A series of silver(I) coordination polymers with saccarinate and flexible aliphatic diamines

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

Yeşilel, Okan Zafer, E-mail: yesilel@ogu.edu.tr; Karamahmut, Bingül; Semerci, Fatih

A series of Ag(I) complexes with aliphatic diamines having a different chain length (NH{sub 2}-(CH{sub 2}){sub n}-NH{sub 2}, n=4–9), with the formulas, [Ag(μ-sac)(μ-db){sub 0.5}]{sub n} (1), ([Ag{sub 4}(sac){sub 4}(μ-dp){sub 2}]·4H{sub 2}O){sub n} (2){sub ,} ([Ag{sub 2}(sac){sub 2}(μ-dz)]·2H{sub 2}O){sub n} (3), ([Ag{sub 2}(sac){sub 2}(μ-dh)]·H{sub 2}O){sub n} (4), ([Ag{sub 2}(sac){sub 2}(μ-do)]·H{sub 2}O){sub n} (5a), [Ag{sub 2}(sac){sub 2}(μ-do){sub 2}] (5b) and [Ag{sub 4}(sac){sub 4}(μ-dn){sub 2}]·2H{sub 2}O (6), where sac=saccharinate, db=1,4-diaminobutane, dp=1,5-diaminopentane, dz=1,6-diaminohexane, dh=1,7-diaminoheptane, do=1,8-diaminooctane and dn=1,9-diaminononane, were synthesized and characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction analysis. In 1, the sac ligand bridges adjacent Ag(I) ions through the nitrogen andmore » carbonyl oxygen atoms to form eight-membered bimetallic rings with the Ag···Ag distance being 3.897 Å, which are linked by db ligands to give a 1D zigzag chain. The complexes 2–5a consist of a one-dimensional (1D) linear cationic chains and discrete mononuclear anions. The discreet complex units are further connected by ligand unsupported argentophilic interactions. In 6, the dn ligands bridge adjacent silver centers to form 24-membered macrometallacyclic rings, which are further connected to the anionic [Ag(sac){sub 2}]{sup -} units by argentophilic Ag1···Ag2 interactions to form a tetranuclear structure. The adjacent dinuclear units are further linked together through ligand-unsupported argentophilic Ag···Ag (3.207(1) Å) interactions, generating a one-dimensional linear chain. The most striking feature of complexes is the presence of the rare intermolecular C-H···Ag interactions. In 5b, the do ligand bridges two Ag(I) ions to form a dinuclear with a 22-membered macrometallacyclic ring. Furthermore, biological activities, luminescence properties and thermal analysis (TG/DTA) of the complexes were investigated. - Graphical abstract: In this study, six new silver coordination compounds were synthesized by using saccharinate and flexible aliphatic diamine derivatives. All the compounds were characterized by elemental analysis, IR and single-crystal X-ray analysis. TG/DTA. Furthermore, biological activities, luminescence properties and thermal analysis (TG/DTA) of the complexes have been investigated. Complexes 1–5a and 6 were synthesized with the same reactant ratio and room temperature by using a mixture of AgNO{sub 3}, sac and different length diamine derivatives. The complex 5b is also synthesized was similar to that of 1 at 80 °C. In the complexes, the diamine derivatives ligands show bis(bridging) coordination mode. The sac ligand exhibits a µ-bridging coordination mode in 1 and N-donor monodentate coordination mode in 2–6. Complexes 1–5 exhibit 1D chain structure while complex 6 are tetranuclear structure. In the crystal packing of complexes, 3D supramolecular frameworks are formed via C-H···Ag, Ag···π and Ag···Ag interactions.« less

A carbon-supported copper complex of 3,5-diamino-1,2,4-triazole as a cathode catalyst for alkaline fuel cell applications.

PubMed

Brushett, Fikile R; Thorum, Matthew S; Lioutas, Nicholas S; Naughton, Matthew S; Tornow, Claire; Jhong, Huei-Ru Molly; Gewirth, Andrew A; Kenis, Paul J A

2010-09-08

The performance of a novel carbon-supported copper complex of 3,5-diamino-1,2,4-triazole (Cu-tri/C) is investigated as a cathode material using an alkaline microfluidic H(2)/O(2) fuel cell. The absolute Cu-tri/C cathode performance is comparable to that of a Pt/C cathode. Furthermore, at a commercially relevant potential, the measured mass activity of an unoptimized Cu-tri/C-based cathode was significantly greater than that of similar Pt/C- and Ag/C-based cathodes. Accelerated cathode durability studies suggested multiple degradation regimes at various time scales. Further enhancements in performance and durability may be realized by optimizing catalyst and electrode preparation procedures.

Interaction of the univalent silver cation with [Gly6]-antamanide: Experimental and theoretical study

NASA Astrophysics Data System (ADS)

Makrlík, Emanuel; Böhm, Stanislav; Kvíčala, Jaroslav; Vaňura, Petr; Ruzza, Paolo

2018-03-01

On the basis of extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Ag+(aq) + 1.Na+(nb) ⇄ 1.Ag+ (nb) + Na+(aq) occurring in the two-phase water - nitrobenzene system (1 = [Gly6]-antamanide; aq = aqueous phase, nb = nitrobenzene phase) was determined as log Kex (Ag+,1·Na+) = 1.5 ± 0.1. Further, the stability constant of the 1·Ag+ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log βnb (1·Ag+) = 4.5 ± 0.2. Finally, by using quantum chemical DFT calculations, the most probable structure of the cationic complex species 1·Ag+ was derived. In the resulting complex, the "central" cation Ag+ is coordinated by four noncovalent interactions to the corresponding four carbonyl oxygen atoms of the parent ligand 1. Besides, the whole 1·Ag+ complex structure is stabilized by two intramolecular hydrogen bonds. The interaction energy of the considered 1·Ag+ complex was found to be -465.5 kJ/mol, confirming also the formation of this cationic species.

Co-targeting deoxyribonucleic acid-dependent protein kinase and poly(adenosine diphosphate-ribose) polymerase-1 promotes accelerated senescence of irradiated cancer cells.

PubMed

Azad, Arun; Bukczynska, Patricia; Jackson, Susan; Haupt, Ygal; Haput, Ygal; Cullinane, Carleen; McArthur, Grant A; Solomon, Benjamin

2014-02-01

To examine the effects of combined blockade of DNA-dependent protein kinase (DNA-PK) and poly(adenosine diphosphate-ribose) polymerase-1 (PARP-1) on accelerated senescence in irradiated H460 and A549 non-small cell lung cancer cells. The effects of KU5788 and AG014699 (inhibitors of DNA-PK and PARP-1, respectively) on clonogenic survival, DNA double-strand breaks (DSBs), apoptosis, mitotic catastrophe, and accelerated senescence in irradiated cells were examined in vitro. For in vivo experiments, H460 xenografts established in athymic nude mice were treated with BEZ235 (a DNA-PK, ATM, and phosphatidylinositol 3-kinase/mammalian target of rapamycin inhibitor) and AG014699 to determine effects on proliferation, DNA DSBs, and accelerated senescence after radiation. Compared with either inhibitor alone, combination treatment with KU57788 and AG014699 reduced postradiation clonogenic survival and significantly increased persistence of Gamma-H2AX (γH2AX) foci in irradiated H460 and A549 cells. Notably, these effects coincided with the induction of accelerated senescence in irradiated cells as reflected by positive β-galactosidase staining, G2-M cell-cycle arrest, enlarged and flattened cellular morphology, increased p21 expression, and senescence-associated cytokine secretion. In irradiated H460 xenografts, concurrent therapy with BEZ235 and AG014699 resulted in sustained Gamma-H2AX (γH2AX) staining and prominent β-galactosidase activity. Combined DNA-PK and PARP-1 blockade increased tumor cell radiosensitivity and enhanced the prosenescent properties of ionizing radiation in vitro and in vivo. These data provide a rationale for further preclinical and clinical testing of this therapeutic combination. Copyright © 2014. Published by Elsevier Inc.

