomy, and memory, although involved in some forms of memory consolidation, avian sleep does not appear to be involved in transferring hippocampal memories to other brain regions. Despite exhibiting the slow-oscillation, SWRs and spindles have not been found in birds. Moreover, although birds independently evolved a brain region--the caudolateral nidopallium (NCL)--involved in performing high-order cognitive functions similar to those performed by the PFC, direct connections between the NCL and hippocampus have not been found in birds, and evidence for the transfer of information from the hippocampus to the NCL or other extra-hippocampal regions is lacking. Although based on the absence of evidence for various traits, collectively, these findings suggest that unlike mammalian SWS, avian SWS may not be involved in transferring memories from the hippocampus. Furthermore, it suggests that the slow-oscillation, the defining feature of mammalian and avian SWS, may serve a more general function independent of that related to coordinating the transfer of information from the hippocampus to the PFC in mammals. Given that SWS is homeostatically regulated (a process intimately related to the slow-oscillation) in mammals and birds, functional hypotheses linked to this process may apply to both taxonomic groups. © 2010 The Authors. Biological Reviews © 2010 Cambridge Philosophical Society.

Mimicking muscle activity with electrical stimulation

NASA Astrophysics Data System (ADS)

Johnson, Lise A.; Fuglevand, Andrew J.

2011-02-01

Functional electrical stimulation is a rehabilitation technology that can restore some degree of motor function in individuals who have sustained a spinal cord injury or stroke. One way to identify the spatio-temporal patterns of muscle stimulation needed to elicit complex upper limb movements is to use electromyographic (EMG) activity recorded from able-bodied subjects as a template for electrical stimulation. However, this requires a transfer function to convert the recorded (or predicted) EMG signals into an appropriate pattern of electrical stimulation. Here we develop a generalized transfer function that maps EMG activity into a stimulation pattern that modulates muscle output by varying both the pulse frequency and the pulse amplitude. We show that the stimulation patterns produced by this transfer function mimic the active state measured by EMG insofar as they reproduce with good fidelity the complex patterns of joint torque and joint displacement.

Pool-Boiling Heat-Transfer Enhancement on Cylindrical Surfaces with Hybrid Wettable Patterns.

PubMed

Kumar C S, Sujith; Chang, Yao Wen; Chen, Ping-Hei

2017-04-10

In this study, pool-boiling heat-transfer experiments were performed to investigate the effect of the number of interlines and the orientation of the hybrid wettable pattern. Hybrid wettable patterns were produced by coating superhydrophilic SiO2 on a masked, hydrophobic, cylindrical copper surface. Using de-ionized (DI) water as the working fluid, pool-boiling heat-transfer studies were conducted on the different surface-treated copper cylinders of a 25-mm diameter and a 40-mm length. The experimental results showed that the number of interlines and the orientation of the hybrid wettable pattern influenced the wall superheat and the HTC. By increasing the number of interlines, the HTC was enhanced when compared to the plain surface. Images obtained from the charge-coupled device (CCD) camera indicated that more bubbles formed on the interlines as compared to other parts. The hybrid wettable pattern with the lowermost section being hydrophobic gave the best heat-transfer coefficient (HTC). The experimental results indicated that the bubble dynamics of the surface is an important factor that determines the nucleate boiling.

Science Notes.

ERIC Educational Resources Information Center

Talbot, Chris; And Others

1991-01-01

Twenty science experiments are presented. Topics include recombinant DNA, physiology, nucleophiles, reactivity series, molar volume of gases, spreadsheets in chemistry, hydrogen bonding, composite materials, radioactive decay, magnetism, speed, charged particles, compression waves, heat transfer, Ursa Major, balloons, current, and expansion of…

Intergenerational transfers in the era of HIV/AIDS: Evidence from rural Malawi

PubMed Central

Kohler, Iliana V.; Kohler, Hans-Peter; Anglewicz, Philip; Behrman, Jere R.

2013-01-01

BACKGROUND Intergenerational transfer patterns in sub-Saharan Africa are poorly understood, despite the alleged importance of support networks to ameliorate the complex implications of the HIV/AIDS epidemic for families. OBJECTIVE There is a considerable need for research on intergenerational support networks and transfers to better understand the mechanisms through which extended families cope with the HIV/AIDS epidemic and potentially alleviate some of its consequences in sub-Saharan Africa, and to comprehend how transfers respond—or not—to perceptions about own and other family members' health. METHODS Using the 2008 round of the Malawi Longitudinal Study of Families and Health (MLSFH), we estimate the age patterns and the multiple directions of financial and non-financial transfer flows in rural Malawi—from prime-aged respondents to their elderly parents and adult children age 15 and up. We also estimate the social, demographic and economic correlates of financial and non-financial transfers of financial intergenerational transfers in this context. RESULTS AND CONCLUSIONS Our findings are that: (1) intergenerational financial and non-financial transfers are widespread and a key characteristic of family relationships in rural Malawi; (2) downward and upward transfers are importantly constrained and determined by the availability of transfer partners (parents or adult children); (3) financial net transfers are strongly age-patterned and the middle generations are net-providers of transfers; (4) non-financial transfers are based on mutual assistance rather than reallocation of resources; and (5) intergenerational transfers are generally not related to health status, including HIV positive status. PMID:23606809

Ab initio molecular dynamics of the reactivity of vitamin C toward hydroxyl and HO₂/O⁻₂ radicals.

PubMed

Lespade, Laure

2017-11-21

Vitamin C is one of the most abundant exogenous antioxidants in the cell, and it is of the utmost importance to elucidate its mechanism of action against radicals. In this study, the reactivity of vitamin C toward OH and [Formula: see text] radicals in aqueous medium was analyzed by ab initio molecular dynamics using CPMD code. The simulations led to results similar to those of static studies or experiments for the pair of [Formula: see text] radicals but bring new insights for the reactivity with hydroxyl radical: the reaction takes place before the formation of an adduct and consists of two steps: first an electron is transferred to hydroxyl radical and then the ascorbyl radical loses a proton. Graphical Abstract Reactivity of vitamin C toward hydroxyl and [Formula: see text] radicals.

A mechanistic model of heat transfer for gas-liquid flow in vertical wellbore annuli.

PubMed

Yin, Bang-Tang; Li, Xiang-Fang; Liu, Gang

2018-01-01

The most prominent aspect of multiphase flow is the variation in the physical distribution of the phases in the flow conduit known as the flow pattern. Several different flow patterns can exist under different flow conditions which have significant effects on liquid holdup, pressure gradient and heat transfer. Gas-liquid two-phase flow in an annulus can be found in a variety of practical situations. In high rate oil and gas production, it may be beneficial to flow fluids vertically through the annulus configuration between well tubing and casing. The flow patterns in annuli are different from pipe flow. There are both casing and tubing liquid films in slug flow and annular flow in the annulus. Multiphase heat transfer depends on the hydrodynamic behavior of the flow. There are very limited research results that can be found in the open literature for multiphase heat transfer in wellbore annuli. A mechanistic model of multiphase heat transfer is developed for different flow patterns of upward gas-liquid flow in vertical annuli. The required local flow parameters are predicted by use of the hydraulic model of steady-state multiphase flow in wellbore annuli recently developed by Yin et al. The modified heat-transfer model for single gas or liquid flow is verified by comparison with Manabe's experimental results. For different flow patterns, it is compared with modified unified Zhang et al. model based on representative diameters.

Matrix photochemistry of small molecules: Influencing reaction dynamics on electronically excited hypersurfaces

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

Laursen, S.L.

Investigations of chemical reactions on electronically excited reaction surfaces are presented. The role of excited-surface multiplicity is of particular interest, as are chemical reactivity and energy transfer in systems in which photochemistry is initiated through a metal atom sensitizer.'' Two approaches are employed: A heavy-atom matrix affords access to forbidden triplet reaction surfaces, eliminating the need for a potentially reactive sensitizer. Later, the role of the metal atom in the photosensitization process is examined directly.

Single-molecule electrocatalysis by single-walled carbon nanotubes.

PubMed

Xu, Weilin; Shen, Hao; Kim, Yoon Ji; Zhou, Xiaochun; Liu, Guokun; Park, Jiwoong; Chen, Peng

2009-12-01

We report a single-molecule fluorescence study of electrocatalysis by single-walled carbon nanotubes (SWNTs) at single-reaction resolution. Applying super-resolution optical imaging, we find that the electrocatalysis occurs at discrete, nanometer-dimension sites on SWNTs. Single-molecule kinetic analysis leads to an electrocatalytic mechanism, allowing quantification of the reactivity and heterogeneity of individual reactive sites. Combined with conductivity measurements, this approach will be powerful to interrogate how the electronic structure of SWNTs affects the electrocatalytic interfacial charge transfer, a process fundamental to photoelectrochemical cells.

Studies on photoinduced H-atom and electron transfer reactions of o-naphthoquinones by laser flash photolysis.

PubMed

Pan, Yang; Fu, Yao; Liu, Shaoxiong; Yu, Haizhu; Gao, Yuhe; Guo, Qingxiang; Yu, Shuqin

2006-06-15

The quenching of the triplets of 1,2-naphthoquinone (NQ) and 1,2-naphthoquinone-4-sulfonic acid sodium salt (NQS) by various electron and H-atom donors was investigated by laser flash photolysis measurement in acetonitrile and benzene. The results showed that the reactivities and configurations of 3NQ* (3NQS*) are governed by solvent polarity. All the quenching rate constants (kq) measured in benzene are larger than those in acetonitrile. The SO3Na substituent at the C-4 position of NQS makes 3NQS* more reactive than 3NQ* in electron/H-atom transfer reactions. Large differences of kq values were discovered in H-atom transfer reactions for alcohols and phenols, which can be explained by different H-abstraction mechanisms. Detection of radical cations of amines/anilines in time-resolved transient absorption spectra confirms an electron transfer mechanism. Triplets are identified as precursors of formed radical anions of NQ and NQS in photoinduced reactions. The dependence of electron transfer rate constants on the free energy changes (DeltaG) was treated by using the Rehm-Weller equation. For the four anilines with different substituents on the para or meta position of amidocyanogen, good correlation between log kq values with Hammett sigma constants testifies the correctness of empirical Hammett equation. Charge density distributions, adiabatic ionization/affinity potentials and redox potentials of NQ (NQS) and some quenchers were studied by quantum chemistry calculation.

Water reactive hydrogen fuel cell power system

DOEpatents

Wallace, Andrew P; Melack, John M; Lefenfeld, Michael

2014-01-21

A water reactive hydrogen fueled power system includes devices and methods to combine reactant fuel materials and aqueous solutions to generate hydrogen. The generated hydrogen is converted in a fuel cell to provide electricity. The water reactive hydrogen fueled power system includes a fuel cell, a water feed tray, and a fuel cartridge to generate power for portable power electronics. The removable fuel cartridge is encompassed by the water feed tray and fuel cell. The water feed tray is refillable with water by a user. The water is then transferred from the water feed tray into a fuel cartridge to generate hydrogen for the fuel cell which then produces power for the user.

Water reactive hydrogen fuel cell power system

DOEpatents

Wallace, Andrew P; Melack, John M; Lefenfeld, Michael

2014-11-25

A water reactive hydrogen fueled power system includes devices and methods to combine reactant fuel materials and aqueous solutions to generate hydrogen. The generated hydrogen is converted in a fuel cell to provide electricity. The water reactive hydrogen fueled power system includes a fuel cell, a water feed tray, and a fuel cartridge to generate power for portable power electronics. The removable fuel cartridge is encompassed by the water feed tray and fuel cell. The water feed tray is refillable with water by a user. The water is then transferred from the water feed tray into the fuel cartridge to generate hydrogen for the fuel cell which then produces power for the user.

An improved method for the calculation of Near-Field Acoustic Radiation Modes

NASA Astrophysics Data System (ADS)

Liu, Zu-Bin; Maury, Cédric

2016-02-01

Sensing and controlling Acoustic Radiation Modes (ARMs) in the near-field of vibrating structures is of great interest for broadband noise reduction or enhancement, as ARMs are velocity distributions defined over a vibrating surface, that independently and optimally contribute to the acoustic power in the acoustic field. But present methods only provide far-field ARMs (FFARMs) that are inadequate for the acoustic near-field problem. The Near-Field Acoustic Radiation Modes (NFARMs) are firstly studied with an improved numerical method, the Pressure-Velocity method, which rely on the eigen decomposition of the acoustic transfers between the vibrating source and a conformal observation surface, including sound pressure and velocity transfer matrices. The active and reactive parts of the sound power are separated and lead to the active and reactive ARMs. NFARMs are studied for a 2D baffled beam and for a 3D baffled plate, and so as differences between the NFARMS and the classical FFARMs. Comparisons of the NFARMs are analyzed when varying frequency and observation distance to the source. It is found that the efficiencies and shapes of the optimal active ARMs are independent on the distance while that of the reactive ones are distinctly related on.

NEW 3D TECHNIQUES FOR RANKING AND PRIORITIZATION OF CHEMICAL INVENTORIES

EPA Science Inventory

New three-dimensional quantitative structure activity (3-D QSAR) techniques for prioritizing chemical inventories for endocrine activity will be presented. The Common Reactivity Pattern (COREPA) approach permits identification of common steric and/or electronic patterns associate...

Transfer fault earthquake in compressionally reactivated back-arc failed rift: 1948 Fukui earthquake (M7.1), Japan

NASA Astrophysics Data System (ADS)

Ishiyama, Tatsuya; Kato, Naoko; Sato, Hiroshi; Koshiya, Shin

2017-04-01

Back-arc rift structures in many subduction zones are recognized as mechanically and thermally weak zones that possibly play important roles in strain accommodation at later post-rift stages within the overriding plates. In case of Miocene back-arc failed rift structures in the Sea of Japan in the Eurasian-Pacific subduction system, the mechanical contrasts between the crustal thrust wedges of the pre-rift continental crust and high velocity lower crust have fundamentally controlled the styles of post-rift, Quaternary active deformation (Ishiyama et al. 2016). In this study, we show a possibility that strike-slip M>7 devastating earthquakes in this region have been gregion enerated by reactivation of transfer faults highly oblique to the rift axes. The 1948 Fukui earthquake (M7.1), onshore shallow seismic event with a strike-slip faulting mechanism (Kanamori, 1973), resulted in more than 3,500 causalities and destructive damages on the infrastructures. While geophysical analyses on geodetic measurements based on leveling and triangulation networks clearly show coseismic left-lateral fault slip on a NNW striking vertical fault plane beneath the Fukui plain (Sagiya, 1999), no evidence for coseismic surface rupture has been identified based on both post-earthquake intensive fieldwork and recent reexamination of stereopair interpretations using 1/3,000 aerial photographs taken in 1948 (Togo et al., 2000). To find recognizable fault-related structures that deform Neogene basin fill sediments, we collected new 9.6-km-long high-resolution seismic reflection data across the geodetically estimated fault plane and adjacent subparallel active strike slip faults, using 925 offline recorders and Envirovib truck as a seismic source. A depth-converted section to 1.5 km depth contains discontinuous seismic reflectors correlated to Miocene volcaniclastic deposits and depression of the overlying Plio-Pleistocene sediments above the geodetically determined fault plane. We interpreted these structural features as negative flower structures related to the strike-slip fault activated during the 1948 seismic event. Locations of these strike-slip faults are consistent with Miocene transfer faults that offset syn- and post-rift sediments and underlying crustal wedges, suggesting that reactivation of transfer faults resulted in active strike-slip faulting including the 1948 seismic event. These findings demonstrate that not only rift-related normal faults but also transfer faults have strong structural inheritances and played essential roles on their active reactivation and seismicity during the post-rift stress regime.

Improvement of resist profile roughness in bilayer resist process

NASA Astrophysics Data System (ADS)

Jeong, Chang-Young; Ryu, Sang-Wook; Park, Ki-Yeop; Lee, Won-Kyu; Lee, Seung-Woog; Lee, Dai-Hoon

2000-06-01

The bi-layer resist (BLR) process, which first accomplish imaging on a thin top layer and transfer it down to a thick organic layer, is one of newly emerging patterning techniques in silicon processing. In this work, we studied the lithographic performance of the BLR process adopting FK- SPTM (Fujifilm Olin Co.) as top layer material and various organic material as bottom layer. Generally, considerable advantages of planarization, reduced substrate reflection, improved process latitude, and of enhanced resolution are achieved. However, the resolution and the process latitude are highly affected by surface interaction between the top resist and the bottom material. Moreover, the BLR process has a sidewall roughness problem related to the material factors of the resist and the degraded aerial image contrast, which can affect the reliability of the device. We found that thermal curing treatment applied after development with the consideration of the glass transition temperature are very effective in reducing the line edge roughness. More smooth and steep patterning is achieved by the thermal treatment. The linewidth controllability is below 10 nm and the k1 value is reduced from 0.5 down to 0.32 in this process. The reactive ion etching adopting O2 gas demonstrated selectivity of the top resist over bottom material more than 15:1, together with residue-free and vertical wall profile.

Use of KRS-XE positive chemically amplified resist for optical mask manufacturing

NASA Astrophysics Data System (ADS)

Ashe, Brian; Deverich, Christina; Rabidoux, Paul A.; Peck, Barbara; Petrillo, Karen E.; Angelopoulos, Marie; Huang, Wu-Song; Moreau, Wayne M.; Medeiros, David R.

2002-03-01

The traditional mask making process uses chain scission-type resists such as PBS, poly(butene-1-sulfone), and ZEP, poly(methyl a-chloroacrylate-co-a-methylstyrene) for making masks with dimensions greater than 180nm. PBS resist requires a wet etch process to produce patterns in chrome. ZEP was employed for dry etch processing to meet the requirements of shrinking dimensions, optical proximity corrections and phase shift masks. However, ZEP offers low contrast, marginal etch resistance, organic solvent development, and concerns regarding resist heating with its high dose requirements1. Chemically Amplified Resist (CAR) systems are a very good choice for dimensions less than 180nm because of their high sensitivity and contrast, high resolution, dry etch resistance, aqueous development, and process latitude2. KRS-XE was developed as a high contrast CA resist based on ketal protecting groups that eliminate the need for post exposure bake (PEB). This resist can be used for a variety of electron beam exposures, and improves the capability to fabricate masks for devices smaller than 180nm. Many factors influence the performance of resists in mask making such as post apply bake, exposure dose, resist develop, and post exposure bake. These items will be discussed as well as the use of reactive ion etching (RIE) selectivity and pattern transfer.

Turbulent flame-wall interaction: a DNS study

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

Chen, Jackie; Hawkes, Evatt R; Sankaran, Ramanan

2010-01-01

A turbulent flame-wall interaction (FWI) configuration is studied using three-dimensional direct numerical simulation (DNS) and detailed chemical kinetics. The simulations are used to investigate the effects of the wall turbulent boundary layer (i) on the structure of a hydrogen-air premixed flame, (ii) on its near-wall propagation characteristics and (iii) on the spatial and temporal patterns of the convective wall heat flux. Results show that the local flame thickness and propagation speed vary between the core flow and the boundary layer, resulting in a regime change from flamelet near the channel centreline to a thickened flame at the wall. This findingmore » has strong implications for the modelling of turbulent combustion using Reynolds-averaged Navier-Stokes or large-eddy simulation techniques. Moreover, the DNS results suggest that the near-wall coherent turbulent structures play an important role on the convective wall heat transfer by pushing the hot reactive zone towards the cold solid surface. At the wall, exothermic radical recombination reactions become important, and are responsible for approximately 70% of the overall heat release rate at the wall. Spectral analysis of the convective wall heat flux provides an unambiguous picture of its spatial and temporal patterns, previously unobserved, that is directly related to the spatial and temporal characteristic scalings of the coherent near-wall turbulent structures.« less

Different blocking agents cause variation in the immunologic detection of proteins transferred to nitrocellulose membranes.

PubMed

Spinola, S M; Cannon, J G

1985-07-16

We compared bovine serum albumin, commercial non-fat dry milk, and Tween 20 as blocking agents for immunologic probing of bacterial proteins transferred to nitrocellulose sheets. There were quantitative and qualitative differences in antigens detected that depended on which blocking agents were used. We suggest that several methods for blocking and washing nitrocellulose should be compared when Western blotting is used to detect immunologically reactive proteins.

Children's Patterns of Emotional Reactivity to Conflict as Explanatory Mechanisms in Links between Interpartner Aggression and Child Physiological Functioning

ERIC Educational Resources Information Center

Davies, Patrick T.; Sturge-Apple, Melissa L.; Cicchetti, Dante; Manning, Liviah G.; Zale, Emily

2009-01-01

Background: This paper examined children's fearful, sad, and angry reactivity to interparental conflict as mediators of associations between their exposure to interparental aggression and physiological functioning. Methods: Participants included 200 toddlers and their mothers. Assessments of interparental aggression and children's emotional…

Proactive and Reactive Aggressive Behavior in Bullying: The Role of Values

ERIC Educational Resources Information Center

Jara, Natalia; Casas, Jose A.; Ortega-Ruiz, Rosario

2017-01-01

The study of violence and bullying in schools is a line of scientific research that has contributed significantly to knowledge on human aggressiveness, especially in children and adolescents. This article shows that there are two patterns of aggressive behavior: proactive and reactive. Both are present in bullying, as are other psychological…

Thermochemistry and Dynamics of Reactive Species: Nitrogen-rich Substituted Heterocycles, and Anionic Components of Ionic Liquids

DTIC Science & Technology

2012-02-23

Transfer and Anionic σ-Adduct Formation ," J. Am. Soc. Mass Spectrom. 22, 1260-72 (2011). 6. S. W. Wren, K. M. Vogelhuber, J. M. Garver, S. Kato, L...Lineberger, and V. M. Bierbaum, "Gas Phase Reactions of 1,3,5-Triazine: Proton Transfer, Hydride Transfer and Anionic σ-Adduct Formation ," J. Am. Soc. Mass...been used to study the furanide anion (C4H3O−), dihalomethyl anions (CHX2−, where X = Cl, Br, and I), the cyanopolyyne anions HC4N− and HCCN

Tape transfer atomization patterning of liquid alloys for microfluidic stretchable wireless power transfer.

PubMed

Jeong, Seung Hee; Hjort, Klas; Wu, Zhigang

2015-02-12

Stretchable electronics offers unsurpassed mechanical compliance on complex or soft surfaces like the human skin and organs. To fully exploit this great advantage, an autonomous system with a self-powered energy source has been sought for. Here, we present a new technology to pattern liquid alloys on soft substrates, targeting at fabrication of a hybrid-integrated power source in microfluidic stretchable electronics. By atomized spraying of a liquid alloy onto a soft surface with a tape transferred adhesive mask, a universal fabrication process is provided for high quality patterns of liquid conductors in a meter scale. With the developed multilayer fabrication technique, a microfluidic stretchable wireless power transfer device with an integrated LED was demonstrated, which could survive cycling between 0% and 25% strain over 1,000 times.

Tape Transfer Atomization Patterning of Liquid Alloys for Microfluidic Stretchable Wireless Power Transfer

PubMed Central

Jeong, Seung Hee; Hjort, Klas; Wu, Zhigang

2015-01-01

Stretchable electronics offers unsurpassed mechanical compliance on complex or soft surfaces like the human skin and organs. To fully exploit this great advantage, an autonomous system with a self-powered energy source has been sought for. Here, we present a new technology to pattern liquid alloys on soft substrates, targeting at fabrication of a hybrid-integrated power source in microfluidic stretchable electronics. By atomized spraying of a liquid alloy onto a soft surface with a tape transferred adhesive mask, a universal fabrication process is provided for high quality patterns of liquid conductors in a meter scale. With the developed multilayer fabrication technique, a microfluidic stretchable wireless power transfer device with an integrated LED was demonstrated, which could survive cycling between 0% and 25% strain over 1,000 times. PMID:25673261

Surface Reactivity Enhancement on a Pd/Bi2Te3 Heterostructure through Robust Topological Surface States

PubMed Central

He, Qing Lin; Lai, Ying Hoi; Lu, Yao; Law, Kam Tuen; Sou, Iam Keong

2013-01-01

We present a study of the surface reactivity of a Pd/Bi2Te3 thin film heterostructure. The topological surface states from Bi2Te3, being delocalized and robust owing to their topological natures, were found to act as an effective electron bath that significantly enhances the surface reactivity of palladium in the presence of two oxidizing agents, oxygen and tellurium respectively, which is consistent with a theoretical calculation. The surface reactivity of the adsorbed tellurium on this heterostructure is also intensified possibly benefitted from the effective transfer of the bath electrons. A partially inserted iron ferromagnetic layer at the interface of this heterostructure was found to play two competing roles arising from the higher-lying d-band center of the Pd/Fe bilayer and the interaction between the ferromagnetism and the surface spin texture of Bi2Te3 on the surface reactivity and their characteristics also demonstrate that the electron bath effect is long-lasting against accumulated thickness of adsorbates. PMID:23970163

Briefly Cuing Memories Leads to Suppression of Their Neural Representations

PubMed Central

Norman, Kenneth A.

2014-01-01

Previous studies have linked partial memory activation with impaired subsequent memory retrieval (e.g., Detre et al., 2013) but have not provided an account of this phenomenon at the level of memory representations: How does partial activation change the neural pattern subsequently elicited when the memory is cued? To address this question, we conducted a functional magnetic resonance imaging (fMRI) experiment in which participants studied word-scene paired associates. Later, we weakly reactivated some memories by briefly presenting the cue word during a rapid serial visual presentation (RSVP) task; other memories were more strongly reactivated or not reactivated at all. We tested participants' memory for the paired associates before and after RSVP. Cues that were briefly presented during RSVP triggered reduced levels of scene activity on the post-RSVP memory test, relative to the other conditions. We used pattern similarity analysis to assess how representations changed as a function of the RSVP manipulation. For briefly cued pairs, we found that neural patterns elicited by the same cue on the pre- and post-RSVP tests (preA–postA; preB–postB) were less similar than neural patterns elicited by different cues (preA–postB; preB–postA). These similarity reductions were predicted by neural measures of memory activation during RSVP. Through simulation, we show that our pattern similarity results are consistent with a model in which partial memory activation triggers selective weakening of the strongest parts of the memory. PMID:24899722

Pathogenic Fungi Regulate Immunity by Inducing Neutrophilic Myeloid-Derived Suppressor Cells

PubMed Central

Rieber, Nikolaus; Singh, Anurag; Öz, Hasan; Carevic, Melanie; Bouzani, Maria; Amich, Jorge; Ost, Michael; Ye, Zhiyong; Ballbach, Marlene; Schäfer, Iris; Mezger, Markus; Klimosch, Sascha N.; Weber, Alexander N.R.; Handgretinger, Rupert; Krappmann, Sven; Liese, Johannes; Engeholm, Maik; Schüle, Rebecca; Salih, Helmut Rainer; Marodi, Laszlo; Speckmann, Carsten; Grimbacher, Bodo; Ruland, Jürgen; Brown, Gordon D.; Beilhack, Andreas; Loeffler, Juergen; Hartl, Dominik

2015-01-01

Summary Despite continuous contact with fungi, immunocompetent individuals rarely develop pro-inflammatory antifungal immune responses. The underlying tolerogenic mechanisms are incompletely understood. Using both mouse models and human patients, we show that infection with the human pathogenic fungi Aspergillus fumigatus and Candida albicans induces a distinct subset of neutrophilic myeloid-derived suppressor cells (MDSCs), which functionally suppress T and NK cell responses. Mechanistically, pathogenic fungi induce neutrophilic MDSCs through the pattern recognition receptor Dectin-1 and its downstream adaptor protein CARD9. Fungal MDSC induction is further dependent on pathways downstream of Dectin-1 signaling, notably reactive oxygen species (ROS) generation as well as caspase-8 activity and interleukin-1 (IL-1) production. Additionally, exogenous IL-1β induces MDSCs to comparable levels observed during C. albicans infection. Adoptive transfer and survival experiments show that MDSCs are protective during invasive C. albicans infection, but not A. fumigatus infection. These studies define an innate immune mechanism by which pathogenic fungi regulate host defense. PMID:25771792

Water-Rock Interaction Simulations of Iron Oxide Mobilization and Precipitation: Implications of Cross-diffusion Reactions for Terrestrial and Mars 'Blueberry' Hematite Concretions

NASA Astrophysics Data System (ADS)

Park, A. J.; Chan, M. A.; Parry, W. T.

2005-12-01

Modeling of how terrestrial concretions form can provide valuable insights into understanding water-rock interactions that led to the formation of hematite concretions at Meridiani Planum, Mars. Numerical simulations of iron oxide concretions in the Jurassic Navajo Sandstone of southern Utah provide physical and chemical input parameters for emulating conditions that may have prevailed on Mars. In the terrestrial example, iron oxide coatings on eolian sand grains are reduced and mobilized by methane or petroleum. Precipitation of goethite or hematite occurs as Fe interacts with oxygen. Conditions that produced Navajo Sandstone concretions can range from a regional scale that is strongly affected by advection of large pore volumes of water, to small sub-meter scale features that are dominantly controlled by diffusive processes. Hematite concretions are results of a small-scale cross-diffusional process, where Fe and oxygen are supplied from two opposite sides from the 'middle' zone of mixing where concretions precipitate. This is an ideal natural system where Liesegang banding and other self-organized patterns can evolve. A complicating variable here is the sedimentologic (both mineralogic and textural) heterogeneity that, in reality, may be the key factor controlling the nucleation and precipitation habits (including possible competitive growth) of hematite concretions. Sym.8 water-rock interaction simulator program was used for the Navajo Sandstone concretions. Sym.8 is a water-rock simulator that accounts for advective and diffusive mass-transfer, and equilibrium and kinetic reactions. The program uses a dynamic composite media texture model to address changing sediment composition and texture to be consistent with the reaction progress. Initial one-dimensional simulation results indicate precipitation heterogeneity in the range of sub-meters, e.g., possible banding and distribution of iron oxide nodules may be centimeters apart for published diffusivities and water chemistries of the solutes involved. This modeling effort underscores the importance of coupled reactions and mass-transfer in formation of iron oxide concretions in both terrestrial and Mars sediments. Methane is interpreted to be the reactive agent that mobilizes iron in Navajo Sandstone. On Mars volatile volcanic gases may be the reactive agents that mobilize iron from volcanic sediments. In both cases, subsequent diffusive and advective mass-transfer coupled to nonlinear chemical reactions produces localized precipitates.

Methodology for evaluating pattern transfer completeness in inkjet printing with irregular edges

NASA Astrophysics Data System (ADS)

Huang, Bo-Cin; Chan, Hui-Ju; Hong, Jian-Wei; Lo, Cheng-Yao

2016-06-01

A methodology for quantifying and qualifying pattern transfer completeness in inkjet printing through examining both pattern dimensions and pattern contour deviations from reference design is proposed, which enables scientifically identifying and evaluating inkjet-printed lines, corners, circles, ellipses, and spirals with irregular edges of bulging, necking, and unpredictable distortions resulting from different process conditions. This methodology not only avoids differences in individual perceptions of ambiguous pattern distortions but also indicates the systematic effects of mechanical stresses applied in different directions to a polymer substrate, and is effective for both optical and electrical microscopy in direct and indirect lithography or lithography-free patterning.

Recent aspects of nitration: New preparative methods and mechanistic studies (A Review)

PubMed Central

Olah, George A.; Narang, Subhash C.; Olah, Judith A.; Lammertsma, Koop

1982-01-01

New preparative methods of electrophilic nitration and transfer nitration are reviewed, including reactions relating to the ambident reactivity of the nitronium ion. Recent aspects of the mechanism of electrophilic aromatic substitution are discussed.

3D-QSPR Method of Computational Technique Applied on Red Reactive Dyes by Using CoMFA Strategy

PubMed Central

Mahmood, Uzma; Rashid, Sitara; Ali, S. Ishrat; Parveen, Rasheeda; Zaheer-ul-Haq; Ambreen, Nida; Khan, Khalid Mohammed; Perveen, Shahnaz; Voelter, Wolfgang

2011-01-01

Cellulose fiber is a tremendous natural resource that has broad application in various productions including the textile industry. The dyes, which are commonly used for cellulose printing, are “reactive dyes” because of their high wet fastness and brilliant colors. The interaction of various dyes with the cellulose fiber depends upon the physiochemical properties that are governed by specific features of the dye molecule. The binding pattern of the reactive dye with cellulose fiber is called the ligand-receptor concept. In the current study, the three dimensional quantitative structure property relationship (3D-QSPR) technique was applied to understand the red reactive dyes interactions with the cellulose by the Comparative Molecular Field Analysis (CoMFA) method. This method was successfully utilized to predict a reliable model. The predicted model gives satisfactory statistical results and in the light of these, it was further analyzed. Additionally, the graphical outcomes (contour maps) help us to understand the modification pattern and to correlate the structural changes with respect to the absorptivity. Furthermore, the final selected model has potential to assist in understanding the charachteristics of the external test set. The study could be helpful to design new reactive dyes with better affinity and selectivity for the cellulose fiber. PMID:22272108

Anharmonic vibrational spectroscopy, NBO charges and global chemical reactivity studies on the charge transfer PDCA-.AHMP+ single crystal using DFT calculations

NASA Astrophysics Data System (ADS)

Faizan, Mohd; Afroz, Ziya; Bhat, Sheeraz Ahmad; Alam, Mohamad Jane; Ahmad, Shabbir; Ahmad, Afaq

2018-04-01

The charge transfer (CT) complex of the 2-amino-4-hydroxy-6-methylpyrimidine and 2,3 pyrazinedicarboxylic acid (PDCA-.AHMP+) was synthesized and its single crystal was grown by solution method. The structure of the crystalline complex has been investigated by single crystal X-ray diffraction (SCXRD). The vibrational features of the complex have been studied with the help of FTIR spectra and DFT computation. The anharmonic corrections in vibrational frequencies are made using the GVPT2 method at B3LYP/6-311++G(d,p) level of theory. The frontier molecular orbitals and global chemical reactivity have been calculated to understand the pharmacological aspect of the synthesized crystal. Furthermore, Hirshfeld electrostatic potential (ESP) surface, void space in the crystal structure and natural as well as Mulliken atomic charges are studied.

The H2 + + He proton transfer reaction: quantum reactive differential cross sections to be linked with future velocity mapping experiments

NASA Astrophysics Data System (ADS)

Hernández Vera, Mario; Wester, Roland; Gianturco, Francesco Antonio

2018-01-01

We construct the velocity map images of the proton transfer reaction between helium and molecular hydrogen ion {{{H}}}2+. We perform simulations of imaging experiments at one representative total collision energy taking into account the inherent aberrations of the velocity mapping in order to explore the feasibility of direct comparisons between theory and future experiments planned in our laboratory. The asymptotic angular distributions of the fragments in a 3D velocity space is determined from the quantum state-to-state differential reactive cross sections and reaction probabilities which are computed by using the time-independent coupled channel hyperspherical coordinate method. The calculations employ an earlier ab initio potential energy surface computed at the FCI/cc-pVQZ level of theory. The present simulations indicate that the planned experiments would be selective enough to differentiate between product distributions resulting from different initial internal states of the reactants.

Brain Ischemia Induces Diversified Neuroantigen-Specific T-Cell Responses That Exacerbate Brain Injury.

PubMed

Jin, Wei-Na; Gonzales, Rayna; Feng, Yan; Wood, Kristofer; Chai, Zhi; Dong, Jing-Fei; La Cava, Antonio; Shi, Fu-Dong; Liu, Qiang

2018-06-01

Autoimmune responses can occur when antigens from the central nervous system are presented to lymphocytes in the periphery or central nervous system in several neurological diseases. However, whether autoimmune responses emerge after brain ischemia and their impact on clinical outcomes remains controversial. We hypothesized that brain ischemia facilitates the genesis of autoimmunity and aggravates ischemic brain injury. Using a mouse strain that harbors a transgenic T-cell receptor to a central nervous system antigen, MOG 35-55 (myelin oligodendrocyte glycoprotein) epitope (2D2), we determined the anatomic location and involvement of antigen-presenting cells in the development of T-cell reactivity after brain ischemia and how T-cell reactivity impacts stroke outcome. Transient middle cerebral artery occlusion and photothrombotic stroke models were used in this study. We also quantified the presence and status of T cells from brain slices of ischemic patients. By coupling transfer of labeled MOG 35-55 -specific (2D2) T cells with tetramer tracking, we show an expansion in reactivity of 2D2 T cells to MOG 91-108 and MOG 103-125 in transient middle cerebral artery occlusion and photothrombotic stroke models. This reactivity and T-cell activation first occur locally in the brain after ischemia. Also, microglia act as antigen-presenting cells that effectively present MOG antigens, and depletion of microglia ablates expansion of 2D2 reactive T cells. Notably, the adoptive transfer of neuroantigen-experienced 2D2 T cells exacerbates Th1/Th17 responses and brain injury. Finally, T-cell activation and MOG-specific T cells are present in the brain of patients with ischemic stroke. Our findings suggest that brain ischemia activates and diversifies T-cell responses locally, which exacerbates ischemic brain injury. © 2018 The Authors.