Weakly nucleophilic potassium aryltrifluoroborates in palladium-catalyzed Suzuki–Miyaura reactions: relative reactivity of K[4-RC6F4BF3] and the role of silver-assistance in acceleration of transmetallation

PubMed Central

Bardin, Vadim V; Shabalin, Anton Yu

2015-01-01

Summary Small differences in the reactivity of weakly nucleophilic potassium aryltrifluoroborates are revealed in the silver-assisted Pd-catalyzed cross-coupling of K[4-RC6F4BF3] (R = H, Bu, MeO, EtO, PrO, iPrO, BuO, t-BuO, CH2=CHCH2O, PhCH2O, PhCH2CH2O, PhO, F, pyrazol-1-yl, pyrrol-1-yl, and indol-1-yl) with ArX (4-BrC6H4CH3, 4-IC6H4F and 3-IC6H4F). An assumed role of silver(I) compounds AgmY (Y = O, NO3, SO4, BF4, F) consists in polarization of the Pd–X bond in neutral complex ArPdLnX with the generation of the related transition state or formation of [ArPdLn][XAgmY] with a highly electrophilic cation and subsequent transmetallation with the weakly nucleophilic borate. Efficiency of AgmY as a polarizing agent decreases in order Ag2O > AgNO3 ≈ Ag2SO4 > Ag[BF4] > AgF. No clear correlation between the reactivity of K[4-RC6F4BF3] and substituent electron parameters, σI and σR°, of the aryl group 4-RC6F4 was found. PMID:26124862

New bioactive silver(I) complexes: Synthesis, characterization, anticancer, antibacterial and anticarbonic anhydrase II activities

NASA Astrophysics Data System (ADS)

Ozdemir, Ummuhan O.; Ozbek, Neslihan; Genc, Zuhal Karagoz; İlbiz, Firdevs; Gündüzalp, Ayla Balaban

2017-06-01

Silver(I) complexes of alkyl sulfonic acide hydrazides were newly synthesized as homologous series. Methanesulfonic acide hydrazide (L1), ethanesulfonic acide hydrazide (L2), propanesulfonic acide hydrazide (L3) and butanesulfonic acide hydrazide (L4) were used for complexation with Ag(I) ions. The silver complexes obtained in the mol ratio of 1:2 have the structural formula as Ag(L1)2NO3 (I), Ag(L2)2NO3 (II), Ag(L3)2NO3(III), (Ag(L4)2NO3 (IV). The Ag(I) complexes exhibit distorted linear two-fold coordination in [AgL2]+ cations with uncoordinated nitrates. Ligands are chelated with silver(I) ions through unsubstituted primary nitrogen in hydrazide group. Ag(I) complexes were characterized by using elemental analysis, spectroscopic methods (FT-IR, LC-MS), magnetic susceptibility and conductivity measurements. Silver(I) complexes were optimized using PBEPBE/LanL2DZ/DEF2SV basic set performed by DFT method with the Gaussian 09 program package. The geometrical parameters, frontier molecular orbitals (HOMOs and LUMOs) and molecular electrostatic potential (MEP) mapped surfaces of the optimized geometries were also determined by this quantum set. The anticancer activities of silver(I) complexes on MCF-7 human breast cancer cell line were investigated by comparing IC50 values. The antibacterial activities of complexes were studied against Gram positive bacteria; S. aureus ATCC 6538, B. subtilis ATCC 6633, B. cereus NRRL-B-3711, E. faecalis ATCC 29212 and Gram negative bacteria; E. coli ATCC 11230, P. aeruginosa ATCC 15442, K. pneumonia ATCC 70063 by using disc diffusion method. The inhibition activities of Ag(I) complexes on carbonic anhydrase II enzyme (hCA II) were also investigated by comparing IC50 and Ki values. The biological activity screening shows that Ag(I) complex of butanesulfonicacidehydrazide (IV) has the highest activity against tested breast cancer cell lines MCF-7, Gram positive/Gram negative bacteria and carbonic anhydrase II (hCA II) isoenzyme.

Effect of tyrphostin AG879 on Kv4.2 and Kv4.3 potassium channels

PubMed Central

Yu, Haibo; Zou, Beiyan; Wang, Xiaoliang; Li, Min

2015-01-01

Background and Purpose A-type potassium channels (IA) are important proteins for modulating neuronal membrane excitability. The expression and activity of Kv4.2 channels are critical for neurological functions and pharmacological inhibitors of Kv4.2 channels may have therapeutic potential for Fragile X syndrome. While screening various compounds, we identified tyrphostin AG879, a tyrosine kinase inhibitor, as a Kv4.2 inhibitor from. In the present study we characterized the effect of AG879 on cloned Kv4.2/Kv channel-interacting protein 2 (KChIP2) channels. Experimental Approach To screen the library of pharmacologically active compounds, the thallium flux assay was performed on HEK-293 cells transiently-transfected with Kv4.2 cDNA using the Maxcyte transfection system. The effects of AG879 were further examined on CHO-K1 cells expressing Kv4.2/KChIP2 channels using a whole-cell patch-clamp technique. Key Results Tyrphostin AG879 selectively and dose-dependently inhibited Kv4.2 and Kv4.3 channels. In Kv4.2/KChIP2 channels, AG879 induced prominent acceleration of the inactivation rate, use-dependent block and slowed the recovery from inactivation. AG879 induced a hyperpolarizing shift in the voltage-dependence of the steady-state inactivation of Kv4.2 channels without apparent effect on the V1/2 of the voltage-dependent activation. The blocking effect of AG879 was enhanced as channel inactivation increased. Furthermore, AG879 significantly inhibited the A-type potassium currents in the cultured hippocampus neurons. Conclusion and Implications AG879 was identified as a selective and potent inhibitor the Kv4.2 channel. AG879 inhibited Kv4.2 channels by preferentially interacting with the open state and further accelerating their inactivation. PMID:25752739

Effect of tyrphostin AG879 on Kv 4.2 and Kv 4.3 potassium channels.

PubMed

Yu, Haibo; Zou, Beiyan; Wang, Xiaoliang; Li, Min

2015-07-01

A-type potassium channels (IA) are important proteins for modulating neuronal membrane excitability. The expression and activity of Kv 4.2 channels are critical for neurological functions and pharmacological inhibitors of Kv 4.2 channels may have therapeutic potential for Fragile X syndrome. While screening various compounds, we identified tyrphostin AG879, a tyrosine kinase inhibitor, as a Kv 4.2 inhibitor from. In the present study we characterized the effect of AG879 on cloned Kv 4.2/Kv channel-interacting protein 2 (KChIP2) channels. To screen the library of pharmacologically active compounds, the thallium flux assay was performed on HEK-293 cells transiently-transfected with Kv 4.2 cDNA using the Maxcyte transfection system. The effects of AG879 were further examined on CHO-K1 cells expressing Kv 4.2/KChIP2 channels using a whole-cell patch-clamp technique. Tyrphostin AG879 selectively and dose-dependently inhibited Kv 4.2 and Kv 4.3 channels. In Kv 4.2/KChIP2 channels, AG879 induced prominent acceleration of the inactivation rate, use-dependent block and slowed the recovery from inactivation. AG879 induced a hyperpolarizing shift in the voltage-dependence of the steady-state inactivation of Kv 4.2 channels without apparent effect on the V1/2 of the voltage-dependent activation. The blocking effect of AG879 was enhanced as channel inactivation increased. Furthermore, AG879 significantly inhibited the A-type potassium currents in the cultured hippocampus neurons. AG879 was identified as a selective and potent inhibitor the Kv 4.2 channel. AG879 inhibited Kv 4.2 channels by preferentially interacting with the open state and further accelerating their inactivation. © 2015 The British Pharmacological Society.

Silver(I) complexes with DNA and RNA studied by Fourier transform infrared spectroscopy and capillary electrophoresis.

PubMed Central

Arakawa, H; Neault, J F; Tajmir-Riahi, H A

2001-01-01

Ag(I) is a strong nucleic acids binder and forms several complexes with DNA such as types I, II, and III. However, the details of the binding mode of silver(I) in the Ag-polynucleotides remains unknown. Therefore, it was of interest to examine the binding of Ag(I) with calf-thymus DNA and bakers yeast RNA in aqueous solutions at pH 7.1-6.6 with constant concentration of DNA or RNA and various concentrations of Ag(I). Fourier transform infrared spectroscopy and capillary electrophoresis were used to analyze the Ag(I) binding mode, the binding constant, and the polynucleotides' structural changes in the Ag-DNA and Ag-RNA complexes. The spectroscopic results showed that in the type I complex formed with DNA, Ag(I) binds to guanine N7 at low cation concentration (r = 1/80) and adenine N7 site at higher concentrations (r = 1/20 to 1/10), but not to the backbone phosphate group. At r = 1/2, type II complexes formed with DNA in which Ag(I) binds to the G-C and A-T base pairs. On the other hand, Ag(I) binds to the guanine N7 atom but not to the adenine and the backbone phosphate group in the Ag-RNA complexes. Although a minor alteration of the sugar-phosphate geometry was observed, DNA remained in the B-family structure, whereas RNA retained its A conformation. Scatchard analysis following capillary electrophoresis showed two binding sites for the Ag-DNA complexes with K(1) = 8.3 x 10(4) M(-1) for the guanine and K(2) = 1.5 x 10(4) M(-1) for the adenine bases. On the other hand, Ag-RNA adducts showed one binding site with K = 1.5 x 10(5) M(-1) for the guanine bases. PMID:11509371

Silver Complexes of Dihalogen Molecules.

PubMed

Malinowski, Przemysław J; Himmel, Daniel; Krossing, Ingo

2016-08-01

The perfluorohexane-soluble and donor-free silver compound Ag(A) (A=Al(OR(F) )4 ; R(F) =C(CF3 )3 ) prepared using a facile novel route has unprecedented capabilities to form unusual and weakly bound complexes. Here, we report on the three dihalogen-silver complexes Ag(Cl2 )A, Ag(Br2 )A, and Ag(I2 )A derived from the soluble silver compound Ag(A) (characterized by single-crystal/powder XRD, Raman spectra, and quantum-mechanical calculations). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simple and scalable growth of AgCl nanorods by plasma-assisted strain relaxation on flexible polymer substrates

NASA Astrophysics Data System (ADS)

Park, Jae Yong; Lee, Illhwan; Ham, Juyoung; Gim, Seungo; Lee, Jong-Lam

2017-06-01

Implementing nanostructures on plastic film is indispensable for highly efficient flexible optoelectronic devices. However, due to the thermal and chemical fragility of plastic, nanostructuring approaches are limited to indirect transfer with low throughput. Here, we fabricate single-crystal AgCl nanorods by using a Cl2 plasma on Ag-coated polyimide. Cl radicals react with Ag to form AgCl nanorods. The AgCl is subjected to compressive strain at its interface with the Ag film because of the larger lattice constant of AgCl compared to Ag. To minimize strain energy, the AgCl nanorods grow in the [200] direction. The epitaxial relationship between AgCl (200) and Ag (111) induces a strain, which leads to a strain gradient at the periphery of AgCl nanorods. The gradient causes a strain-induced diffusion of Ag atoms to accelerate the nanorod growth. Nanorods grown for 45 s exhibit superior haze up to 100% and luminance of optical device increased by up to 33%.

Selected topics in particle accelerators: Proceedings of the CAP meetings. Volume 5

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

Parsa, Z.

1995-10-01

This Report includes copies of transparencies and notes from the presentations made at the Center for Accelerator Physics at Brookhaven National Laboratory Editing and changes to the authors` contributions in this Report were made only to fulfill the publication requirements. This volume includes notes and transparencies on nine presentations: ``The Energy Exchange and Efficiency Consideration in Klystrons``, ``Some Properties of Microwave RF Sources for Future Colliders + Overview of Microwave Generation Activity at the University of Maryland``, ``Field Quality Improvements in Superconducting Magnets for RHIC``, ``Hadronic B-Physics``, ``Spiking Pulses from Free Electron Lasers: Observations and Computational Models``, ``Crystalline Beams inmore » Circular Accelerators``, ``Accumulator Ring for AGS & Recent AGS Performance``, ``RHIC Project Machine Status``, and ``Gamma-Gamma Colliders.``« less

Insertion of Ag atoms into layered MoO{sub 3} via a template route

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

Shao, Ke, E-mail: shaoke@szu.edu.cn; Wang, Hao

2012-11-15

Graphical abstract: PVP–Ag{sup +} complex self-assembled with inorganic (Mo{sub x}O{sub y}){sub ∞}{sup n−} chains into a layered hybrid, in which the PVP–Ag complex was intercalated between the (Mo{sub x}O{sub y}){sub ∞}{sup n−} layers. Calcinations of this hybrid at 500 °C lead to formation of Ag/MoO{sub 3} nanohybrid. By this method we have successfully inserted Ag atoms into the semiconductor MoO{sub 3} lattice. Display Omitted Highlights: ► We fabricated a PVP–Ag/polyoxomolybdate layered hybrid via in situ self-assembly. ► The PVP–Ag complex has been inserted between the molybdenum oxide layers. ► This layered hybrid transformed into Ag/MoO{sub 3} nanocomposite after calcinations. ►more » HR-TEM images show that Ag atoms of about 1 nm have been inserted in the MoO{sub 3} layers. -- Abstract: We report insertion of Ag atoms into layered MoO{sub 3} via an in situ template route. PVP–Ag{sup +} complex self-assembled with inorganic (Mo{sub x}O{sub y}){sub ∞}{sup n−} chains into a layered hybrid, in which the PVP–Ag complex was intercalated between the (Mo{sub x}O{sub y}){sub ∞}{sup n−} layers. Calcinations of this hybrid at 500 °C lead to formation of Ag/MoO{sub 3} hybrid, in which Ag nanoparticles of about 1 nm have been inserted between the MoO{sub 3} layers. By this method pillared MoO{sub 3} has been obtained very easily. We believe that this research opens new routes to fabricate novel intercalation compounds and metal/semiconductor nanohybrids via an efficient and green route.« less

The AGS Ggamma Meter and Calibrating the Gauss Clock

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

Ahrens, Leif

2014-03-31

During AGS Polarized Proton acceleration periods, one output from the AGS Ggamma Meter, namely the energy (or Ggamma) calculated from the magnetic field in the AGS main magnets and the beam radius- both measured in particular instant, is used to figure out the times in the AGS magnet acceleration cycle when the beam passes through a particular set of depolarizing resonances. The resonance set occur whenever a particle’s Ggamma (energy*(G/m) becomes nearly equal to n*Qx (i.e. any integer multiplied by the horizontal betatron tune). This deliverable is why the machinery is referred to as the ''Ggamma Meter'' rather than themore » AGS energy meter. The Ggamma Meter takes as inputs a set of measurements of frequency (F(t)), radius (r(t)), and gauss clock counts (GCC(t)). The other energy (GgammaBr) assumes the field when the gauss clock starts counting is known. The change in field to time t is given by the measured accumulated gauss clock counts multiplied by the gauss clock calibration (gauss/GCC). In order to deal with experimental data, this calibration factor gets an added ad hoc complication, namely a correction dependent on the rate of change the counting rate. The Ggamma meter takes GCC(t) and together with the past history for this cycle calculates B(t).« less

Nano-Ag complexes prepared by γ-radiolysis and their structures and physical properties

NASA Astrophysics Data System (ADS)

Kim, Hwa-Jung; Choi, Seong-Ho; Park, Hae-Jun

2012-10-01

In this study, nano-silver (nano-Ag) complexes showing different properties have been synthesized as follows. Polypyrrolidone (PVP)-stabilized silver colloids (NAg), nano-Ag bound to silica (SiO2) (NSS), and nano-Ag bound to a complex of SiO2 and polyaniline (PANI) (NSSPAI) were prepared via γ-irradiation at room temperature. NAg and NSS used PVP as a colloidal stabilizer, while NSSPAI did not use PVP as a colloidal stabilizer. Interesting bonding properties occurred in the nano-Ag complex and anticipated structural changes were clearly shown through a surface analysis of x-ray photoelectron spectroscopy (XPS). The morphologies by field emission-scanning electron microscopy (FE-SEM) analysis showed that nano-Ag complexes have various particle sizes ranging from 10 to 30 nm. NSS (average, 10 nm) and NSSPAI (average, 30 nm) showed a uniformly spherical shape and size, while NAg did not. From the reflection peaks in the x-ray diffraction (XRD) patterns, surface crystallinity of the nano-Ag complexes was indicated to be in the same degree as that of NSSPAI>NSS>NAg. Also, in the contact angle (CA) determination, surface hydrophobicity of NSSPAI was stronger than those of NSS and NAg, relatively. The different nano-Ag complexes prepared by γ-irradiation can be applicable in various industry fields due to the increase in specific property.