Literature Survey on Operational Voltage Control and Reactive Power Management on Transmission and Sub-Transmission Networks

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

Elizondo, Marcelo A.; Samaan, Nader A.; Makarov, Yuri V.

Voltage and reactive power system control is generally performed following usual patterns of loads, based on off-line studies for daily and seasonal operations. This practice is currently challenged by the inclusion of distributed renewable generation, such as solar. There has been focus on resolving this problem at the distribution level; however, the transmission and sub-transmission levels have received less attention. This paper provides a literature review of proposed methods and solution approaches to coordinate and optimize voltage control and reactive power management, with an emphasis on applications at transmission and sub-transmission level. The conclusion drawn from the survey is thatmore » additional research is needed in the areas of optimizing switch shunt actions and coordinating all available resources to deal with uncertain patterns from increasing distributed renewable generation in the operational time frame. These topics are not deeply explored in the literature.« less

COREPA-M: NEW MULTI-DIMENSIONAL FUNCTIONALITY OF THE COREPA METHOD

EPA Science Inventory

The COmmon REactivity PAttern (COREPA) method is a recently developed pattern recognition technique accounting for conformational flexibility of chemicals in 3-D quantitative structure-activity relationships (QSARs). The method is based on the assumption that non-congeneric chemi...

P-wave velocity anisotropy related to sealed fractures reactivation tracing the structural diagenesis in carbonates

NASA Astrophysics Data System (ADS)

Matonti, C.; Guglielmi, Y.; Viseur, S.; Garambois, S.; Marié, L.

2017-05-01

Fracture properties are important in carbonate reservoir characterization, as they are responsible for a large part of the fluid transfer properties at all scales. It is especially true in tight rocks where the matrix transfer properties only slightly contribute to the fluid flow. Open fractures are known to strongly affect seismic velocities, amplitudes and anisotropy. Here, we explore the impact of fracture evolution on the geophysical signature and directional Vp anisotropy of fractured carbonates through diagenesis. For that purpose, we studied a meter-scale, parallelepiped quarry block of limestone using a detailed structural and diagenetic characterization, and numerous Vp measurements. The block is affected by two en-échelon fracture clusters, both being formed in opening mode (mode 1) and cemented, but only one being reactivated in shear. We compared the diagenetic evolution of the fractures, which are almost all 100% filled with successive calcite cements, with the P-wave velocities measured across this meter-scale block of carbonate, which recorded the tectonic and diagenetic changes of a South Provence sedimentary basin. We found that a directional Vp anisotropy magnitude as high as 8-16% correlates with the reactivated fractures' cluster dip angle, which is explained by the complex filling sequence and softer material present inside the fractures that have been reactivated during the basin's tectonic inversion. We show that although a late karstification phase preferentially affected these reactivated fractures, it only amplified the pre-existing anisotropy due to tectonic shear. We conclude that Vp anisotropy measurements may help to identify the fracture sealing/opening processes associated with polyphased tectonic history, the anisotropy being independent of the current stress-state. This case shows that velocity anisotropies induced by fractures resulted here from a cause that is different from how these features have often been interpreted: selective reactivation of sealed fractures clusters rather than direction of currently open ones.

Deformation, static recrystallization, and reactive melt transport in shallow subcontinental mantle xenoliths (Tok Cenozoic volcanic field, SE Siberia)

NASA Astrophysics Data System (ADS)

Tommasi, Andréa; Vauchez, Alain; Ionov, Dmitri A.

2008-07-01

Partial melting and reactive melt transport may change the composition, microstructures, and physical properties of mantle rocks. Here we explore the relations between deformation and reactive melt transport through detailed microstructural analysis and crystallographic orientation measurements in spinel peridotite xenoliths that sample the shallow lithospheric mantle beneath the southeastern rim of the Siberian craton. These xenoliths have coarse-grained, annealed microstructures and show petrographic and chemical evidence for variable degrees of reaction with silicate melts and fluids, notably Fe-enrichment and crystallization of metasomatic clinopyroxene (cpx). Olivine crystal preferred orientations (CPO) range from strong to weak. [010]-fiber patterns, characterized by a point concentration of [010] normal to the foliation and by dispersion of [100] in the foliation plane with a weak maximum parallel to the lineation, predominate relative to the [100]-fiber patterns usually observed in lithospheric mantle xenoliths and peridotite massifs. Variations in olivine CPO patterns or intensity are not correlated with modal and chemical compositions. This, together with the analysis of microstructures, suggests that reactive melt percolation postdated both deformation and static recrystallization. Preferential crystallization of metasomatic cpx along (010) olivine grain boundaries points to an influence of the preexisting deformation fabrics on melt transport, with higher permeability along the foliation. Similarity between orthopyroxene (opx) and cpx CPO suggests that cpx orientations may be inherited from those of opx during melt-rock reaction. As observed in previous studies, reactive melt transport does not weaken olivine CPO and seismic anisotropy in the upper mantle, except in melt accumulation domains. In contrast, recovery and selective grain growth during static recrystallization may lead to development of [010]-fiber olivine CPO and, if foliations are horizontal, result in apparent isotropy for vertically propagating SKS waves, but strong anisotropy for horizontally propagating surface waves.

A twin study of cardiac reactivity and its relationship to parental blood pressure.

PubMed

Carroll, D; Hewitt, J K; Last, K A; Turner, J R; Sims, J

1985-01-01

The cardiac reactivity of 40 monozygotic and 40 dizygotic pairs of young male twins was monitored during psychological challenge, as afforded by a video game. The observed pattern of variation could not be accounted for solely by environmental factors. In fact, a simple genetic model that implicated additive genetic effects, along with those stemming from individual environments, best fitted the data. In addition, cardiac reactions were substantially greater for subjects whose parents both had relatively elevated blood pressure. Overall, these data suggest individual differences in cardiac reactivity have a heritable component, and that high reactivity may be a precursor of elevated blood pressure.

Direct metal transfer printing on flexible substrate for fabricating optics functional devices

NASA Astrophysics Data System (ADS)

Jiang, Yingjie; Zhou, Xiaohong; Zhang, Feng; Shi, Zhenwu; Chen, Linsen; Peng, Changsi

2015-11-01

New functional materials and devices based on metal patterns can be widely used in many new and expanding industries,such as flat panel displays, alternative energy,sensors and so on. In this paper, we introduce a new transfer printing method for fabricating metal optics functional devices. This method can directly transfer a metal pattern from a polyethylene terephthalate (PET)supported UV or polydimethylsiloxane (PDMS) pattern to another PET substrate. Purely taking advantage of the anaerobic UV curing adhesive (a-UV) on PET substrate, metal film can be easily peeled off from micro/nano-structured surface. As a result, metal film on the protrusion can be selectively transferred onto the target substrate, to make it the metal functional surface. But which on the bottom can not be transferred. This method provides low cost fabrication of metal thin film devices by avoiding high cost lithography process. Compared with conventional approach, this method can get more smooth rough edges and has wider tolerance range for the original master mold. Future developments and potential applications of this metal transfer method will be addressed.

Simulating Student Flow: Institutional Research Applications.

ERIC Educational Resources Information Center

Fawcett, Greg

Monitoring and subsequently simulating student transfer patterns from one academic major (or level) to another typically enables an institution to estimate future student enrollment distributions across academic areas. At the University of Missouri-Columbia (UMC), a student flow model not only simulates the patterns of student transfer but also…

Xanthohumol induces generation of reactive oxygen species and triggers apoptosis through inhibition of mitochondrial electron transfer chain complex I.

PubMed

Zhang, Bo; Chu, Wei; Wei, Peng; Liu, Ying; Wei, Taotao

2015-12-01

Xanthohumol is a prenylflavonoid extracted from hops (Humulus lupulus). It possesses anti-cancer and anti-inflammatory activities in vitro and in vivo, and offers therapeutic benefits for treatment of metabolic syndromes. However, the precise mechanisms underlying its pharmacological effects remain to be elucidated, together with its cellular target. Here, we provide evidence that xanthohumol directly interacts with the mitochondrial electron transfer chain complex I (NADH dehydrogenase), inhibits the oxidative phosphorylation, triggers the production of reactive oxygen species, and induces apoptosis. In addition, we show that as a result of the inhibition of the mitochondrial oxidative phosphorylation, xanthohumol exposure causes a rapid decrease of mitochondrial transmembrane potential. Furthermore, we showed that xanthohumol up-regulates the glycolytic capacity in cells, and thus compensates cellular ATP generation. Dissection of the multiple steps of aerobic respiration by extracellular flux assays revealed that xanthohumol specifically inhibits the activity of mitochondrial complex I, but had little effect on that of complex II, III and IV. Inhibition of complex I by xanthohumol caused the overproduction of reactive oxygen species, which are responsible for the induction of apoptosis in cancer cells. We also found that isoxanthohumol, the structural isomer of xanthohumol, is inactive to cells, suggesting that the reactive 2-hydroxyl group of xanthohumol is crucial for its targeting to the mitochondrial complex I. Together, the remodeling of cell metabolism revealed here has therapeutic potential for the use of xanthohumol. Copyright © 2015 Elsevier Inc. All rights reserved.

NHC→SiCl4 : an ambivalent carbene-transfer reagent.

PubMed

Böttcher, Tobias; Steinhauer, Simon; Lewis-Alleyne, Lesley C; Neumann, Beate; Stammler, Hans-Georg; Bassil, Bassem S; Röschenthaler, Gerd-Volker; Hoge, Berthold

2015-01-07

The addition of BCl3 to the carbene-transfer reagent NHC→SiCl4 (NHC=1,3-dimethylimidazolidin-2-ylidene) gave the tetra- and pentacoordinate trichlorosilicon(IV) cations [(NHC)SiCl3 ](+) and [(NHC)2 SiCl3 ](+) with tetrachloroborate as counterion. This is in contrast to previous reactions, in which NHC→SiCl4 served as a transfer reagent for the NHC ligand. The addition of BF3 ⋅OEt2 , on the other hand, gave NHC→BF3 as the product of NHC transfer. In addition, the highly Lewis acidic bis(pentafluoroethyl)silane (C2 F5 )2 SiCl2 was treated with NHC→SiCl4 . In acetonitrile, the cationic silicon(IV) complexes [(NHC)SiCl3 ](+) and [(NHC)2 SiCl3 ](+) were detected with [(C2 F5 )SiCl3 ](-) as counterion. A similar result was already reported for the reaction of NHC→SiCl4 with (C2 F5 )2 SiH2 , which gave [(NHC)2 SiCl2 H][(C2 F5 )SiCl3 ]. If the reaction medium was changed to dichloromethane, the products of carbene transfer, NHC→Si(C2 F5 )2 Cl2 and NHC→Si(C2 F5 )2 ClH, respectively, were obtained instead. The formation of the latter species is a result of chloride/hydride metathesis. These compounds may serve as valuable precursors for electron-poor silylenes. Furthermore, the reactivity of NHC→SiCl4 towards phosphines is discussed. The carbene complex NHC→PCl3 shows similar reactivity to NHC→SiCl4 , and may even serve as a carbene-transfer reagent as well. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Auditory orientation in crickets: Pattern recognition controls reactive steering

NASA Astrophysics Data System (ADS)

Poulet, James F. A.; Hedwig, Berthold

2005-10-01

Many groups of insects are specialists in exploiting sensory cues to locate food resources or conspecifics. To achieve orientation, bees and ants analyze the polarization pattern of the sky, male moths orient along the females' odor plume, and cicadas, grasshoppers, and crickets use acoustic signals to locate singing conspecifics. In comparison with olfactory and visual orientation, where learning is involved, auditory processing underlying orientation in insects appears to be more hardwired and genetically determined. In each of these examples, however, orientation requires a recognition process identifying the crucial sensory pattern to interact with a localization process directing the animal's locomotor activity. Here, we characterize this interaction. Using a sensitive trackball system, we show that, during cricket auditory behavior, the recognition process that is tuned toward the species-specific song pattern controls the amplitude of auditory evoked steering responses. Females perform small reactive steering movements toward any sound patterns. Hearing the male's calling song increases the gain of auditory steering within 2-5 s, and the animals even steer toward nonattractive sound patterns inserted into the speciesspecific pattern. This gain control mechanism in the auditory-to-motor pathway allows crickets to pursue species-specific sound patterns temporarily corrupted by environmental factors and may reflect the organization of recognition and localization networks in insects. localization | phonotaxis

Evidence for photochemical production of reactive oxygen species in desert soils.

PubMed

Georgiou, Christos D; Sun, Henry J; McKay, Christopher P; Grintzalis, Konstantinos; Papapostolou, Ioannis; Zisimopoulos, Dimitrios; Panagiotidis, Konstantinos; Zhang, Gaosen; Koutsopoulou, Eleni; Christidis, George E; Margiolaki, Irene

2015-05-11

The combination of intense solar radiation and soil desiccation creates a short circuit in the biogeochemical carbon cycle, where soils release significant amounts of CO2 and reactive nitrogen oxides by abiotic oxidation. Here we show that desert soils accumulate metal superoxides and peroxides at higher levels than non-desert soils. We also show the photogeneration of equimolar superoxide and hydroxyl radical in desiccated and aqueous soils, respectively, by a photo-induced electron transfer mechanism supported by their mineralogical composition. Reactivity of desert soils is further supported by the generation of hydroxyl radical via aqueous extracts in the dark. Our findings extend to desert soils the photogeneration of reactive oxygen species by certain mineral oxides and also explain previous studies on desert soil organic oxidant chemistry and microbiology. Similar processes driven by ultraviolet radiation may be operating in the surface soils on Mars.

Stress-Induced Out-of-Context Activation of Memory

PubMed Central

Ježek, Karel; Lee, Benjamin B.; Kelemen, Eduard; McCarthy, Katharine M.; McEwen, Bruce S.; Fenton, André A.

2010-01-01

Inappropriate recollections and responses in stressful conditions are hallmarks of post-traumatic stress disorder and other anxiety and mood disorders, but how stress contributes to the disorders is unclear. Here we show that stress itself reactivates memories even if the memory is unrelated to the stressful experience. Forced-swim stress one day after learning enhanced memory recall. One-day post-learning amnestic treatments were ineffective unless administered soon after the swim, indicating that a stressful experience itself can reactivate unrelated consolidated memories. The swim also triggered inter-hemispheric transfer of a lateralized memory, confirming stress reactivates stable memories. These novel effects of stress on memory required the hippocampus although the memories themselves did not, indicating hippocampus-dependent modulation of extrahippocampal memories. These findings that a stressful experience itself can activate memory suggest the novel hypothesis that traumatic stress reactivates pre-trauma memories, linking them to memory for the trauma and pathological facilitation of post-traumatic recall. PMID:21203585

Memory reactivation in healthy aging: evidence of stimulus-specific dedifferentiation.

PubMed

St-Laurent, Marie; Abdi, Hervé; Bondad, Ashley; Buchsbaum, Bradley R

2014-03-19

We investigated how aging affects the neural specificity of mental replay, the act of conjuring up past experiences in one's mind. We used functional magnetic resonance imaging (fMRI) and multivariate pattern analysis to quantify the similarity between brain activity elicited by the perception and memory of complex multimodal stimuli. Young and older human adults viewed and mentally replayed short videos from long-term memory while undergoing fMRI. We identified a wide array of cortical regions involved in visual, auditory, and spatial processing that supported stimulus-specific representation at perception as well as during mental replay. Evidence of age-related dedifferentiation was subtle at perception but more salient during mental replay, and age differences at perception could not account for older adults' reduced neural reactivation specificity. Performance on a post-scan recognition task for video details correlated with neural reactivation in young but not in older adults, indicating that in-scan reactivation benefited post-scan recognition in young adults, but that some older adults may have benefited from alternative rehearsal strategies. Although young adults recalled more details about the video stimuli than older adults on a post-scan recall task, patterns of neural reactivation correlated with post-scan recall in both age groups. These results demonstrate that the mechanisms supporting recall and recollection are linked to accurate neural reactivation in both young and older adults, but that age affects how efficiently these mechanisms can support memory's representational specificity in a way that cannot simply be accounted for by degraded sensory processes.

Correlation transfer from basal ganglia to thalamus in Parkinson's disease

PubMed Central

Pamela, Reitsma; Brent, Doiron; Jonathan, Rubin

2011-01-01

Spike trains from neurons in the basal ganglia of parkinsonian primates show increased pairwise correlations, oscillatory activity, and burst rate compared to those from neurons recorded during normal brain activity. However, it is not known how these changes affect the behavior of downstream thalamic neurons. To understand how patterns of basal ganglia population activity may affect thalamic spike statistics, we study pairs of model thalamocortical (TC) relay neurons receiving correlated inhibitory input from the internal segment of the globus pallidus (GPi), a primary output nucleus of the basal ganglia. We observe that the strength of correlations of TC neuron spike trains increases with the GPi correlation level, and bursty firing patterns such as those seen in the parkinsonian GPi allow for stronger transfer of correlations than do firing patterns found under normal conditions. We also show that the T-current in the TC neurons does not significantly affect correlation transfer, despite its pronounced effects on spiking. Oscillatory firing patterns in GPi are shown to affect the timescale at which correlations are best transferred through the system. To explain this last result, we analytically compute the spike count correlation coefficient for oscillatory cases in a reduced point process model. Our analysis indicates that the dependence of the timescale of correlation transfer is robust to different levels of input spike and rate correlations and arises due to differences in instantaneous spike correlations, even when the long timescale rhythmic modulations of neurons are identical. Overall, these results show that parkinsonian firing patterns in GPi do affect the transfer of correlations to the thalamus. PMID:22355287

New powerful statistics for alignment-free sequence comparison under a pattern transfer model.

PubMed

Liu, Xuemei; Wan, Lin; Li, Jing; Reinert, Gesine; Waterman, Michael S; Sun, Fengzhu

2011-09-07

Alignment-free sequence comparison is widely used for comparing gene regulatory regions and for identifying horizontally transferred genes. Recent studies on the power of a widely used alignment-free comparison statistic D2 and its variants D*2 and D(s)2 showed that their power approximates a limit smaller than 1 as the sequence length tends to infinity under a pattern transfer model. We develop new alignment-free statistics based on D2, D*2 and D(s)2 by comparing local sequence pairs and then summing over all the local sequence pairs of certain length. We show that the new statistics are much more powerful than the corresponding statistics and the power tends to 1 as the sequence length tends to infinity under the pattern transfer model. Copyright © 2011 Elsevier Ltd. All rights reserved.

New Powerful Statistics for Alignment-free Sequence Comparison Under a Pattern Transfer Model

PubMed Central

Liu, Xuemei; Wan, Lin; Li, Jing; Reinert, Gesine; Waterman, Michael S.; Sun, Fengzhu

2011-01-01

Alignment-free sequence comparison is widely used for comparing gene regulatory regions and for identifying horizontally transferred genes. Recent studies on the power of a widely used alignment-free comparison statistic D2 and its variants D2∗ and D2s showed that their power approximates a limit smaller than 1 as the sequence length tends to infinity under a pattern transfer model. We develop new alignment-free statistics based on D2, D2∗ and D2s by comparing local sequence pairs and then summing over all the local sequence pairs of certain length. We show that the new statistics are much more powerful than the corresponding statistics and the power tends to 1 as the sequence length tends to infinity under the pattern transfer model. PMID:21723298

Surface patterning by pulsed-laser-induced transfer of metals and compounds

NASA Astrophysics Data System (ADS)

Toth, Zsolt; Mogyorosi, Peter; Szoerenyi, Tamas

1990-08-01

Besults of a systematic study on Q-switched nthy laser induced rrrn2 area transfer of supported titanium and chranium thin films and Ge/Se multilayer structures are reported. The appearance of the prints is governed by film-support adhesion and source-target spacing. Best quality prints are produced by ablating well adhering ntal films in close proximity ( spacing < 15 pm) to the target to be patterned. Transfer fran stacked elenntaxy layers as a source offers a unique possibility of depositing acinpound films by mixing the constituents and transferring the material onto the target substrate in a single step.

Cumulative Effects of Prenatal Substance Exposure and Early Adversity on Foster Children's HPA-Axis Reactivity during a Psychosocial Stressor

ERIC Educational Resources Information Center

Fisher, Philip A.; Kim, Hyoun K.; Bruce, Jacqueline; Pears, Katherine C.

2012-01-01

Dysregulated hypothalamic-pituitary-adrenocortical (HPA) axis stress response has been reported among individuals with prenatal substance exposure and those with early adversity exposure. However, few researchers have examined the combined effects of these risk factors. Patterns of HPA reactivity among maltreated foster children with and without…

Thermochemical reactor systems and methods

DOEpatents

Lipinski, Wojciech; Davidson, Jane Holloway; Chase, Thomas Richard

2016-11-29

Thermochemical reactor systems that may be used to produce a fuel, and methods of using the thermochemical reactor systems, utilizing a reactive cylindrical element, an optional energy transfer cylindrical element, an inlet gas management system, and an outlet gas management system.

Multifunctional interphase

NASA Astrophysics Data System (ADS)

Rosy, Noked, Malachi

2018-04-01

Realization of rechargeable batteries with alkali metal anodes is challenged by their high reactivity and dendritic growth. Now, an alloy-based, artificial solid electrolyte interphase is shown to allow smooth metal deposition, enhance interfacial charge transfer, protect against parasitic reactions and offer extra energy storage.

Experiment of flow regime map and local condensing heat transfer coefficients inside three dimensional inner microfin tubes

NASA Astrophysics Data System (ADS)

Du, Yang; Xin, Ming Dao

1999-03-01

This paper developed a new type of three dimensional inner microfin tube. The experimental results of the flow patterns for the horizontal condensation inside these tubes are reported in the paper. The flow patterns for the horizontal condensation inside the new made tubes are divided into annular flow, stratified flow and intermittent flow within the test conditions. The experiments of the local heat transfer coefficients for the different flow patterns have been systematically carried out. The experiments of the local heat transfer coefficients changing with the vapor dryness fraction have also been carried out. As compared with the heat transfer coefficients of the two dimensional inner microfin tubes, those of the three dimensional inner microfin tubes increase 47-127% for the annular flow region, 38-183% for the stratified flow and 15-75% for the intermittent flow, respectively. The enhancement factor of the local heat transfer coefficients is from 1.8-6.9 for the vapor dryness fraction from 0.05 to 1.

Effects of perturbation-based slip training using a virtual reality environment on slip-induced falls.

PubMed

Parijat, Prakriti; Lockhart, Thurmon E; Liu, Jian

2015-04-01

The purpose of the current study was to design and evaluate the effectiveness of virtual reality training in improving recovery reactions and reducing fall frequency in older adults. Twenty-four older adults were recruited and randomly assigned to two groups (virtual reality training and control). Both groups underwent three sessions including baseline slip, training and transfer of training on slippery surface. Both groups experienced two slips, one during baseline and the other during the transfer of training trial. The training group underwent 12 simulated slips using a visual perturbation induced by tilting a virtual reality scene while walking on the treadmill and the control group performed normal walking during the training session. Kinematic and kinetic data were collected during all the sessions. Results demonstrated a reduced incidence of falls in the training group during the transfer of training trial as compared to the control group. The training group was able to transfer reactive control strategies learned during training to the second slip trial. The reactive adjustments included reduced slip distance. Additionally, gait parameters reflective of gait instability (stride length, step width, variability in stride velocity) reduced after walking in the VR environment for 15-20 min. The results indicated a beneficial effect of the virtual reality training in reducing slip severity and recovery kinematics in healthy older adults.

Catalytic Proton Coupled Electron Transfer from Metal Hydrides to Titanocene Amides, Hydrazides and Imides: Determination of Thermodynamic Parameters Relevant to Nitrogen Fixation.

PubMed

Pappas, Iraklis; Chirik, Paul J

2016-10-03

The hydrogenolysis of titanium-nitrogen bonds in a series of bis(cyclopentadienyl) titanium amides, hydrazides and imides by proton coupled electron transfer (PCET) is described. Twelve different N-H bond dissociation free energies (BDFEs) among the various nitrogen-containing ligands were measured or calculated, and effects of metal oxidation state and N-ligand substituent were determined. Two metal hydride complexes, (η 5 -C 5 Me 5 )(py-Ph)Rh-H (py-Ph = 2-pyridylphenyl, [Rh]-H) and (η 5 -C 5 R 5 )(CO) 3 Cr-H ([Cr] R -H, R= H, Me) were evaluated for formal H atom transfer reactivity and were selected due to their relatively weak M-H bond strengths yet ability to activate and cleave molecular hydrogen. Despite comparable M-H BDFEs, disparate reactivity between the two compounds was observed and was traced to the vastly different acidities of the M-H bonds and overall redox potentials of the molecules. With [Rh]-H, catalytic syntheses of ammonia, silylamine and N,N-dimethylhydrazine have been accomplished from the corresponding titanium(IV) complex using H 2 as the stoichiometric H atom source. The data presented in this study provides the thermochemical foundation for the synthesis of NH 3 by proton coupled electron transfer at a well-defined transition metal center.

Refining the reaction mechanism of O2 towards its co-substrate in cofactor-free dioxygenases

PubMed Central

2016-01-01

Cofactor-less oxygenases perform challenging catalytic reactions between singlet co-substrates and triplet oxygen, in spite of apparently violating the spin-conservation rule. In 1-H-3-hydroxy-4-oxoquinaldine-2,4-dioxygenase, the active site has been suggested by quantum chemical computations to fine tune triplet oxygen reactivity, allowing it to interact rapidly with its singlet substrate without the need for spin inversion, and in urate oxidase the reaction is thought to proceed through electron transfer from the deprotonated substrate to an aminoacid sidechain, which then feeds the electron to the oxygen molecule. In this work, we perform additional quantum chemical computations on these two systems to elucidate several intriguing features unaddressed by previous workers. These computations establish that in both enzymes the reaction proceeds through direct electron transfer from co-substrate to O2 followed by radical recombination, instead of minimum-energy crossing points between singlet and triplet potential energy surfaces without formal electron transfer. The active site does not affect the reactivity of oxygen directly but is crucial for the generation of the deprotonated form of the co-substrates, which have redox potentials far below those of their protonated forms and therefore may transfer electrons to oxygen without sizeable thermodynamic barriers. This mechanism seems to be shared by most cofactor-less oxidases studied so far. PMID:28028471

Effects of Perturbation-Based Slip Training using a Virtual Reality Environment on Slip-induced Falls

PubMed Central

Parijat, Prakriti; Lockhart, Thurmon E.; Liu, Jian

2015-01-01

The purpose of the current study was to design and evaluate the effectiveness of virtual reality training in improving recovery reactions and reducing fall frequency in older adults. Twenty-four older adults were recruited and randomly assigned to two groups (virtual reality training and control). Both groups underwent three sessions including baseline slip, training and transfer of training on slippery surface. Both groups experienced two slips, one during baseline and the other during the transfer of training trial. The training group underwent twelve simulated slips using a visual perturbation induced by tilting a virtual reality scene while walking on the treadmill and the control group performed normal walking during the training session. Kinematic and kinetic data were collected during all the sessions. Results demonstrated a reduced incidence of falls in the training group during the transfer of training trial as compared to the control group. The training group was able to transfer reactive control strategies learned during training to the second slip trial. The reactive adjustments included reduced slip distance. Additionally, gait parameters reflective of gait instability (stride length, step width, variability in stride velocity) reduced after walking in the VR environment for 15–20 min. The results indicated a beneficial effect of the virtual reality training in reducing slip severity and recovery kinematics in healthy older adults. PMID:25245221

Refining the reaction mechanism of O2 towards its co-substrate in cofactor-free dioxygenases.

PubMed

Silva, Pedro J

2016-01-01

Cofactor-less oxygenases perform challenging catalytic reactions between singlet co-substrates and triplet oxygen, in spite of apparently violating the spin-conservation rule. In 1- H -3-hydroxy-4-oxoquinaldine-2,4-dioxygenase, the active site has been suggested by quantum chemical computations to fine tune triplet oxygen reactivity, allowing it to interact rapidly with its singlet substrate without the need for spin inversion, and in urate oxidase the reaction is thought to proceed through electron transfer from the deprotonated substrate to an aminoacid sidechain, which then feeds the electron to the oxygen molecule. In this work, we perform additional quantum chemical computations on these two systems to elucidate several intriguing features unaddressed by previous workers. These computations establish that in both enzymes the reaction proceeds through direct electron transfer from co-substrate to O 2 followed by radical recombination, instead of minimum-energy crossing points between singlet and triplet potential energy surfaces without formal electron transfer. The active site does not affect the reactivity of oxygen directly but is crucial for the generation of the deprotonated form of the co-substrates, which have redox potentials far below those of their protonated forms and therefore may transfer electrons to oxygen without sizeable thermodynamic barriers. This mechanism seems to be shared by most cofactor-less oxidases studied so far.

Numerical investigation of the droplet condensation on the horizontal surface with patterned wettability

NASA Astrophysics Data System (ADS)

Cho, Jaeyong; Lee, Joonsang

2017-11-01

The condensation is the one of the efficient heat transfer phenomenon that transfers the heat along an interface between two phases. This condensation is affected by the wettability of surface. Heat transfer rate can be improved by controlling the wettability of surface. Recently, the researches with patterned wettability, which is composed by a combination of hydrophilic and hydrophobic surface, have been performed to improve the heat transfer rate of condensation. In this study, we performed numerical simulation for condensation of droplet on the patterned wettability, and we analyze condensation phenomenon on the wettability pattered surface through the kinetic energy, heat flux curve, and droplet shape in the vicinity of the droplet. When we performed numerical simulations and analyzing the condensation with patterned wettability, we used the lattice Boltzmann method for the base model, and phase change was solved by Peng-Robinson equation of sate. We can find that the droplet is generated at the bottom surface and high condensation rate can be maintained on the patterned wettability. This work was also supported by the National Research Foundation of Korea (NRF) Grant funded by the Korean Government (MSIP) (No. 2015R1A5A1037668) and BrainKorea21plus.

Sedimentary organic matter distributions, burrowing activity, and biogeochemical cycling: Natural patterns and experimental artifacts

NASA Astrophysics Data System (ADS)

Michaud, Emma; Aller, Robert, C.; Stora, Georges

2010-11-01

The coupling between biogenic reworking activity and reactive organic matter patterns within deposits is poorly understood and often ignored. In this study, we examined how common experimental treatments of sediment affect the burrowing behavior of the polychaete Nephtys incisa and how these effects may interact with reactive organic matter distributions to alter diagenetic transport - reaction balances. Sediment and animals were recovered from a subtidal site in central Long Island Sound, USA. The upper 15 cm of the sediment was sectioned into sub-intervals, and each interval separately sieved and homogenized. Three initial distributions of sediment and organic substrate reactivity were setup in a series of microcosms: (1) a reconstituted natural pattern with surface-derived sediment overlying sediment obtained from progressively deeper material to a depth of 15 cm (Natural); (2) a 15 cm thick sediment layer composed only of surface-derived sediment (Rich); and (3) a 15 cm thick layer composed of uniformally mixed sediment from the original 15 cm sediment profile (Averaged). The two last treatments are comparable to that used in microcosms in many previous studies of bioturbation and interspecific functional interaction experiments. Sediment grain size distributions were 97.5% silt-clay and showed no depth dependent patterns. Sediment porosity gradients were slightly altered by the treatments. Nepthys were reintroduced and aquariums were X-rayed regularly over 5 months to visualize and quantify spatial and temporal dynamics of burrows. The burrowing behaviour of adult populations having similar total biovolume, biomass, abundance, and individual sizes differed substantially as a function of treatment. Burrows in sediment with natural property gradients were much shallower and less dense than those in microcosms with altered gradients. The burrow volume/biovolume ratio was also lower in the substrate with natural organic reactivity gradients. Variation in food resources or in sediment mechanical properties associated with treatments, the latter in part coupled to remineralization processes such as exopolymer production, may explain the burrowing responses. In addition to demonstrating how species may respond to physical sedimentation events (substrate homogenization) and patterns of reactive organic matter redistribution, these experiments suggest that infaunal species interactions in microcosms, including the absolute and relative fluxes of remineralized solutes, may be subject to artifacts depending on exactly how sediments are introduced experimentally. Nonlocal transport and cylinder microenvironment transport - reaction models readily demonstrate how the multiple interactions between burrowing patterns and remineralization rate distributions can alter relative flux balances, decomposition pathways, and time to steady state.

Amine-reactive forms of a luminescent diethylenetriaminepentaacetic acid chelate of terbium and europium: attachment to DNA and energy transfer measurements.

PubMed

Li, M; Selvin, P R

1997-01-01

An isothiocyanate form of a lanthanide chelate which is highly luminescent when bound to terbium or europium has been synthesized. The chelate consists of diethylenetriaminepentaacetic acid (DTPA) covalently joined to a chromophore, 7-amino-4-methyl-2(1H)-quinolinone (cs124), and to L-p-aminophenylalanine, in which the aromatic amine was further converted to an isothiocyanate group. Ethylenediamine was also used in place of aminophenylalanine, but the isothiocyanate formed from the aliphatic amine was significantly less reactive. Site-specific attachments to triglycine and to the 5' ends of amine-modified DNA oligomers have been made. In addition, as an alternative method of coupling to macromolecules, DTPA anhydride-cs124 can be used to react specifically with a 5' amine group on base-deprotected synthetic DNA oligomers. Synthesis and purification is relatively straightforward in both cases, and luminescent properties are favorable for several applications, including as nonisotopic labels, as long-lifetime alternatives to fluorophores in imaging and diagnostics and particularly as donors in luminescence resonance energy transfer. Energy transfer measurements are consistent with previously reported measurements using different attachment mechanisms.

Nanosilicon dot arrays with a bit pitch and a track pitch of 25 nm formed by electron-beam drawing and reactive ion etching for 1 Tbit/in.{sup 2} storage

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

Hosaka, Sumio; Sano, Hirotaka; Shirai, Masumi

2006-11-27

The formation of very fine Si dots with a bit pitch and a track pitch of less than 25 nm using electron-beam (EB) lithography on ZEP520 and calixarene EB resists and CF{sub 4} reactive ion etching has been demonstrated. The experimental results indicate that the calixarene resist is very suitable for forming an ultrahigh-packed bit array pattern of Si dots. This result promises to open the way toward 1 Tbit/in.{sup 2} storage using patterned media with a dot size of <15 nm.

Microplasma array patterning of reactive oxygen and nitrogen species onto polystyrene

NASA Astrophysics Data System (ADS)

Szili, Endre J.; Dedrick, James; Oh, Jun-Seok; Bradley, James W.; Boswell, Roderick W.; Charles, Christine; Short, Robert D.; Al-Bataineh, Sameer A.

2017-02-01

We investigate an approach for the patterning of reactive oxygen and nitrogen species (RONS) onto polystyrene using atmospheric-pressure microplasma arrays. The spectrally integrated and time-resolved optical emission from the array is characterised with respect to the applied voltage, applied-voltage frequency and pressure; and the array is used to achieve spatially resolved modification of polystyrene at three pressures: 500 Torr, 760 Torr and 1000 Torr. As determined by time-of-flight secondary ion mass spectrometry (ToF-SIMS), regions over which surface modification occurs are clearly restricted to areas that are exposed to individual microplasma cavities. Analysis of the negative-ion ToF-SIMS mass spectra from the centre of the modified microspots shows that the level of oxidation is dependent on the operating pressure, and closely correlated with the spatial distribution of the optical emission. The functional groups that are generated by the microplasma array on the polystyrene surface are shown to readily participate in an oxidative reaction in phosphate buffered saline solution (pH 7.4). Patterns of oxidised and chemically reactive functionalities could potentially be applied to the future development of biomaterial surfaces, where spatial control over biomolecule or cell function is needed.