Preparation and self-sterilizing properties of Ag@TiO2-styrene-acrylic complex coatings.

PubMed

Zhou, Xiang-dong; Chen, Feng; Yang, Jin-tao; Yan, Xiao-hui; Zhong, Ming-qiang

2013-04-01

In this study, we report a simple and cost-effective method for self-sterilized complex coatings obtained by Ag@TiO2 particle incorporation into styrene-acrylic latex. The Ag@TiO2 particles were prepared via a coupling agent modification process. The composite latices characterized by transmission electron microscopy (TEM) study were highly homogeneous at the nanometric scale, and the Ag@TiO2 particles were well dispersed and exhibited an intimate contact between both the organic and inorganic components. The Ag@TiO2 nanoparticles significantly enhanced the absorption in the visible region and engendered a good heat-insulating effect of the complex coatings. Moreover, the Ag@TiO2 nanoparticle incorporation into this polymer matrix renders self-sterilized nanocomposite materials upon light excitation, which are tested against Escherichia coli and Staphylococcus aureus. The complex coatings display an impressive performance in the killing of all micro-organisms with a maximum for a Ag@TiO2 loading concentration of 2-5 wt.%. The weathering endurance of the complex coating was also measured. Copyright © 2012 Elsevier B.V. All rights reserved.

Silver(I) complexes of the weakly coordinating solvents SO(2) and CH(2)Cl(2): crystal structures, bonding, and energetics of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)].

PubMed

Decken, Andreas; Knapp, Carsten; Nikiforov, Grigori B; Passmore, Jack; Rautiainen, J Mikko; Wang, Xinping; Zeng, Xiaoqing

2009-06-22

Pushing the limits of coordination chemistry: The most weakly coordinated silver complexes of the very weakly coordinating solvents dichloromethane and liquid sulfur dioxide were prepared. Special techniques at low temperatures and the use of weakly coordinating anions allowed structural characterization of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(Cl(2)CH(2))(2)][SbF(6)] (see figure). An investigation of the bonding shows that these complexes are mainly stabilized by electrostatic monopole-dipole interactions.The synthetically useful solvent-free silver(I) salt Ag[Al(pftb)(4)] (pftb=--OC(CF(3))(3)) was prepared by metathesis reaction of Li[Al(pftb)(4)] with Ag[SbF(6)] in liquid SO(2). The solvated complexes [Ag(OSO)][Al(pftb)(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)] were prepared and isolated by special techniques at low temperatures and structurally characterized by single-crystal X-ray diffraction. The SO(2) complexes provide the first examples of coordination of the very weak Lewis base SO(2) to silver(I). The SO(2) molecule in [Ag(OSO)][Al(pftb)(4)] is eta(1)-O coordinated to Ag(+), while the SO(2) ligands in [Ag(OSO)(2/2)][SbF(6)] bridge two Ag(+) ions in an eta(2)-O,O' (trans,trans) manner. [Ag(CH(2)Cl(2))(2)][SbF(6)] contains [Ag(CH(2)Cl(2))(2)](+) ions linked through [SbF(6)](-) ions to give a polymeric structure. The solid-state silver(I) ion affinities (SIA) of SO(2) and CH(2)Cl(2), based on bond lengths and corresponding valence units in the corresponding complexes and tensimetric titrations of Ag[Al(pftb)(4)] and Ag[SbF(6)] with SO(2) vapor, show that SO(2) is a weaker ligand to Ag(+) than the commonly used weakly coordinating solvent CH(2)Cl(2) and indicated that binding strength of SO(2) to silver(I) in the silver(I) salts increases with increasing size of the corresponding counteranion ([Al(pftb)(4)](-)>[SbF(6)](-)). The experimental findings are in good agreement with theoretical gas-phase ligand-binding energies of [Ag(L)(n)](+) (L=SO(2), CH(2)Cl(2); n=1, 2) and solid-state enthalpies obtained from Born-Fajans-Haber cycles by using the volume-based thermodynamics (VBT) approach. Bonding analysis (VB, NBO, MO) of [Ag(L)(n)](+) suggests that these complexes are almost completely stabilized by electrostatic interaction, that is, monopole-dipole interaction, with almost no covalent contribution by electron donation from the ligand orbitals into the vacant 5s orbital of Ag(+). All experimental findings and theoretical considerations demonstrate that SO(2) is less covalently bound to Ag(+) than CH(2)Cl(2) and support the thesis that SO(2) is a polar but non-coordinating solvent towards Ag(+).

A Molecular Census of Arcuate Hypothalamus and Median Eminence Cell Types

PubMed Central

Campbell, John N.; Macosko, Evan Z.; Fenselau, Henning; Pers, Tune H.; Lyubetskaya, Anna; Tenen, Danielle; Goldman, Melissa; Verstegen, Anne M.J.; Resch, Jon M.; McCarroll, Steven A.; Rosen, Evan D.; Lowell, Bradford B.; Tsai, Linus

2017-01-01

The hypothalamic arcuate-median eminence complex (Arc-ME) controls energy balance, fertility, and growth through molecularly distinct cell types, many of which remain unknown. To catalog cell types in an unbiased way, we profiled gene expression in 20,921 individual cells in and around the adult mouse Arc-ME using Drop-seq. We identify 50 transcriptionally distinct Arc-ME cell populations, including a rare tanycyte population at the Arc-ME diffusion barrier, a novel leptin-sensing neuronal population, multiple AgRP and POMC subtypes, and an orexigenic somatostatin neuronal population. We extended Drop-seq to detect dynamic expression changes across relevant physiological perturbations, revealing cell type-specific responses to energy status, including distinctly responsive subtypes of AgRP and POMC neurons. Finally, integrating our data with human GWAS data implicates two previously unknown neuronal subtypes in the genetic control of obesity. This resource will accelerate biological discovery by providing insights into molecular and cell type diversity from which function can be inferred. PMID:28166221

Novel mechanism of antibodies to hepatitis B virus in blocking viral particle release from cells.

PubMed

Neumann, Avidan U; Phillips, Sandra; Levine, Idit; Ijaz, Samreen; Dahari, Harel; Eren, Rachel; Dagan, Shlomo; Naoumov, Nikolai V

2010-09-01

Antibodies are thought to exert antiviral activities by blocking viral entry into cells and/or accelerating viral clearance from circulation. In particular, antibodies to hepatitis B virus (HBV) surface antigen (HBsAg) confer protection, by binding circulating virus. Here, we used mathematical modeling to gain information about viral dynamics during and after single or multiple infusions of a combination of two human monoclonal anti-HBs (HepeX-B) antibodies in patients with chronic hepatitis B. The antibody HBV-17 recognizes a conformational epitope, whereas antibody HBV-19 recognizes a linear epitope on the HBsAg. The kinetic profiles of the decline of serum HBV DNA and HBsAg revealed partial blocking of virion release from infected cells as a new antiviral mechanism, in addition to acceleration of HBV clearance from the circulation. We then replicated this approach in vitro, using cells secreting HBsAg, and compared the prediction of the mathematical modeling obtained from the in vivo kinetics. In vitro, HepeX-B treatment of HBsAg-producing cells showed cellular uptake of antibodies, resulting in intracellular accumulation of viral particles. Blocking of HBsAg secretion also continued after HepeX-B was removed from the cell culture supernatants. These results identify a novel antiviral mechanism of antibodies to HBsAg (anti-HBs) involving prolonged blocking of the HBV and HBsAg subviral particles release from infected cells. This may have implications in designing new therapies for patients with chronic HBV infection and may also be relevant in other viral infections.

Microstructural effects on constitutive and fatigue fracture behavior of TinSilverCopper solder

NASA Astrophysics Data System (ADS)

Tucker, Jonathon P.

As microelectronic package construction becomes more diverse and complex, the need for accurate, geometry-independent material constitutive and failure models increases. Evaluations of packages based on accelerated environmental tests (such as accelerated thermal cycling or power cycling) only provide package-dependent reliability information. In addition, extrapolations of such test data to life predictions under field conditions are often empirical. Besides geometry, accelerated environmental test data must account for microstructural factors such as alloy composition or isothermal aging condition, resulting in expensive experimental variation. In this work, displacement-controlled, creep, and fatigue lap shear tests are conducted on specially designed SnAgCu test specimens with microstructures representative to those found in commercial microelectronic packages. The data are used to develop constitutive and fatigue fracture material models capable of describing deformation and fracture behavior for the relevant temperature and strain rate ranges. Furthermore, insight is provided into the microstructural variation of solder joints and the subsequent effect on material behavior. These models are appropriate for application to packages of any geometrical construction. The first focus of the thesis is on Pb-mixed SnAgCu solder alloys. During the transition from Pb-containing solders to Pb-free solders, joints composed of a mixture of SnPb and SnAgCu often result from either mixed assemblies or rework. Three alloys of 1, 5 and 20 weight percent Pb were selected so as to represent reasonable ranges of Pb contamination expected from different 63Sn37Pb components mixed with Sn3.0Ag0.5Cu. Displacement-controlled (constant strain rate) and creep tests were performed at temperatures of 25°C, 75°C, and 125°C using a double lap shear test setup that ensures a nearly homogeneous state of plastic strain at the joint interface. Rate-dependent constitutive models for Pb-contaminated SnAgCu solder alloys ranging from the traditional time-hardening creep model to the viscoplastic Anand model are described. The second focus of the thesis is on fatigue damage accumulation in SnAgCu solder alloys. While, typical fatigue fracture models are empirical, recently a non-empirical model termed Maximum Entropy Fracture Model (MEFM) was proposed. MEFM is a thermodynamically consistent and information theory inspired damage accumulation theory for ductile solids. This model has been validated recently for Sn3.8Ag0.7Cu solder alloy, and uses a single damage accumulation parameter to relate the probability of fracture to accumulated entropic dissipation. Isothermal cycling fatigue tests on Sn3.0Ag0.5Cu and mixed SnPb/Sn3.0Ag0.5Cu solder alloys at varying strain rates and temperatures are conducted using a custom-built microscale mechanical tester capable of submicron displacement resolution. MEFM is applied here in conjunction with the Anand viscoplasticity model to predict the softening occurring over successive cycles as a result of damage accumulation. The damage accumulation parameters for Sn3.0Ag0.5Cu in different aged states are related to a microstructural parameter which quantitatively describes the state of coarsening. In addition, damage accumulation parameters for the three mixed solder alloys are reported. This approach allows for a non-empirical prediction of both constitutive and fracture behavior of packages of different geometries and different microstructural states under thermo-mechanical fatigue. Approaches to solder joint reliability predictions from materials science and mechanics perspectives differ dramatically. Materials science methods identify key failure mechanisms, but most models cannot predict failure. In contrast, mechanics approaches often provide estimates of joint lifetime, but fail to provide insight into microstructural influences. This work attempts to connect the two fields by relating constitutive behavior and fatigue fracture models for different alloys and aging conditions to one or more microstructural parameters.

Silver(i) complexes with 1'-(diphenylphosphino)-1-cyanoferrocene: the art of improvisation in coordination.

PubMed

Škoch, Karel; Uhlík, Filip; Císařová, Ivana; Štěpnička, Petr

2016-06-28

1'-(Diphenylphosphino)-1-cyanoferrocene () reacts with silver(i) halides at a 1 : 1 metal-to-ligand ratio to afford the heterocubane complexes [Ag(μ3-X)(-κP)]4, where X = Cl (), Br (), and I (). In addition, the reaction with AgCl with 2 equiv. of leads to chloride-bridged dimer [(μ-Cl)2{Ag(-κP)2}2] () and, presumably, also to [(μ(P,N)-){AgCl(-κP)}]2 (). While similar reactions with AgCN furnished only the insoluble coordination polymer [(-κP)2Ag(NC)Ag(CN)]n (), those with AgSCN afforded the heterocubane [Ag(-κP)(μ-SCN-S,S,N)]4 () and the thiocyanato-bridged disilver(i) complex [Ag(-κP)2(μ-SCN-S,N)]2 (), thereby resembling reactions in the AgCl- system. Attempted reactions with AgF led to ill-defined products, among which [Ag(-κP)2(μ-HF2)]2 () and [(μ-SiF6){Ag(-κP)2}2] () could be identified. The latter compound was prepared also from Ag2[SiF6] and . Reactions between and AgClO4 or Ag[BF4] afforded disilver complexes [(μ(P,N)-)Ag(ClO4-κO)]2 () and [(μ(P,N)-)Ag(BF4-κF)]2 () featuring pseudolinear Ag(i) centers that are weakly coordinated by the counter anions. A similar reaction with Ag[SbF6] followed by crystallization from ethyl acetate produced an analogous complex, albeit with coordinated solvent, [(μ(P,N)-)Ag(AcOEt-κO)]2[SbF6]2 (). Ultimately, a compound devoid of any additional ligands at the Ag(i) centers, [(μ(P,N)-)Ag]2[B(C6H3(CF3)2-3,5)4]2 (), was obtained from the reaction of with silver(i) tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. The reaction of Ag[BF4] with two equivalents of produced unique coordination polymer [Ag(-κP)(μ(P,N)-)]n[BF4]n (), the structure of which contained one of the phosphinoferrocene ligands coordinated as a P,N-chelate and the other forming a bridge to an adjacent Ag(i) center. All of these compounds were structurally characterized by single-crystal X-ray crystallography, revealing that the lengths of the bonds between silver and its anionic ligand(s) typically exceed the sum of the respective covalent radii, which is in line with the results of theoretical calculations at the density-functional theory (DFT) level, suggesting that standard covalent dative bonds are formed between silver and phosphorus (soft acid/soft base interactions) while the interactions between silver and the ligand's nitrile group (if coordinated) or the supporting anion are of predominantly electrostatic nature.

Toward full spectrum speciation of silver nanoparticles and ionic silver by on-line coupling of hollow fiber flow field-flow fractionation and minicolumn concentration with multiple detectors.