Cell-Mediated Immune Function and Cytokine Regulation During Space Flight

NASA Technical Reports Server (NTRS)

Sams, Clarence F.; Pierson, Duane L.; Paloski, W. H. (Technical Monitor)

2000-01-01

The changes in immune function which occur during space flight potentially expose the crews to an increased risk for development of illness. Decreased cellular immune function has been repeatedly documented after space flight and confirmed during flight by in vivo delayed-type hypersensitivity testing. However, correlation of immune changes with a clinically significant risk factor has not yet been performed. Our hypothesis is that space flight induces a decrease in cell-mediated immune function accompanied by a shift from a type 1 cytokine pattern (favoring cell-mediated immunity) to a type 2 cytokine pattern (favoring humoral immunity). We further hypothesize that reactivation of latent viruses will occur during space flight in association with the decreased cellular immunity. To test these hypotheses, we will determine the effects of space flight on cell-mediated immunity and viral reactivation. We will utilize delayed-type hypersensitivity testing as an in vivo measure of integrated cell-mediated immune function. The production of cytokines and immunoregulatory factors by lymphocytes and monocytes will be measured to determine whether changes in cytokine patterns are associated with the space flight-induced immune dysregulation. Correlation of antigen-specific immune changes with reactivation of latent herpes viruses will be determined by measuring peripheral levels of viral (CMV, VZV, EBV) antigen-specific T cells and comparing to the levels of EBV-infected B-cells by fluorescence in situ hybridization and flow cytometry. A comparison of cell-mediated immune function, cytokine regulation and viral reactivation will provide new insights into crew member health risks during flight.

Transfer Patterns of Students, University of Hawaii System, Fall 1975.

ERIC Educational Resources Information Center

Hawaii Univ., Honolulu. Management Systems Office.

In fall 1975, 4,702 students transferred into the University of Hawaii (UH) System, representing a 15.5 percent increase over the number of transfers in 1974. Of the total, 56 percent transferred from within the UH System, 6 percent transferred from other Hawaii institutions, and 36 percent transferred from out-of-state institutions. The total…

Positive and negative ZnO micropatterning on functionalized polymer surfaces.

PubMed

Yang, Peng; Zou, Shengli; Yang, Wantai

2008-09-01

Patterned ZnO deposition on substrates has received increasing attention because of its great potential in photocatalysis, energy conversion, and electro-optical techniques. Chemical solution growth is especially promising for organic substrates due to its very mild reaction conditions. Here this method is used on functionality-patterned polymer surfaces in order to fabricate positive and negative ZnO micropatterns. A ZnO film made of arrayed rods, typically 500-750 nm in diameter and 2.5 microm in length, is selectively obtained on sulfated and hydroxylated regions of biaxially oriented poly(propylene), giving rise to positive patterns. For reactive polyesters such as poly(ethylene terephthalate), the ZnO rods selectively remain on the unmodified original regions, creating negative patterns. Unlike complex photolithography procedures, the irradiation and patterning processes do not require the use of positive or negative photoresists, and possible damage from acidic solutions on the underlying substrate during the chemical etching process is avoided. The process thus proves to be a simple, creditable, and low-cost method, which could be easily applied on a variety of inert and reactive polymer surfaces.

Children's patterns of emotional reactivity to conflict as explanatory mechanisms in links between interpartner aggression and child physiological functioning.

PubMed

Davies, Patrick T; Sturge-Apple, Melissa L; Cicchetti, Dante; Manning, Liviah G; Zale, Emily

2009-11-01

This paper examined children's fearful, sad, and angry reactivity to interparental conflict as mediators of associations between their exposure to interparental aggression and physiological functioning. Participants included 200 toddlers and their mothers. Assessments of interparental aggression and children's emotional reactivity were derived from maternal surveys and a semi-structured interview. Cortisol levels and cardiac indices of sympathetic nervous system (SNS) and parasympathetic nervous system (PNS) activity were used to assess toddler physiological functioning. Results indicated that toddler exposure to interparental aggression was associated with greater cortisol levels and PNS activity and diminished SNS activity. Toddler angry emotional reactivity mediated associations between interparental aggression and cortisol and PNS functioning. Fearful emotional reactivity was a mediator of the link between interparental aggression and SNS functioning. The results are interpreted within conceptualizations of how exposure and reactivity to family risk organize individual differences in physiological functioning.

The Pathology of Reactive Lymphadenopathies: A Discussion of Common Reactive Patterns and Their Malignant Mimics.

PubMed

Slack, Graham W

2016-09-01

-Distinguishing between a reactive and a neoplastic lymphoid proliferation is a clinically significant task frequently performed by the surgical pathologist in routine practice. -To highlight common situations in lymph node pathology where reactive changes and lymphoma may be misdiagnosed. -Data sources are peer-reviewed journal articles, textbooks, and clinical experience. -This review aims to refresh and enhance the surgical pathologist's awareness of the shared and distinguishing features of select reactive and neoplastic lymphoproliferations, which in turn will allow the surgical pathologist to make more accurate diagnoses and avoid the pitfalls of misdiagnosis. This will be done by describing a selection of commonly encountered reactive histologic changes observed in lymph nodes, present the lymphomas with which they share overlapping features, outline the features that distinguish them, and describe an approach to making an accurate diagnosis and avoiding a misdiagnosis in each scenario.

Task complexity and maximal isometric strength gains through motor learning

PubMed Central

McGuire, Jessica; Green, Lara A.; Gabriel, David A.

2014-01-01

Abstract This study compared the effects of a simple versus complex contraction pattern on the acquisition, retention, and transfer of maximal isometric strength gains and reductions in force variability. A control group (N = 12) performed simple isometric contractions of the wrist flexors. An experimental group (N = 12) performed complex proprioceptive neuromuscular facilitation (PNF) contractions consisting of maximal isometric wrist extension immediately reversing force direction to wrist flexion within a single trial. Ten contractions were completed on three consecutive days with a retention and transfer test 2‐weeks later. For the retention test, the groups performed their assigned contraction pattern followed by a transfer test that consisted of the other contraction pattern for a cross‐over design. Both groups exhibited comparable increases in strength (20.2%, P < 0.01) and reductions in mean torque variability (26.2%, P < 0.01), which were retained and transferred. There was a decrease in the coactivation ratio (antagonist/agonist muscle activity) for both groups, which was retained and transferred (35.2%, P < 0.01). The experimental group exhibited a linear decrease in variability of the torque‐ and sEMG‐time curves, indicating transfer to the simple contraction pattern (P < 0.01). The control group underwent a decrease in variability of the torque‐ and sEMG‐time curves from the first day of training to retention, but participants returned to baseline levels during the transfer condition (P < 0.01). However, the difference between torque RMS error versus the variability in torque‐ and sEMG‐time curves suggests the demands of the complex task were transferred, but could not be achieved in a reproducible way. PMID:25428951

CXCR1 as a novel target for directing reactive T cells toward melanoma: implications for adoptive cell transfer immunotherapy.

PubMed

Sapoznik, Sivan; Ortenberg, Rona; Galore-Haskel, Gilli; Kozlovski, Stav; Levy, Daphna; Avivi, Camila; Barshack, Iris; Cohen, Cyrille J; Besser, Michal J; Schachter, Jacob; Markel, Gal

2012-10-01

Adoptive cell transfer therapy with reactive T cells is one of the most promising immunotherapeutic modalities for metastatic melanoma patients. Homing of the transferred T cells to all tumor sites in sufficient numbers is of great importance. Here, we seek to exploit endogenous chemotactic signals in order to manipulate and enhance the directional trafficking of transferred T cells toward melanoma. Chemokine profiling of 15 melanoma cultures shows that CXCL1 and CXCL8 are abundantly expressed and secreted from melanoma cultures. However, the complimentary analysis on 40 melanoma patient-derived tumor-infiltrating lymphocytes (TIL) proves that the corresponding chemokine receptors are either not expressed (CXCR2) or expressed at low levels (CXCR1). Using the in vitro transwell system, we demonstrate that TIL cells preferentially migrate toward melanoma and that endogenously expressing CXCR1 TIL cells are significantly enriched among the migrating lymphocytes. The role of the chemokines CXCL1 and CXCL8 is demonstrated by partial abrogation of this enrichment with anti-CXCL1 and anti-CXCL8 neutralizing antibodies. The role of the chemokine receptor CXCR1 is validated by the enhanced migration of CXCR1-engineered TIL cells toward melanoma or recombinant CXCL8. Cytotoxicity and IFNγ secretion activity are unaltered by CXCR1 expression profile. Taken together, these results mark CXCR1 as a candidate for genetic manipulations to enhance trafficking of adoptively transferred T cells. This approach is complimentary and potentially synergistic with other genetic strategies designed to enhance anti-tumor potency.

Exercise training attenuates experimental autoimmune encephalomyelitis by peripheral immunomodulation rather than direct neuroprotection.

PubMed

Einstein, Ofira; Fainstein, Nina; Touloumi, Olga; Lagoudaki, Roza; Hanya, Ester; Grigoriadis, Nikolaos; Katz, Abram; Ben-Hur, Tamir

2018-01-01

Conflicting results exist on the effects of exercise training (ET) on Experimental Autoimmune Encephalomyelitis (EAE), nor is it known how exercise impacts on disease progression. We examined whether ET ameliorates the development of EAE by modulating the systemic immune system or exerting direct neuroprotective effects on the CNS. Healthy mice were subjected to 6weeks of motorized treadmill running. The Proteolipid protein (PLP)-induced transfer EAE model in mice was utilized. To assess effects of ET on systemic autoimmunity, lymph-node (LN)-T cells from trained- vs. sedentary donor mice were transferred to naïve recipients. To assess direct neuroprotective effects of ET, PLP-reactive LN-T cells were transferred into recipient mice that were trained prior to EAE transfer or to sedentary mice. EAE severity was assessed in vivo and the characteristics of encephalitogenic LN-T cells derived from PLP-immunized mice were evaluated in vitro. LN-T cells obtained from trained mice induced an attenuated clinical and pathological EAE in recipient mice vs. cells derived from sedentary animals. Training inhibited the activation, proliferation and cytokine gene expression of PLP-reactive T cells in response to CNS-derived autoantigen, but strongly enhanced their proliferation in response to Concanavalin A, a non-specific stimulus. However, there was no difference in EAE severity when autoreactive encephalitogenic T cells were transferred to trained vs. sedentary recipient mice. ET inhibits immune system responses to an auto-antigen to attenuate EAE, rather than generally suppressing the immune system, but does not induce a direct neuro-protective effect against EAE. Copyright © 2017 Elsevier Inc. All rights reserved.

Genetic dissection of the maize (Zea mays L.) MAMP response

USDA-ARS?s Scientific Manuscript database

Microbe-associated molecular patterns (MAMPs) are highly conserved molecules commonly found in microbes which can be recognized by plant pattern recognition receptors (PRRs). Recognition triggers a suite of responses including production of reactive oxygen species (ROS) and nitric oxide (NO) and ex...

A pilot study of physiological reactivity in children and maternal figures who lost relatives in a terrorist attack.

PubMed

Pfefferbaum, Betty; Tucker, Phebe; Jeon-Slaughter, Haekyung; Allen, James R; Hammond, Donna R; Whittlesey, Suzanne W; Vinekar, Shreekumar S; Feng, Yan

2013-01-01

Trauma is thought to interfere with normal grief by superimposing symptoms of posttraumatic stress disorder. This exploratory pilot study examined the association between traumatic grief and objectively measured physiological reactivity to a trauma interview in 73 children who lost relatives in the Oklahoma City bombing as well as a potential link between children and their maternal figures in physiological reactivity. Although the authors found no association between posttraumatic stress and objectively measured physiological reactivity among children, they found significant differences in objectively measured reactivity associated with loss and grief. Children who lost "close" relatives evidenced greater objectively measured reactivity than those who lost "distant" relatives. For the most part, children with higher levels of grief evidenced greater objectively measured reactivity than those with lower levels of grief. The most interesting of the findings was the parallel pattern in objectively measured physiological reactivity between children and their maternal figures along with a positive association between children's objectively measured physiological reactivity and maternal figures' self-reported physiological reactivity. Research using larger representative samples studied early and over time is indicated to determine the potential significance of these findings.

Measuring Memory Reactivation With Functional MRI: Implications for Psychological Theory.

PubMed

Levy, Benjamin J; Wagner, Anthony D

2013-01-01

Environmental cues often remind us of earlier experiences by triggering the reactivation of memories of events past. Recent evidence suggests that memory reactivation can be observed using functional MRI and that distributed pattern analyses can even provide evidence of reactivation on individual trials. The ability to measure memory reactivation offers unique and powerful leverage on theoretical issues of long-standing interest in cognitive psychology, providing a means to address questions that have proven difficult to answer with behavioral data alone. In this article, we consider three instances. First, reactivation measures can indicate whether memory-based inferences (i.e., generalization) arise through the encoding of integrated cross-event representations or through the flexible expression of separable event memories. Second, online measures of memory reactivation may inform theories of forgetting by providing information about when competing memories are reactivated during competitive retrieval situations. Finally, neural reactivation may provide a window onto the role of replay in memory consolidation. The ability to track memory reactivation, including at the individual trial level, provides unique leverage that is not afforded by behavioral measures and thus promises to shed light on such varied topics as generalization, integration, forgetting, and consolidation. © The Author(s) 2013.

Spiral pattern in a radial displacement in a Hele-Shaw cell

NASA Astrophysics Data System (ADS)

Ban, Mitsumasa; Nagatsu, Yuichiro; Hayashi, Atsushi; Kato, Yoshihiro; Tada, Yutaka

2008-11-01

When a reactive and miscible less-viscous liquid displaces a more-viscous liquid in a Hele-Shaw cell, reactive miscible viscous fingering takes place. We have experimentally shown that the pattern created by the displacement of a more-viscous fluid by a less-viscous one in a radial Hele-Shaw cell develops not radially but spirally when a more-viscous sodium polyacrylate solution is displaced by a less-viscous trivalent iron ion (Fe^3+) solution with a sufficiently high concentration of Fe^3+. Another experiment in order to investigate the mechanism of spiral pattern formation revealed that an instantaneous chemical reaction takes place between the two fluids and at high Fe^3+ concentrations it produces a film of the gel at the contact plane. The gel is formed by three-dimensional network structures between the polyacrylate solution and the trivalent iron ion (Fe^3+) solution. We have proposed a physical model that the gel's film is responsible for the form of the spiral pattern.

Dating couples' attachment styles and patterns of cortisol reactivity and recovery in response to a relationship conflict.

PubMed

Powers, Sally I; Pietromonaco, Paula R; Gunlicks, Meredith; Sayer, Aline

2006-04-01

This study investigated theoretically predicted links between attachment style and a physiological indicator of stress, salivary cortisol levels, in 124 heterosexual dating couples. Cortisol was assessed at 7 points before and after an experimental conflict negotiation task, creating a trajectory of stress reactivity and recovery for each participant. Growth modeling of cortisol data tested hypotheses that (a) insecurely attached individuals show patterns of greater physiological stress reactions to interpersonal conflict than do securely attached individuals and (b) people with insecurely attached partners show patterns of greater stress in reaction to relationship conflict than those with securely attached partners. Hypothesis 1 was supported, but men and women differed in the type of insecure attachment that predicted stress trajectories. Hypothesis 2 was supported for men, but not for women. The discussion emphasizes the role of gender role norms and partner characteristics in understanding connections between adult attachment and patterns of cortisol responses to interpersonal stress.

New activity pattern in human interactive dynamics

NASA Astrophysics Data System (ADS)

Formentin, Marco; Lovison, Alberto; Maritan, Amos; Zanzotto, Giovanni

2015-09-01

We investigate the response function of human agents as demonstrated by written correspondence, uncovering a new pattern for how the reactive dynamics of individuals is distributed across the set of each agent’s contacts. In long-term empirical data on email, we find that the set of response times considered separately for the messages to each different correspondent of a given writer, generate a family of heavy-tailed distributions, which have largely the same features for all agents, and whose characteristic times grow exponentially with the rank of each correspondent. We furthermore show that this new behavioral pattern emerges robustly by considering weighted moving averages of the priority-conditioned response-time probabilities generated by a basic prioritization model. Our findings clarify how the range of priorities in the inputs from one’s environment underpin and shape the dynamics of agents embedded in a net of reactive relations. These newly revealed activity patterns might be universal, being present in other general interactive environments, and constrain future models of communication and interaction networks, affecting their architecture and evolution.

Design of experiment for optimization of plasma-polymerized octafluorocyclobutane coating on very high aspect ratio silicon molds.

PubMed

Yeo, L P; Yan, Y H; Lam, Y C; Chan-Park, Mary B

2006-11-21

As-fabricated deep reactive ion etched (DRIE) silicon mold with very high aspect ratio (>10) feature patterns is unsuitable for poly(dimethylsiloxane) (PDMS) replication because of the strong interaction between the Si surface and the replica and the corrugated mold sidewalls. The silicon mold can be conveniently passivated via plasma polymerization of octafluorocyclobutane (C4F8), which is also employed in the DRIE process itself, to enable the mold to be used repeatedly. To optimize the passivation conditions, we have undertaken a Box-Behnken experimental design on the basis of three passivation process parameters (plasma power, C4F8 flow rate, and deposition time). The measured responses were fluorinated film thickness, demolding status/success, demolding force, and fluorine/carbon ratio on the fifth replica surface. The optimal passivation process conditions were predicted to be an input power of 195 W, a C4F8 flow rate of 57 sccm, and a deposition time of 364 s; these were verified experimentally to have high accuracy. Demolding success requires medium-deposited film thickness (66-91 nm), and the thickness of the deposited films correlated strongly with deposition time. At moderate to high ranges, increased plasma power or gas flow rate promoted polymerization over reactive etching of the film. It was also found that small quantities of the fluorinated surface were transferred from the Si mold to the PDMS at each replication, entailing progressive wear of the fluorinated layer.

From ‘petal effect’ to ‘lotus effect’ on the highly flexible Silastic S elastomer microstructured using a fluorine based reactive ion etching process

NASA Astrophysics Data System (ADS)

Frankiewicz, Christophe; Zoueshtiagh, Farzam; Talbi, Abdelkrim; Streque, Jérémy; Pernod, Philippe; Merlen, Alain

2014-11-01

A fluorine-based reactive ion etching (RIE) process has been applied on a new family of silicone elastomers named ‘Silastic S’ for the first time. Excellent mechanical properties are the principal advantage of this elastomer. The main objective of this study was (i) to develop a new process with an electrodeposited thin Nickel (Ni) layer as a mask to obtain a more precise pattern transfer for deep etching (ii) to investigate the etch rates and the etch profiles obtained under various plasma conditions (gas mixture ratios and pressure). The resulting process exhibits etch rates that range from 20 µm h-1 to 40 µm h-1. The process was optimized to obtain anisotropic profiles of the edges. Finally, it is shown that (iii) the wetting contact angle could be easily modified with this process from 103° to 162°, with a hysteresis that ranges from 2° to 140°. The process is, at present, the only reported solution to reproduce the ‘petal effect’ (high contact angle hysteresis value) on a highly flexible substrate. A possibility to control the contact angle hysteresis from the ‘petal effect’ to the ‘lotus effect’ (low contact angle hysteresis value) has been investigated to allow a precise control on the required energy to pin or unpin the contact line of water droplets. This opens multiple possibilities to exploit this elastomer in many microfluidics applications.

CTLs directed against HER2 specifically cross-react with HER3 and HER4.

PubMed

Conrad, Heinke; Gebhard, Kerstin; Krönig, Holger; Neudorfer, Julia; Busch, Dirk H; Peschel, Christian; Bernhard, Helga

2008-06-15

The human epidermal growth factor receptor 2 (HER2) has been targeted as a breast cancer-associated Ag by T cell-based immunotherapeutical strategies such as cancer vaccines and adoptive T cell transfer. The prerequisite for a successful T cell-based therapy is the induction of T cells capable of recognizing the HER2-expressing tumor cells. In this study, we generated human cytotoxic T cell clones directed against the HER2(369-377) epitope known to be naturally presented with HLA-A*0201. Those HER2-reactive CTLs, which were also tumor lytic, exhibited a similar lysis pattern dividing the targets in lysable and nonlysable tumor cells. Several HER2-expressing tumor cells became susceptible to CTL-mediated lysis after IFN-gamma treatment and, in parallel, up-regulated molecules of the Ag-presenting machinery, indicating that the tumor itself also contributes to the success of CTL-mediated killing. Some of the HER2(369-377)-reactive T cells specifically cross-reacted with the corresponding peptides derived from the family members HER3 and/or HER4 due to a high sequence homology. The epitopes HER3(356-364) and HER4(361-369) were endogenously processed and contributed to the susceptibility of cell lysis by HER cross-reacting CTLs. The principle of "double" or "triple targeting" the HER Ags by cross-reacting T cells will impact the further development of T cell-based therapies.

Surveys of research in the Chemistry Division, Argonne National Laboratory

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

Grazis, B.M.

1992-01-01

Research reports are presented on reactive intermediates in condensed phase (radiation chemistry, photochemistry), electron transfer and energy conversion, photosynthesis and solar energy conversion, metal cluster chemistry, chemical dynamics in gas phase, photoionization-photoelectrons, characterization and reactivity of coal and coal macerals, premium coal sample program, chemical separations, heavy elements coordination chemistry, heavy elements photophysics/photochemistry, f-electron interactions, radiation chemistry of high-level wastes (gas generation in waste tanks), ultrafast molecular electronic devices, and nuclear medicine. Separate abstracts have been prepared. Accelerator activites and computer system/network services are also reported.

Surveys of research in the Chemistry Division, Argonne National Laboratory

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

Grazis, B.M.

1992-11-01

Research reports are presented on reactive intermediates in condensed phase (radiation chemistry, photochemistry), electron transfer and energy conversion, photosynthesis and solar energy conversion, metal cluster chemistry, chemical dynamics in gas phase, photoionization-photoelectrons, characterization and reactivity of coal and coal macerals, premium coal sample program, chemical separations, heavy elements coordination chemistry, heavy elements photophysics/photochemistry, f-electron interactions, radiation chemistry of high-level wastes (gas generation in waste tanks), ultrafast molecular electronic devices, and nuclear medicine. Separate abstracts have been prepared. Accelerator activites and computer system/network services are also reported.

Spying on the neighbors' pool

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

Xantheas, S. S.

2016-12-01

The structure and properties of the aqueous proton is of fundamental interest in many areas of chemistry and biology. Acids and bases are molecules that are able to transfer (donate / accept) a proton according to Brønsted and Lowry, a process that was further explained by Lewis in terms of changes in their electronic structure in an attempt to offer a generalization of the Arrhenius theory. Simple proton transfers or the ones coupled to an electron transfer determine speciation, valence and reactivity in aqueous media and explain electrochemical processes, while voltage-gated proton channels have severe implications to the function ofmore » a number of tissues and species.« less

Prediction of mass transfer coefficients in non-Newtonian fermentation media using first-principles methods.

PubMed

Radl, Stefan; Khinast, Johannes G

2007-08-01

Bubble flows in non-Newtonian fluids were analyzed using first-principles methods with the aim to compute and predict mass transfer coefficients in such fermentation media. The method we used is a Direct Numerical Simulation (DNS) of the reactive multiphase flow with deformable boundaries and interfaces. With this method, we are able for the first time to calculate mass transfer coefficients in non-Newtonian liquids of different rheologies without any experimental data. In the current article, shear-thinning fluids are considered. However, the results provide the basis for further investigations, such as the study of viscoelastic fluids. (c) 2007 Wiley Periodicals, Inc.

Chirality Transfer in Gold(I)-Catalysed Direct Allylic Etherifications of Unactivated Alcohols: Experimental and Computational Study.

PubMed

Barker, Graeme; Johnson, David G; Young, Paul C; Macgregor, Stuart A; Lee, Ai-Lan

2015-09-21

Gold(I)-catalysed direct allylic etherifications have been successfully carried out with chirality transfer to yield enantioenriched, γ-substituted secondary allylic ethers. Our investigations include a full substrate-scope screen to ascertain substituent effects on the regioselectivity, stereoselectivity and efficiency of chirality transfer, as well as control experiments to elucidate the mechanistic subtleties of the chirality-transfer process. Crucially, addition of molecular sieves was found to be necessary to ensure efficient and general chirality transfer. Computational studies suggest that the efficiency of chirality transfer is linked to the aggregation of the alcohol nucleophile around the reactive π-bound Au-allylic ether complex. With a single alcohol nucleophile, a high degree of chirality transfer is predicted. However, if three alcohols are present, alternative proton transfer chain mechanisms that erode the efficiency of chirality transfer become competitive. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

76 FR 14965 - Combined Notice of Filings #1

Federal Register 2010, 2011, 2012, 2013, 2014

2011-03-18

...-000. Applicants: Troy Energy, LLC. Description: Troy Energy, LLC's Transfer of Reactive Power Revenue... DEPARTMENT OF ENERGY Federal Energy Regulatory Commission Combined Notice of Filings 1 Take notice...-2424-001. Applicants: Pinetree Power-Tamworth, Inc. Description: Second Supplemental Request for...

The Leaf Fell (the Leaf): The Online Processing of Unaccusatives

PubMed Central

Friedmann, Naama; Taranto, Gina; Shapiro, Lewis P.; Swinney, David

2012-01-01

According to the Unaccusative Hypothesis, unaccusative subjects are base-generated in object position and move to subject position. We examined this hypothesis using the cross-modal lexical priming technique, which tests whether and when an antecedent is reactivated during the online processing of a sentence. We compared sentences containing unergative verbs with sentences containing unaccusatives, both alternating and nonalternating, and found that subjects of unaccusatives reactivate after the verb, while subjects of unergatives do not. Alternating unaccusatives showed a mixed pattern of reactivation. The research directly supports the Unaccusative Hypothesis. PMID:22822348

Study of the efficiency for ion transfer through bent capillaries.

PubMed

Chen, Tsung-Chi; Xu, Wei; Garimella, Sandilya; Ouyang, Zheng

2012-11-01

Discontinuous atmospheric pressure interfaces (DAPIs) with bent capillaries represent a highly simplified and flexible means for introducing ions into a vacuum manifold for mass analysis or gas phase ion reactions. In this work, a series of capillaries of different radians and curvatures were used with DAPI for studying the impact of the capillary bending on the ion transfer. The variation of transfer efficiency was systematically characterized for dry and solvated ions. The efficiency loss for dry ions was less than one order of magnitude, even with a three-turn bent capillary. The transfer of solvated ions generated by electrospray was found to be minimally impacted by the bending of the transfer capillary. For multiply protonated ions, the transfer efficiency for ions at lower charge states could be relatively well retained, presumably due to the lower reactivity associated with proton transfer reaction and the compensation in intensity by conversion of ions at higher charge states. Copyright © 2012 John Wiley & Sons, Ltd.

Solid phase studies and geochemical modelling of low-cost permeable reactive barriers.

PubMed

Bartzas, Georgios; Komnitsas, Kostas

2010-11-15

A continuous column experiment was carried out under dynamic flow conditions in order to study the efficiency of low-cost permeable reactive barriers (PRBs) to remove several inorganic contaminants from acidic solutions. A 50:50 w/w waste iron/sand mixture was used as candidate reactive media in order to activate precipitation and promote sorption and reduction-oxidation mechanisms. Solid phase studies of the exhausted reactive products after column shutdown, using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD), confirmed that the principal Fe corrosion products identified in the reactive zone are amorphous iron (hydr)oxides (maghemite/magnetite and goethite), intermediate products (sulfate green rust), and amorphous metal sulfides such as amFeS and/or mackinawite. Geochemical modelling of the metal removal processes, including interactions between reactive media, heavy metal ions and sulfates, and interpretation of the ionic profiles was also carried out by using the speciation/mass transfer computer code PHREEQC-2 and the WATEQ4F database. Mineralogical characterization studies as well as geochemical modelling calculations also indicate that the effect of sulfate and silica sand on the efficiency of the reactive zone should be considered carefully during design and operation of low-cost field PRBs. Copyright © 2010 Elsevier B.V. All rights reserved.

Inertial Sensor Based Analysis of Lie-to-Stand Transfers in Younger and Older Adults

PubMed Central

Schwickert, Lars; Boos, Ronald; Klenk, Jochen; Bourke, Alan; Becker, Clemens; Zijlstra, Wiebren

2016-01-01

Many older adults lack the capacity to stand up again after a fall. Therefore, to analyse falls it is relevant to understand recovery patterns, including successful and failed attempts to get up from the floor in general. This study analysed different kinematic features of standing up from the floor. We used inertial sensors to describe the kinematics of lie-to-stand transfer patterns of younger and healthy older adults. Fourteen younger (20–50 years of age, 50% men) and 10 healthy older community dwellers (≥60 years; 50% men) conducted four lie-to-stand transfers from different initial lying postures. The analysed temporal, kinematic, and elliptic fitting complexity measures of transfer performance were significantly different between younger and older subjects (i.e., transfer duration, angular velocity (RMS), maximum vertical acceleration, maximum vertical velocity, smoothness, fluency, ellipse width, angle between ellipses). These results show the feasibility and potential of analysing kinematic features to describe the lie-to-stand transfer performance, to help design interventions and detection approaches to prevent long lies after falls. It is possible to describe age-related differences in lie-to-stand transfer performance using inertial sensors. The kinematic analysis remains to be tested on patterns after real-world falls. PMID:27529249

Patterns of Sensitivity to Emotion in Children with Williams Syndrome and Autism: Relations between Autonomic Nervous System Reactivity and Social Functioning

ERIC Educational Resources Information Center

Järvinen, Anna; Ng, Rowena; Crivelli, Davide; Neumann, Dirk; Grichanik, Mark; Arnold, Andrew J.; Lai, Philip; Trauner, Doris; Bellugi, Ursula

2015-01-01

Williams syndrome (WS) and autism spectrum disorder (ASD) are associated with atypical social-emotional functioning. Affective visual stimuli were used to assess autonomic reactivity and emotion identification, and the social responsiveness scale was used to determine the level social functioning in children with WS and ASD contrasted with typical…

Organometallics in High Energy Chemistry.

DTIC Science & Technology

1983-10-31

Luines Physeical ftaenc Chemistry DepatneWu. SJI International. Menlo PWr *. CaiOwrnia M10 Rceived Nouvber 8. 1IM The otslytic formation of6nw carbon...support the idea that the metalloazocyclopropane intermediate is the reactive intermediate that leads to transalkylation. A discussion of the...exceptionally good correlation between the catalytic reactivity patterns of palladium black in its reactions with tertiary amines and those of homogeneous

Allyl transfer to aldehydes and ketones by Brønsted acid activation of allyl and crotyl 1,3,2-dioxazaborolidines.

PubMed

Reilly, Maureen K; Rychnovsky, Scott D

2010-11-05

Alkyl dioxazaborolidines are air-stable and often crystalline organoboranes. A variety of Brønsted acids activate allyl dioxazaborolidines to generate reactive allyl-transfer reagents in situ. These reagents add to aldehydes and ketones to generate the corresponding alcohols in good yields under mild conditions. The E- and Z-crotyl reagents react diastereoselectively with aldehydes and ketones to produce anti and syn adducts, respectively, a result consistent with a cyclic transition state (type I mechanism).

A neural network model for transference and repetition compulsion based on pattern completion.

PubMed

Javanbakht, Arash; Ragan, Charles L

2008-01-01

In recent years because of the fascinating growth of the body of neuroscientific knowledge, psychoanalytic scientists have worked on models for the neurological substrates of key psychoanalytic concepts. Transference is an important example. In this article, the psychological process of transference is described, employing the neurological function of pattern completion in hippocampal and thalamo-cortical pathways. Similarly, repetition compulsion is seen as another type of such neurological function; however, it is understood as an attempt for mastery of the unknown, rather than simply for mastery of past experiences and perceptions. Based on this suggested model of neurological function, the myth of the psychoanalyst as blank screen is seen as impossible and ineffective, based on neurofunctional understandings of neuropsychological process. The mutative effect of psychoanalytic therapy, correcting patterns of pathological relatedness, is described briefly from conscious and unconscious perspectives. While cognitive understanding (insight) helps to modify transferentially restored, maladaptive patterns of relatedness, the development of more adaptive patterns is also contingent upon an affective experience (working through), which alters the neurological substrates of unconscious, pathological affective patterns and their neurological functional correlates.

Longitudinal Patterns of Autonomic Nervous System Responding to Emotion Evocation among Children with Conduct Problems and/or Depression

PubMed Central

Pang, Karen C.; Beauchaine, Theodore P.

2012-01-01

Conduct disorder (CD) and depression co-occur at far greater levels than chance, despite largely separate diagnostic criteria. One potential shared mechanism of this comorbidity is emotion dysregulation, which characterizes both internalizing and externalizing disorders. Previous research demonstrates that respiratory sinus arrhythmia (RSA)—a peripheral biomarker of emotion regulation—is attenuated among children with CD, and among children with depression. However, few studies have examined biomarkers of emotion regulation as a function of heterotypic comorbidity. We evaluated longitudinal patterns of RSA and RSA reactivity to emotion evocation across three annual assessments among 207 children diagnosed at ages 8–12 years with CD (n=30), depression (n=28), comorbid CD and depression (n=80), or no psychiatric condition (n=69). Using continuous symptom counts as predictors, Depression × CD interactions were observed for both Time 1 resting RSA and Time 1 RSA reactivity. Conduct disorder, depression, and their interaction were all associated with low resting RSA at Time 1. In addition, concurrently elevated CD and depression scores predicted the greatest RSA reactivity to emotion evocation. Psychopathology scores were unrelated to developmental changes in RSA and RSA reactivity over time. PMID:22826111

The neural signatures of distinct psychopathic traits

PubMed Central

Carré, Justin M.; Hyde, Luke W.; Neumann, Craig S.; Viding, Essi; Hariri, Ahmad R.

2016-01-01

Recent studies suggest that psychopathy may be associated with dysfunction in the neural circuitry supporting both threat- and reward-related processes. However, these studies have involved small samples and often focused on extreme groups. Thus, it is unclear to what extent current findings may generalize to psychopathic traits in the general population. Furthermore, no studies have systematically and simultaneously assessed associations between distinct psychopathy facets and both threat- and reward-related brain function in the same sample of participants. Here, we examined the relationship between threat-related amygdala reactivity and reward-related ventral striatum (VS) reactivity and variation in four facets of self-reported psychopathy in a sample of 200 young adults. Path models indicated that amygdala reactivity to fearful facial expressions is negatively associated with the interpersonal facet of psychopathy, whereas amygdala reactivity to angry facial expressions is positively associated with the lifestyle facet. Furthermore, these models revealed that differential VS reactivity to positive versus negative feedback is negatively associated with the lifestyle facet. There was suggestive evidence for gender-specific patterns of association between brain function and psychopathy facets. Our findings are the first to document differential associations between both threat- and reward-related neural processes and distinct facets of psychopathy and thus provide a more comprehensive picture of the pattern of neural vulnerabilities that may predispose to maladaptive outcomes associated with psychopathy. PMID:22775289

The neural signatures of distinct psychopathic traits.

PubMed

Carré, Justin M; Hyde, Luke W; Neumann, Craig S; Viding, Essi; Hariri, Ahmad R

2013-01-01

Recent studies suggest that psychopathy may be associated with dysfunction in the neural circuitry supporting both threat- and reward-related processes. However, these studies have involved small samples and often focused on extreme groups. Thus, it is unclear to what extent current findings may generalize to psychopathic traits in the general population. Furthermore, no studies have systematically and simultaneously assessed associations between distinct psychopathy facets and both threat- and reward-related brain function in the same sample of participants. Here, we examined the relationship between threat-related amygdala reactivity and reward-related ventral striatum (VS) reactivity and variation in four facets of self-reported psychopathy in a sample of 200 young adults. Path models indicated that amygdala reactivity to fearful facial expressions is negatively associated with the interpersonal facet of psychopathy, whereas amygdala reactivity to angry facial expressions is positively associated with the lifestyle facet. Furthermore, these models revealed that differential VS reactivity to positive versus negative feedback is negatively associated with the lifestyle facet. There was suggestive evidence for gender-specific patterns of association between brain function and psychopathy facets. Our findings are the first to document differential associations between both threat- and reward-related neural processes and distinct facets of psychopathy and thus provide a more comprehensive picture of the pattern of neural vulnerabilities that may predispose to maladaptive outcomes associated with psychopathy.

Element-specific behaviour and sediment properties modulate transfer and bioaccumulation of trace elements in a highly-contaminated area (Augusta Bay, Central Mediterranean Sea).