PubMed

Tan, Zhi-Qiang; Liu, Jing-Fu; Guo, Xiao-Ru; Yin, Yong-Guang; Byeon, Seul Kee; Moon, Myeong Hee; Jiang, Gui-Bin

2015-08-18

The intertransformation of silver nanoparticles (AgNPs) and ionic silver (Ag(I)) in the environment determines their transport, uptake, and toxicity, demanding methods to simultaneously separate and quantify AgNPs and Ag(I). For the first time, hollow fiber flow field-flow fractionation (HF5) and minicolumn concentration were on-line coupled together with multiple detectors (including UV-vis spectrometry, dynamic light scattering, and inductively coupled plasma mass spectrometry) for full spectrum separation, characterization, and quantification of various Ag(I) species (i.e., free Ag(I), weak and strong Ag(I) complexes) and differently sized AgNPs. While HF5 was employed for filtration and fractionation of AgNPs (>2 nm), the minicolumn packed with Amberlite IR120 resin functioned to trap free Ag(I) or weak Ag(I) complexes coming from the radial flow of HF5 together with the strong Ag(I) complexes and tiny AgNPs (<2 nm), which were further discriminated in a second run of focusing by oxidizing >90% of tiny AgNPs to free Ag(I) and trapped in the minicolumn. The excellent performance was verified by the good agreement of the characterization results of AgNPs determined by this method with that by transmission electron microscopy, and the satisfactory recoveries (70.7-108%) for seven Ag species, including Ag(I), the adduct of Ag(I) and cysteine, and five AgNPs with nominal diameters of 1.4 nm, 10 nm, 20 nm, 40 nm, and 60 nm in surface water samples.

AgPO2F2 and Ag9(PO2F2)14: the first Ag(i) and Ag(i)/Ag(ii) difluorophosphates with complex crystal structures.

PubMed

Malinowski, Przemysław J; Kurzydłowski, Dominik; Grochala, Wojciech

2015-12-07

The reaction of AgF2 with P2O3F4 yields a mixed valence Ag(I)/Ag(II) difluorophosphate salt with AgAg(PO2F2)14 stoichiometry - the first Ag(ii)-PO2F2 system known. This highly moisture sensitive brown solid is thermally stable up to 120 °C, which points at further feasible extension of the chemistry of Ag(ii)-PO2F2 systems. The crystal structure shows a very complex bonding pattern, comprising of polymeric Ag(PO2F2)14(4-) anions and two types of Ag(I) cations. One particular Ag(II) site present in the crystal structure of Ag9(PO2F2)14 is the first known example of square pyramidal penta-coordinated Ag(ii) in an oxo-ligand environment. Ag(i)PO2F2 - the product of the thermal decomposition of Ag9(PO2F2)14 - has also been characterized by thermal analysis, IR spectroscopy and X-ray powder diffraction. It has a complicated crystal structure as well, which consists of infinite 1D [Ag(I)O4/2] chains which are linked to more complex 3D structures via OPO bridges. The PO2F2(-) anions bind to cations in both compounds as bidentate oxo-ligands. The terminal F atoms tend to point inside the van der Waals cavities in the crystal structure of both compounds. All important structural details of both title compounds were corroborated by DFT calculations.

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

Azad, Arun, E-mail: arun.azad@bccancer.bc.ca; Department of Pathology, St. Vincent's Hospital, University of Melbourne, Parkville, Victoria; Bukczynska, Patricia

Purpose: To examine the effects of combined blockade of DNA-dependent protein kinase (DNA-PK) and poly(adenosine diphosphate-ribose) polymerase-1 (PARP-1) on accelerated senescence in irradiated H460 and A549 non-small cell lung cancer cells. Methods and Materials: The effects of KU5788 and AG014699 (inhibitors of DNA-PK and PARP-1, respectively) on clonogenic survival, DNA double-strand breaks (DSBs), apoptosis, mitotic catastrophe, and accelerated senescence in irradiated cells were examined in vitro. For in vivo experiments, H460 xenografts established in athymic nude mice were treated with BEZ235 (a DNA-PK, ATM, and phosphatidylinositol 3-kinase/mammalian target of rapamycin inhibitor) and AG014699 to determine effects on proliferation, DNA DSBs,more » and accelerated senescence after radiation. Results: Compared with either inhibitor alone, combination treatment with KU57788 and AG014699 reduced postradiation clonogenic survival and significantly increased persistence of Gamma-H2AX (γH2AX) foci in irradiated H460 and A549 cells. Notably, these effects coincided with the induction of accelerated senescence in irradiated cells as reflected by positive β-galactosidase staining, G2-M cell-cycle arrest, enlarged and flattened cellular morphology, increased p21 expression, and senescence-associated cytokine secretion. In irradiated H460 xenografts, concurrent therapy with BEZ235 and AG014699 resulted in sustained Gamma-H2AX (γH2AX) staining and prominent β-galactosidase activity. Conclusion: Combined DNA-PK and PARP-1 blockade increased tumor cell radiosensitivity and enhanced the prosenescent properties of ionizing radiation in vitro and in vivo. These data provide a rationale for further preclinical and clinical testing of this therapeutic combination.« less

Coinage metal coordination chemistry of stable primary, secondary and tertiary ferrocenylethyl-based phosphines.

PubMed

Azizpoor Fard, M; Rabiee Kenaree, A; Boyle, P D; Ragogna, P J; Gilroy, J B; Corrigan, J F

2016-02-21

Ferrocene-based phosphines constitute an important auxiliary ligand in inorganic chemistry. Utilizing the (ferrocenylethyl)phosphines (FcCH2CH2)3-nHnP (Fc = ferrocenyl; n = 2, 1; n = 1, 2; n = 0, 3) the synthesis of a series of coordination complexes [(FcCH2CH2)3-nHnPCuCl]4 (n = 2, 1-CuCl; n = 0, 3-CuCl), [(FcCH2CH2)2HPCuCl] (2-CuCl), {[(FcCH2CH2)H2P]2AgCl}2 (1-AgCl), [(FcCH2CH2)2HPAgCl] (2-AgCl), [(FcCH2CH2)3PAgCl]4 (3-AgCl), [(FcCH2CH2)3PM(OAc)]4 (M = Cu, 3-CuOAc M = Ag, 3-AgOAc), [(FcCH2CH2)3-nHnPAuCl] (n = 1, 2-AuCl; n = 0, 3-AuCl), via the reaction between the free phosphine and MX (M = Cu, Ag and Au; X = Cl, OAc), is described. The reaction between the respective phosphine with a suspension of metal-chloride or -acetate in a 1 : 1 ratio in THF at ambient temperature affords coordinated phosphine-coinage metal complexes. Varying structural motifs are observed in the solid state, as determined via single crystal X-ray analysis of 1-CuCl, 3-CuCl, 1-AgCl, 3-AgCl, 3-CuOAc, 3-AgOAc, 2-AuCl and 3-AuCl. Complexes 1-CuCl and 3-CuCl are tetrameric Cu(i) cubane-like structures with a Cu4Cl4 core, whereas silver complexes with primary and tertiary phosphine reveal two different structural types. The structure of 1-AgCl, unlike the rest, displays the coordination of two phosphines to each silver atom and shows a quadrangle defined by two Ag and two Cl atoms. In contrast, 3-AgCl is distorted from a cubane structure via elongation of one of the ClAg distances. 3-CuOAc and 3-AgOAc are isostructural with step-like cores, while complexes 2-AuCl and 3-AuCl reveal a linear geometry of a phosphine gold(i) chloride devoid of any aurophilic interactions. All of the complexes were characterized in solution by multinuclear (1)H, (13)C{(1)H} and (31)P NMR spectroscopic techniques; the redox chemistry of the series of complexes was examined using cyclic voltammetry. This class of complexes has been found to exhibit one reversible Fe(ii)/Fe(iii) oxidation couple, suggesting the absence of electronic communication between the ferrocenyl units on individual phosphine ligands as well as between different phosphines on the polymetallic cores.

Identification of p53 unbound to T-antigen in human cells transformed by simian virus 40 T-antigen.

PubMed

O'Neill, F J; Hu, Y; Chen, T; Carney, H

1997-02-27

In several clones of SV40-transformed human cells, we investigated the relative amounts of large T-Antigen (T-Ag) and p53 proteins, both unbound and associated within complexes, with the goal of identifying changes associated with transformation and immortalization. Cells were transformed by wild type (wt) T-Ag, a functionally temperature sensitive T-Ag (tsA58) and other T-Ag variants. Western analysis showed that while most of the T-Ag was ultimately bound by p53, most of the p53 remained unbound to T-Ag. Unbound p53 remained in the supernatant after a T-Ag immunoprecipitation and p53 was present in two to fourfold excess of T-Ag. In one transformant there was five to tenfold more p53 than T-Ag. p53 was present in transformants in amounts at least 200-fold greater than in untransformed human cells. In wt and variant T-Ag transformants, including those generated with tsA58 T-Ag, large amounts of unbound p53 were present in both pre-crisis and immortal cells and when the cells were grown at permissive or non-permissive temperatures. We also found that in transformants produced by tsA58, an SV40/JCV chimeric T-Ag and other variants, T-Ag appeared to form a complex with p53 slowly perhaps because one or both proteins matured slowly. The presence in transformed human cells of large amounts of unbound p53 and in excess of T-Ag suggests that sequestration of p53 by T-Ag, resulting from complex formation, is required neither for morphological transformation nor immortalization of human cells. Rather, these results support the proposal that high levels of p53, the T-Ag/p53 complexes, or other biochemical event(s), lead to transformation and immortalization of human cells by T-Ag.

Localized saddle-point search and application to temperature-accelerated dynamics

NASA Astrophysics Data System (ADS)

Shim, Yunsic; Callahan, Nathan B.; Amar, Jacques G.

2013-03-01

We present a method for speeding up temperature-accelerated dynamics (TAD) simulations by carrying out a localized saddle-point (LSAD) search. In this method, instead of using the entire system to determine the energy barriers of activated processes, the calculation is localized by only including a small chunk of atoms around the atoms directly involved in the transition. Using this method, we have obtained N-independent scaling for the computational cost of the saddle-point search as a function of system size N. The error arising from localization is analyzed using a variety of model systems, including a variety of activated processes on Ag(100) and Cu(100) surfaces, as well as multiatom moves in Cu radiation damage and metal heteroepitaxial growth. Our results show significantly improved performance of TAD with the LSAD method, for the case of Ag/Ag(100) annealing and Cu/Cu(100) growth, while maintaining a negligibly small error in energy barriers.

Silver Nanoparticles Synthesized by Decomposition of a Silver Organic Complex with Valence Tautomerism and Their Properties

NASA Astrophysics Data System (ADS)

Harbatsevich, H. I.; Loginova, N. V.; Koval‧chuk, T. V.; Osipovich, N. P.; Gres, A. T.

2017-03-01

Features of the formation of silver nanoparticles (Ag-NPs) via intramolecular redox transformation of the Ag(I) complex of 4,6-di-tert-butyl-2,3-dihydroxybenzaldehyde isonicotinoylhydrazone in organic solvents with donor numbers DN > 19 were studied. The stability of the organic sols depended on the nature of the dispersion medium and the presence of oxygen and water in it. The physical chemistry and morphology of the Ag-NP in the organic sol were investigated using molecular absorption spectroscopy, transmission electron microscopy, and atomic force microscopy. The silver sol consisted of spherical Ag-NPs 5-20 nm in size with a characteristic absorption band near 440 nm. It was found that the silver complex with valence tautomerism was a promising precursor for Ag-NPs. The synthesized Ag-NPs showed high antimicrobial activity compared with standard antibiotics and Ag-containing agents (MIC = 0.007 μmol/mL).

Silver Nanoparticles Formed in a Colloidal System and a Polymer Matrix

NASA Astrophysics Data System (ADS)

Potapov, A. L.; Agabekov, V. E.; Belyi, V. N.

2018-05-01

The growth kinetics and particle-size distribution of Ag particles in a polyvinyl alcohol (PVA) composite, PVA film, and aqueous sol were studied using UV and visible spectroscopy, atomic force microscopy, and dynamic light scattering. A hypsochromic shift (55 nm) of the Ag nanoparticle (NP) surface plasmon absorption maximum was measured on going from the PVA composite to the film. The kinetics of Ag NP formation and their sizes were shown to depend considerably on UV irradiation, ultrasound action, and PVA concentration. It was established that UV irradiation accelerated Ag NP formation in the presence of reductants and destroyed the resulting NPs with a deficit of reductant. Partial destruction of the Ag NPs occurred under the influence of ultrasound whereas ultrasound action after UV irradiation reduced Ag+ on the clusters.

Charge-transfer optical absorption mechanism of DNA:Ag-nanocluster complexes

NASA Astrophysics Data System (ADS)

Longuinhos, R.; Lúcio, A. D.; Chacham, H.; Alexandre, S. S.

2016-05-01

Optical properties of DNA:Ag-nanoclusters complexes have been successfully applied experimentally in Chemistry, Physics, and Biology. Nevertheless, the mechanisms behind their optical activity remain unresolved. In this work, we present a time-dependent density functional study of optical absorption in DNA:Ag4. In all 23 different complexes investigated, we obtain new absorption peaks in the visible region that are not found in either the isolated Ag4 or isolated DNA base pairs. Absorption from red to green are predominantly of charge-transfer character, from the Ag4 to the DNA fragment, while absorption in the blue-violet range are mostly associated to electronic transitions of a mixed character, involving either DNA-Ag4 hybrid orbitals or intracluster orbitals. We also investigate the role of exchange-correlation functionals in the calculated optical spectra. Significant differences are observed between the calculations using the PBE functional (without exact exchange) and the CAM-B3LYP functional (which partly includes exact exchange). Specifically, we observe a tendency of charge-transfer excitations to involve purines bases, and the PBE spectra error is more pronounced in the complexes where the Ag cluster is bound to the purines. Finally, our results also highlight the importance of adding both the complementary base pair and the sugar-phosphate backbone in order to properly characterize the absorption spectrum of DNA:Ag complexes.

Charge-transfer optical absorption mechanism of DNA:Ag-nanocluster complexes.

PubMed

Longuinhos, R; Lúcio, A D; Chacham, H; Alexandre, S S

2016-05-01

Optical properties of DNA:Ag-nanoclusters complexes have been successfully applied experimentally in Chemistry, Physics, and Biology. Nevertheless, the mechanisms behind their optical activity remain unresolved. In this work, we present a time-dependent density functional study of optical absorption in DNA:Ag_{4}. In all 23 different complexes investigated, we obtain new absorption peaks in the visible region that are not found in either the isolated Ag_{4} or isolated DNA base pairs. Absorption from red to green are predominantly of charge-transfer character, from the Ag_{4} to the DNA fragment, while absorption in the blue-violet range are mostly associated to electronic transitions of a mixed character, involving either DNA-Ag_{4} hybrid orbitals or intracluster orbitals. We also investigate the role of exchange-correlation functionals in the calculated optical spectra. Significant differences are observed between the calculations using the PBE functional (without exact exchange) and the CAM-B3LYP functional (which partly includes exact exchange). Specifically, we observe a tendency of charge-transfer excitations to involve purines bases, and the PBE spectra error is more pronounced in the complexes where the Ag cluster is bound to the purines. Finally, our results also highlight the importance of adding both the complementary base pair and the sugar-phosphate backbone in order to properly characterize the absorption spectrum of DNA:Ag complexes.

Synthesis of β-AgVO3 nanowires decorated with Ag2CrO4, with improved visible light photocatalytic performance

NASA Astrophysics Data System (ADS)

Ouyang, Qi; Li, Zhonghua; Liu, Jiawen

2018-05-01

Silver chromate‑silver vanadate (Ag2CrO4/β-AgVO3) heterojunction composites are synthesized through a facile precipitation process. The Ag2CrO4/β-AgVO3 hybrids obtained exhibit better photocatalytic activity in degradation of RhB than both pure Ag2CrO4 and β-AgVO3 under visible light irradiation. The 20 wt% Ag2CrO4/β-AgVO3 heterojunction possesses the best photocatalytic ability for degrading RhB: 24.4 times that of pristine β-AgVO3 nanowires and 3.2 times that of individual Ag2CrO4 particles. The phase of the nanocomposites was analyzed using x-ray diffraction as well as x-ray photoelectron spectroscopy. Their morphology was observed via scanning electron microscopy and transmission electron microscopy. The improvement in photocatalytic performance is chiefly ascribed to the synergies between Ag2CrO4/β-AgVO3 heterostructure, which can enhance the light absorbance ability and also accelerate the separation and transfer of photoinduced electrons and holes under visible light irradiation; this is also confirmed by UV–vis diffuse reflection spectrometry and fluorescence emission spectra.