PubMed

Signa, Geraldina; Mazzola, Antonio; Di Leonardo, Rossella; Vizzini, Salvatrice

2017-11-01

High sediment contamination in the coastal area of Priolo Bay, adjacent to the highly-polluted Augusta Harbour, poses serious risks for the benthic communities inhabiting the area. Nevertheless, the transfer of trace elements and consequent bioaccumulation in the biota is an overlooked issue. This study aimed to assess the transfer and bioaccumulation patterns of As, Cd, Ni and Hg to the dominant macroalgae and benthic invertebrates of Priolo Bay. Results revealed different patterns among trace elements (TEs), not driven by sediment contamination but rather by element-specific behaviour coupled with sediment physicochemical properties. Specifically, As accumulated in macroalgae but not in invertebrates, indicating bioavailability of dissolved As only, and a lack of effective trophic transfer. Ni was confined to surface sediment and transfer to biota was not highlighted. Cd and Hg showed the highest concentrations in invertebrates and bioaccumulated especially in filter feeders and carnivores, revealing the importance of suspended particulate and diet as transfer pathways. Total organic carbon (TOC), fine-grained sediments and redox potential were the most important sediment features in shaping the sediment contamination spatial patterns as well as those of TE transfer and bioaccumulation. In particular, As and Cd transfer to macroalgae, and especially Hg bioaccumulation in benthic invertebrates was controlled by sediment properties, resulting in limited transfer and accumulation in the most contaminated stations. Copyright © 2017 Elsevier Ltd. All rights reserved.

IDO and galectin-3 hamper the ex vivo generation of clinical grade tumor-specific T cells for adoptive cell therapy in metastatic melanoma.

PubMed

Melief, Sara M; Visser, Marten; van der Burg, Sjoerd H; Verdegaal, Els M E

2017-07-01

Adoptive T cell transfer (ACT) with ex vivo-expanded tumor-reactive T cells proved to be successful for the treatment of metastatic melanoma patients. Mixed lymphocyte tumor cell cultures (MLTC) can be used to generate tumor-specific T cells for ACT; however, in a number of cases tumor-reactive T cell, expansion is far from optimal. We hypothesized that this is due to tumor intrinsic and extrinsic factors and aimed to identify and manipulate these factors so to optimize our clinical, GMP-compliant MLTC protocol. We found that the tumor cell produced IDO and/or galectin-3, and the accumulation of CD4 + CD25 hi FoxP3 + T cells suppressed the expansion of tumor-specific T cells in the MLTC. Strategies to eliminate CD4 + CD25 hi FoxP3 + T cells during culture required the depletion of the whole CD4 + T cell population and were found to be undesirable. Blocking of IDO and galectin-3 was feasible and resulted in improved efficiency of the MLTC. Implementation of these findings in clinical protocols for ex vivo expansion of tumor-reactive T cells holds promise for an increased therapeutic potential of adoptive cell transfer treatments with tumor-specific T cells.

Implementation of an original approach on the Mines-Douai Comparative Reactivity Method (MD-CRM) instrument to identify part of the missing OH reactivity at an urban site

NASA Astrophysics Data System (ADS)

Dusanter, S.; Michoud, V.; Leonardis, T.; Riffault, V.; Zhang, S.; Locoge, N.

2015-12-01

Due to the large number of Volatile Organic Compounds (VOCs) expected in the atmosphere (104-105) (Goldstein and Galbally, ES&T, 2007), exhaustive measurements of VOCs appear to be currently unfeasible using common analytical techniques. In this context, measurements of the total sink of OH, referred as total OH reactivity, can provide a critical test to assess the completeness of trace gas measurements during field campaigns. This can be done by comparing the measured total OH reactivity to values calculated from trace gas measurements. Indeed, large discrepancies are usually found between measured and calculated OH reactivity values revealing the presence of important unmeasured reactive species, which have yet to be identified. A Comparative Reactivity Method (CRM) instrument has been setup at Mines Douai to allow sequential measurements of VOCs and OH reactivity using the same Proton Transfer Reaction-Time of Flight Mass Spectrometer. This approach aims at identifying unmeasured reactive VOCs based on a method proposed by Kato et al. (Atmos. Environ., 2011), taking advantage of VOC oxidations occurring in the CRM sampling reactor. MD-CRM has been deployed at an urban site in Dunkirk (France) during July 2014 to test this new approach. During this campaign, a large fraction of the OH reactivity was not explained by collocated measurements of trace gases (67% on average). In this presentation, we will first describe the approach that was implemented in the CRM instrument to identify part of the observed missing OH reactivity and we will then discuss the OH reactivity budget regarding the origin of air masses reaching the measurement site.

Establishment of HSV1 Latency in Immunodeficient Mice Facilitates Efficient In Vivo Reactivation

PubMed Central

Ramakrishna, Chandran; Ferraioli, Adrianna; Calle, Aleth; Nguyen, Thanh K.; Openshaw, Harry; Lundberg, Patric S.; Lomonte, Patrick; Cantin, Edouard M.

2015-01-01

The establishment of latent infections in sensory neurons is a remarkably effective immune evasion strategy that accounts for the widespread dissemination of life long Herpes Simplex Virus type 1 (HSV1) infections in humans. Periodic reactivation of latent virus results in asymptomatic shedding and transmission of HSV1 or recurrent disease that is usually mild but can be severe. An in-depth understanding of the mechanisms regulating the maintenance of latency and reactivation are essential for developing new approaches to block reactivation. However, the lack of a reliable mouse model that supports efficient in vivo reactivation (IVR) resulting in production of infectious HSV1 and/or disease has hampered progress. Since HSV1 reactivation is enhanced in immunosuppressed hosts, we exploited the antiviral and immunomodulatory activities of IVIG (intravenous immunoglobulins) to promote survival of latently infected immunodeficient Rag mice. Latently infected Rag mice derived by high dose (HD), but not low dose (LD), HSV1 inoculation exhibited spontaneous reactivation. Following hyperthermia stress (HS), the majority of HD inoculated mice developed HSV1 encephalitis (HSE) rapidly and synchronously, whereas for LD inoculated mice reactivated HSV1 persisted only transiently in trigeminal ganglia (Tg). T cells, but not B cells, were required to suppress spontaneous reactivation in HD inoculated latently infected mice. Transfer of HSV1 memory but not OVA specific or naïve T cells prior to HS blocked IVR, revealing the utility of this powerful Rag latency model for studying immune mechanisms involved in control of reactivation. Crossing Rag mice to various knockout strains and infecting them with wild type or mutant HSV1 strains is expected to provide novel insights into the role of specific cellular and viral genes in reactivation, thereby facilitating identification of new targets with the potential to block reactivation. PMID:25760441

Transfer Printing Method to Obtain Polarized Light Emission in Organic Light-Emitting Device

NASA Astrophysics Data System (ADS)

Noh, Hee Yeon; Park, Chang-sub; Park, Ji-Sub; Kang, Shin-Won; Kim, Hak-Rin

2012-06-01

We demonstrate a transfer printing method to obtain polarized light emission in organic light-emitting devices (OLEDs). On a rubbed self-assembled monolayer (SAM), a spin-coated liquid crystalline light-emissive polymer is aligned along the rubbing direction because of the anisotropic interfacial intermolecular interaction. Owing to the low surface energy of the SAM surface, the light-emissive layer was easily transferred to a patterned poly(dimethylsiloxane) (PDMS) stamp surface without degrading the ordering. Finally, a polarized light-emissive OLED device was prepared by transferring the patterned light-emissive layer to the charge transport layer of the OLED structure.

Depressive Symptoms, Rumination, and Emotion Reactivity Among Youth: Moderation by Gender.

PubMed

Somers, Jennifer A; Borelli, Jessica L; Hilt, Lori M

2018-06-07

The emotion context-insensitivity hypothesis (ECI; Rottenberg et al., 2005) posits that depressive symptoms are associated with blunted emotional reactivity and is supported by the results of a meta-analysis (Bylsma et al., 2008). Yet it remains unclear how strongly ECI holds across emotional response domains, whether ECI operates similarly in male and female individuals, and whether this pattern of underreactivity is observed in youth. In contrast, rumination, a cognitive style strongly associated with depressive symptoms, may be associated with heightened reactivity. We assessed the effects of youth's depressive symptoms and rumination on subjective and physiological emotion reactivity (N = 160; M age  = 12.67, SD age  = 1.12; 48% female; 94% non-Hispanic). State sadness and respiratory sinus arrhythmia were assessed during a baseline activity (nature video) and a sad mood induction. As hypothesized, depressive symptoms predicted less subjective emotional reactivity, whereas rumination predicted more subjective reactivity. Exploratory analyses revealed that associations for physiological reactivity differed by child gender. ECI may be stronger in terms of subjective rather than physiological emotional reactivity.

Cutting Edge: Nonobese Diabetic Mice Deficient in Chromogranin A Are Protected from Autoimmune Diabetes.

PubMed

Baker, Rocky L; Bradley, Brenda; Wiles, Timothy A; Lindsay, Robin S; Barbour, Gene; Delong, Thomas; Friedman, Rachel S; Haskins, Kathryn

2016-01-01

T cells reactive to β cell Ags are critical players in the development of autoimmune type 1 diabetes. Using a panel of diabetogenic CD4 T cell clones derived from the NOD mouse, we recently identified the β cell secretory granule protein, chromogranin A (ChgA), as a new autoantigen in type 1 diabetes. CD4 T cells reactive to ChgA are pathogenic and rapidly transfer diabetes into young NOD recipients. We report in this article that NOD.ChgA(-/-) mice do not develop diabetes and show little evidence of autoimmunity in the pancreatic islets. Using tetramer analysis, we demonstrate that ChgA-reactive T cells are present in these mice but remain naive. In contrast, in NOD.ChgA(+/+) mice, a majority of the ChgA-reactive T cells are Ag experienced. Our results suggest that the presence of ChgA and subsequent activation of ChgA-reactive T cells are essential for the initiation and development of autoimmune diabetes in NOD mice. Copyright © 2015 by The American Association of Immunologists, Inc.

Consistency functional map propagation for repetitive patterns

NASA Astrophysics Data System (ADS)

Wang, Hao

2017-09-01

Repetitive patterns appear frequently in both man-made and natural environments. Automatically and robustly detecting such patterns from an image is a challenging problem. We study repetitive pattern alignment by embedding segmentation cue with a functional map model. However, this model cannot tackle the repetitive patterns directly due to the large photometric and geometric variations. Thus, a consistency functional map propagation (CFMP) algorithm that extends the functional map with dynamic propagation is proposed to address this issue. This propagation model is acquired in two steps. The first one aligns the patterns from a local region, transferring segmentation functions among patterns. It can be cast as an L norm optimization problem. The latter step updates the template segmentation for the next round of pattern discovery by merging the transferred segmentation functions. Extensive experiments and comparative analyses have demonstrated an encouraging performance of the proposed algorithm in detection and segmentation of repetitive patterns.

Chronic variable stress and intravenous methamphetamine self-administration – role of individual differences in behavioral and physiological reactivity to novelty

PubMed Central

Taylor, S.B.; Watterson, L.R.; Kufahl, P.R.; Nemirovsky, N.E.; Tomek, S.E.; Conrad, C.D.; Olive, M.F.

2016-01-01

Stress is a contributing factor to the development and maintenance of addiction in humans. However, few studies have shown that stress potentiates the rewarding and/or reinforcing effects of methamphetamine in rodent models of addiction. The present study assessed the effects of exposure to 14 days of chronic variable stress (CVS), or no stress as a control (CON), on the rewarding and reinforcing effects of methamphetamine in adult rats using the conditioned place preference (Experiment 1) and intravenous self-administration (Experiment 2) paradigms. In Experiment 2, we also assessed individual differences in open field locomotor activity, anxiety-like behavior in the elevated plus maze (EPM), and physiological responses to a novel environment as possible predictors of methamphetamine intake patterns. Exposure to CVS for 14 days did not affect overall measures of methamphetamine conditioned reward or reinforcement. However, analyses of individual differences and direct vs. indirect effects revealed that rats exhibiting high physiological reactivity and locomotor activity in the EPM and open field tests self-administered more methamphetamine and reached higher breakpoints for drug reinforcement than rats exhibiting low reactivity. In addition, CVS exposure significantly increased the proportion of rats that exhibited high reactivity, and high reactivity was significantly correlated with increased levels of methamphetamine intake. These findings suggest that individual differences in physiological and locomotor reactivity to novel environments, as well as their interactions with stress history, predict patterns of drug intake in rodent models of methamphetamine addiction. Such predictors may eventually inform future strategies for implementing individualized treatment strategies for amphetamine use disorders. PMID:27163191

Patterns of Physical and Relational Aggression in a School-Based Sample of Boys and Girls

ERIC Educational Resources Information Center

Crapanzano, Ann Marie; Frick, Paul J.; Terranova, Andrew M.

2010-01-01

The current study investigated the patterns of aggressive behavior displayed in a sample of 282 students in the 4th through 7th grades (M age = 11.28; SD = 1.82). Using cluster analyses, two distinct patterns of physical aggression emerged for both boys and girls with one aggressive cluster showing mild levels of reactive aggression and one group…

Prophylactic versus reactive treatment of acneiform skin rashes from epidermal growth factor receptor inhibitors in metastatic colorectal cancer.

PubMed

Dascalu, Bogdan; Kennecke, Hagen F; Lim, Howard J; Renouf, Daniel J; Ruan, Jenny Y; Chang, Jennifer T; Cheung, Winson Y

2016-02-01

There are concerns regarding potential negative effects of prophylactic treatment of epidermal growth factor receptor (EGFR)-inhibitor-related rashes on metastatic colorectal cancer (mCRC) outcomes. We aimed to characterize treatment patterns of EGFR-inhibitor-induced rashes and evaluate prophylactic versus reactive approaches to rash management in relation to overall survival (OS). Patients diagnosed with KRAS wild-type mCRC from July 2010 to June 2012 in British Columbia and prescribed cetuximab or panitumumab were reviewed to describe patterns of use of oral antibiotics and steroid creams. Using Cox regression, the relationship between prophylactic versus reactive rash management and OS was characterized. A total 119 patients were analyzed: median age was 63 years, 61 % were male, 34 % received cetuximab, 66 % received panitumumab, and median number of EGFR inhibitor treatment was nine cycles. Rash occurred in >90 % of patients, and reactive was favored over prophylactic treatment (66 vs. 34 %). Older patients and those with Eastern Cooperative Oncology Group (ECOG) performance status 0/1 were more likely to receive prophylactic creams (44 vs. 20 % for age <60, p = 0.01) and oral antibiotics (62 vs. 12 % for ECOG ≥2, p = 0.01), respectively. Median OS was 7.0 months. The number of treatment cycles and OS were similar in both prophylactic and reactive groups (both p > 0.05). In Cox regression, ECOG >2 correlated with worse survival (hazard ratio (HR) 22.01, 95 % confidence interval (CI) 5.25-92.30, p < 0.01). However, survival outcomes were similar between patients prescribed antibiotics prophylactically versus reactively (HR = 1.10, 95 % CI 0.43-2.80, p = 0.85), and steroid creams prophylactically versus reactively (HR = 2.00, 95 % CI 0.58-6.92, p = 0.27). Prophylactic treatment of EGFR-inhibitor-related rashes is associated with similar outcomes compared to reactive rash treatment in mCRC.

Work on a quantum dipole by a single-photon pulse.

PubMed

Valente, D; Brito, F; Ferreira, R; Werlang, T

2018-06-01

Energy transfer from a quantized field to a quantized dipole is investigated. We find that a single photon can transfer energy to a two-level dipole by inducing a dynamic Stark shift, going beyond the well-known absorption and emission processes. A quantum thermodynamical perspective allows us to unravel these two energy transfer mechanisms and to identify the former as a generalized work and the latter as a generalized heat. We show two necessary conditions for the generalized work transfer by a single photon to occur, namely, off-resonance and finite linewidth of the pulse. We also show that the generalized work performed by a single-photon pulse equals the reactive (dispersive) contribution of the work performed by a semiclassical pulse in the low-excitation regime.

Phenotype and function of T cells infiltrating visceral metastases from gastrointestinal cancers and melanoma: implications for adoptive cell transfer therapy.

PubMed

Turcotte, Simon; Gros, Alena; Hogan, Katherine; Tran, Eric; Hinrichs, Christian S; Wunderlich, John R; Dudley, Mark E; Rosenberg, Steven A

2013-09-01

Adoptive cell transfer of tumor-infiltrating lymphocytes (TILs) can mediate cancer regression in patients with metastatic melanoma, but whether this approach can be applied to common epithelial malignancies remains unclear. In this study, we compared the phenotype and function of TILs derived from liver and lung metastases from patients with gastrointestinal (GI) cancers (n = 14) or melanoma (n = 42). Fewer CD3(+) T cells were found to infiltrate GI compared with melanoma metastases, but the proportions of CD8(+) cells, T cell differentiation stage, and expression of costimulatory molecules were similar for both tumor types. Clinical-scale expansion up to ~50 × 10(9) T cells on average was obtained for all patients with GI cancer and melanoma. From GI tumors, however, TIL outgrowth in high-dose IL-2 yielded 22 ± 1.4% CD3(+)CD8(+) cells compared with 63 ± 2.4% from melanoma (p < 0.001). IFN-γ ELISA demonstrated MHC class I-mediated reactivity of TIL against autologous tumor in 5 of 7 GI cancer patients tested (9% of 188 distinct TIL cultures) and in 9 of 10 melanoma patients (43% of 246 distinct TIL cultures). In these assays, MHC class I-mediated up-regulation of CD137 (4-1BB) expression on CD8(+) cells suggested that 0-3% of TILs expanded from GI cancer metastases were tumor-reactive. This study implies that the main challenge to the development of TIL adoptive cell transfer for metastatic GI cancers may not be the in vitro expansion of bulk TILs, but the ability to select and enrich for tumor-reactive T cells.

Phenotype and Function of T Cells Infiltrating Visceral Metastases from Gastrointestinal Cancers and Melanoma: Implications for Adoptive Cell Transfer Therapy

PubMed Central

Turcotte, Simon; Gros, Alena; Hogan, Katherine; Tran, Eric; Hinrichs, Christian S.; Wunderlich, John R.; Dudley, Mark E.

2013-01-01

Adoptive cell transfer of tumor-infiltrating lymphocytes (TILs) can mediate cancer regression in patients with metastatic melanoma, but whether this approach can be applied to common epithelial malignancies remains unclear. In this study, we compared the phenotype and function of TILs derived from liver and lung metastases from patients with gastrointestinal (GI) cancers (n = 14) or melanoma (n = 42). Fewer CD3+ T cells were found to infiltrate GI compared with melanoma metastases, but the proportions of CD8+ cells, T cell differentiation stage, and expression of costimulatory molecules were similar for both tumor types. Clinical-scale expansion up to ∼50 × 109 T cells on average was obtained for all patients with GI cancer and melanoma. From GI tumors, however, TIL outgrowth in high-dose IL-2 yielded 22 ± 1.4% CD3+CD8+ cells compared with 63 ± 2.4% from melanoma (p < 0.001). IFN-γ ELISA demonstrated MHC class I–mediated reactivity of TIL against autologous tumor in 5 of 7 GI cancer patients tested (9% of 188 distinct TIL cultures) and in 9 of 10 melanoma patients (43% of 246 distinct TIL cultures). In these assays, MHC class I–mediated up-regulation of CD137 (4-1BB) expression on CD8+ cells suggested that 0–3% of TILs expanded from GI cancer metastases were tumor-reactive. This study implies that the main challenge to the development of TIL adoptive cell transfer for metastatic GI cancers may not be the in vitro expansion of bulk TILs, but the ability to select and enrich for tumor-reactive T cells. PMID:23904171

Placental transfer of conjugated bisphenol A and subsequent reactivation in the rat fetus.

PubMed

Nishikawa, Miyu; Iwano, Hidetomo; Yanagisawa, Risa; Koike, Nanako; Inoue, Hiroki; Yokota, Hiroshi

2010-09-01

Bisphenol A (BPA), a well-known endocrine disruptor, is highly glucuronidated in the liver, and the resultant BPA-glucuronide (BPA-GA) is excreted primarily into bile. However, in rodents, prenatal exposure to low doses of BPA can adversely affect the fetus, despite the efficient drug-metabolizing systems of the dams. The transport mechanisms of BPA from mother to fetus are unknown. To test our hypothesis that BPA-GA-an inactive metabolite-is passed through the placenta to the fetus, where it affects the fetus after reactivation, we investigated the placental transfer of BPA-GA and reactivation to BPA in the fetus. After performing uterine perfusion with BPA-GA in pregnant rats, we examined the expression and localization of the placental transporters for drug metabolites in the perfusate by reverse-transcriptase polymerase chain reaction and immunohistochemistry. We also investigated the deconjugation of BPA-GA in the fetus and examined uridine 5 -diphospho-glucuronosyltransferase (UGT) activity toward BPA and the expression of UGT isoforms in fetal liver. We detected BPA-GA and deconjugated BPA in the fetus and amniotic fluid after perfusion. In the trophoblast cells, organic anion-transporting polypeptide 4a1 (Oatp4a1) was localized on the apical membrane, and multidrug resistance-associated protein 1 (Mrp1) was localized to the basolateral membrane. We observed deconjugation of BPA-GA in the fetus; furthermore, we found the expression of UGT2B1, which metabolizes BPA, to be quite low in the fetus. These results demonstrate that BPA-GA is transferred into the fetus and deconjugated in the fetus because of its vulnerable drug-metabolizing system.

NY-ESO-1 antigen-reactive T cell receptors exhibit diverse therapeutic capability

PubMed Central

Sommermeyer, Daniel; Conrad, Heinke; Krönig, Holger; Gelfort, Haike; Bernhard, Helga; Uckert, Wolfgang

2013-01-01

The cancer-testis antigen NY-ESO-1 has been used as a target for different immunotherapies like vaccinations and adoptive transfer of antigen-specific cytotoxic T cells, as it is expressed in various tumor types and has limited expression in normal cells. The in vitro generation of T cells with defined antigen specificity by T cell receptor (TCR) gene transfer is an established method to create cells for immunotherapy. However, an extensive characterization of TCR which are candidates for treatment of patients is crucial for successful therapies. The TCR has to be efficiently expressed, their affinity to the desired antigen should be high enough to recognize low amounts of endogenously processed peptides on tumor cells, and the TCR should not be cross-reactive to other antigens. We characterized three NY-ESO-1 antigen-reactive cytotoxic T lymphocyte clones which were generated by different approaches of T cell priming (autologous, allogeneic), and transferred their TCR into donor T cells for more extensive evaluations. Although one TCR most efficiently bound MHC-multimers loaded with NY-ESO-1 peptide, T cells expressing this transgenic TCR were not able to recognize endogenously processed antigen. A second TCR recognized HLA-A2 independent of the bound peptide beside its much stronger recognition of NY-ESO-1 bound to HLA-A2. A third TCR displayed an intermediate but peptide-specific performance in all functional assays and, therefore, is the most promising candidate TCR for further clinical development. Our data indicate that multiple parameters of TCR gene-modified T cells have to be evaluated to identify an optimal TCR candidate for adoptive therapy. PMID:22907642

Placental Transfer of Conjugated Bisphenol A and Subsequent Reactivation in the Rat Fetus

PubMed Central

Nishikawa, Miyu; Iwano, Hidetomo; Yanagisawa, Risa; Koike, Nanako; Inoue, Hiroki; Yokota, Hiroshi

2010-01-01

Background Bisphenol A (BPA), a well-known endocrine disruptor, is highly glucuronidated in the liver, and the resultant BPA-glucuronide (BPA-GA) is excreted primarily into bile. However, in rodents, prenatal exposure to low doses of BPA can adversely affect the fetus, despite the efficient drug-metabolizing systems of the dams. The transport mechanisms of BPA from mother to fetus are unknown. Objectives To test our hypothesis that BPA-GA—an inactive metabolite—is passed through the placenta to the fetus, where it affects the fetus after reactivation, we investigated the placental transfer of BPA-GA and reactivation to BPA in the fetus. Methods After performing uterine perfusion with BPA-GA in pregnant rats, we examined the expression and localization of the placental transporters for drug metabolites in the perfusate by reverse-transcriptase polymerase chain reaction and immunohistochemistry. We also investigated the deconjugation of BPA-GA in the fetus and examined uridine 5′-diphospho-glucuronosyltransferase (UGT) activity toward BPA and the expression of UGT isoforms in fetal liver. Results We detected BPA-GA and deconjugated BPA in the fetus and amniotic fluid after perfusion. In the trophoblast cells, organic anion-transporting polypeptide 4a1 (Oatp4a1) was localized on the apical membrane, and multidrug resistance-associated protein 1 (Mrp1) was localized to the basolateral membrane. We observed deconjugation of BPA-GA in the fetus; furthermore, we found the expression of UGT2B1, which metabolizes BPA, to be quite low in the fetus. Conclusions These results demonstrate that BPA-GA is transferred into the fetus and deconjugated in the fetus because of its vulnerable drug-metabolizing system. PMID:20382578

Approach to a Pregnant Woman with Anti D + Anti C Reactivity Pattern: A Diagnostic Conundrum

PubMed Central

Rai, Preeti; Sharma, Geetika; Garg, Jyoti

2017-01-01

The Rhesus G antigen is present on all RBCs that are C+ and also on most D+ RBCs. Due to this co-distribution of G with either C or D antigen, it mimics a reactivity pattern of anti C + anti D on Indirect Antiglobulin Test (IAT), though the role of Anti G in causing Hemolytic Disease of Newborn (HDN) is controversial. The differentiation of anti D, anti C, and anti G is essential particularly in pregnant females. We hereby report a rare case of anti G with anti D and anti C in a pregnant woman with emphasis on approach to identify anti D+C+G and its implications. PMID:29207719

College Departure: Exploring Student Aid Effects on Multiple Mobility Patterns from Four-Year Institutions

ERIC Educational Resources Information Center

Kim, Dongbin; Saatcioglu, Argun; Neufeld, Amy

2012-01-01

College departure involves multiple mobility patterns that include lateral transfer (from a four-year to another four-year institution), reverse transfer (from a four-year to a two-year institution), and stop out (taking time out of higher education altogether). This study addresses how financial aid influences the likelihood of such mobility…

Rapid Transfer of Abstract Rules to Novel Contexts in Human Lateral Prefrontal Cortex

PubMed Central

Cole, Michael W.; Etzel, Joset A.; Zacks, Jeffrey M.; Schneider, Walter; Braver, Todd S.

2011-01-01

Flexible, adaptive behavior is thought to rely on abstract rule representations within lateral prefrontal cortex (LPFC), yet it remains unclear how these representations provide such flexibility. We recently demonstrated that humans can learn complex novel tasks in seconds. Here we hypothesized that this impressive mental flexibility may be possible due to rapid transfer of practiced rule representations within LPFC to novel task contexts. We tested this hypothesis using functional MRI and multivariate pattern analysis, classifying LPFC activity patterns across 64 tasks. Classifiers trained to identify abstract rules based on practiced task activity patterns successfully generalized to novel tasks. This suggests humans can transfer practiced rule representations within LPFC to rapidly learn new tasks, facilitating cognitive performance in novel circumstances. PMID:22125519

Moving bed reactor for solar thermochemical fuel production

DOEpatents

Ermanoski, Ivan

2013-04-16

Reactors and methods for solar thermochemical reactions are disclosed. Embodiments of reactors include at least two distinct reactor chambers between which there is at least a pressure differential. In embodiments, reactive particles are exchanged between chambers during a reaction cycle to thermally reduce the particles at first conditions and oxidize the particles at second conditions to produce chemical work from heat. In embodiments, chambers of a reactor are coupled to a heat exchanger to pre-heat the reactive particles prior to direct exposure to thermal energy with heat transferred from reduced reactive particles as the particles are oppositely conveyed between the thermal reduction chamber and the fuel production chamber. In an embodiment, particle conveyance is in part provided by an elevator which may further function as a heat exchanger.

Variability in emotional responsiveness and coping style during active avoidance as a window onto psychological vulnerability to stress.

PubMed

Gorka, Adam X; LaBar, Kevin S; Hariri, Ahmad R

2016-05-01

Individual differences in coping styles are associated with psychological vulnerability to stress. Recent animal research suggests that coping styles reflect trade-offs between proactive and reactive threat responses during active avoidance paradigms, with proactive responses associated with better stress tolerance. Based on these preclinical findings, we developed a novel instructed active avoidance paradigm to characterize patterns of proactive and reactive responses using behavioral, motoric, and autonomic measures in humans. Analyses revealed significant inter-individual variability not only in the magnitude of general emotional responsiveness but also the likelihood to specifically express proactive or reactive responses. In men but not women, individual differences in general emotional responsiveness were linked to increased trait anxiety while proactive coping style was linked to increased trait aggression. These patterns are consistent with preclinical findings and suggest that instructed active avoidance paradigms may be useful in assessing psychological vulnerability to stress using objective behavioral measures. Copyright © 2016. Published by Elsevier Inc.

Hispanic Students and Transfer in the Community College.

ERIC Educational Resources Information Center

Cohen, Arthur M.

A discussion is presented of Hispanic community college students and the prospects and problems related to their transfer to four-year institutions and progress toward the baccalaureate degree. First, the question of Hispanic student transfer rates is placed in the context of community college enrollment/transfer patterns in general and Hispanic…

Frequency-selective near-field radiative heat transfer between photonic crystal slabs: a computational approach for arbitrary geometries and materials.

PubMed

Rodriguez, Alejandro W; Ilic, Ognjen; Bermel, Peter; Celanovic, Ivan; Joannopoulos, John D; Soljačić, Marin; Johnson, Steven G

2011-09-09

We demonstrate the possibility of achieving enhanced frequency-selective near-field radiative heat transfer between patterned (photonic-crystal) slabs at designable frequencies and separations, exploiting a general numerical approach for computing heat transfer in arbitrary geometries and materials based on the finite-difference time-domain method. Our simulations reveal a tradeoff between selectivity and near-field enhancement as the slab-slab separation decreases, with the patterned heat transfer eventually reducing to the unpatterned result multiplied by a fill factor (described by a standard proximity approximation). We also find that heat transfer can be further enhanced at selective frequencies when the slabs are brought into a glide-symmetric configuration, a consequence of the degeneracies associated with the nonsymmorphic symmetry group.

A Novel Technique for Micro-patterning Proteins and Cells on Polyacrylamide Gels

PubMed Central

Tang, Xin; Ali, M. Yakut; Saif, M. Taher A.

2012-01-01

Spatial patterning of proteins (extracellular matrix, ECM) for living cells on polyacrylamide (PA) hydrogels has been technically challenging due to the compliant nature of the hydrogels and their aqueous environment. Traditional micro-fabrication process is not applicable. Here we report a simple, novel and general method to pattern a variety of commonly used cell adhesion molecules, i.e. Fibronectin (FN), Laminin (LN) and Collagen I (CN), etc. on PA gels. The pattern is first printed on a hydrophilic glass using polydimethylsiloxane (PDMS) stamp and micro-contact printing (μCP). Pre-polymerization solution is applied on the patterned glass and is then sandwiched by a functionalized glass slide, which covalently binds to the gel. The hydrophilic glass slide is then peeled off from the gel when the protein patterns detach from the glass, but remain intact with the gel. The pattern is thus transferred to the gel. The mechanism of pattern transfer is studied in light of interfacial mechanics. It is found that hydrophilic glass offers strong enough adhesion with ECM proteins such that a pattern can be printed, but weak enough adhesion such that they can be completely peeled off by the polymerized gel. This balance is essential for successful pattern transfer. As a demonstration, lines of FN, LN and CN with widths varying from 5–400 μm are patterned on PA gels. Normal fibroblasts (MKF) are cultured on the gel surfaces. The cell attachment and proliferation are confined within these patterns. The method avoids the use of any toxic chemistry often used to pattern different proteins on gel surfaces. PMID:23002394

Unified Behavior Framework for Reactive Robot Control in Real-Time Systems

DTIC Science & Technology

2007-03-01

maintain coherent operation in concurrent programs by employing standard communication and synchronization patterns. Some typical ones are: semaphores ...through the semaphore . Signals, whether persistent or transient, are used to communicate between threads as a means of synchronizing their progress...tasks to be decomposed into collections of low-level primitive behaviors, Figure 2.b. This approach takes on the self- contradictory term, reactive

Exploring the anionic reactivity of ynimines, useful precursors of metalated ketenimines.

PubMed

Laouiti, Anouar; Couty, François; Marrot, Jérome; Boubaker, Taoufik; Rammah, Mohamed M; Rammah, Mohamed B; Evano, Gwilherm

2014-04-18

Insights into the reactivity of ynimines under anionic conditions are reported. They were shown to be excellent precursors of metalated ketenimines, which can be generated in situ by the reaction of ynimines with organolithium reagents or strong bases. The metalated ketenimines can then be trapped with various electrophiles and, depending on their substitution pattern, afford original and divergent entries to various building blocks.

Neural mechanisms of interference control in working memory: effects of interference expectancy and fluid intelligence.

PubMed

Burgess, Gregory C; Braver, Todd S

2010-09-20

A critical aspect of executive control is the ability to limit the adverse effects of interference. Previous studies have shown activation of left ventrolateral prefrontal cortex after the onset of interference, suggesting that interference may be resolved in a reactive manner. However, we suggest that interference control may also operate in a proactive manner to prevent effects of interference. The current study investigated the temporal dynamics of interference control by varying two factors - interference expectancy and fluid intelligence (gF) - that could influence whether interference control operates proactively versus reactively. A modified version of the recent negatives task was utilized. Interference expectancy was manipulated across task blocks by changing the proportion of recent negative (interference) trials versus recent positive (facilitation) trials. Furthermore, we explored whether gF affected the tendency to utilize specific interference control mechanisms. When interference expectancy was low, activity in lateral prefrontal cortex replicated prior results showing a reactive control pattern (i.e., interference-sensitivity during probe period). In contrast, when interference expectancy was high, bilateral prefrontal cortex activation was more indicative of proactive control mechanisms (interference-related effects prior to the probe period). Additional results suggested that the proactive control pattern was more evident in high gF individuals, whereas the reactive control pattern was more evident in low gF individuals. The results suggest the presence of two neural mechanisms of interference control, with the differential expression of these mechanisms modulated by both experimental (e.g., expectancy effects) and individual difference (e.g., gF) factors.

Computational Study of Chemical Reactivity Using Information-Theoretic Quantities from Density Functional Reactivity Theory for Electrophilic Aromatic Substitution Reactions.

PubMed

Wu, Wenjie; Wu, Zemin; Rong, Chunying; Lu, Tian; Huang, Ying; Liu, Shubin

2015-07-23

The electrophilic aromatic substitution for nitration, halogenation, sulfonation, and acylation is a vastly important category of chemical transformation. Its reactivity and regioselectivity is predominantly determined by nucleophilicity of carbon atoms on the aromatic ring, which in return is immensely influenced by the group that is attached to the aromatic ring a priori. In this work, taking advantage of recent developments in quantifying nucleophilicity (electrophilicity) with descriptors from the information-theoretic approach in density functional reactivity theory, we examine the reactivity properties of this reaction system from three perspectives. These include scaling patterns of information-theoretic quantities such as Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy and information gain at both molecular and atomic levels, quantitative predictions of the barrier height with both Hirshfeld charge and information gain, and energetic decomposition analyses of the barrier height for the reactions. To that end, we focused in this work on the identity reaction of the monosubstituted-benzene molecule reacting with hydrogen fluoride using boron trifluoride as the catalyst in the gas phase. We also considered 19 substituting groups, 9 of which are ortho/para directing and the other 9 meta directing, besides the case of R = -H. Similar scaling patterns for these information-theoretic quantities found for stable species elsewhere were disclosed for these reactions systems. We also unveiled novel scaling patterns for information gain at the atomic level. The barrier height of the reactions can reliably be predicted by using both the Hirshfeld charge and information gain at the regioselective carbon atom. The energy decomposition analysis ensued yields an unambiguous picture about the origin of the barrier height, where we showed that it is the electrostatic interaction that plays the dominant role, while the roles played by exchange-correlation and steric effects are minor but indispensable. Results obtained in this work should shed new light for better understanding of the factors governing the reactivity for this class of reactions and assisting ongoing efforts for the design of new and more efficient catalysts for such kind of transformations.

Charge-transfer mechanism for electrophilic aromatic nitration and nitrosation via the convergence of (ab initio) molecular-orbital and Marcus-Hush theories with experiments.

PubMed

Gwaltney, Steven R; Rosokha, Sergiy V; Head-Gordon, Martin; Kochi, Jay K

2003-03-19

The highly disparate rates of aromatic nitrosation and nitration, despite the very similar (electrophilic) properties of the active species: NO(+) and NO(2)(+) in Chart 1, are quantitatively reconciled. First, the thorough mappings of the potential-energy surfaces by high level (ab initio) molecular-orbital methodologies involving extensive coupled-cluster CCSD(T)/6-31G optimizations establish the intervention of two reactive intermediates in nitration (Figure 8) but only one in nitrosation (Figure 7). Second, the same distinctive topologies involving double and single potential-energy minima (Figures 6 and 5) also emerge from the semiquantitative application of the Marcus-Hush theory to the transient spectral data. Such a striking convergence from quite different theoretical approaches indicates that the molecular-orbital and Marcus-Hush (potential-energy) surfaces are conceptually interchangeable. In the resultant charge-transfer mechanism, the bimolecular interactions of arene donors with both NO(+) and NO(2)(+) spontaneously lead (barrierless) to pi-complexes in which electron transfer is concurrent with complexation. Such a pi-complex in nitration is rapidly converted to the sigma-complex, whereas this Wheland adduct in nitrosation merely represents a high energy (transition-state) structure. Marcus-Hush analysis thus demonstrates how the strongly differentiated (arene) reactivities toward NO(+) and NO(2)(+) can actually be exploited in the quantitative development of a single coherent (electron-transfer) mechanism for both aromatic nitrosation and nitration.

EFFECTS OF MOVEABLE PLATFORM TRAINING IN PREVENTING SLIP-INDUCED FALLS IN OLDER ADULTS

PubMed Central

Parijat, Prakriti; Lockhart, Thurmon E

2011-01-01

Identifying effective interventions is vitalin preventing slip-induced fall accidents in older adults. The purpose of the current study was to evaluate the efficacy of moveable platform training in improving recovery reactions and reducing fall frequency in older adults. Twenty-four older adults were recruited and randomly assigned to two groups (training and control). Both groups underwent three sessions including baseline slip, training, and transfer of training on a slippery surface. Both groups experienced two slips on a slippery surface, one during the baseline and the other (after two weeks) during the transfer of training session. In the training session, the training group underwent twelve simulated slips using a moveable platform while the control group performed normal walking trials. Kinematic, kinetic, and EMG data were collected during all the sessions. Results indicated a reduced incidence of falls in the training group during the transfer of training trial as compared to the control group. The training group was able to transfer proactive and reactive control strategies learned during training to the second slip trial. The proactive adjustments include increased center-of-mass velocity and transitional acceleration after training. Reactive adjustments include reduction in muscle onset and time to peak activations of knee flexors and ankle plantarflexors, reduced ankle and knee coactivation, reduced slip displacement, and reduced time to peak knee flexion, trunk flexion, and hip flexion velocities. In general, the results indicated a beneficial effect of perturbation training in reducing slip severity and recovery kinematics in healthy older adults. PMID:22134467

REGENERATION/REACTIVATION OF CARBON ADSORBENTS BY RADIO FREQUENCY (RF) INDUCTION HEATING

EPA Science Inventory

We will use the experimental results to verify the numerical models and then use the models in parametric studies to determine the relative importance of each of the governing phenomena: electrical properties, heat transfer, RF applicator and adsorbent bed geometry...

Redox linked flavin sites in extracellular decaheme proteins involved in microbe-mineral electron transfer.

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

Edwards, Marcus J.; White, Gaye F.; Norman, Michael

2015-07-01

Extracellular microbe-mineral electron transfer is a major driving force for the oxidation of organic carbon in many subsurface environments. Extracellular multi-heme cytochromes of the Shewenella genus play a major role in this process but the mechanism of electron exchange at the interface between cytochrome and acceptor is widely debated. The 1.8 Å x-ray crystal structure of the decaheme MtrC revealed a highly conserved CX₈C disulfide that, when substituted for AX₈A, severely compromised the ability of S. oneidensis to grow under aerobic conditions. Reductive cleavage of the disulfide in the presence of flavin mononucleotide (FMN) resulted in the reversible formation ofmore » a stable flavocytochrome. Similar results were also observed with other decaheme cytochromes, OmcA, MtrF and UndA. The data suggest that these decaheme cytochromes can transition between highly reactive flavocytochromes or less reactive cytochromes, and that this transition is controlled by a redox active disulfide that responds to the presence of oxygen.« less

Understanding blue-light photoreceptors

NASA Astrophysics Data System (ADS)

Crane, Brian

Blue-light sensing proteins coordinate many biological processes that include phototropism, photomorphism, stress responses, virulence and the entrainment of circadian clocks. Three major types of blue-light sensors all bind flavin nucleotides as chromophores, but the photochemistry employed and conformational responses invoked differ considerably among the classes. Nevertheless, photoinduced electron transfer reactions play a key role in many mechanisms. How such reactivity leads to conformational signaling will be discussed for both cryptochromes (CRYs) and light- oxygen- voltage (LOV) domains. In CRYs, blue-light mediated flavin reduction promotes proton transfer within the active center that then leads to displacement of a key signaling element. For LOV proteins, blue light causes formation of a covalent cysteinyl-flavin adduct, which rearranges hydrogen bonding and restructures the N-terminal region of the protein. Interestingly, a new class of LOV-like sensor does not undergo adduct formation and instead can operate by flavin photoreduction, like CRY. Conserved aspects of reactivity in these proteins provide lessons for the design of new photosensors, which may find use as tools in optogenetics Supported by NIH GM079679.

Real-time imaging of oxidative and nitrosative stress in the liver of live animals for drug-toxicity testing

PubMed Central

Shuhendler, Adam J.; Pu, Kanyi; Cui, Lina; Uetrecht, Jack P.

2014-01-01

Current drug-safety assays for hepatotoxicity rely on biomarkers with low predictive power. The production of radical species, specifically reactive oxygen species (ROS) and reactive nitrogen species (RNS), has been proposed as an early unifying event linking the bioactivation of drugs to hepatotoxicity and as a more direct and mechanistic indicator of hepatotoxic potential. Here we present a nanosensor for rapid, real-time in vivo imaging of drug-induced ROS and RNS for direct evaluation of acute hepatotoxicity. By combining fluorescence resonance energy transfer (FRET) and chemiluminescence resonance energy transfer (CRET), our semiconducting polymer–based nanosensor simultaneously and differentially detects RNS and ROS using two optically independent channels. Drug-induced hepatotoxicity and its remediation are imaged longitudinally in mice following systemic challenge with acetaminophen or isoniazid. Dose-dependent ROS and RNS activity is detected in the liver within minutes of drug challenge, preceding histological changes, protein nitration and DNA double strand break induction. PMID:24658645

Enhanced anti-tumour immunity requires the interplay between resident and circulating memory CD8+ T cells

PubMed Central

Enamorado, Michel; Iborra, Salvador; Priego, Elena; Cueto, Francisco J.; Quintana, Juan A.; Martínez-Cano, Sarai; Mejías-Pérez, Ernesto; Esteban, Mariano; Melero, Ignacio; Hidalgo, Andrés; Sancho, David

2017-01-01

The goal of successful anti-tumoural immunity is the development of long-term protective immunity to prevent relapse. Infiltration of tumours with CD8+ T cells with a resident memory (Trm) phenotype correlates with improved survival. However, the interplay of circulating CD8+ T cells and Trm cells remains poorly explored in tumour immunity. Using different vaccination strategies that fine-tune the generation of Trm cells or circulating memory T cells, here we show that, while both subsets are sufficient for anti-tumour immunity, the presence of Trm cells improves anti-tumour efficacy. Transferred central memory T cells (Tcm) generate Trm cells following viral infection or tumour challenge. Anti-PD-1 treatment promotes infiltration of transferred Tcm cells within tumours, improving anti-tumour immunity. Moreover, Batf3-dependent dendritic cells are essential for reactivation of circulating memory anti-tumour response. Our findings show the plasticity, collaboration and requirements for reactivation of memory CD8+ T cells subsets needed for optimal tumour vaccination and immunotherapy. PMID:28714465

Redox Conditions Affect Ultrafast Exciton Transport in Photosynthetic Pigment-Protein Complexes.

PubMed

Allodi, Marco A; Otto, John P; Sohail, Sara H; Saer, Rafael G; Wood, Ryan E; Rolczynski, Brian S; Massey, Sara C; Ting, Po-Chieh; Blankenship, Robert E; Engel, Gregory S

2018-01-04

Pigment-protein complexes in photosynthetic antennae can suffer oxidative damage from reactive oxygen species generated during solar light harvesting. How the redox environment of a pigment-protein complex affects energy transport on the ultrafast light-harvesting time scale remains poorly understood. Using two-dimensional electronic spectroscopy, we observe differences in femtosecond energy-transfer processes in the Fenna-Matthews-Olson (FMO) antenna complex under different redox conditions. We attribute these differences in the ultrafast dynamics to changes to the system-bath coupling around specific chromophores, and we identify a highly conserved tyrosine/tryptophan chain near the chromophores showing the largest changes. We discuss how the mechanism of tyrosine/tryptophan chain oxidation may contribute to these differences in ultrafast dynamics that can moderate energy transfer to downstream complexes where reactive oxygen species are formed. These results highlight the importance of redox conditions on the ultrafast transport of energy in photosynthesis. Tailoring the redox environment may enable energy transport engineering in synthetic light-harvesting systems.

Preferential cross-linking of the small subunit of the electron-transfer flavoprotein to general acyl-CoA dehydrogenase.

PubMed Central

Steenkamp, D J

1987-01-01

The interaction between pig liver mitochondrial electron-transfer flavoprotein (ETF) and general acyl-CoA dehydrogenase (GAD) was investigated by means of the heterobifunctional reagent N-succinimidyl 3-(2-pyridyldithio)propionate. Neither ETF or GAD contained reactive thiol groups. The substitution of 9.4 lysine residues/FAD group in GAD with pyridyl disulphide structures did not affect the catalytic activity of the enzyme. Thiol groups were introduced into ETF by thiolation with methyl 4-mercaptobutyrimidate. ETF containing 10.5 reactive thiol groups/FAD group showed undiminished electron-acceptor activity with respect to GAD. The reaction of thiolated ETF and GAD containing pyridyl disulphide structures resulted in a decreased staining intensity of the small subunit of ETF on SDS/polyacrylamide-gel electrophoresis. Preferential cross-linking of the smaller subunit of ETF to GAD did not take place when ETF was first treated with SDS, but was unaffected by reduction of GAD by octanoyl-CoA. Images Fig. 2. Fig. 3. Fig. 5. PMID:3115254

Effects of Charge Transfer on the Adsorption of CO on Small Molybdenum-Doped Platinum Clusters.

PubMed

Ferrari, Piero; Vanbuel, Jan; Tam, Nguyen Minh; Nguyen, Minh Tho; Gewinner, Sandy; Schöllkopf, Wieland; Fielicke, André; Janssens, Ewald

2017-03-23

The interaction of carbon monoxide with platinum alloy nanoparticles is an important problem in the context of fuel cell catalysis. In this work, molybdenum-doped platinum clusters have been studied in the gas phase to obtain a better understanding of the fundamental nature of the Pt-CO interaction in the presence of a dopant atom. For this purpose, Pt n + and MoPt n-1 + (n=3-7) clusters were studied by combined mass spectrometry and density functional theory calculations, making it possible to investigate the effects of molybdenum doping on the reactivity of platinum clusters with CO. In addition, IR photodissociation spectroscopy was used to measure the stretching frequency of CO molecules adsorbed on Pt n + and MoPt n-1 + (n=3-14), allowing an investigation of dopant-induced charge redistribution within the clusters. This electronic charge transfer is correlated with the observed changes in reactivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Proactive transfer of learning depends on the evolution of prior learned task in memory.

PubMed

Tallet, Jessica; Kostrubiec, Viviane; Zanone, Pier-Giorgio

2010-06-01

The aim of the present study was to investigate the processes underlying the proactive interference effect using bimanual coordination. Our rationale was that interference would only occur when the prior learned A coordination pattern enters in competition with the required subsequent B pattern. We hypothesized that competition would arise only if the A pattern persists in memory before introducing the B pattern. In the experimental group, both A and B patterns were practiced and recalled, whereas in the control group only the B pattern was practiced and recalled. In Experiment 1, which involved initially bistable participants, the persistence of the A pattern led to interference, while, surprisingly, the A pattern forgetting entailed facilitation. In Experiment 2, which involved initially tristable participants, no such transfer effect was found. The apparently contradictory results can be interpreted coherently in the light of dynamical principles of learning. (c) 2010 Elsevier B.V. All rights reserved.

Salivary Alpha-Amylase Reactivity in Breast Cancer Survivors

PubMed Central

Wan, Cynthia; Couture-Lalande, Marie-Ève; Narain, Tasha A.; Lebel, Sophie; Bielajew, Catherine

2016-01-01

The two main components of the stress system are the hypothalamic-pituitary-adrenal (HPA) and sympathetic-adrenal-medullary (SAM) axes. While cortisol has been commonly used as a biomarker of HPA functioning, much less attention has been paid to the role of the SAM in this context. Studies have shown that long-term breast cancer survivors display abnormal reactive cortisol patterns, suggesting a dysregulation of their HPA axis. To fully understand the integrity of the stress response in this population, this paper explored the diurnal and acute alpha-amylase profiles of 22 breast cancer survivors and 26 women with no history of cancer. Results revealed that breast cancer survivors displayed identical but elevated patterns of alpha-amylase concentrations in both diurnal and acute profiles relative to that of healthy women, F (1, 39) = 17.95, p < 0.001 and F (1, 37) = 7.29, p = 0.010, respectively. The average area under the curve for the diurnal and reactive profiles was 631.54 ± 66.94 SEM and 1238.78 ± 111.84 SEM, respectively. This is in sharp contrast to their cortisol results, which showed normal diurnal and blunted acute patterns. The complexity of the stress system necessitates further investigation to understand the synergistic relationship of the HPA and SAM axes. PMID:27023572

Salivary Alpha-Amylase Reactivity in Breast Cancer Survivors.

PubMed

Wan, Cynthia; Couture-Lalande, Marie-Ève; Narain, Tasha A; Lebel, Sophie; Bielajew, Catherine

2016-03-23

The two main components of the stress system are the hypothalamic-pituitary-adrenal (HPA) and sympathetic-adrenal-medullary (SAM) axes. While cortisol has been commonly used as a biomarker of HPA functioning, much less attention has been paid to the role of the SAM in this context. Studies have shown that long-term breast cancer survivors display abnormal reactive cortisol patterns, suggesting a dysregulation of their HPA axis. To fully understand the integrity of the stress response in this population, this paper explored the diurnal and acute alpha-amylase profiles of 22 breast cancer survivors and 26 women with no history of cancer. Results revealed that breast cancer survivors displayed identical but elevated patterns of alpha-amylase concentrations in both diurnal and acute profiles relative to that of healthy women, F (1, 39) = 17.95, p < 0.001 and F (1, 37) = 7.29, p = 0.010, respectively. The average area under the curve for the diurnal and reactive profiles was 631.54 ± 66.94 SEM and 1238.78 ± 111.84 SEM, respectively. This is in sharp contrast to their cortisol results, which showed normal diurnal and blunted acute patterns. The complexity of the stress system necessitates further investigation to understand the synergistic relationship of the HPA and SAM axes.

Protein Conformational Dynamics Probed by Single-Molecule Electron Transfer

NASA Astrophysics Data System (ADS)

Yang, Haw; Luo, Guobin; Karnchanaphanurach, Pallop; Louie, Tai-Man; Rech, Ivan; Cova, Sergio; Xun, Luying; Xie, X. Sunney

2003-10-01

Electron transfer is used as a probe for angstrom-scale structural changes in single protein molecules. In a flavin reductase, the fluorescence of flavin is quenched by a nearby tyrosine residue by means of photo-induced electron transfer. By probing the fluorescence lifetime of the single flavin on a photon-by-photon basis, we were able to observe the variation of flavin-tyrosine distance over time. We could then determine the potential of mean force between the flavin and the tyrosine, and a correlation analysis revealed conformational fluctuation at multiple time scales spanning from hundreds of microseconds to seconds. This phenomenon suggests the existence of multiple interconverting conformers related to the fluctuating catalytic reactivity.

Predictive performance modeling framework for a novel enclosed particle receiver configuration and application for thermochemical energy storage

DOE PAGES

Martinek, Janna; Wendelin, Timothy; Ma, Zhiwen

2018-04-05

Concentrating solar power (CSP) plants can provide dispatchable power with a thermal energy storage capability for increased renewable-energy grid penetration. Particle-based CSP systems permit higher temperatures, and thus, potentially higher solar-to-electric efficiency than state-of-the-art molten-salt heat-transfer systems. This paper describes a detailed numerical analysis framework for estimating the performance of a novel, geometrically complex, enclosed particle receiver design. The receiver configuration uses arrays of small tubular absorbers to collect and subsequently transfer solar energy to a flowing particulate medium. The enclosed nature of the receiver design renders it amenable to either an inert heat-transfer medium, or a reactive heat-transfer medium that requires a controllable ambient environment. The numerical analysis framework described in this study is demonstrated for the case of thermal reduction of CaCr 0.1Mn 0.9O 3-more » $$\\delta$$ for thermochemical energy storage. The modeling strategy consists of Monte Carlo ray tracing for absorbed solar-energy distributions from a surround heliostat field, computational fluid dynamics modeling of small-scale local tubular arrays, surrogate response surfaces that approximately capture simulated tubular array performance, a quasi-two-dimensional reduced-order description of counter-flow reactive solids and purge gas, and a radiative exchange model applied to embedded-cavity structures at the size scale of the full receiver. In this work we apply the numerical analysis strategy to a single receiver configuration, but the framework can be generically applicable to alternative enclosed designs. In conclusion, we assess sensitivity of receiver performance to surface optical properties, heat-transfer coefficients, solids outlet temperature, and purge-gas feed rates, and discuss the significance of model assumptions and results for future receiver development.« less

Predictive performance modeling framework for a novel enclosed particle receiver configuration and application for thermochemical energy storage

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

Martinek, Janna; Wendelin, Timothy; Ma, Zhiwen

Concentrating solar power (CSP) plants can provide dispatchable power with a thermal energy storage capability for increased renewable-energy grid penetration. Particle-based CSP systems permit higher temperatures, and thus, potentially higher solar-to-electric efficiency than state-of-the-art molten-salt heat-transfer systems. This paper describes a detailed numerical analysis framework for estimating the performance of a novel, geometrically complex, enclosed particle receiver design. The receiver configuration uses arrays of small tubular absorbers to collect and subsequently transfer solar energy to a flowing particulate medium. The enclosed nature of the receiver design renders it amenable to either an inert heat-transfer medium, or a reactive heat-transfer medium that requires a controllable ambient environment. The numerical analysis framework described in this study is demonstrated for the case of thermal reduction of CaCr 0.1Mn 0.9O 3-more » $$\\delta$$ for thermochemical energy storage. The modeling strategy consists of Monte Carlo ray tracing for absorbed solar-energy distributions from a surround heliostat field, computational fluid dynamics modeling of small-scale local tubular arrays, surrogate response surfaces that approximately capture simulated tubular array performance, a quasi-two-dimensional reduced-order description of counter-flow reactive solids and purge gas, and a radiative exchange model applied to embedded-cavity structures at the size scale of the full receiver. In this work we apply the numerical analysis strategy to a single receiver configuration, but the framework can be generically applicable to alternative enclosed designs. In conclusion, we assess sensitivity of receiver performance to surface optical properties, heat-transfer coefficients, solids outlet temperature, and purge-gas feed rates, and discuss the significance of model assumptions and results for future receiver development.« less

Streambed peat lenses as redox-reactivity hotspots in lowland river hyporheic zones

NASA Astrophysics Data System (ADS)

Naden, Emma; Krause, Stefan; Cassidy, Nigel

2010-05-01

Hyporheic zones, as the direct interfaces between aquifers and rivers, are often characterised by increased redox reactivity and chemical transformation capacity. Depending on redox conditions and reaction types, hyporheic mixing of groundwater and surface water can lead to either attenuation or enrichment of pollutants or nutrients with diametrical implications for in-stream and aquifer hydro-ecological status. This study combines geophysical methods with distributed temperature sensor networks and nested multi-level sampling and analysis of hyporheic redox conditions and nutrient concentrations to investigate the reactive transport of nitrate at the aquifer-river interface of a UK lowland river. In stream Electric Resistivity Tomography and Ground Penetrating Radar (including core based ground truthing) have been applied to map the complex spatial patterns of highly conductive sandy and gravely sediments in contrast to semi-confining, low conductivity peat lenses which have been found to be characteristic for most lowland rivers. Reach scale (1km) spatial patterns and temporal dynamics of aquifer-river exchange have been identified by heat tracer experiments based on fibre-optical Distributed Temperature Sensing techniques combined with vertical thermocouple-arrays for tracing hyporheic flow paths. Spatial patterns of hyporheic redox conditions, dissolved oxygen (DO) and organic carbon (DOC) content as well as concentrations of major anions have been monitored in 48 nested multi-level mini-piezometers. Our investigations indicate that streambed temperature patterns were dominantly controlled by groundwater up-welling, causing cold spots in sandy and gravely sediments with high up-welling rates and low hyporheic residence times and warmer areas at the streambed surface where groundwater - surface water exchange was inhibited by streambed peat lenses. The flow-inhibiting peat structures have been found to cause semi-confined conditions in the up-welling groundwater, resulting in long residence times and increased redox-reactivity. Anoxic conditions and high DOC contents combined with long residence times underneath peat layers cause highly efficient denitrification rates, reducing nitrate concentrations from > 50mg/l to below the level of detection. In contrast, sandy and gravely areas of fast groundwater up-welling where characterized by only marginal changes in nitrate concentrations. The investigations lead to the development of a conceptual model of aquifer - river exchange and hyporheic reactivity in lowland rivers including temperature traceable hyporheic reactivity hotspots with high denitrification potential. The results for this exemplary field site highlight the substantial nutrient attenuation capacity of hyporheic zones at lowland rivers and emphasize the great importance of their consideration for river restoration programs and the assessment of water quality and ecological status.

Vascular stents with submicrometer-scale surface patterning realized via titanium deep reactive ion etching

NASA Astrophysics Data System (ADS)

Gott, Shannon C.; Jabola, Benjamin A.; Rao, Masaru P.

2015-08-01

Herein, we report progress towards realization of vascular stents that will eventually provide opportunity for evaluating cellular response to rationally-designed, submicrometer-scale surface patterning in physiologically-relevant contexts, i.e. those that provide exposure to the complex multicellular milieu, flow-induced shear, and tissue-device interactions present in vivo. Specifically, using our novel titanium deep reactive ion etching technique (Ti DRIE), we discuss recent advances that have enabled: (a) fabrication of precisely-defined, grating-based surface patterns on planar Ti foils with minimum feature sizes as small as 0.15 μm (b) creation of cylindrical stents from micromachined planar Ti foils; and (c) integration of these processes to produce the first submicrometer-scale surface-patterned Ti stents that are compatible with conventional balloon catheter deployment techniques. We also discuss results from elastoplastic finite element simulations and preliminary mechanical testing of these devices to assess their mechanical performance. These efforts represent key steps towards our long-term goal of developing a new paradigm in stenting, where rationally-designed surface patterning provides a physical means for facilitating healing, and thus, improving outcomes in vascular intervention applications.

Peroxide Activation for Electrophilic Reactivity by the Binuclear Non-heme Iron Enzyme AurF

DOE PAGES

Park, Kiyoung; Li, Ning; Kwak, Yeonju; ...

2017-05-01

Binuclear non-heme iron enzymes activate O 2 for diverse chemistries that include oxygenation of organic substrates and hydrogen atom abstraction. This process often involves the formation of peroxo-bridged biferric intermediates, only some of which can perform electrophilic reactions. To elucidate the geometric and electronic structural requirements to activate peroxo reactivity, the active peroxo intermediate in 4-aminobenzoate N-oxygenase (AurF) has been characterized spectroscopically and computationally. A magnetic circular dichroism study of reduced AurF shows that its electronic and geometric structures are poised to react rapidly with O 2. Nuclear resonance vibrational spectroscopic definition of the peroxo intermediate formed in this reactionmore » shows that the active intermediate has a protonated peroxo bridge. Density functional theory computations on the structure established here show that the protonation activates peroxide for electrophilic/single-electron-transfer reactivity. As a result, this activation of peroxide by protonation is likely also relevant to the reactive peroxo intermediates in other binuclear non-heme iron enzymes.« less

Peroxide Activation for Electrophilic Reactivity by the Binuclear Non-heme Iron Enzyme AurF

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

Park, Kiyoung; Li, Ning; Kwak, Yeonju

Binuclear non-heme iron enzymes activate O 2 for diverse chemistries that include oxygenation of organic substrates and hydrogen atom abstraction. This process often involves the formation of peroxo-bridged biferric intermediates, only some of which can perform electrophilic reactions. To elucidate the geometric and electronic structural requirements to activate peroxo reactivity, the active peroxo intermediate in 4-aminobenzoate N-oxygenase (AurF) has been characterized spectroscopically and computationally. A magnetic circular dichroism study of reduced AurF shows that its electronic and geometric structures are poised to react rapidly with O 2. Nuclear resonance vibrational spectroscopic definition of the peroxo intermediate formed in this reactionmore » shows that the active intermediate has a protonated peroxo bridge. Density functional theory computations on the structure established here show that the protonation activates peroxide for electrophilic/single-electron-transfer reactivity. As a result, this activation of peroxide by protonation is likely also relevant to the reactive peroxo intermediates in other binuclear non-heme iron enzymes.« less

Non-equilibrium reactive flux: A unified framework for slow and fast reaction kinetics.

PubMed

Bose, Amartya; Makri, Nancy

2017-10-21

The flux formulation of reaction rate theory is recast in terms of the expectation value of the reactive flux with an initial condition that corresponds to a non-equilibrium, factorized reactant density. In the common case of slow reactive processes, the non-equilibrium expression reaches the plateau regime only slightly slower than the equilibrium flux form. When the reactants are described by a single quantum state, as in the case of electron transfer reactions, the factorized reactant density describes the true initial condition of the reactive process. In such cases, the time integral of the non-equilibrium flux expression yields the reactant population as a function of time, allowing characterization of the dynamics in cases where there is no clear separation of time scales and thus a plateau regime cannot be identified. The non-equilibrium flux offers a unified approach to the kinetics of slow and fast chemical reactions and is ideally suited to mixed quantum-classical methods.

Diffusion-controlled reactions: hydrodynamic interaction between charged, uniformly reactive spherical reactants.

PubMed

Allison, Stuart

2006-12-28

In this work, different models of hydrodynamic interaction (HI) are examined in the diffusion-controlled reaction between uniformly reactive charged spherical particles. In addition to Oseen "stick" and "slip" models of HI, one is considered that accounts for the disturbance of fluid flow by the ions around one reactive partner as they interact with a neighboring reactive species. This interaction is closely related to the "electrophoretic effect" in electrokinetics and can be described by a fairly simple electrophoretic, or E-tensor. These models are applied to the electron-transfer quenching reaction of Ru(bpy)3(2+) and methyl viologen (MV2+) over a wide range of NaCl concentrations (Chiorboli, C. et al., J. Phys. Chem. 1988, 92, 156). The back reaction is also considered. From a comparison of the salt dependence of the model and experimental rates, it is concluded that the "E-tensor" model works best and ignoring HI altogether works worst. The Oseen "stick" and "slip" models fall between these.

Effect of mechanical activation on structure changes and reactivity in further chemical modification of lignin.

PubMed

Zhao, Xiaohong; Zhang, Yanjuan; Hu, Huayu; Huang, Zuqiang; Yang, Mei; Chen, Dong; Huang, Kai; Huang, Aimin; Qin, Xingzhen; Feng, Zhenfei

2016-10-01

Lignin was treated by mechanical activation (MA) in a customized stirring ball mill, and the structure and reactivity in further esterification were studied. The chemical structure and morphology of MA-treated lignin and the esterified products were analyzed by chemical analysis combined with UV/vis spectrometer, FTIR,NMR, SEM and particle size analyzer. The results showed that MA contributed to the increase of aliphatic hydroxyl, phenolic hydroxyl, carbonyl and carboxyl groups but the decrease of methoxyl groups. Moreover, MA led to the decrease of particle size and the increase of specific surface area and roughness of surface in lignin. The reactivity of lignin was enhanced significantly for the increase of hydroxyl content and the improvement of mass transfer in chemical reaction caused by the changes of molecular structure and morphological structure. The process of MA is green and simple, and is an effective method for enhancing the reactivity of lignin. Copyright © 2016 Elsevier B.V. All rights reserved.

Laser direct synthesis and patterning of silver nano/microstructures on a polymer substrate.

PubMed

Liu, Yi-Kai; Lee, Ming-Tsang

2014-08-27

This study presents a novel approach for the rapid fabrication of conductive nano/microscale metal structures on flexible polymer substrate (polyimide). Silver film is simultaneously synthesized and patterned on the polyimide substrate using an advanced continuous wave (CW) laser direct writing technology and a transparent, particle-free reactive silver ion ink. The location and shape of the resulting silver patterns are written by a laser beam from a digitally controlled micromirror array device. The silver patterns fabricated by this laser direct synthesis and patterning (LDSP) process exhibit the remarkably low electrical resistivity of 2.1 μΩ cm, which is compatible to the electrical resistivity of bulk silver. This novel LDSP process requires no vacuum chamber or photomasks, and the steps needed for preparation of the modified reactive silver ink are simple and straightforward. There is none of the complexity and instability associated with the synthesis of the nanoparticles that are encountered for the conventional laser direct writing technology which involves nanoparticle sintering process. This LDSP technology is an advanced method of nano/microscale selective metal patterning on flexible substrates that is fast and environmentally benign and shows potential as a feasible process for the roll-to-roll manufacturing of large area flexible electronic devices.

Patterning of supported gold monolayers via chemical lift-off lithography

PubMed Central

Slaughter, Liane S; Cheung, Kevin M; Kaappa, Sami; Cao, Huan H; Yang, Qing; Young, Thomas D; Serino, Andrew C; Malola, Sami; Olson, Jana M; Link, Stephan

2017-01-01

The supported monolayer of Au that accompanies alkanethiolate molecules removed by polymer stamps during chemical lift-off lithography is a scarcely studied hybrid material. We show that these Au–alkanethiolate layers on poly(dimethylsiloxane) (PDMS) are transparent, functional, hybrid interfaces that can be patterned over nanometer, micrometer, and millimeter length scales. Unlike other ultrathin Au films and nanoparticles, lifted-off Au–alkanethiolate thin films lack a measurable optical signature. We therefore devised fabrication, characterization, and simulation strategies by which to interrogate the nanoscale structure, chemical functionality, stoichiometry, and spectral signature of the supported Au–thiolate layers. The patterning of these layers laterally encodes their functionality, as demonstrated by a fluorescence-based approach that relies on dye-labeled complementary DNA hybridization. Supported thin Au films can be patterned via features on PDMS stamps (controlled contact), using patterned Au substrates prior to lift-off (e.g., selective wet etching), or by patterning alkanethiols on Au substrates to be reactive in selected regions but not others (controlled reactivity). In all cases, the regions containing Au–alkanethiolate layers have a sub-nanometer apparent height, which was found to be consistent with molecular dynamics simulations that predicted the removal of no more than 1.5 Au atoms per thiol, thus presenting a monolayer-like structure. PMID:29259879

HCV T Cell Receptor Chain Modifications to Enhance Expression, Pairing, and Antigen Recognition in T Cells for Adoptive Transfer.

PubMed

Foley, Kendra C; Spear, Timothy T; Murray, David C; Nagato, Kaoru; Garrett-Mayer, Elizabeth; Nishimura, Michael I

2017-06-16

T cell receptor (TCR)-gene-modified T cells for adoptive cell transfer can mediate objective clinical responses in melanoma and other malignancies. When introducing a second TCR, mispairing between the endogenous and introduced α and β TCR chains limits expression of the introduced TCR, which can result in impaired efficacy or off-target reactivity and autoimmunity. One approach to promote proper TCR chain pairing involves modifications of the introduced TCR genes: introducing a disulfide bridge, substituting murine for human constant regions, codon optimization, TCR chain leucine zipper fusions, and a single-chain TCR. We have introduced these modifications into our hepatitis C virus (HCV) reactive TCR and utilize a marker gene, CD34t, which allows us to directly compare transduction efficiency with TCR expression and T cell function. Our results reveal that of the TCRs tested, T cells expressing the murine Cβ2 TCR or leucine zipper TCR have the highest levels of expression and the highest percentage of lytic and interferon-γ (IFN-γ)-producing T cells. Our studies give us a better understanding of how TCR modifications impact TCR expression and T cell function that may allow for optimization of TCR-modified T cells for adoptive cell transfer to treat patients with malignancies.

Adoptive transfer of cytomegalovirus-specific CTL to stem cell transplant patients after selection by HLA–peptide tetramers

PubMed Central

Cobbold, Mark; Khan, Naeem; Pourgheysari, Batoul; Tauro, Sudhir; McDonald, Dorothy; Osman, Husam; Assenmacher, Mario; Billingham, Lucinda; Steward, Colin; Crawley, Charles; Olavarria, Eduardo; Goldman, John; Chakraverty, Ronjon; Mahendra, Premini; Craddock, Charles; Moss, Paul A.H.

2005-01-01

Stem cell transplantation is used widely in the management of a range of diseases of the hemopoietic system. Patients are immunosuppressed profoundly in the early posttransplant period, and reactivation of cytomegalovirus (CMV) remains a significant cause of morbidity and mortality. Adoptive transfer of donor-derived CMV-specific CD8+ T cell clones has been shown to reduce the rate of viral reactivation; however, the complexity of this approach severely limits its clinical application. We have purified CMV-specific CD8+ T cells from the blood of stem cell transplant donors using staining with HLA–peptide tetramers followed by selection with magnetic beads. CMV-specific CD8+ cells were infused directly into nine patients within 4 h of selection. Median cell dosage was 8.6 × 103/kg with a purity of 98% of all T cells. CMV-specific CD8+ T cells became detectable in all patients within 10 d of infusion, and TCR clonotype analysis showed persistence of infused cells in two patients studied. CMV viremia was reduced in every case and eight patients cleared the infection, including one patient who had a prolonged history of CMV infection that was refractory to antiviral therapy. This novel approach to adoptive transfer has considerable potential for antigen-specific T cell therapy. PMID:16061727

Triplet state dissolved organic matter in aquatic photochemistry: reaction mechanisms, substrate scope, and photophysical properties.

PubMed

McNeill, Kristopher; Canonica, Silvio

2016-11-09

Excited triplet states of chromophoric dissolved organic matter ( 3 CDOM*) play a major role among the reactive intermediates produced upon absorption of sunlight by surface waters. After more than two decades of research on the aquatic photochemistry of 3 CDOM*, the need for improving the knowledge about the photophysical and photochemical properties of these elusive reactive species remains considerable. This critical review examines the efforts to date to characterize 3 CDOM*. Information on 3 CDOM* relies mainly on the use of probe compounds because of the difficulties associated with directly observing 3 CDOM* using transient spectroscopic methods. Singlet molecular oxygen ( 1 O 2 ), which is a product of the reaction between 3 CDOM* and dissolved oxygen, is probably the simplest indicator that can be used to estimate steady-state concentrations of 3 CDOM*. There are two major modes of reaction of 3 CDOM* with substrates, namely triplet energy transfer or oxidation (via electron transfer, proton-coupled electron transfer or related mechanisms). Organic molecules, including several environmental contaminants, that are susceptible to degradation by these two different reaction modes are reviewed. It is proposed that through the use of appropriate sets of probe compounds and model photosensitizers an improved estimation of the distribution of triplet energies and one-electron reduction potentials of 3 CDOM* can be achieved.

Inverse problem analysis for identification of reaction kinetics constants in microreactors for biodiesel synthesis

NASA Astrophysics Data System (ADS)

Pontes, P. C.; Naveira-Cotta, C. P.

2016-09-01

The theoretical analysis for the design of microreactors in biodiesel production is a complicated task due to the complex liquid-liquid flow and mass transfer processes, and the transesterification reaction that takes place within these microsystems. Thus, computational simulation is an important tool that aids in understanding the physical-chemical phenomenon and, consequently, in determining the suitable conditions that maximize the conversion of triglycerides during the biodiesel synthesis. A diffusive-convective-reactive coupled nonlinear mathematical model, that governs the mass transfer process during the transesterification reaction in parallel plates microreactors, under isothermal conditions, is here described. A hybrid numerical-analytical solution via the Generalized Integral Transform Technique (GITT) for this partial differential system is developed and the eigenfunction expansions convergence rates are extensively analyzed and illustrated. The heuristic method of Particle Swarm Optimization (PSO) is applied in the inverse analysis of the proposed direct problem, to estimate the reaction kinetics constants, which is a critical step in the design of such microsystems. The results present a good agreement with the limited experimental data in the literature, but indicate that the GITT methodology combined with the PSO approach provide a reliable computational algorithm for direct-inverse analysis in such reactive mass transfer problems.

Reaction Dynamics of Proton-Coupled Electron Transfer from Reduced ZnO Nanocrystals.

PubMed

Braten, Miles N; Gamelin, Daniel R; Mayer, James M

2015-10-27

The creation of systems that efficiently interconvert chemical and electrical energies will be aided by understanding proton-coupled electron transfers at solution-semiconductor interfaces. Steps in developing that understanding are described here through kinetic studies of reactions of photoreduced colloidal zinc oxide (ZnO) nanocrystals (NCs) with the nitroxyl radical TEMPO. These reactions proceed by proton-coupled electron transfer (PCET) to give the hydroxylamine TEMPOH. They occur on the submillisecond to seconds time scale, as monitored by stopped-flow optical spectroscopy. Under conditions of excess TEMPO, the reactions are multiexponential in character. One of the contributors to this multiexponential kinetics may be a distribution of reactive proton sites. A graphical overlay method shows the reaction to be first order in [TEMPO]. Different electron concentrations in otherwise identical NC samples were achieved by three different methods: differing photolysis times, premixing with an unphotolyzed sample, or prereaction with TEMPO. The reaction velocities were consistently higher for NCs with higher numbers of electrons. For instance, NCs with an average of 2.6 e(-)/NC reacted faster than otherwise identical samples containing ≤1 e(-)/NC. Surprisingly, NC samples with the same average number of electrons but prepared in different ways often had different reaction profiles. These results show that properties beyond electron content determine PCET reactivity of the particles.

A quasi-classical study of energy transfer in collisions of hyperthermal H atoms with SO2 molecules.

PubMed

da Silva, Ramon S; Garrido, Juan D; Ballester, Maikel Y

2017-08-28

A deep understanding of energy transfer processes in molecular collisions is at central attention in physical chemistry. Particularly vibrational excitation of small molecules colliding with hot light atoms, via a metastable complex formation, has shown to be an efficient manner of enhancing reactivity. A quasi-classical trajectory study of translation-to-vibration energy transfer (T-V ET) in collisions of hyperthermal H( 2 S) atoms with SO 2 (X̃ 1 A ' ) molecules is presented here. For such a study, a double many-body expansion potential energy surface previously reported for HSO 2 ( 2 A) is used. This work was motivated by recent experiments by Ma et al. studying collisions of H + SO 2 at the translational energy of 59 kcal/mol [J. Ma et al., Phys. Rev. A 93, 040702 (2016)]. Calculations reproduce the experimental evidence that during majority of inelastic non-reactive collision processes, there is a metastable intermediate formation (HOSO or HSO 2 ). Nevertheless, the analysis of the trajectories shows that there are two distinct mechanisms in the T-V ET process: direct and indirect. Direct T-V processes are responsible for the high population of SO 2 with relatively low vibrational excitation energy, while indirect ones dominate the conversion from translational energy to high values of the vibrational counterpart.

Children’s Patterns of Emotional Reactivity to Conflict as Explanatory Mechanisms in Links Between Interpartner Aggression and Child Physiological Functioning

PubMed Central

Davies, Patrick T.; Sturge-Apple, Melissa L.; Cicchetti, Dante; Manning, Liviah G.; Zale, Emily

2009-01-01

Background This paper examined children’s fearful, sad, and angry reactivity to interparental conflict as mediators of associations between their exposure to interparental aggression and physiological functioning. Methods Participants included 200 toddlers and their mothers. Assessments of interparental aggression and children’s emotional reactivity were derived from maternal surveys and a semi-structured interview. Cortisol levels and cardiac indices of sympathetic nervous system (SNS) and parasympathetic nervous system (PNS) activity were used to assess toddler physiological functioning. Results Results indicated that toddler exposure to interparental aggression was associated with greater cortisol levels and PNS activity and diminished SNS activity. Toddler angry emotional reactivity mediated associations between interparental aggression and cortisol and PNS functioning. Fearful emotional reactivity was a mediator of the link between interparental aggression and SNS functioning. Conclusions The results are interpreted within conceptualizations of how exposure and reactivity to family risk organizing individual differences in physiological functioning. PMID:19744183

Modeling and sensitivity analysis of mass transfer in active multilayer polymeric film for food applications

NASA Astrophysics Data System (ADS)

Bedane, T.; Di Maio, L.; Scarfato, P.; Incarnato, L.; Marra, F.

2015-12-01

The barrier performance of multilayer polymeric films for food applications has been significantly improved by incorporating oxygen scavenging materials. The scavenging activity depends on parameters such as diffusion coefficient, solubility, concentration of scavenger loaded and the number of available reactive sites. These parameters influence the barrier performance of the film in different ways. Virtualization of the process is useful to characterize, design and optimize the barrier performance based on physical configuration of the films. Also, the knowledge of values of parameters is important to predict the performances. Inverse modeling and sensitivity analysis are sole way to find reasonable values of poorly defined, unmeasured parameters and to analyze the most influencing parameters. Thus, the objective of this work was to develop a model to predict barrier properties of multilayer film incorporated with reactive layers and to analyze and characterize their performances. Polymeric film based on three layers of Polyethylene terephthalate (PET), with a core reactive layer, at different thickness configurations was considered in the model. A one dimensional diffusion equation with reaction was solved numerically to predict the concentration of oxygen diffused into the polymer taking into account the reactive ability of the core layer. The model was solved using commercial software for different film layer configurations and sensitivity analysis based on inverse modeling was carried out to understand the effect of physical parameters. The results have shown that the use of sensitivity analysis can provide physical understanding of the parameters which highly affect the gas permeation into the film. Solubility and the number of available reactive sites were the factors mainly influencing the barrier performance of three layered polymeric film. Multilayer films slightly modified the steady transport properties in comparison to net PET, giving a small reduction in the permeability and oxygen transfer rate values. Scavenging capacity of the multilayer film increased linearly with the increase of the reactive layer thickness and the oxygen absorption reaction at short times decreased proportionally with the thickness of the external PET layer.

Modeling and sensitivity analysis of mass transfer in active multilayer polymeric film for food applications

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

Bedane, T.; Di Maio, L.; Scarfato, P.

The barrier performance of multilayer polymeric films for food applications has been significantly improved by incorporating oxygen scavenging materials. The scavenging activity depends on parameters such as diffusion coefficient, solubility, concentration of scavenger loaded and the number of available reactive sites. These parameters influence the barrier performance of the film in different ways. Virtualization of the process is useful to characterize, design and optimize the barrier performance based on physical configuration of the films. Also, the knowledge of values of parameters is important to predict the performances. Inverse modeling and sensitivity analysis are sole way to find reasonable values ofmore » poorly defined, unmeasured parameters and to analyze the most influencing parameters. Thus, the objective of this work was to develop a model to predict barrier properties of multilayer film incorporated with reactive layers and to analyze and characterize their performances. Polymeric film based on three layers of Polyethylene terephthalate (PET), with a core reactive layer, at different thickness configurations was considered in the model. A one dimensional diffusion equation with reaction was solved numerically to predict the concentration of oxygen diffused into the polymer taking into account the reactive ability of the core layer. The model was solved using commercial software for different film layer configurations and sensitivity analysis based on inverse modeling was carried out to understand the effect of physical parameters. The results have shown that the use of sensitivity analysis can provide physical understanding of the parameters which highly affect the gas permeation into the film. Solubility and the number of available reactive sites were the factors mainly influencing the barrier performance of three layered polymeric film. Multilayer films slightly modified the steady transport properties in comparison to net PET, giving a small reduction in the permeability and oxygen transfer rate values. Scavenging capacity of the multilayer film increased linearly with the increase of the reactive layer thickness and the oxygen absorption reaction at short times decreased proportionally with the thickness of the external PET layer.« less

Dynamic analysis of gas-core reactor system

NASA Technical Reports Server (NTRS)

Turner, K. H., Jr.

1973-01-01

A heat transfer analysis was incorporated into a previously developed model CODYN to obtain a model of open-cycle gaseous core reactor dynamics which can predict the heat flux at the cavity wall. The resulting model was used to study the sensitivity of the model to the value of the reactivity coefficients and to determine the system response for twenty specified perturbations. In addition, the model was used to study the effectiveness of several control systems in controlling the reactor. It was concluded that control drums located in the moderator region capable of inserting reactivity quickly provided the best control.

The state of the art of conventional flow visualization techniques for wind tunnel testing

NASA Technical Reports Server (NTRS)

Settles, G. S.

1982-01-01

Conventional wind tunnel flow visualization techniques which consist of surface flow methods, tracers, and optical methods are presented. Different surface flow methods are outlined: (1) liquid films (oil and fluorescent dye and UV lighting, renewable film via porous dispenser in model, volatile carrier fluid, cryogenic colored oil dots, oil film interferometry); (2) reactive surface treatment (reactive gas injection, reversible dye); (3) transition and heat transfer detectors (evaporation, sublimation, liquid crystals, phase change paints, IR thermography); and (4) tufts (fluorescent mini tufts, cryogenic suitability). Other methods are smoke wire techniques, vapor screens, and optical methods.

The laser versus the lamp: Reactivity of the diphenyl ketyl radical in the ground and excited states

NASA Astrophysics Data System (ADS)

Baumann, H.; Merckel, C.; Timpe, H.-J.; Graness, A.; Kleinschmidt, J.; Gould, I. R.; Turro, N. J.

1984-01-01

The diphenyl ketyl radical which is formed upon photolysis of α-phenyl benzoin is produced in its excited state upon intense pulsed laser irradiation. Using the techniques of time-resolved absorption and emission spectroscopy, reaction rate constants for the ground and excited states of this radical were obtained. For the radical quenchers employed, the excited state reactivity is found to be typically several orders of magnitude greater than that of the ground state. It is concluded that the excited state of diphenyl ketyl radical reacts predominantly by electron transfer processes.

Cannabis cue reactivity and craving among never, infrequent and heavy cannabis users.

PubMed

Henry, Erika A; Kaye, Jesse T; Bryan, Angela D; Hutchison, Kent E; Ito, Tiffany A

2014-04-01

Substance cue reactivity is theorized as having a significant role in addiction processes, promoting compulsive patterns of drug-seeking and drug-taking behavior. However, research extending this phenomenon to cannabis has been limited. To that end, the goal of the current work was to examine the relationship between cannabis cue reactivity and craving in a sample of 353 participants varying in self-reported cannabis use. Participants completed a visual oddball task whereby neutral, exercise, and cannabis cue images were presented, and a neutral auditory oddball task while event-related brain potentials (ERPs) were recorded. Consistent with past research, greater cannabis use was associated with greater reactivity to cannabis images, as reflected in the P300 component of the ERP, but not to neutral auditory oddball cues. The latter indicates the specificity of cue reactivity differences as a function of substance-related cues and not generalized cue reactivity. Additionally, cannabis cue reactivity was significantly related to self-reported cannabis craving as well as problems associated with cannabis use. Implications for cannabis use and addiction more generally are discussed.

Cannabis Cue Reactivity and Craving Among Never, Infrequent and Heavy Cannabis Users

PubMed Central

Henry, Erika A; Kaye, Jesse T; Bryan, Angela D; Hutchison, Kent E; Ito, Tiffany A

2014-01-01

Substance cue reactivity is theorized as having a significant role in addiction processes, promoting compulsive patterns of drug-seeking and drug-taking behavior. However, research extending this phenomenon to cannabis has been limited. To that end, the goal of the current work was to examine the relationship between cannabis cue reactivity and craving in a sample of 353 participants varying in self-reported cannabis use. Participants completed a visual oddball task whereby neutral, exercise, and cannabis cue images were presented, and a neutral auditory oddball task while event-related brain potentials (ERPs) were recorded. Consistent with past research, greater cannabis use was associated with greater reactivity to cannabis images, as reflected in the P300 component of the ERP, but not to neutral auditory oddball cues. The latter indicates the specificity of cue reactivity differences as a function of substance-related cues and not generalized cue reactivity. Additionally, cannabis cue reactivity was significantly related to self-reported cannabis craving as well as problems associated with cannabis use. Implications for cannabis use and addiction more generally are discussed. PMID:24264815

Diagrams for comprehensive molecular orbital-based chemical reaction analyses: reactive orbital energy diagrams.

PubMed

Tsuneda, Takao; Singh, Raman Kumar; Chattaraj, Pratim Kumar

2018-05-15

Reactive orbital energy diagrams are presented as a tool for comprehensively performing orbital-based reaction analyses. The diagrams rest on the reactive orbital energy theory, which is the expansion of conceptual density functional theory (DFT) to an orbital energy-based theory. The orbital energies on the intrinsic reaction coordinates of fundamental reactions are calculated by long-range corrected DFT, which is confirmed to provide accurate orbital energies of small molecules, combining with a van der Waals (vdW) correlation functional, in order to examine the vdW effect on the orbital energies. By analysing the reactions based on the reactive orbital energy theory using these accurate orbital energies, it is found that vdW interactions significantly affect the orbital energies in the initial reaction processes and that more than 70% of reactions are determined to be initially driven by charge transfer, while the remaining structural deformation (dynamics)-driven reactions are classified into identity, cyclization and ring-opening, unimolecular dissociation, and H2 reactions. The reactive orbital energy diagrams, which are constructed using these results, reveal that reactions progress so as to delocalize the occupied reactive orbitals, which are determined as contributing orbitals and are usually not HOMOs, by hybridizing the unoccupied reactive orbitals, which are usually not LUMOs. These diagrams also raise questions about conventional orbital-based diagrams such as frontier molecular orbital diagrams, even for the well-established interpretation of Diels-Alder reactions.

Fragmentation and reactivity in collisions of protonated diglycine with chemically modified perfluorinated alkylthiolate-self-assembled monolayer surfaces

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

Barnes, George L.; Yang Li; Hase, William L.

2011-03-07

Direct dynamics simulations are reported for quantum mechanical (QM)/molecular mechanical (MM) trajectories of N-protonated diglycine (gly{sub 2}-H{sup +}) colliding with chemically modified perfluorinated octanethiolate self-assembled monolayer (SAM) surfaces. The RM1 semiempirical theory is used for the QM component of the trajectories. RM1 activation and reaction energies were compared with those determined from higher-level ab initio theories. Two chemical modifications are considered in which a head group (-COCl or -CHO) is substituted on the terminal carbon of a single chain of the SAM. These surfaces are designated as the COCl-SAM and CHO-SAM, respectively. Fragmentation, peptide reaction with the SAM, and covalentmore » linkage of the peptide or its fragments with the SAM surface are observed. Peptide fragmentation via concerted CH{sub 2}-CO bond breakage is the dominant pathway for both surfaces. HCl formation is the dominant species produced by reaction with the COCl-SAM, while for the CHO-SAM a concerted H-atom transfer from the CHO-SAM to the peptide combined with either a H-atom or radical transfer from the peptide to the surface to form singlet reaction products is the dominant pathway. A strong collision energy dependence is found for the probability of peptide fragmentation, its reactivity, and linkage with the SAM. Surface deposition, i.e., covalent linkage between the surface and the peptide, is compared to recent experimental observations of such bonding by Laskin and co-workers [Phys. Chem. Chem. Phys. 10, 1512 (2008)]. Qualitative differences in reactivity are seen between the COCl-SAM and CHO-SAM showing that chemical identity is important for surface reactivity. The probability of reactive surface deposition, which is most closely analogous to experimental observables, peaks at a value of around 20% for a collision energy of 50 eV.« less

Spatially Controlled Noncovalent Functionalization of 2D Materials Based on Molecular Architecture.

PubMed

Bang, Jae Jin; Porter, Ashlin G; Davis, Tyson C; Hayes, Tyler R; Claridge, Shelley A

2018-05-15

Polymerizable amphiphiles can be assembled into lying-down phases on 2D materials such as graphite and graphene to create chemically orthogonal surface patterns at 5-10 nm scales, locally modulating functionality of the 2D basal plane. Functionalization can be carried out through Langmuir-Schaefer conversion, in which a subset of molecules is transferred out of a standing phase film on water onto the 2D substrate. Here, we leverage differences in molecular structure to spatially control transfer at both nanoscopic and microscopic scales. We compare transfer properties of five different single- and dual-chain amphiphiles, demonstrating that those with strong lateral interactions (e.g., hydrogen-bonding networks) exhibit the lowest transfer efficiencies. Since molecular structures also influence microscopic domain morphologies in Langmuir films, we show that it is possible to transfer such microscale patterns, taking advantage of variations in the local transfer rates based on the structural heterogeneity in Langmuir films. Nanoscale domain morphologies also vary in ways that are consistent with predicted relative transfer and diffusion rates. These results suggest strategies to tailor noncovalent functionalization of 2D substrates through controlled LS transfer.

Emotional Reactivity and Regulation in Head Start Children: Links to Ecologically-Valid Behaviors and Internalizing Problems

PubMed Central

Morgan, Judith K.; Izard, Carroll E.; Hyde, Christopher

2013-01-01

Children’s emotional reactivity may interact with their regulatory behaviors to contribute to internalizing problems and social functioning even early in development. Ninety-one preschool children participated in a longitudinal project examining children’s reactivity and regulatory behaviors as predictors of internalizing problems and positive and negative social behavior in the classroom. Children who paired negative emotion expression with disengagement during a laboratory task showed higher levels of internalizing problems and more negative social behavior in the classroom six months later. Positive emotion expression paired with engagement during a laboratory task predicted more positive social behavior in the classroom six months later. Physiological reactivity and regulation also predicted children’s social behavior in the classroom. Findings suggest that preschool children with maladaptive reactivity and regulatory patterns may be at greater risk for internalizing problems even in early childhood. PMID:25067866

Emerging technologies to remove nonpoint phosphorus sources from surface water and groundwater

USDA-ARS?s Scientific Manuscript database

New innovative remediation practices are currently being developed that address phosphorus transfers from soils and applied sources to surface and ground waters. These practices include reactive barriers placed along field ditches and drainage ways, retention filters at the end of tile drains, mater...

S-Nitrosylation and the Development of Pulmonary Hypertension

DTIC Science & Technology

2010-02-01

cleavage, catalyzed by transition metal ions and reactive oxygen species, or through enzymatic degradation. One specific enzyme that regulates S...Hb causes a change in its conformation, resulting in the transfer of nitrosonium (NO+) equivalents from the heme (Fe+2) to the thiol (cysteine β93

Three-dimensional orientation of iris in an ocular prosthesis using a customized scale.

PubMed

Gupta, Lokendra; Aparna, I N; Dhanasekar, B; Prabhu, Nayana; Malla, Nirjalla; Agarwal, Priyanka

2014-04-01

The success of an ocular prosthesis depends largely on the correct orientation of the iris disk. Various methods have been put forth to achieve this. This article emphasizes one such simplified method, wherein a customized scale has been used to orient the iris disk mediolaterally, superoinferiorly, and anteroposteriorly in an ocular prosthesis. A scleral wax pattern was fabricated. The customized scale was used to measure the dimension and orientation of the natural iris. These measurements were then transferred to the scleral wax pattern with the customized scale. An iris disk was fabricated using black crayon on the scleral wax pattern according to the measurements. The scleral wax pattern, including the iris disk, was then placed in the eye socket to verify its dimension and orientation. A prefabricated iris disk was modified according to the measured dimensions and transferred to the final scleral wax pattern. The transfer of these dimensions to the definitive prosthesis was achieved successfully, ultimately improving the patient's social and psychological well being. © 2013 by the American College of Prosthodontists.

Origins of low energy-transfer efficiency between patterned GaN quantum well and CdSe quantum dots

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

Xu, Xingsheng, E-mail: xsxu@semi.ac.cn

For hybrid light emitting devices (LEDs) consisting of GaN quantum wells and colloidal quantum dots, it is necessary to explore the physical mechanisms causing decreases in the quantum efficiencies and the energy transfer efficiency between a GaN quantum well and CdSe quantum dots. This study investigated the electro-luminescence for a hybrid LED consisting of colloidal quantum dots and a GaN quantum well patterned with photonic crystals. It was found that both the quantum efficiency of colloidal quantum dots on a GaN quantum well and the energy transfer efficiency between the patterned GaN quantum well and the colloidal quantum dots decreasedmore » with increases in the driving voltage or the driving time. Under high driving voltages, the decreases in the quantum efficiency of the colloidal quantum dots and the energy transfer efficiency can be attributed to Auger recombination, while those decreases under long driving time are due to photo-bleaching and Auger recombination.« less

Transfer of tactile perceptual learning to untrained neighboring fingers reflects natural use relationships

PubMed Central

Harrar, Vanessa; Oliver, Jonathan; Johansen-Berg, Heidi; Spence, Charles

2015-01-01

Tactile learning transfers from trained to untrained fingers in a pattern that reflects overlap between the representations of fingers in the somatosensory system (e.g., neurons with multifinger receptive fields). While physical proximity on the body is known to determine the topography of somatosensory representations, tactile coactivation is also an established organizing principle of somatosensory topography. In this study we investigated whether tactile coactivation, induced by habitual inter-finger cooperative use (use pattern), shapes inter-finger overlap. To this end, we used psychophysics to compare the transfer of tactile learning from the middle finger to its adjacent fingers. This allowed us to compare transfer to two fingers that are both physically and cortically adjacent to the middle finger but have differing use patterns. Specifically, the middle finger is used more frequently with the ring than with the index finger. We predicted this should lead to greater representational overlap between the former than the latter pair. Furthermore, this difference in overlap should be reflected in differential learning transfer from the middle to index vs. ring fingers. Subsequently, we predicted temporary learning-related changes in the middle finger's representation (e.g., cortical magnification) would cause transient interference in perceptual thresholds of the ring, but not the index, finger. Supporting this, longitudinal analysis revealed a divergence where learning transfer was fast to the index finger but relatively delayed to the ring finger. Our results support the theory that tactile coactivation patterns between digits affect their topographic relationships. Our findings emphasize how action shapes perception and somatosensory organization. PMID:26631145

Transfer of tactile perceptual learning to untrained neighboring fingers reflects natural use relationships.

PubMed

Dempsey-Jones, Harriet; Harrar, Vanessa; Oliver, Jonathan; Johansen-Berg, Heidi; Spence, Charles; Makin, Tamar R

2016-03-01

Tactile learning transfers from trained to untrained fingers in a pattern that reflects overlap between the representations of fingers in the somatosensory system (e.g., neurons with multifinger receptive fields). While physical proximity on the body is known to determine the topography of somatosensory representations, tactile coactivation is also an established organizing principle of somatosensory topography. In this study we investigated whether tactile coactivation, induced by habitual inter-finger cooperative use (use pattern), shapes inter-finger overlap. To this end, we used psychophysics to compare the transfer of tactile learning from the middle finger to its adjacent fingers. This allowed us to compare transfer to two fingers that are both physically and cortically adjacent to the middle finger but have differing use patterns. Specifically, the middle finger is used more frequently with the ring than with the index finger. We predicted this should lead to greater representational overlap between the former than the latter pair. Furthermore, this difference in overlap should be reflected in differential learning transfer from the middle to index vs. ring fingers. Subsequently, we predicted temporary learning-related changes in the middle finger's representation (e.g., cortical magnification) would cause transient interference in perceptual thresholds of the ring, but not the index, finger. Supporting this, longitudinal analysis revealed a divergence where learning transfer was fast to the index finger but relatively delayed to the ring finger. Our results support the theory that tactile coactivation patterns between digits affect their topographic relationships. Our findings emphasize how action shapes perception and somatosensory organization. Copyright © 2016 the American Physiological Society.

Sequential development of structural heterogeneity in the Granny Creek oil field of West Virginia

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

Wilson, T.H.; Zheng, L.; Shumaker, R.C.

1993-08-01

Analysis of Vibroseis and weight-drop seismic data over the Granny Creek oil field in the Appalachian foreland of West Virginia indicates that the field's development has been effected by episodic Paleozoic reactivation of fault blocks rooted in the Precambrian crystalline basement. The imprint of structures associated with the Rome trough penetrates the overlying Paleozoic sedimentary cover. Reactivation histories of individual fault blocks vary considerably throughout the Paleozoic. In general, the relative displacement of these basement fault blocks decrease exponentially during the Paleozoic; however, this pattern is interrupted by periods of increased tectonic activity and relative inversion of offsets along somemore » faults. The distribution of late-stage detached structures during the Alleghenian orogeny also appears, in part, to be controlled by mechanical anisotrophy within the detached section related to the reactivation of deeper structures in the crystalline basement. The net effect is a complex time-variable pattern of structures that partly controls the location of the reservoir and heterogeneity within the geometric framework of the reservoir. Structural heterogeneity in the Granny Creek area is subdivided on the basis of scale into structures associated with variations of oil production within the reservoir. Variations of production within the field are related, in part, to small detached structures and reactivated basement faults.« less

NIR-Mediated Nanohybrids of Upconversion Nanophosphors and Fluorescent Conjugated Polymers for High-Efficiency Antibacterial Performance Based on Fluorescence Resonance Energy Transfer.

PubMed

Li, Junting; Zhao, Qi; Shi, Feng; Liu, Chenghui; Tang, Yanli

2016-12-01

A novel nanohybrid comprised of upconversion nanophosphors (UCNPs) and fluorescent conjugated polymers (PFVCN) is rationally fabricated. The new UCNP/PFVCN nanohybrids combine the excellent antibacterial ability of PFVCN and the near IR (NIR) absorbing property of UCNPs, which allows for NIR-mediated antibacterial through the effective fluorescence resonance energy transfer from UCNPs to PFVCN accompanied with generation of reactive oxygen species to kill bacteria. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Beyond alkyl transfer: Synthesis of main group metal (Mg, Ca, Zn) silyl and tris(oxazolinyl)borato complexes and their stoichiometric and catalytic reactions with borane Lewis acids and carbonyls

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

Lampland, Nicole Lynn

2015-05-09

Recently, the fundamental knowledge of main group metal chemistry has grown. This progress is crucial for the further development of main group metal compounds in silicon chemistry and catalysis and for advancing their applications as green alternatives to many rare earth and transition metal compounds. This thesis focuses on reactivity beyond the welldocumented alkyl-transfer applications for main group metals, and it highlights examples of reactions with Lewis acids and the reduction of carbonyls.

Allyl Transfer to Aldehydes and Ketones by Brønsted Acid Activation of Allyl and Crotyl 1,3,2-Dioxazaborolidines

PubMed Central

Reilly, Maureen K.; Rychnovsky, Scott D.

2010-01-01

Alkyl dioxazaborolidines are air-stable and often crystalline organoboranes. A variety of Brønsted acids activate allyl dioxazaborolidines to generate reactive allyl-transfer reagents in situ. These reagents add to aldehydes and ketones to generate the corresponding alcohols in good yields under mild conditions. The E- and Z-crotyl reagents react diastereoselectively with aldehydes and ketones to produce anti and syn adducts, respectively, a result consistent with a cyclic transition state (Type I mechanism). PMID:20942379

Interhospital transfer of critically ill and injured children: an evaluation of transfer patterns, resource utilization, and clinical outcomes.

PubMed

Odetola, Folafoluwa O; Davis, Matthew M; Cohn, Lisa M; Clark, Sarah J

2009-03-01

To describe patterns of transfer, resource utilization, and clinical outcomes associated with interhospital transfer of critically ill and injured children. Secondary analysis of administrative claims data. Children 0 to 18 years in the Michigan Medicaid program who underwent interhospital transfer for intensive care from January 1, 2002 to December 31, 2004. The 3 sources of transfer from referring hospitals were: emergency department (ED), ward, or intensive care unit (ICU). Mortality and duration of hospital stay at the receiving hospitals. Of 1643 interhospital transfer admissions to intensive care at receiving hospitals, 62%, 31%, and 7% were from the ED, ward, and ICU of referring hospitals, respectively. Nineteen percent had comorbid illness, while 11% had organ dysfunction at the referring hospital. After controlling for comorbid illness, patient age, and pretransfer organ dysfunction; compared with ED transfers, mortality in the receiving hospital was higher for ward transfers (odds ratio [OR], 1.76; 95% confidence interval [CI], 1.02-3.03) but not for ICU transfers. Also, compared with ED transfers, hospital stay was longer by 1.5 days for ward transfers and by 13.5 days for ICU transfers. In this multiyear, statewide sample, mortality and resource utilization were higher among children who underwent interhospital transfer to intensive care after initial hospitalization, compared with those transferred directly from emergency to intensive care. Decision-making underlying initial triage and subsequent interhospital transfer of critically ill children warrants further study. (c) 2009 Society of Hospital Medicine.

Parabolic dune reactivation and migration at Napeague, NY, USA: Insights from aerial and GPR imagery

NASA Astrophysics Data System (ADS)

Girardi, James D.; Davis, Dan M.

2010-02-01

Observations from mapping since the 19th century and aerial imagery since 1930 have been used to study changes in the aeolian geomorphology of coastal parabolic dunes over the last ~ 170 years in the Walking Dune Field, Napeague, NY. The five large parabolic dunes of the Walking Dune Field have all migrated across, or are presently interacting with, a variably forested area that has affected their migration, stabilization and morphology. This study has concentrated on a dune with a particularly complex history of stabilization, reactivation and migration. We have correlated that dune's surface evolution, as revealed by aerial imagery, with its internal structures imaged using 200 MHz and 500 MHz Ground Penetrating Radar (GPR) surveys. Both 2D (transect) and high-resolution 3D GPR imagery image downwind dipping bedding planes which can be grouped by apparent dip angle into several discrete packages of beds that reflect distinct decadal-scale episodes of dune reactivation and growth. From aerial and high resolution GPR imagery, we document a unique mode of reactivation and migration linked to upwind dune formation and parabolic dune interactions with forest trees. This study documents how dune-dune and dune-vegetation interactions have influenced a unique mode of blowout deposition that has alternated on a decadal scale between opposite sides of a parabolic dune during reactivation and migration. The pattern of recent parabolic dune reactivation and migration in the Walking Dune Field appears to be somewhat more complex, and perhaps more sensitive to subtle environmental pressures, than an idealized growth model with uniform deposition and purely on-axis migration. This pattern, believed to be prevalent among other parabolic dunes in the Walking Dune Field, may occur also in many other places where similar observational constraints are unavailable.

Chronic variable stress and intravenous methamphetamine self-administration - Role of individual differences in behavioral and physiological reactivity to novelty.

PubMed

Taylor, S B; Watterson, L R; Kufahl, P R; Nemirovsky, N E; Tomek, S E; Conrad, C D; Olive, M F

2016-09-01

Stress is a contributing factor to the development and maintenance of addiction in humans. However, few studies have shown that stress potentiates the rewarding and/or reinforcing effects of methamphetamine in rodent models of addiction. The present study assessed the effects of exposure to 14 days of chronic variable stress (CVS), or no stress as a control (CON), on the rewarding and reinforcing effects of methamphetamine in adult rats using the conditioned place preference (Experiment 1) and intravenous self-administration (Experiment 2) paradigms. In Experiment 2, we also assessed individual differences in open field locomotor activity, anxiety-like behavior in the elevated plus maze (EPM), and physiological responses to a novel environment as possible predictors of methamphetamine intake patterns. Exposure to CVS for 14 days did not affect overall measures of methamphetamine conditioned reward or reinforcement. However, analyses of individual differences and direct vs. indirect effects revealed that rats exhibiting high physiological reactivity and locomotor activity in the EPM and open field tests self-administered more methamphetamine and reached higher breakpoints for drug reinforcement than rats exhibiting low reactivity. In addition, CVS exposure significantly increased the proportion of rats that exhibited high reactivity, and high reactivity was significantly correlated with increased levels of methamphetamine intake. These findings suggest that individual differences in physiological and locomotor reactivity to novel environments, as well as their interactions with stress history, predict patterns of drug intake in rodent models of methamphetamine addiction. Such predictors may eventually inform future strategies for implementing individualized treatment strategies for amphetamine use disorders. Copyright © 2016 Elsevier Ltd. All rights reserved.

Distilling Heterogeneity among Children with Disruptive Behavior: Associations between Symptom Patterns and Social Functioning.

PubMed

Aitken, Madison; Henry, Shanelle; Andrade, Brendan F

2017-10-16

Children with disruptive behavior (DB) are a heterogeneous group who exhibit several characteristics that may contribute to poor social functioning. The present study identified profiles of reactive aggression, proactive aggression, callous-unemotional (CU) traits, and prosocial behavior in a sample of children with DB. Associations with social functioning (social interaction, social status) were then examined, along with sex differences in profile membership. Parent ratings of 304 clinic-referred children ages 6-12 years with DB were analyzed using latent profile analysis. Five profiles were identified: 1) Moderate prosocial behavior, reactive aggression, and CU, and low proactive aggression (labelled Moderate); 2) Relatively high prosocial behavior and low reactive and proactive aggression and CU traits (Prosocial); 3) High prosocial behavior and reactive aggression, moderate proactive aggression, and low-moderate CU (Reactive-Prosocial); 4) Low prosocial behavior, high CU, high-moderate reactive aggression, and low-moderate proactive aggression (Reactive-CU); and 5) Low prosocial behavior and high reactive and proactive aggression and CU (Aggressive-CU). Profiles characterized by CU traits, reactive aggression, and low prosocial behavior were associated with the most problematic parent-rated social interaction and social status. The results highlight the need to differentiate profiles of psychopathology in children with DB to better address factors most associated with social functioning.

Lesions along the upper motor neuronal pathway with locked-in features after lightning strike and cardiac arrest: a case-review analysis.

PubMed

Abdulla, Susanne; Conrad, Anton; Schwemm, Karl-Peter; Stienstra, Mark P; Gorsselink, Edward L; Dengler, Reinhard; Abdulla, Walied

2014-01-01

This study describes a case of lesions of the upper motor neuronal pathway with locked-in features after lightning strike and cardiac arrest. A case-review analysis. In a 29-year-old male who was hit by a lightning strike during farming activities, cardiopulmonary resuscitation was provided first by co-workers and continued with success by the medical rescue service. After conducting advanced life support under monitoring and therapeutic hypothermia, quadriplegia with facial diplegia was recognized. A review was undertaken detailing the clinical course. MR imaging presented signs consistent with hypoxia-induced damage and diffusion-weighted MR images revealed pronounced damages along the upper motor neuronal pathway. A reactive electroencephalogram pattern, sustained eye movement and the patient communicating via eye-blinking were interpreted as locked-in features. Two weeks after admission the patient was transferred to a neurological rehabilitation centre for further professional care. Direct damage of the upper motor neuron pathway due to the current of the lightning should be considered, albeit the relative contribution of hypoxia-induced damage cannot be separated.

Bio-inspired Fabrication of Complex Hierarchical Structure in Silicon.

PubMed

Gao, Yang; Peng, Zhengchun; Shi, Tielin; Tan, Xianhua; Zhang, Deqin; Huang, Qiang; Zou, Chuanping; Liao, Guanglan

2015-08-01

In this paper, we developed a top-down method to fabricate complex three dimensional silicon structure, which was inspired by the hierarchical micro/nanostructure of the Morpho butterfly scales. The fabrication procedure includes photolithography, metal masking, and both dry and wet etching techniques. First, microscale photoresist grating pattern was formed on the silicon (111) wafer. Trenches with controllable rippled structures on the sidewalls were etched by inductively coupled plasma reactive ion etching Bosch process. Then, Cr film was angled deposited on the bottom of the ripples by electron beam evaporation, followed by anisotropic wet etching of the silicon. The simple fabrication method results in large scale hierarchical structure on a silicon wafer. The fabricated Si structure has multiple layers with uniform thickness of hundreds nanometers. We conducted both light reflection and heat transfer experiments on this structure. They exhibited excellent antireflection performance for polarized ultraviolet, visible and near infrared wavelengths. And the heat flux of the structure was significantly enhanced. As such, we believe that these bio-inspired hierarchical silicon structure will have promising applications in photovoltaics, sensor technology and photonic crystal devices.

Arrays of ferromagnetic nanorings with variable thickness fabricated by capillary force lithography.

PubMed

Lee, Su Yeon; Jeong, Jong-Ryul; Kim, Shin-Hyun; Kim, Sarah; Yang, Seung-Man

2009-11-03

A new promising strategy is reported for the fabrication of ferromagnetic nanoring arrays with novel geometrical features through the use of capillary force lithography and subsequent reactive ion etching. In particular, we fabricated two different types of elliptic rings with variable width and height: one with pinching zones near the major axes and the other with pinching zones near the minor axes. We used PDMS stamps with either elliptic hole or antihole arrays for creating these elliptic rings with variable thickness by virtue of the uneven capillary rise, which was induced by the distributed Laplace pressure around the walls of elliptic holes or antiholes with nonuniform local curvatures. We transferred the polymer ring patterns to array of elliptical NiFe rings by Ar ion milling and characterized magnetic properties in terms of nonuniform ring width using magnetic force microscopy measurements. Our results demonstrated that the magnetic domain wall can be positioned in a controlled manner by using these novel elliptical ferromagnetic rings with local pinching zones and that the proposed CFL method can be utilized as a simple and effective fabrication tool.

Effects of ultrasonic energy on dyeing of polyamide (microfibre)/Lycra blends.

PubMed

Merdan, Nigar; Akalin, Mehmet; Kocak, Dilara; Usta, Ismail

2004-04-01

Although ultrasonic energy is widely used cleaning and degreasing of parts and assemblies in automotive and other industries, the use of ultrasonic energy in an industrial scale for textile washing is very new. This is due to the complexity of controlling the combination of chemical and mechanical effects, whereas with degreasing of machine parts only the mechanical effects is applied. The use of ultrasonic energy in dyeing PA/Lycra fabrics with reactive dyes has been studied spectrophotometrically in this work. PA/Lycra (85/15) blends have been dyed using conventional and ultrasonic dyeing techniques with three reactive dyes containing different chromophore and reactive groups. The dyeing carried out conventionally and by the use of ultrasonic techniques. The results were compared in terms of percentage exhaustion; total dye transferred to the washing bath after dyeing and the fastness properties.

Redox and Reactive Oxygen Species Regulation of Mitochondrial Cytochrome c Oxidase Biogenesis

PubMed Central

Bourens, Myriam; Fontanesi, Flavia; Soto, Iliana C.; Liu, Jingjing

2013-01-01

Abstract Significance: Cytochrome c oxidase (COX), the last enzyme of the mitochondrial respiratory chain, is the major oxygen consumer enzyme in the cell. COX biogenesis involves several redox-regulated steps. The process is highly regulated to prevent the formation of pro-oxidant intermediates. Recent Advances: Regulation of COX assembly involves several reactive oxygen species and redox-regulated steps. These include: (i) Intricate redox-controlled machineries coordinate the expression of COX isoenzymes depending on the environmental oxygen concentration. (ii) COX is a heme A-copper metalloenzyme. COX copper metallation involves the copper chaperone Cox17 and several other recently described cysteine-rich proteins, which are oxidatively folded in the mitochondrial intermembrane space. Copper transfer to COX subunits 1 and 2 requires concomitant transfer of redox power. (iii) To avoid the accumulation of reactive assembly intermediates, COX is regulated at the translational level to minimize synthesis of the heme A-containing Cox1 subunit when assembly is impaired. Critical Issues: An increasing number of regulatory pathways converge to facilitate efficient COX assembly, thus preventing oxidative stress. Future Directions: Here we will review on the redox-regulated COX biogenesis steps and will discuss their physiological relevance. Forthcoming insights into the precise regulation of mitochondrial COX biogenesis in normal and stress conditions will likely open future perspectives for understanding mitochondrial redox regulation and prevention of oxidative stress. Antioxid. Redox Signal. 19, 1940–1952. PMID:22937827

Endogenous T-Cell Therapy: Clinical Experience.

PubMed

Yee, Cassian; Lizee, Greg; Schueneman, Aaron J

2015-01-01

Adoptive cellular therapy represents a robust means of augmenting the tumor-reactive effector population in patients with cancer by adoptive transfer of ex vivo expanded T cells. Three approaches have been developed to achieve this goal: the use of tumor-infiltrating lymphocytes or tumor-infiltrating lymphocytess extracted from patient biopsy material; the redirected engineering of lymphocytes using vectors expressing a chimeric antigen receptor and T-cell receptor; and third, the isolation and expansion of often low-frequency endogenous T cells (ETCs) reactive to tumor antigens from the peripheral blood of patients. This last form of adoptive transfer of T cells, known as ETC therapy, requires specialized methods to isolate and expand from peripheral blood the very low-frequency tumor-reactive T cells, methods that have been developed over the last 2 decades, to the point where such an approach may be broadly applicable not only for the treatment of melanoma but also for that of other solid tumor malignancies. One compelling feature of ETC is the ability to rapidly deploy clinical trials following identification of a tumor-associated target epitope, a feature that may be exploited to develop personalized antigen-specific T-cell therapy for patients with almost any solid tumor. With a well-validated antigen discovery pipeline in place, clinical studies combining ETC with agents that modulate the immune microenvironment can be developed that will transform ETC into a feasible treatment modality.

Behavioral Characteristics and Instructional Patterns of Expert Teaching, and the Transfer of Those Behaviors into a Musical Setting: Two Case Studies

ERIC Educational Resources Information Center

Johnson, Christopher; Williams, Lindsey; Parisi, Joseph; Brunkan, Melissa

2016-01-01

The purpose of the present investigation was to analyze the teaching characteristics and instructional patterns of an expert teacher, and then to examine whether those observed teaching aspects could transfer into a musical setting. A teacher of swimming was videotaped giving the first four swim lessons to a 2-year-old child. Recordings were…

Biocompatible patterning of proteins on wettability gradient surface by thermo-transfer printing.

PubMed

Kim, Sungho; Ryu, Yong-Sang; Suh, Jeng-Hun; Keum, Chang-Min; Sohn, Youngjoo; Lee, Sin-Doo

2014-08-01

We develop a simple and biocompatible method of patterning proteins on a wettability gradient surface by thermo-transfer printing. The wettability gradient is produced on a poly(dimethylsiloxane) (PDMS)-modified glass substrate through the temperature gradient during thermo-transfer printing. The water contact angle on the PDMS-modified surface is found to gradually increase along the direction of the temperature gradient from a low to a high temperature region. Based on the wettability gradient, the gradual change in the adsorption and immobilization of proteins (cholera toxin B subunit) is achieved in a microfluidic cell with the PDMS-modified surface.

The effect of iron to manganese substitution on microperoxidase 8 catalysed peroxidase and cytochrome P450 type of catalysis.

PubMed

Primus, J L; Boersma, M G; Mandon, D; Boeren, S; Veeger, C; Weiss, R; Rietjens, I M

1999-06-01

This study describes the catalytic properties of manganese microperoxidase 8 [Mn(III)MP8] compared to iron microperoxidase 8 [Fe(III)MP8]. The mini-enzymes were tested for pH-dependent activity and operational stability in peroxidase-type conversions, using 2-methoxyphenol and 3,3'-dimethoxybenzidine, and in a cytochrome P450-like oxygen transfer reaction converting aniline to para-aminophenol. For the peroxidase type of conversions the Fe to Mn replacement resulted in a less than 10-fold decrease in the activity at optimal pH, whereas the aniline para-hydroxylation is reduced at least 30-fold. In addition it was observed that the peroxidase type of conversions are all fully blocked by ascorbate and that aniline para-hydroxylation by Fe(III)MP8 is increased by ascorbate whereas aniline para-hydroxylation by Mn(III)MP8 is inhibited by ascorbate. Altogether these results indicate that different types of reactive metal oxygen intermediates are involved in the various conversions. Compound I/II, scavenged by ascorbate, may be the reactive species responsible for the peroxidase reactions, the polymerization of aniline and (part of) the oxygen transfer to aniline in the absence of ascorbate. The para-hydroxylation of aniline by Fe(III)MP8, in the presence of ascorbate, must be mediated by another reactive iron-oxo species which could be the electrophilic metal(III) hydroperoxide anion of microperoxidase 8 [M(III)OOH MP8]. The lower oxidative potential of Mn, compared to Fe, may affect the reactivity of both compound I/II and the metal(III) hydroperoxide anion intermediate, explaining the differential effect of the Fe to Mn substitution on the pH-dependent behavior, the rate of catalysis and the operational stability of MP8.

Gas-phase reactivity of lanthanide cations with fluorocarbons: C-F versus C-H and C-C bond activation

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

Cornehl, H.H.; Hornung, G.; Schwarz, H.

1996-10-16

The gas-phase reactivity of the fluorinated hydrocarbons CF{sub 4}, CHF{sub 3}, CH{sub 3}F, C{sub 2}F{sub 6}, 1,1-C{sub 2}H{sub 4}F{sub 2}, and C{sub 6}F{sub 6} with the lanthanide cations Ce{sup +}, Pr{sup +}, Sm{sup +}, Ho{sup +}, Tm{sup +}, and Yb{sup +} and the reactivity of C{sub 6}H{sub 5}F with all lanthanide cations Ln{sup +} (Ln = La-Lu, with the exception of Pm{sup +}) have been examined by Fourier-transform ion cyclotron resonance mass spectrometry. The perfluorinated compounds tetrafluoromethane and hexafluoroethane as well as trifluoromethane do not react with any lanthanide cation. Selective activation of the strong C-F bonds in fluoromethane, 1,1-difluoroethane,more » hexafluorobenzene, and fluorobenzene appears as a general reaction scheme along the 4f row. Experimental evidence is given for a `harpoon`-like mechanism for the F atom abstraction process which operates via an initial electron transfer from the lanthanide cation to the fluorinated substrate in the encounter complex Ln{sup +}RF. The most reactive lanthanides La{sup +}, Ce{sup +}, Gd{sup +}, and Tb{sup +} and also the formal closed-shell species Lu{sup +} exhibit additional C-H and C-C bond activation pathways in the reaction with fluorobenzene, namely dehydrohalogenation as well as loss of a neutral acetylene molecule. In the case of Tm{sup +} and Yb{sup +} the formation of neutral LnF{sub 3} is observed in a multistep process via C-C coupling and charge transfer. 17 refs., 2 figs., 2 tabs.« less

Driving force analysis of proton tunnelling across a reactivity series for an enzyme-substrate complex.

PubMed

Hothi, Parvinder; Hay, Sam; Roujeinikova, Anna; Sutcliffe, Michael J; Lee, Michael; Leys, David; Cullis, Paul M; Scrutton, Nigel S

2008-11-24

Quantitative structure-activity relationships are widely used to probe C-H bond breakage by quinoprotein enzymes. However, we showed recently that p-substituted benzylamines are poor reactivity probes for the quinoprotein aromatic amine dehydrogenase (AADH) because of a requirement for structural change in the enzyme-substrate complex prior to C-H bond breakage. This rearrangement is partially rate limiting, which leads to deflated kinetic isotope effects for p-substituted benzylamines. Here we report reactivity (driving force) studies of AADH with p-substituted phenylethylamines for which the kinetic isotope effect (approximately 16) accompanying C-H/C-(2)H bond breakage is elevated above the semi-classical limit. We show bond breakage occurs by quantum tunnelling and that within the context of the environmentally coupled framework for H-tunnelling the presence of the p-substituent places greater demand on the apparent need for fast promoting motions. The crystal structure of AADH soaked with phenylethylamine or methoxyphenylethylamine indicates that the structural change identified with p-substituted benzylamines should not limit the reaction with p-substituted phenylethylamines. This is consistent with the elevated kinetic isotope effects measured with p-substituted phenylethylamines. We find a good correlation in the rate constant for proton transfer with bond dissociation energy for the reactive C-H bond, consistent with a rate that is limited by a Marcus-like tunnelling mechanism. As the driving force becomes larger, the rate of proton transfer increases while the Marcus activation energy becomes smaller. This is the first experimental report of the driving force perturbation of H-tunnelling in enzymes using a series of related substrates. Our study provides further support for proton tunnelling in AADH.

Secondary targets of nitrite-derived reactive nitrogen species: nitrosation/nitration pathways, antioxidant defense mechanisms and toxicological implications.

PubMed

d'Ischia, Marco; Napolitano, Alessandra; Manini, Paola; Panzella, Lucia

2011-12-19

Nitrite, the primary metabolite of nitric oxide (NO) and a widely diffused component of human diet, plays distinct and increasingly appreciated roles in human physiology. However, when exposed to acidic environments, typically in the stomach, or under oxidative stress conditions, it may be converted to a range of reactive nitrogen species (RNS) which in turn can target a variety of biomolecules. Typical consequences of toxicological relevance include protein modification, DNA base deamination and the formation of N-nitrosamines, among the most potent mutagenic and carcinogenic compounds for humans. Besides primary biomolecules, nitrite can cause structural modifications to a variety of endogenous and exogenous organic compounds, ranging from polyunsaturated fatty acids to estrogens, tocopherol, catecholamines, furans, retinoids, dietary phenols, and a range of xenobiotics. The study of the interactions between nitrite and key food components, including phenolic antioxidants, has therefore emerged as an area of great promise for delineating innovative strategies in cancer chemoprevention. Depending on substrates and conditions, diverse reaction pathways may compete to determine product features and distribution patterns. These include nitrosation and nitration but also oxidation, via electron transfer to nitrosonium ion or nitrogen dioxide. This contribution aims to provide an overview of the main classes of compounds that can be targeted by nitrite and to discuss at chemical levels the possible reaction mechanisms under conditions that model those occurring in the stomach. The toxicological implications of the nitrite-modified molecules are finally addressed, and a rational chemical approach to the design of potent antinitrosing agents is illustrated. © 2011 American Chemical Society

Secreted Oral Epithelial Cell Membrane Vesicles Induce Epstein-Barr Virus Reactivation in Latently Infected B Cells

PubMed Central

Lin, Zhen; Swan, Kenneth; Zhang, Xin; Cao, Subing; Brett, Zoe; Drury, Stacy; Fewell, Claire; Puetter, Adriane; Wang, Xia; Ferris, MaryBeth; Sullivan, Deborah E.; Li, Li

2016-01-01

ABSTRACT In the oral epithelium, peripheral stores of Epstein-Barr virus (EBV) are transmitted from infiltrating B cells to epithelial cells. Once the virus is transmitted to epithelial cells, the highly permissive nature of this cell type for lytic replication allows virus amplification and exchange to other hosts. Since the initial transfer of EBV from B cells to epithelial cells requires transitioning of the B-cell to a state that induces virus reactivation, we hypothesized that there might be epithelium-specific signals that allow the infiltrating B cells to sense the appropriate environment to initiate reactivation and begin this exchange process. We previously found that the epithelium-specific miR-200 family of microRNAs promotes EBV lytic replication. Here we show that there are high levels of miR-200 family members in oral and tonsillar epithelia and in saliva. Analysis of cultured oral epithelial cells (OKF6) showed that they actively secrete membrane vesicles (exosomes) that are enriched with miR-200 family members. Coculturing of EBV-positive B cells with OKF6 cells induced viral reactivation. Further, treatment of EBV-positive B cells with OKF6 cell-derived membrane vesicles promoted reactivation. Using a cell system that does not naturally express miR-200 family members, we found that enforced expression of a miR-200 family member produced membrane vesicles that were able to induce the lytic cascade in EBV-positive B cells. We propose that membrane vesicles secreted by oral and tonsillar epithelial cells may serve as a tissue-specific environmental cue that initiates reactivation in B cells, promoting the transfer of virus from peripheral B-cell stores to the oral epithelium to facilitate virus amplification and exchange to other hosts. IMPORTANCE Epstein-Barr virus (EBV) is an important human pathogen that is causally associated with several lymphomas and carcinomas. The switch from latency to the lytic cycle is critical for successful host infection and for EBV pathogenesis. Although the EBV lytic cycle can be triggered by certain agents in vitro, the mechanisms that signal reactivation in vivo are poorly understood. We previously reported that endogenously expressed miR-200 family members likely play a role in facilitating the lytic tendencies of EBV in epithelial cells. Here we show that membrane vesicles secreted from oral epithelial cells contain miR-200 family members and that they can be transmitted to proximal EBV-positive B cells, where they trigger reactivation. We propose that this intercellular communication pathway may serve as a sensor mechanism for infiltrating B cells to recognize an appropriate environment to initiate reactivation, thereby allowing the exchange of virus to the oral epithelium. PMID:26764001

Chemomechanically engineered 3D organotypic platforms of bladder cancer dormancy and reactivation.

PubMed

Pavan Grandhi, Taraka Sai; Potta, Thrimoorthy; Nitiyanandan, Rajeshwar; Deshpande, Indrani; Rege, Kaushal

2017-10-01

Tumors undergo periods of dormancy followed by reactivation leading to metastatic disease. Arrest in the G0/G1 phase of the cell cycle and resistance to chemotherapeutic drugs are key hallmarks of dormant tumor cells. Here, we describe a 3D platform of bladder cancer cell dormancy and reactivation facilitated by a novel aminoglycoside-derived hydrogel, Amikagel. These 3D dormant tumor microenvironments (3D-DTMs) were arrested in the G0/G1 phase and were highly resistant to anti-proliferative drugs. Inhibition of targets in the cellular protein production machinery led to induction of endoplasmic reticulum (ER) stress and complete ablation of 3D-DTMs. Nanoparticle-mediated calcium delivery significantly accelerated ER stress-mediated 3D-DTM death. Transfer of 3D-DTMs onto weaker and adhesive Amikagels resulted in selective reactivation of a sub-population of N-cadherin deficient cells from dormancy. Whole-transcriptome analyses further indicated key biochemical differences between dormant and proliferative cancer cells. Taken together, our results indicate that 3D bladder cancer microenvironments of dormancy and reactivation can facilitate fundamental advances and novel drug discovery in cancer. Copyright © 2017. Published by Elsevier Ltd.

A new method for total OH reactivity measurements using a fast Gas Chromatographic Photo-Ionization Detector (GC-PID)

NASA Astrophysics Data System (ADS)

Nölscher, A. C.; Sinha, V.; Bockisch, S.; Klüpfel, T.; Williams, J.

2012-05-01

The primary and most important oxidant in the atmosphere is the hydroxyl radical (OH). Currently OH sinks, particularly gas phase reactions, are poorly constrained. One way to characterize the overall sink of OH is to measure directly the ambient loss rate of OH, the total OH reactivity. To date direct measurements of total OH reactivity have been either performed using a Laser Induced Fluorescence (LIF) system ("pump-and-probe" or "flow reactor") or the Comparative Reactivity Method (CRM) with a Proton Transfer Reaction Mass Spectrometer (PTR-MS). Both techniques require large, complex and expensive detection systems. This study presents a feasibility assessment for CRM total OH reactivity measurements using a new detector, a Gas Chromatographic Photo-Ionization Detector (GC-PID). Such a system is smaller, more portable, less power consuming and less expensive than other total OH reactivity measurement techniques. Total OH reactivity is measured by the CRM using a competitive reaction between a reagent (here pyrrole) with OH alone and in the presence of atmospheric reactive molecules. The new CRM method for total OH reactivity has been tested with parallel measurements of the GC-PID and the previously validated PTR-MS as detector for the reagent pyrrole during laboratory experiments, plant chamber and boreal field studies. Excellent agreement of both detectors was found when the GC-PID was operated under optimum conditions. Time resolution (60-70 s), sensitivity (LOD 3-6 s-1) and overall uncertainty (25% in optimum conditions) for total OH reactivity were equivalent to PTR-MS based total OH reactivity measurements. One drawback of the GC-PID system was the steady loss of sensitivity and accuracy during intensive measurements lasting several weeks, and a possible toluene interference. Generally, the GC-PID system has been shown to produce closely comparable results to the PTR-MS and thus in suitable environments (e.g. forests) it presents a viably economical alternative for groups interested in total OH reactivity observations.

Total OH reactivity measurements using a new fast Gas Chromatographic Photo-Ionization Detector (GC-PID)

NASA Astrophysics Data System (ADS)

Nölscher, A. C.; Sinha, V.; Bockisch, S.; Klüpfel, T.; Williams, J.

2012-12-01

The primary and most important oxidant in the atmosphere is the hydroxyl radical (OH). Currently OH sinks, particularly gas phase reactions, are poorly constrained. One way to characterize the overall sink of OH is to measure directly the ambient loss rate of OH, the total OH reactivity. To date, direct measurements of total OH reactivity have been either performed using a Laser-Induced Fluorescence (LIF) system ("pump-and-probe" or "flow reactor") or the Comparative Reactivity Method (CRM) with a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS). Both techniques require large, complex and expensive detection systems. This study presents a feasibility assessment for CRM total OH reactivity measurements using a new detector, a Gas Chromatographic Photoionization Detector (GC-PID). Such a system is smaller, more portable, less power consuming and less expensive than other total OH reactivity measurement techniques. Total OH reactivity is measured by the CRM using a competitive reaction between a reagent (here pyrrole) with OH alone and in the presence of atmospheric reactive molecules. The new CRM method for total OH reactivity has been tested with parallel measurements of the GC-PID and the previously validated PTR-MS as detector for the reagent pyrrole during laboratory experiments, plant chamber and boreal field studies. Excellent agreement of both detectors was found when the GC-PID was operated under optimum conditions. Time resolution (60-70 s), sensitivity (LOD 3-6 s-1) and overall uncertainty (25% in optimum conditions) for total OH reactivity were similar to PTR-MS based total OH reactivity measurements. One drawback of the GC-PID system was the steady loss of sensitivity and accuracy during intensive measurements lasting several weeks, and a possible toluene interference. Generally, the GC-PID system has been shown to produce closely comparable results to the PTR-MS and thus in suitable environments (e.g. forests) it presents a viably economical alternative for groups interested in total OH reactivity observations.

The Effect of Astaxanthin and Regular Training on Dynamic Pattern of Oxidative Stress on Male under Strenuous Exercise

NASA Astrophysics Data System (ADS)

Sylviana, N.; Gunawan, H.; Lesmana, R.; Purba, A.; Akbar, I. B.

2017-03-01

Strenuous physical activity will induced higher Reactive Oxygen Species (ROS) level in human body that can be measured by serum Malondialdehyde (MDA) level. Malondialdehyde is product of lipid peroxidation process that define as oxidative damage of lipid biomolecule by reactivity of reactive oxygen species. Still, the dynamic pattern of Malondialdehyde (MDA) level under strenuous exercise is not fully understood. Potent antioxidant such as Astaxanthin and training may be altered the level of MDA. Thus, purpose of this study is to understand effect of astaxanthin to MDA dynamic pattern on training male after strenuous physical activity. It was a double blind, experimental study, conducted on thirty young male age, divided into untrained and trained groups. Supplement Astaxanthin was given to 15 subject as well as placebo for one week after supplementation, Subjects were tested with anaerobic strenuous physical activity. The values were analyzed with ANOVA test followed by Duncan test showed that in every groups, mean of MDA before test was similar, start increase significantly after tested, begin decrease at 6th hour post test and back to baseline at 24th hour post-test ( p<0.05), except for group of untrained male with placebo still increase twice from baseline. The lowest mean of MDA was found on group of trained male with Astaxanthin supplementation and the highest was found on group of untrained male with placebo (p<0.05). These findings support that Astaxanthin and training might has positive effect to oxidative stress condition without altered its dynamic pattern in male after strenuous physical activity

Regioisomer-Specific Mechanochromism of Naphthopyran in Polymeric Materials.

PubMed

Robb, Maxwell J; Kim, Tae Ann; Halmes, Abigail J; White, Scott R; Sottos, Nancy R; Moore, Jeffrey S

2016-09-28

Transformation of naphthopyran into a colored merocyanine species in polymeric materials is achieved using mechanical force. We demonstrate that the mechanochemical reactivity of naphthopyran is critically dependent on the regiochemistry, with only one particular substitution pattern leading to successful mechanochemical activation. Two alternative regioisomers with different polymer attachment points are demonstrated to be mechanochemically inactive. This trend in reactivity is accurately predicted by DFT calculations, reinforcing predictive capabilities in mechanochemical systems. We rationalize the reactivity differences between naphthopyran regioisomers in terms of the alignment of the target C-O pyran bond with the direction of the applied mechanical force and its effect on mechanochemical transduction along the reaction coordinate.

Condensation heat transfer and pressure drop of R-410A in a 7.0 mm O.D. microfin tube at low mass fluxes

NASA Astrophysics Data System (ADS)

Kim, Nae-Hyun

2016-12-01

R-410A condensation heat transfer and pressure drop data are provided for a 7.0 mm O.D. microfin tube at low mass fluxes (50-250 kg/m2 s). The heat transfer coefficient of the microfin tube shows a minimum behavior with the mass flux. At a low mass flux, where flow pattern is stratified, condensation induced by surface tension by microfins overwhelms condensation induced by shear, and the heat transfer coefficient decreases as mass flux increases. At a high mass flux, where flow pattern is annular, condensation induced by shear governs the heat transfer, and the heat transfer coefficient increases as mass flux increases. The pressure drop of the microfin tube is larger than that of the smooth tube at the annular flow regime. On the contrary, the pressure drop of the smooth tube is larger than that of the microfin tube at the stratified flow regime.

Hot Moments in Cold Spots - Investigating Reactive Transport Patterns at Aquifer-River Interfaces by Heat Tracers and Distributed Sensor Networks

NASA Astrophysics Data System (ADS)

Krause, Stefan; Angermann, Lisa; Naden, Emma; Cassidy, Nigel; Blume, Theresa

2010-05-01

The mixing of groundwater and surface water in hyporheic zones often coincides with high redox reactivity and chemical transformation potential. Depending on redox conditions and reaction types, hyporheic mixing of groundwater and surface water can lead to either attenuation or enrichment of pollutants or nutrients with diametrical implications for stream and aquifer hydro-ecological conditions. This study investigates the reactive transport of nitrate and a chlorinated solvent (Trichloroethylene - TCE) at the aquifer-river interface of a UK lowland river. In this study, distributed temperature sensor networks and hydro-geophysical methods, which have been applied for identifying structural streambed heterogeneity and tracing aquifer river exchange, were combined with hydro-chemical analyses of hyporheic multi-component reactive transport. In stream Electric Resistivity Tomography has been applied to map the complex spatial distribution of highly conductive sandy and gravely sediments in contrast to semi-confining, low conductivity peat lenses. Reach scale (1km) spatial patterns and temporal dynamics of aquifer-river exchange have been identified by heat tracer experiments based on fibre-optic Distributed Temperature Sensing in combination with 2D thermocouple-arrays and small scale heat pulse injection methods for tracing shallow (25 cm) hyporheic flow paths. Spatial patterns of hyporheic redox conditions, dissolved oxygen and organic carbon (DOC) content as well as concentrations of major anions, TCE and its decay products have been observed in 48 nested multi-level piezometers and passive DET (Diffusive Equilibrium in Thin film) gel probes. Our results indicate that patterns of cold spots in streambed sediments can be attributed to fast groundwater up-welling in sandy and gravely sediments resulting in low hyporheic residence times. Contrasting conditions were found at warmer areas at the streambed surface where groundwater - surface water exchange was inhibited by the existence of peat or clay lenses within the streambed. These flow-inhibiting structures have been shown to cause semi-confined conditions in the up-welling groundwater, resulting in long residence times and increased redox-reactivity. Anoxic conditions and high DOC contents combined with long residence times underneath peat layers cause highly efficient denitrification rates, reducing nitrate concentrations from > 50mg/l to below the level of detection. In contrast, sandy and gravely areas of fast groundwater up-welling where characterized by only marginal changes in nitrate concentrations. Observation of the reactive transport of the chlorinated solvent groundwater plume into the river suggest that natural attenuation of TCE, which competes with nitrate for DOC as reductive agent, is limited to the semi-confined, anoxic, low nitrate - high DOC groundwater pockets underneath streambed peat lenses. The investigations supported the development of a conceptual model of aquifer - river exchange and hyporheic reactivity in lowland rivers including temperature traceable "hyporheic super-reactors" of great importance for river restoration, water quality and ecology status.

Hot Moments in Cold Spots - Using Heat Tracers and Distributed Sensor Networks to Investigate Reactive Transport Patterns at Aquifer-River Interfaces

NASA Astrophysics Data System (ADS)

Krause, S.; Angermann, L.; Naden, E.; Cassidy, N. J.

2009-12-01

The mixing of groundwater and surface water in hyporheic zones often coincides high redox reactivity and chemical transformation potential. Depending on redox conditions and reaction types, hyporheic mixing of groundwater and surface water can lead to either attenuation or enrichment of pollutants or nutrients with diametrical implications for stream and aquifer hydro-ecology. This study investigates the reactive transport of nitrate and the chlorinated solvent Trichloroethylene (TCE) at the aquifer-river interface of a UK lowland river. The investigations are based on novel distributed sensor networks and hydro-geophysical methods for the identification of structural streambed heterogeneity and the tracing of aquifer river exchange combined with hydro-chemical analyses of hyporheic multi-component reactive transport. In stream Electric Resistivity Tomography and Ground Penetrating Radar have been applied to map the complex spatial distribution of highly conductive sandy and gravely sediments in contrast to semi-confining, low conductivity peat lenses. Reach scale (1km) spatial patterns and temporal dynamics of aquifer-river exchange have been identified by heat tracer experiments based on fibre-optic Distributed Temperature Sensing in combination with 2D thermocouple-arrays and small scale heat pulse injection methods for tracing shallow (25 cm) hyporheic flow paths. Spatial patterns of hyporheic redox conditions, dissolved oxygen and organic carbon (DOC) content as well as concentrations of major anions, TCE and its decay products have been observed in 48 nested multi-level piezometers and passive DET (Diffusive Equilibrium in Thin film) gel probes. Our results indicate that patterns of cold spots in streambed sediments can be attributed to fast groundwater up-welling in sandy and gravely sediments resulting in low hyporheic residence times. Contrasting conditions were found at warmer areas at the streambed surface where groundwater - surface water exchange was inhibited by the existence of peat or clay lenses within the streambed. These flow-inhibiting structures have been shown to cause semi-confined conditions in the up-welling groundwater, resulting in long residence times and increased redox-reactivity. Anoxic conditions and high DOC contents combined with long residence times underneath peat layers cause highly efficient denitrification rates, reducing nitrate concentrations from > 50mg/l to below the level of detection. In contrast, sandy and gravely areas of fast groundwater up-welling where characterized by only marginal changes in nitrate concentrations. Observation of the reactive transport of the chlorinated solvent groundwater plume into the river suggest that natural attenuation of TCE, which competes with nitrate for DOC as reductive agent, is limited to the semi-confined, anoxic, low nitrate - high DOC groundwater pockets underneath streambed peat lenses. The investigations supported the development of a conceptual model of aquifer - river exchange and hyporheic reactivity in lowland rivers including temperature traceable “hyporheic super-reactors” of great importance for river restoration, water quality and ecology status.

Electrochemical deposition onto self-assembled monolayers: new insights into micro- and nanofabrication.

PubMed

Schilardi, Patricia L; Dip, Patricio; dos Santos Claro, Paula C; Benítez, Guillermo A; Fonticelli, Mariano H; Azzaroni, Omar; Salvarezza, Roberto C

2005-12-16

Pattern transfer with high resolution is a frontier topic in the emerging field of nanotechnologies. Electrochemical molding is a possible route for nanopatterning metal, alloys and oxide surfaces with high resolution in a simple and inexpensive way. This method involves electrodeposition onto a conducting master covered by a self-assembled alkanethiolate monolayer (SAMs). This molecular film enables direct surface-relief pattern transfer from the conducting master to the inner face of the electrodeposit, and also allows an easy release of the electrodeposited film due their excellent anti-adherent properties. Replicas of the original conductive master can be also obtained by a simple two-step procedure. SAM quality and stability under electrodeposition conditions combined with the formation of smooth electrodeposits are crucial to obtain high-quality pattern transfer with sub-50 nm resolution.

Elementary reaction modeling of reversible CO/CO2 electrochemical conversion on patterned nickel electrodes

NASA Astrophysics Data System (ADS)

Luo, Yu; Shi, Yixiang; Li, Wenying; Cai, Ningsheng

2018-03-01

CO/CO2 are the major gas reactant/product in the fuel electrode of reversible solid oxide cells (RSOC). This study proposes a two-charge-transfer-step mechanism to describe the reaction and transfer processes of CO-CO2 electrochemical conversion on a patterned Ni electrode of RSOC. An elementary reaction model is developed to couple two charge transfer reactions, C(Ni)+O2-(YSZ) ↔ CO(Ni)+(YSZ) +2e- and CO(Ni)+O2-(YSZ) ↔ CO2(Ni)+(YSZ)+2e-, with adsorption/desorption, surface chemical reactions and surface diffusion. This model well validates in both solid oxide electrolysis cell (SOEC) and solid oxide fuel cell (SOFC) modes by the experimental data from a patterned Ni electrode with 10 μm stripe width at different pCO (0-0.25 atm), pCO2 (0-0.35 atm) and operating temperature (600-700 °C). This model indicates SOEC mode is dominated by charge transfer step C(Ni)+O2-(YSZ)↔CO(Ni)+(YSZ) +2e-, while SOFC mode by CO(Ni)+ O2-(YSZ)↔CO2(Ni)+(YSZ)+2e- on the patterned Ni electrode. The sensitivity analysis shows charge transfer step is the major rate-determining step for RSOC, besides, surface diffusion of CO and CO2 as well as CO2 adsorption also plays a significant role in the electrochemical reaction of SOEC while surface diffusion of CO and CO2 desorption could be co-limiting in SOFC.

Dicobalt-μ-oxo polyoxometalate compound, [(α(2)-P2W17O61Co)2O](14-): a potent species for water oxidation, C-H bond activation, and oxygen transfer.

PubMed

Barats-Damatov, Delina; Shimon, Linda J W; Weiner, Lev; Schreiber, Roy E; Jiménez-Lozano, Pablo; Poblet, Josep M; de Graaf, Coen; Neumann, Ronny

2014-02-03

High-valent oxo compounds of transition metals are often implicated as active species in oxygenation of hydrocarbons through carbon-hydrogen bond activation or oxygen transfer and also in water oxidation. Recently, several examples of cobalt-catalyzed water oxidation have been reported, and cobalt(IV) species have been suggested as active intermediates. A reactive species, formally a dicobalt(IV)-μ-oxo polyoxometalate compound [(α2-P2W17O61Co)2O](14-), [(POMCo)2O], has now been isolated and characterized by the oxidation of a monomeric [α2-P2W17O61Co(II)(H2O)](8-), [POMCo(II)H2O], with ozone in water. The crystal structure shows a nearly linear Co-O-Co moiety with a Co-O bond length of ∼1.77 Å. In aqueous solution [(POMCo)2O] was identified by (31)P NMR, Raman, and UV-vis spectroscopy. Reactivity studies showed that [(POMCo)2O]2O] is an active compound for the oxidation of H2O to O2, direct oxygen transfer to water-soluble sulfoxides and phosphines, indirect epoxidation of alkenes via a Mn porphyrin, and the selective oxidation of alcohols by carbon-hydrogen bond activation. The latter appears to occur via a hydrogen atom transfer mechanism. Density functional and CASSCF calculations strongly indicate that the electronic structure of [(POMCo)2O]2O] is best defined as a compound having two cobalt(III) atoms with two oxidized oxygen atoms.

Scheduling observational and physical practice: influence on the coding of simple motor sequences.

PubMed

Ellenbuerger, Thomas; Boutin, Arnaud; Blandin, Yannick; Shea, Charles H; Panzer, Stefan

2012-01-01

The main purpose of the present experiment was to determine the coordinate system used in the development of movement codes when observational and physical practice are scheduled across practice sessions. The task was to reproduce a 1,300-ms spatial-temporal pattern of elbow flexions and extensions. An intermanual transfer paradigm with a retention test and two effector (contralateral limb) transfer tests was used. The mirror effector transfer test required the same pattern of homologous muscle activation and sequence of limb joint angles as that performed or observed during practice, and the non-mirror effector transfer test required the same spatial pattern movements as that performed or observed. The test results following the first acquisition session replicated the findings of Gruetzmacher, Panzer, Blandin, and Shea (2011) . The results following the second acquisition session indicated a strong advantage for participants who received physical practice in both practice sessions or received observational practice followed by physical practice. This advantage was found on both the retention and the mirror transfer tests compared to the non-mirror transfer test. These results demonstrate that codes based in motor coordinates can be developed relatively quickly and effectively for a simple spatial-temporal movement sequence when participants are provided with physical practice or observation followed by physical practice, but physical practice followed by observational practice or observational practice alone limits the development of codes based in motor coordinates.

Self-assembling holographic biosensors and biocomputers.

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

Light, Yooli Kim; Bachand, George David; Schoeniger, Joseph S.

2006-05-01

We present concepts for self-assembly of diffractive optics with potential uses in biosensors and biocomputers. The simplest such optics, diffraction gratings, can potentially be made from chemically-stabilized microtubules migrating on nanopatterned tracks of the motor protein kinesin. We discuss the fabrication challenges involved in patterning sub-micron-scale structures with proteins that must be maintained in aqueous buffers to preserve their activity. A novel strategy is presented that employs dry contact printing onto glass-supported amino-silane monolayers of heterobifunctional crosslinkers, followed by solid-state reactions of these cross-linkers, to graft patterns of reactive groups onto the surface. Successive solution-phase addition of cysteine-mutant proteins andmore » amine-reactive polyethylene glycol allows assembly of features onto the printed patterns. We present data from initial experiments showing successful micro- and nanopatterning of lines of single-cysteine mutants of kinesin interleaved with lines of polyethylene, indicating that this strategy can be employed to arrays of features with resolutions suitable for gratings.« less

Reverse Transfer: Exploring the Effects of Foreign Language Rhetorical Patterns on L1 Writing Performance of Iranian EFL Learners

ERIC Educational Resources Information Center

Babaii, Esmat; Ramazani, Kambiz

2017-01-01

The relationship between language learners' L1 and L2 writing productions has attracted the attention of researchers since Kaplan (1966). Along this research line, the present study aimed to explore the reverse transfer of rhetorical patterns from English (L2) to Persian (L1) in the argumentative essays of EFL students in Iran. Sixty MA university…

Wettability Patterning for Enhanced Dropwise Condensation

NASA Astrophysics Data System (ADS)

Ghosh, Aritra; Ganguly, Ranjan; Megaridis, Constantine

2014-11-01

Dropwise condensation (DwC), in order to be sustainable, requires removal of the condensate droplets. This removal is frequently facilitated by gravity. The rate of DwC heat transfer depends strongly on the maximum departing droplet diameter. Based on wettability patterning, we present a facile technique designed to control the maximum droplet size in DwC within vapor/air atmospheres, and demonstrate how this approach can be used to enhance the corresponding heat transfer rate. We examine various hydrophilic-superhydrophilic patterns, which, respectively sustain DwC and filmwise (FwC) condensation on the substrate. The fabrication method does notemploy any hydrophobizing agent. By juxtaposing parallel lines of hydrophilic (CA ~ 78°) and superhydrophilic (CA ~ 0°) regions on the condensing surface, we create alternating domains of DwC and FwC. The average droplet size on the DwC domain is reduced by ~ 60% compared to the theoretical maximum, which corresponds to the line width. We compare heat transfer rate between unpatternend DwC surfaces and patterned DwC surfaces. Even after sacrificing 40% of condensing area, we achieve up to 20% improvement in condensate collection rate using an interdigitated superhydrophilic pattern, inspired by the vein network of plant leaves. The bioinspired interdigitated pattern is found to outperform the straight hydrophilic-superhydrophilic pattern, particularly under higher vapor loadings in an air/vapor ambient atmosphere. NSF STTR Grant 1331817 via NBD Nano.

Sequence and Structure Analysis of Distantly-Related Viruses Reveals Extensive Gene Transfer between Viruses and Hosts and among Viruses

PubMed Central

Caprari, Silvia; Metzler, Saskia; Lengauer, Thomas; Kalinina, Olga V.

2015-01-01

The origin and evolution of viruses is a subject of ongoing debate. In this study, we provide a full account of the evolutionary relationships between proteins of significant sequence and structural similarity found in viruses that belong to different classes according to the Baltimore classification. We show that such proteins can be found in viruses from all Baltimore classes. For protein families that include these proteins, we observe two patterns of the taxonomic spread. In the first pattern, they can be found in a large number of viruses from all implicated Baltimore classes. In the other pattern, the instances of the corresponding protein in species from each Baltimore class are restricted to a few compact clades. Proteins with the first pattern of distribution are products of so-called viral hallmark genes reported previously. Additionally, this pattern is displayed by the envelope glycoproteins from Flaviviridae and Bunyaviridae and helicases of superfamilies 1 and 2 that have homologs in cellular organisms. The second pattern can often be explained by horizontal gene transfer from the host or between viruses, an example being Orthomyxoviridae and Coronaviridae hemagglutinin esterases. Another facet of horizontal gene transfer comprises multiple independent introduction events of genes from cellular organisms into otherwise unrelated viruses. PMID:26492264

Pitch chroma discrimination, generalization, and transfer tests of octave equivalence in humans.

PubMed

Hoeschele, Marisa; Weisman, Ronald G; Sturdy, Christopher B

2012-11-01

Octave equivalence occurs when notes separated by an octave (a doubling in frequency) are judged as being perceptually similar. Considerable evidence points to the importance of the octave in music and speech. Yet, experimental demonstration of octave equivalence has been problematic. Using go/no-go operant discrimination and generalization, we studied octave equivalence in humans. In Experiment 1, we found that a procedure that failed to show octave equivalence in European starlings also failed in humans. In Experiment 2, we modified the procedure to control for the effects of pitch height perception by training participants in Octave 4 and testing in Octave 5. We found that the pattern of responding developed by discrimination training in Octave 4 generalized to Octave 5. We replicated and extended our findings in Experiment 3 by adding a transfer phase: Participants were trained with either the same or a reversed pattern of rewards in Octave 5. Participants transferred easily to the same pattern of reward in Octave 5 but struggled to learn the reversed pattern. We provided minimal instruction, presented no ordered sequences of notes, and used only sine-wave tones, but participants nonetheless constructed pitch chroma information from randomly ordered sequences of notes. Training in music weakly hindered octave generalization but moderately facilitated both positive and negative transfer.

Reactive postural control deficits in patients with posterior parietal cortex lesions after stroke and the influence of auditory cueing.

PubMed

Lin, Ying-Hui; Tang, Pei-Fang; Wang, Yao-Hung; Eng, Janice J; Lin, Keh-Chung; Lu, Lu; Jeng, Jiann-Shing; Chen, Shih-Ching

2014-10-01

The purpose of this study was to investigate the ways in which stroke-induced posterior parietal cortex (PPC) lesions affect reactive postural responses and whether providing auditory cues modulates these responses. Seventeen hemiparetic patients after stroke, nine with PPC lesions (PPCLesion) and eight with intact PPCs (PPCSpared), and nine age-matched healthy adults completed a lateral-pull perturbation experiment under noncued and cued conditions. The activation rates of the gluteus medius muscle ipsilateral (GMi) and contralateral to the pull direction, the rates of occurrence of three types of GM activation patterns, and the GMi contraction latency were investigated. In noncued pulls toward the paretic side, of the three groups, the PPCLesion group exhibited the lowest activation rate (56%) of the GMi (P < 0.05), which is the primary postural muscle involved in this task, and the highest rate of occurrence (33%) of the gluteus medius muscle contralateral-activation-only pattern (P < 0.05), which is a compensatory activation pattern. In contrast, in cued pulls toward the paretic side, the PPCLesion group was able to increase the activation rate of the GMi to a level (81%) such that there became no significant differences in activation rate of the GMi among the three groups (P > 0.05). However, there were no significant differences in the GM activation patterns and GMi contraction latency between the noncued and cued conditions for the PPCLesion group (P > 0.05). The PPCLesion patients had greater deficits in recruiting paretic muscles and were more likely to use the compensatory muscle activation pattern for postural reactions than the PPCSpared patients, suggesting that PPC is part of the neural circuitry involved in reactive postural control in response to lateral perturbations. The auditory cueing used in this study, however, did not significantly modify the muscle activation patterns in the PPCLesion patients. More research is needed to explore the type and structure of cueing that could effectively improve patterns and speed of postural responses in these patients.

Investigation of the antioxidant and radical scavenging activities of some phenolic Schiff bases with different free radicals.

PubMed

Marković, Zoran; Đorović, Jelena; Petrović, Zorica D; Petrović, Vladimir P; Simijonović, Dušica

2015-11-01

The antioxidant properties of some phenolic Schiff bases in the presence of different reactive particles such as (•)OH, (•)OOH, (CH2=CH-O-O(•)), and (-•)O2 were investigated. The thermodynamic values, ΔH BDE, ΔH IP, and ΔH PA, were used for this purpose. Three possible mechanisms for transfer of hydrogen atom, concerted proton-electron transfer (CPET), single electron transfer followed by proton transfer (SET-PT), and sequential proton loss electron transfer (SPLET) were considered. These mechanisms were tested in solvents of different polarity. On the basis of the obtained results it was shown that SET-PT antioxidant mechanism can be the dominant mechanism when Schiff bases react with radical cation, while SPLET and CPET are competitive mechanisms for radical scavenging of hydroxy radical in all solvents under investigation. Examined Schiff bases react with the peroxy radicals via SPLET mechanism in polar and nonpolar solvents. The superoxide radical anion reacts with these Schiff bases very slowly.

Proton transfer from water to ketyl radical anion: Assessment of critical size of hydrated cluster and free energy barrier in solution from first principles simulations

NASA Astrophysics Data System (ADS)

Biswas, Sohag; Dasgupta, Teesta; Mallik, Bhabani S.

2016-09-01

We present the reactivity of an organic intermediate by studying the proton transfer process from water to ketyl radical anion using gas phase electronic structure calculations and the metadynamics method based first principles molecular dynamics (FPMD) simulations. Our results indicate that during the micro solvation of anion by water molecules systematically, the presence of minimum three water molecules in the gas phase cluster is sufficient to observe the proton transfer event. The analysis of trajectories obtained from initial FPMD simulation of an aqueous solution of the anion does not show any evident of complete transfer of the proton from water. The cooperativity of water molecules and the relatively weak anion-water interaction in liquid state prohibit the full release of the proton. Using biasing potential through first principles metadynamics simulations, we report the observation of proton transfer reaction from water to ketyl radical anion with a barrier height of 16.0 kJ/mol.

Patterns of C-reactive protein ratio response to antibiotics in pediatric sepsis: A prospective cohort study.

PubMed

Lanziotti, Vanessa Soares; Póvoa, Pedro; Prata-Barbosa, Arnaldo; Pulcheri, Lucas Berbet; Rabello, Ligia S C F; Lapa E Silva, José Roberto; Soares, Marcio; Salluh, Jorge I F

2018-04-01

Evaluate sequential C-reactive protein (CRP) measurements and patterns of CRP-ratio response to antibiotic therapy during first 7days in Pediatric Intensive Care Unit (PICU) of septic children. Prospective, cohort study of children (1month-12years) admitted at 3 PICUs, with diagnosis of sepsis with <72h course. CRP-ratio was calculated in relation to D0_CRP value. Children were classified according to an individual pattern of CRP-ratio response: fast - CRP_D4 of therapy was <0.4 of D0_CRP; slow - continuous but slow decrease of CRP; non - CRP remained ≥0.8 of D0_CRP; biphasic - initial CRP decrease to levels <0.8 of D0_CRP followed by secondary rise ≥0.8. 103 septic children (age-median: 2yrs; 54% male) were prospectively included (infection focus: 65% respiratory, 12.5% central nervous system). Overall PICU mortality was 11.7%. 102 children could be classified according to a predefined CRP-ratio response pattern. Time-dependent analysis of CRP-ratio and CRP course of the different patterns were significantly different. Besides, PICU mortality rate was significantly different according CRP-ratio response patterns: fast response 4.5%; slow response 5.8%; non-response 29.4%; biphasic response 42.8%. In pediatric sepsis, CRP-ratio serial evaluation was useful in early identification of patients with poor outcome. Copyright © 2017 Elsevier Inc. All rights reserved.

Development of a robust reverse tone pattern transfer process

NASA Astrophysics Data System (ADS)

Khusnatdinov, Niyaz; Doyle, Gary; Resnick, Douglas J.; Ye, Zhengmao; LaBrake, Dwayne; Milligan, Brennan; Alokozai, Fred; Chen, Jerry

2017-03-01

Pattern transfer is critical to any lithographic technology, and plays a significant role in defining the critical features in a device layer. As both the memory and logic roadmaps continue to advance, greater importance is placed on the scheme used to do the etching. For many critical layers, a need has developed which requires a multilayer stack to be defined in order to perform the pattern transfer. There are many cases however, where this standard approach does not provide the best results in terms of critical dimension (CD) fidelity and CD uniformity. As an example, when defining a contact pattern, it may be advantageous to apply a bright field mask (in order to maximize the normalized inverse log slope (NILS)) over the more conventional dark field mask. The result of applying the bright field mask in combination with positive imaging resist is to define an array of pillar patterns, which then must be converted back to holes before etching the underlying dielectric material. There have been several publications on tone reversal that is introduced in the resist process itself, but often an etch transfer process is applied to reverse the pattern tone. The purpose of this paper is to describe the use of a three layer reverse tone process (RTP) that is capable of reversing the tone of every printed feature type. The process utilizes a resist pattern, a hardmask layer and an additional protection layer. The three layer approach overcomes issues encountered when using a single masking layer. Successful tone reversal was demonstrated both on 300mm wafers and imprint masks, including the largest features in the pattern, with dimensions as great as 60 microns. Initial in-field CD uniformity is promising. CDs shifted by about 2.6nm and no change was observed in either LER or LWR. Follow-up work is required to statistically qualify in-field CDU and also understand both across wafer uniformity and feature linearity.

Optimal reactive planning with security constraints

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

Thomas, W.R.; Cheng, D.T.Y.; Dixon, A.M.

1995-12-31

The National Grid Company (NGC) of England and Wales has developed a computer program, SCORPION, to help system planners optimize the location and size of new reactive compensation plant on the transmission system. The reactive power requirements of the NGC system have risen as a result of increased power flows and the shorter timescale on which power stations are commissioned and withdrawn from service. In view of the high costs involved, it is important that reactive compensation be installed as economically as possible, without compromising security. Traditional methods based on iterative use of a load flow program are labor intensivemore » and subjective. SCORPION determines a near-optimal pattern of new reactive sources which are required to satisfy voltage constraints for normal and contingent states of operation of the transmission system. The algorithm processes the system states sequentially, instead of optimizing all of them simultaneously. This allows a large number of system states to be considered with an acceptable run time and computer memory requirement. Installed reactive sources are treated as continuous, rather than discrete, variables. However, the program has a restart facility which enables the user to add realistically sized reactive sources explicitly and thereby work towards a realizable solution to the planning problem.« less

SU-8 negative photoresist for optical mask manufacturing

NASA Astrophysics Data System (ADS)

Bogdanov, Alexei L.

2000-06-01

The requirements for better control, linearity, and uniformity of critical dimension (CD) on photomasks in fabrication of 180 and 150 nm generation devices result in increasing demand for thinner, more etching durable, and more sensitive e-beam resists. Novolac based resists with chemical amplification have been a choice for their sensitivity and stability during etching. However, difficult CD control due to the acid catalyzer diffusion and quite narrow post exposure bake (PEB) process window are some of the major drawbacks of these resists. SU-8 is recently introduced to the market negative photoresist. High sensitivity, fairly good adhesion properties, and relatively simple processing of SU-8 make it a good substitution for novolac based chemically amplified negative e-beam resists in optical mask manufacturing. The replacement of traditional chemically amplified resists by SU- 8 can increase the process latitude and reduce resist costs. Among the obvious drawbacks of SU-8 are the use of solvent- based developer and demand of oxygen plasma for resist removal. In this paper the use of SU-8 for optical mask manufacturing is reported. All steps of resist film preparation, exposure and development are paid a share of attention. Possibilities to use reactive ion etching (RIE) with oxygen in order to increase resist mask contrast are discussed. Special exposure strategy (pattern outlining) was employed to further improve the edge definition. The resist PEB temperature and time were studied to estimate their weight in overall CD control performance. Specially designed test patterns with 0.25 micrometer design rule could be firmly transferred into a chromium layer both by wet etching and ion milling. Influence of exposure dose variation on the pattern CD change was studied.

Age and isolation influence steroids release and chemical signaling in male mice.

PubMed

Mucignat-Caretta, Carla; Cavaggioni, Andrea; Redaelli, Marco; Da Dalt, Laura; Zagotto, Giuseppe; Gabai, Gianfranco

2014-05-01

Social interactions in mice involve olfactory signals, which convey information about the emitter. In turn, the mouse social and physiological status may modify the release of chemical cues. In this study, the influences of age and social isolation on the endocrine response and the release of chemical signals were investigated in male CD1 mice, allocated into four groups: Young Isolated (from weaning till 60days; N=6), Adult Isolated (till 180days; N=6), Young Grouped (6 mice/cage; till 60days; N=18), Adult Grouped (6 mice/cage; till 180days; N=18). Mice were transferred in a clean cage to observe the micturition pattern and then sacrificed. Body and organs weights, serum testosterone, dehydroepiandrosterone, corticosterone and the ratio Major Urinary Protein/creatinine were measured. Urinary volatile molecules potentially involved in pheromonal communication were identified. Androgen secretion was greater in isolated mice (P<0.05), suggesting a greater reactivity of the Hypothalamic-Pituitary-Gonadal axis. Grouped mice presented a higher degree of adrenal activity, and young mice showed a higher serum corticosterone (P<0.05) suggesting a greater stimulation of the Hypothalamic-Pituitary-Adrenal axis. The micturition pattern typical of dominant male, consisting in voiding numerous droplets, was observed in Young Isolated mice only, which showed a higher protein/creatinine ratio (P<0.05). Urinary 2-s-butyl-thiazoline was higher in both Young and Adult Isolated mice (P<0.005). Young Isolated mice showed the most prominent difference in both micturition pattern and potentially active substance emission, while long term isolation resulted in a less extreme phenotype; therefore social isolation had a higher impact on young mice hormone and pheromone release. Copyright © 2014 Elsevier Inc. All rights reserved.

Effect of the different chain transfer agents on molecular weight and optical properties of poly(methyl methacrylate)

NASA Astrophysics Data System (ADS)

Çetinkaya, Onur; Demirci, Gökhan; Mergo, Paweł

2017-08-01

Investigation of molecular weight and optical properties of poly(methyl metacrylate) (PMMA) polymerized in house with different chain transfer agents was studied. Isopropyl alcohol (IPA), n-butyl mercaptan (nBMC) and pentamethyl disilane (PMDS) were used as chain transfer agents. The molecular weight (Mw) of PMMA samples were measured by Ostwald viscometer. Mw of bulk polymer samples were decreased with increase the concentration of chain transfer agents (CTA). Since reactivity of used CTAs is not same, molecular weights of samples which were produced with different type of CTA but same concentration of CTA was varied. Higher concentration of n-BMC showed higher scattering. Transmission of samples could not be correlated with different concentration of CTA. Refractive index of samples was not affected by concentration of CTA nevertheless higher molecular weight of CTA showed higher refractive index.

Wear and interfacial transport of material

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1975-01-01

Bonding across the interface for two solids in contact and the subsequent transfer of material from one surface to another is a direct result of the interfacial bonds being stronger than the cohesive bonds in either of the two solids. Surface tools such as LEED, Auger emission spectroscopy, field ion microscopy, and the atom probe are used to examine adhesive contacts and to determine the direction, nature, quantity of material transfer and properties of the solids which effect transfer and wear. The electronic nature, cohesive binding energies, surface structure, lattice disregistry and distribution of species in surface layers are all found to effect adhesion and transfer or transport for clean surfaces in solid state contact. The influence of adsorbed and reacted surface films from fractions of a monolayer to multilayer reactive films are considered. It is shown that even fractions of a monolayer of surface active species such as oxygen and sulfur can markedly inhibit adhesion and transport.

Beta cells transfer vesicles containing insulin to phagocytes for presentation to T cells.

PubMed

Vomund, Anthony N; Zinselmeyer, Bernd H; Hughes, Jing; Calderon, Boris; Valderrama, Carolina; Ferris, Stephen T; Wan, Xiaoxiao; Kanekura, Kohsuke; Carrero, Javier A; Urano, Fumihiko; Unanue, Emil R

2015-10-06

Beta cells from nondiabetic mice transfer secretory vesicles to phagocytic cells. The passage was shown in culture studies where the transfer was probed with CD4 T cells reactive to insulin peptides. Two sets of vesicles were transferred, one containing insulin and another containing catabolites of insulin. The passage required live beta cells in a close cell contact interaction with the phagocytes. It was increased by high glucose concentration and required mobilization of intracellular Ca2+. Live images of beta cell-phagocyte interactions documented the intimacy of the membrane contact and the passage of the granules. The passage was found in beta cells isolated from islets of young nonobese diabetic (NOD) mice and nondiabetic mice as well as from nondiabetic humans. Ultrastructural analysis showed intraislet phagocytes containing vesicles having the distinct morphology of dense-core granules. These findings document a process whereby the contents of secretory granules become available to the immune system.

Cell membrane reactivity of MIB-1 antibody to Ki67 in human tumors: fact or artifact?

PubMed

Leonardo, Eugenio; Volante, Marco; Barbareschi, Mattia; Cavazza, Alberto; Dei Tos, Angelo Paolo; Bussolati, Gianni; Papotti, Mauro

2007-06-01

Ki67 immunohistochemistry is a widely used marker of the tumor proliferative fraction. Apart from the nuclear staining of dividing cells, MIB-1 monoclonal antibody was also found to stain the cell membrane of some tumor types. Indeed, such membrane reactivity was proposed as a diagnostic feature of hyalinizing trabecular tumor (HTT) of the thyroid. To verify the diagnostic role of Ki67 membrane pattern, 6 HTTs, 8 pulmonary sclerosing hemangiomas (SH), and 6 other human tumors with MIB-1 cell membrane immunoreactivity were stained by immunoperoxidase with 5 different anti-Ki67 antibodies in different experimental conditions. We show here that the cell membrane reactivity reported in HTT is produced only by MIB-1 and not by other antibodies to Ki67 (including commercially available mouse and rabbit monoclonal antibodies). In addition, this peculiar pattern is obtained only if the reaction is performed at room temperature, because automated immunostainers which operate at 37 degrees C do not produce any MIB-1 membrane localization. The same findings were obtained in the other 6 tumors. Conversely, sclerosing hemangioma of the lung did not produce any MIB-1 cell membrane reactivity in our hands. A cross-reactivity of the MIB-1 monoclonal antibody with an epitope expressed at the cell membrane level (rather than an artifact) seems the most likely explanation for this finding, because the immunoreactivity is generally intense and uniform in the membrane positive tumors. We conclude that when Ki67 immunohistochemistry is used for diagnostic purposes in a suspected HTT, only MIB-1 clone at room temperature should be employed.

Spatial Patterns of Groundwater Biogeochemical Reactivity in an Intertidal Beach Aquifer

NASA Astrophysics Data System (ADS)

Kim, Kyra H.; Heiss, James W.; Michael, Holly A.; Cai, Wei-Jun; Laattoe, Tariq; Post, Vincent E. A.; Ullman, William J.

2017-10-01

Beach aquifers host a dynamic and reactive mixing zone between fresh and saline groundwater of contrasting origin and composition. Seawater, driven up the beachface by waves and tides, infiltrates into the aquifer and meets the seaward-discharging fresh groundwater, creating and maintaining a reactive intertidal circulation cell. Within the cell, land-derived nutrients delivered by fresh groundwater are transformed or attenuated. We investigated this process by collecting pore water samples from multilevel wells along a shore-perpendicular transect on a beach near Cape Henlopen, Delaware, and analyzing solute and particulate concentrations. Pore water incubation experiments were conducted to determine rates of oxygen consumption and nitrogen gas production. A numerical model was employed to support field and laboratory interpretations. Results showed that chemically sensitive parameters such as pH and ORP diverged from salinity distribution patterns, indicating biogeochemical reactivity within the circulation cell. The highest respiration rates were found in the landward freshwater-saltwater mixing zone, supported by high dissolved inorganic carbon. Chlorophyll a, a proxy for phytoplankton, and particulate carbon did not co-occur with the highest respiration rates but were heterogeneously distributed in deeper and hypoxic areas of the cell. The highest rates of N2 production were also found in the mixing zone coinciding with elevated O2 consumption rates but closer to the lower discharge point. Model results were consistent with these observations, showing heightened denitrification in the mixing zone. The results of this work emphasize the relationship between the physical flow processes of the circulation cell and its biogeochemical reactivity and highlight the environmental significance of sandy beaches.

Selective and nonselective transfer: positive and negative priming in a multiple-task environment.

PubMed

Leboe, Jason P; Whittlesea, Bruce W A; Milliken, Bruce

2005-09-01

Processing of a probe stimulus can be affected either positively or negatively by presenting a related stimulus immediately before it. According to structural accounts, such effects occur because processing of the prime activates or inhibits the mental representation of the probe before it is presented. In contrast, transfer-appropriate processing accounts suggest that success in processing a probe depends on resources made available by earlier experiences of related stimuli. The authors manipulated the similarity between the prime and probe on color, lexical status, and orthographic structure, requiring either lexical decision or color identification on each. The authors observed a complex pattern of positive and negative transfer that cannot easily be explained through activation-inhibition of mental structures. Instead, that pattern provides evidence in favor of transfer-appropriate processing.

Effect of Reynolds number on flow and mass transfer characteristics of a 90 degree elbow

NASA Astrophysics Data System (ADS)

Fujisawa, Nobuyuki; Ikarashi, Yuya; Yamagata, Takayuki; Taguchi, Syoichi

2016-11-01

The flow and mass transfer characteristics of a 90 degree elbow was studied experimentally by using the mass transfer measurement by plaster dissolution method, the surface flow visualization by oil film method and stereo PIV measurement. The experiments are carried out in a water tunnel of a circular pipe of 56mm in diameter with a working fluid of water. The Reynolds number was varied from 30000 to 200000. The experimental result indicated the change of the mass transfer coefficient distribution in the elbow with increasing the Reynolds number. This phenomenon is further examined by the surface flow visualization and measurement of secondary flow pattern in the elbow, and the results showed the suggested change of the secondary flow pattern in the elbow with increasing the Reynolds numbers.

Episodic retrieval involves early and sustained effects of reactivating information from encoding.

PubMed

Johnson, Jeffrey D; Price, Mason H; Leiker, Emily K

2015-02-01

Several fMRI studies have shown a correspondence between the brain regions activated during encoding and retrieval, consistent with the view that memory retrieval involves hippocampally-mediated reinstatement of cortical activity. With the limited temporal resolution of fMRI, the precise timing of such reactivation is unclear, calling into question the functional significance of these effects. Whereas reactivation influencing retrieval should emerge with neural correlates of retrieval success, that signifying post-retrieval monitoring would trail retrieval. The present study employed EEG to provide a temporal landmark of retrieval success from which we could investigate the sub-trial time course of reactivation. Pattern-classification analyses revealed that early-onsetting reactivation differentiated the outcome of recognition-memory judgments and was associated with individual differences in behavioral accuracy, while reactivation was also evident in a sustained form later in the trial. The EEG findings suggest that, whereas prior fMRI findings could be interpreted as reflecting the contribution of reinstatement to retrieval success, they could also indicate the maintenance of episodic information in service of post-retrieval evaluation. Copyright © 2014 Elsevier Inc. All rights reserved.

Relational victimization and depressive symptoms: The role of autonomic nervous system reactivity in emerging adults.

PubMed

Holterman, Leigh Ann; Murray-Close, Dianna K; Breslend, Nicole L

2016-12-01

The goal of the current study was to investigate the association between relational victimization, defined as being the target of aggressive acts that damage relationships (e.g., gossip, social exclusion) and depressive symptoms during the relatively understudied developmental period of emerging adulthood. In addition, as individual differences in stress reactivity may influence the outcomes associated with victimization by peers, the moderating roles of sympathetic nervous system (SNS; as measured by skin conductance reactivity) and parasympathetic nervous system (PNS; as measured by respiratory sinus arrhythmia) reactivity to social and non-social stressors were examined. Findings indicated that relational victimization was positively related to depressive symptoms in individuals demonstrating coactivation (i.e., high SNS and PNS reactivity) and coinhibition (blunted SNS and PNS reactivity) to both social and non-social stressor tasks. These patterns may reflect a breakdown of regulation in the body's physiological response to stress, thus increasing risk for depressive symptoms in the context of peer stress. Findings highlight potential areas for future interventions. Copyright © 2016 Elsevier B.V. All rights reserved.

Clinical and immunological investigations of respiratory disease in workers using reactive dyes.

PubMed Central

Docker, A; Wattie, J M; Topping, M D; Luczynska, C M; Newman Taylor, A J; Pickering, C A; Thomas, P; Gompertz, D

1987-01-01

A questionnaire survey of over 400 workers handling reactive dyes showed that over 15% had work related respiratory or nasal symptoms. Forty nine employees with symptoms were referred to chest clinics for detailed assessment. It was considered that in 19 the symptoms could be attributed to an irritant response to a variety of chemicals, including hydrochloric acid vapour, sulphur dioxide, and reactive dyes. Symptoms in 24 were attributed to an allergic reaction to a specific agent; in most (21) to one or more reactive dyes. Two patterns of allergic lower respiratory symptoms were identified; an immediate response of short duration and a longer lasting response, usually of several hours, sometimes accompanied by nocturnal asthma. A radioallergosorbent test (RAST) screen containing the most commonly used reactive dyes was used to detect specific IgE. Allergic symptoms to reactive dyes were strongly associated with specific IgE (17/21 employees) and atopy (18/21). Irritant symptoms were also associated with atopy (13/19) but only weakly associated with specific IgE (7/19). PMID:3651352

Calculation of a double reactive azeotrope using stochastic optimization approaches

NASA Astrophysics Data System (ADS)

Mendes Platt, Gustavo; Pinheiro Domingos, Roberto; Oliveira de Andrade, Matheus

2013-02-01

An homogeneous reactive azeotrope is a thermodynamic coexistence condition of two phases under chemical and phase equilibrium, where compositions of both phases (in the Ung-Doherty sense) are equal. This kind of nonlinear phenomenon arises from real world situations and has applications in chemical and petrochemical industries. The modeling of reactive azeotrope calculation is represented by a nonlinear algebraic system with phase equilibrium, chemical equilibrium and azeotropy equations. This nonlinear system can exhibit more than one solution, corresponding to a double reactive azeotrope. The robust calculation of reactive azeotropes can be conducted by several approaches, such as interval-Newton/generalized bisection algorithms and hybrid stochastic-deterministic frameworks. In this paper, we investigate the numerical aspects of the calculation of reactive azeotropes using two metaheuristics: the Luus-Jaakola adaptive random search and the Firefly algorithm. Moreover, we present results for a system (with industrial interest) with more than one azeotrope, the system isobutene/methanol/methyl-tert-butyl-ether (MTBE). We present convergence patterns for both algorithms, illustrating - in a bidimensional subdomain - the identification of reactive azeotropes. A strategy for calculation of multiple roots in nonlinear systems is also applied. The results indicate that both algorithms are suitable and robust when applied to reactive azeotrope calculations for this "challenging" nonlinear system.

Oligoclonal bands in multiple sclerosis reactive against two herpesviruses and association with magnetic resonance imaging findings

PubMed Central

Virtanen, JO; Wohler, J; Fenton, K; Reich, DS; Jacobson, S

2016-01-01

Background Two human herpesviruses, human herpesvirus 6 (HHV-6), and Epstein-Barr virus (EBV), have been repeatedly linked to multiple sclerosis (MS). Objective The aim of this study was to investigate HHV-6 and EBV reactive oligoclonal bands (OCBs), and viral DNA in the intrathecal compartment in MS. Methods The reactivity of OCBs in cerebrospinal fluid (CSF) for EBV and HHV-6 antigens and stability of virus reactive OCBs over time were studied in a well-characterized MS patient cohort. Associations between virus reactive OCBs and viral DNA in CSF (and any clinical and/or radiological findings) were investigated. Results Of patients with MS, 38% had OCBs reactive to either one of the viruses studied, compared to none in the patients with other inflammatory neurological diseases (p=0.005). The banding pattern of virus reactive OCBs remained the same over time. Furthermore, MS patients with viral DNA in CSF had more contrast enhancing lesions (CELs). Conclusion The stable presence of herpesvirus reactive OCBs in CSF further strengthens the association of MS with these viruses. The finding that herpesviruses might be linked to the appearance of active lesions warrants investigation of new therapeutic strategies to treat these viruses in MS. PMID:23722324

Early life adversity reduces stress reactivity and enhances impulsive behavior: Implications for health behaviors

PubMed Central

Lovallo, William R.

2012-01-01

Altered reactivity to stress, either in the direction of exaggerated reactivity or diminished reactivity, may signal a dysregulation of systems intended to maintain homeostasis and a state of good health. Evidence has accumulated that diminished reactivity to psychosocial stress may signal poor health outcomes. One source of diminished cortisol and autonomic reactivity is the experience of adverse rearing during childhood and adolescence. The Oklahoma Family Health Patterns Project has examined a cohort of 426 healthy young adults with and without a family history of alcoholism. Regardless of family history, persons who had experienced high degrees of adversity prior to age 16 had a constellation of changes including reduced cortisol and heart rate reactivity, diminished cognitive capacity, and unstable regulation of affect, leading to behavioral impulsivity and antisocial tendencies. We present a model whereby this constellation of physiological, cognitive, and affective tendencies is consistent with altered central dopaminergic activity leading to changes in brain function that may foster impulsive and risky behaviors. These in turn may promote greater use of alcohol other drugs along with adopting poor health behaviors. This model provides a pathway from early life adversity to low stress reactivity that forms a basis for risky behaviors and poor health outcomes. PMID:23085387

Toward computational models of magma genesis and geochemical transport in subduction zones

NASA Astrophysics Data System (ADS)

Katz, R.; Spiegelman, M.

2003-04-01

The chemistry of material erupted from subduction-related volcanoes records important information about the processes that lead to its formation at depth in the Earth. Self-consistent numerical simulations provide a useful tool for interpreting this data as they can explore the non-linear feedbacks between processes that control the generation and transport of magma. A model capable of addressing such issues should include three critical components: (1) a variable viscosity solid flow solver with smooth and accurate pressure and velocity fields, (2) a parameterization of mass transfer reactions between the solid and fluid phases and (3) a consistent fluid flow and reactive transport code. We report on progress on each of these parts. To handle variable-viscosity solid-flow in the mantle wedge, we are adapting a Patankar-based FAS multigrid scheme developed by Albers (2000, J. Comp. Phys.). The pressure field in this scheme is the solution to an elliptic equation on a staggered grid. Thus we expect computed pressure fields to have smooth gradient fields suitable for porous flow calculations, unlike those of commonly used penalty-method schemes. Use of a temperature and strain-rate dependent mantle rheology has been shown to have important consequences for the pattern of flow and the temperature structure in the wedge. For computing thermal structure we present a novel scheme that is a hybrid of Crank-Nicholson (CN) and Semi-Lagrangian (SL) methods. We have tested the SLCN scheme on advection across a broad range of Peclet numbers and show the results. This scheme is also useful for low-diffusivity chemical transport. We also describe our parameterization of hydrous mantle melting [Katz et. al., G3, 2002 in review]. This parameterization is designed to capture the melting behavior of peridotite--water systems over parameter ranges relevant to subduction. The parameterization incorporates data and intuition gained from laboratory experiments and thermodynamic calculations yet it remains flexible and computationally efficient. Given accurate solid-flow fields, a parameterization of hydrous melting and a method for calculating thermal structure (enforcing energy conservation), the final step is to integrate these components into a consistent framework for reactive-flow and chemical transport in deformable porous media. We present preliminary results for reactive flow in 2-D static and upwelling columns and discuss possible mechanical and chemical consequences of open system reactive melting with application to arcs.

Neural reactivations during sleep determine network credit assignment

PubMed Central

Gulati, Tanuj; Guo, Ling; Ramanathan, Dhakshin S.; Bodepudi, Anitha; Ganguly, Karunesh

2018-01-01

A fundamental goal of motor learning is to establish neural patterns that produce a desired behavioral outcome. It remains unclear how and when the nervous system solves this “credit–assignment” problem. Using neuroprosthetic learning where we could control the causal relationship between neurons and behavior, here we show that sleep–dependent processing is required for credit-assignment and the establishment of task-related functional connectivity reflecting the casual neuron-behavior relationship. Importantly, we found a strong link between the microstructure of sleep reactivations and credit assignment, with downscaling of non–causal activity. Strikingly, decoupling of spiking to slow–oscillations using optogenetic methods eliminated rescaling. Thus, our results suggest that coordinated firing during sleep plays an essential role in establishing sparse activation patterns that reflect the causal neuron–behavior relationship. PMID:28692062

Redox Non-Innocence of Nitrosobenzene at Nickel

DOE PAGES

Kundu, Subrata; Stieber, S. Chantal; Ferrier, Maryline Ghislaine; ...

2016-08-22

Nitrosobenzene (PhNO) serves as a stable analogue of nitroxyl (HNO), a biologically relevant, redox-active nitric oxide derivative. Capture of nitrosobenzene at the electrondeficient β-diketiminato nickel(I) complex [ iPr 2NN F6]Ni results in reduction of the PhNO ligand to a (PhNO) ./ ⁻ species coordinated to a square planar Ni II center in [ iPr 2NN F6]Ni(η 2- ONPh). Ligand centered reduction leads to the (PhNO) -2 moiety bound to Ni II supported by XAS studies. Ultimately, systematic investigation of structure–reactivity patterns of (PhNO) ./ ⁻ and (PhNO) 2- ligands reveals parallels with superoxo (O 2) ./ ⁻ and peroxo (Omore » 2) 2- ligands, respectively, and forecasts reactivity patterns of the more transient HNO ligand.« less