Ag/AgBr-loaded mesoporous silica for rapid sterilization and promotion of wound healing.

PubMed

Jin, Chen; Liu, Xiangmei; Tan, Lei; Cui, Zhenduo; Yang, Xianjin; Zheng, Yufeng; Yeung, Kelvin Wai Kwok; Chu, Paul K; Wu, Shuilin

2018-06-25

Bacterial infection is a major concern during the wound healing process. Herein, Ag/AgBr-loaded mesoporous silica nanoparticles (Ag/AgBr/MSNs) are designed to harvest visible light for rapid sterilization and acceleration of wound healing. The Ag/AgBr nanostructure has remarkable photocatalysis ability due to the critical factor that it can generate electron-hole pairs easily after light absorption. This remarkable photocatalytic effect enhances the antibacterial activity by producing reactive oxygen species (ROS). The bacterial killing efficiency of Ag/AgBr/MSNs is 95.62% and 99.99% against Staphylococcus aureus and Escherichia coli, respectively, within 15 min under simulated solar light irradiation due to the generation of ROS. Furthermore, the composites can arrest the bacterial growth and damage the bacterial membrane through electrostatic interaction. The gradual release of Ag+ not only prevents bacterial infection with good long-term effectiveness but also stimulates the immune function to produce a large number of white blood cells and neutrophils, which favors the promotion of the wound healing process. This platform provides an effective strategy to prevent bacterial infection during wound healing.

MICROWAVE SPECTRA OF Ar\\cdot\\cdot\\cdotAgI AND H_{2}O\\cdot\\cdot\\cdotAgI PRODUCED BY LASER ABLATION

NASA Astrophysics Data System (ADS)

Mullaney, John C.; Medcraft, Chris; Walker, Nick; Legon, Anthony

2017-06-01

Complexes of argon and water with silver iodide have been formed in the gas phase by laser ablation of a silver iodide rod and studied using a chirped-pulse Fourier transform microwave spectrometer. Ar\\cdot\\cdot\\cdotAgI was characterized by its rotational spectrum and ab initio calculations carried out at the CCSD(T)(F12c)/cc-pVTZ-F12 explicitly correlated level of theory. The molecule was shown to be linear in the ground state, with atoms in the order shown. The Ar\\cdot\\cdot\\cdotAg and Ag-I bond lengths, r_{0}(Ar\\cdot\\cdot\\cdotAg) = 2.6759 Å{} and r_{0}(Ag-I) = 2.5356 Å, were determined. Other factors such as the dissociation energy, the intermolecular quadratic stretching force constant and the change in ionicity of AgI upon forming the complex were also determined and will be discussed with comparison to the series Ar\\cdot\\cdot\\cdotAgX (X = F, Cl, Br and I). Data of the H_{2}O\\cdot\\cdot\\cdotAgI complex will also be presented with isotopic studies ongoing.

Effect of photobiomodulation (670 nm) associated with vitamin A on the inflammatory phase of wound healing.

PubMed

Otterço, A N; Brassolatti, P; Andrade, A L M; Avó, L R S; Bossini, P S; Parizotto, N A E

2018-05-22

Wound healing is a complex biological process with specific phases. Photobiomodulation (PBM) decreases the inflammatory infiltrate, stimulating fibroblast proliferation and angiogenesis, and therefore, is indicated for wound healing. Vitamin A is used to reverse the inhibitory effects on wound healing and accelerate the healthy granulation tissue. The study aimed to evaluate the effect of topical vitamin A and PBM (GaAlAs) in inflammatory phase of cutaneous wounds. Forty Wistar male rats were separated into four groups: (1) control (CG); (2) laser group (LG) GaAlAs, 670 nm, 30 mW, energy per point of 0.9 J, radiating by 1 point in 30 s; (3) vitamin A group (VitAG); and (4) laser group plus vitamin A (LG + VitAG). Wounds were surgically made by a punch biopsy with 10 mm of diameter on the back of the animals and all treatments were started according to the experiment. The treatments were administered for four consecutive days and biopsy was performed on day 4. We performed both H&E and immunohistochemistry analysis. The results were compared between groups by one-way analysis of variance ANOVA test with post hoc Tukey (p < 0.05). Inflammatory infiltrate increased significantly in LG compared to CG and VitAG (p < 0.05). Regarding angiogenesis, VEGF expression was increased significantly in LG and LG + VitAG groups, p < 0.01. The results indicate that proposed treatments were effective on the healing process improved by LG and LG + VitAG. We show that laser plus vitamin A enhances healing by reducing the wound area and may have potential application for clinical management of cutaneous wounds.

Characterization of the intermediate-range order in new superionic conducting AgI-Ag2S-AgPO3 glasses by neutron diffraction

NASA Astrophysics Data System (ADS)

Kartini, E.; Kennedy, S. J.; Itoh, K.; Fukunaga, T.; Suminta, S.; Kamiyama, T.

Superionic conducting glasses are of considerable technological interest because of their use in batteries, sensors, and displays. We have investigated the new ternary systems AgI-Ag2S-AgPO3 where the ratio AgI:Ag2S is 1:1. The system (AgI)x(Ag2S)x(AgPO3)1-2x, for a AgI+Ag2S fraction less than 82mol%, yields glasses. We have used a neutron-diffraction technique to obtain the total scattering structure factor S(Q) of this system at room temperature by using the HIT spectrometer at the High Energy Accelerator (KEK), Tsukuba, Japan. As for AgI-AgPO3 glasses, S(Q) shows a peak at anomalously low Q in the range from 0.6 to 0.9 Å-1. This peak is not observed in the corresponding glass Ag2S-AgPO3 or pure AgPO3. The peak depends strongly on the dopant salt. Its intensity increases as the amount of (AgI+Ag2S) increases and its position shifts to lower Q, while the number density of the glasses decreases with x. This peak can be associated with an intermediate structure of particles lying inside a continuous host with the characteristic length between 5 and 10 Å [1].

Strong enhancement effect of silver nanowires on fluorescent property of Eu3+-ligand complexes and desired fluorescent iPP composite materials

NASA Astrophysics Data System (ADS)

Zhang, Yu; Wang, Xinzhi; Tang, Jianguo; Wang, Wei; Wang, Jinping; Belfiore, Laurence A.

2017-04-01

In this contribution, we obtained the strong enhancement effect of silver nanowires(AgNWs) on fluorescent property of Eu3+-antenna complexes through the function of the surface plasmon resonance(SPR) effect. The key structural characteristics are: (1) AgNWs are covered by the Eu3+-ligand complex and spaced by SiO2 nano-layer between AgNWs and Eu3+-ligand complex (this structure is marked as AgNWs@SiO2@EuTP), and (2) AgNWs as nano-material with large ratio of length to diameter show their good dispersion and processability in isotactic polypropylene (iPP). We obtained the important data about the optimal spacer thickness of SiO2 is 15 nm that was not found in previous publications. The enhanced intensity of fluorescence of EuTP by AgNWs in AgNWs@SiO2@EuTP is 9 times compared with that of EuTP. All of these outstanding properties and fine structures were characterized by TEM, FT-IR, XRD, and fluorescence spectrophotometer. On the other hand, the desired fluorescent iPP composite material was obtained through blending AgNWs@SiO2@EuTP into iPP host. Very importantly, the enhancement effect of AgNWs on EuTP fluorescence in AgNWs@SiO2@EuTP is refrained from the quenching caused by host polymer of iPP.

Mixed-complexity artificial grammar learning in humans and macaque monkeys: evaluating learning strategies.

PubMed

Wilson, Benjamin; Smith, Kenny; Petkov, Christopher I

2015-03-01

Artificial grammars (AG) can be used to generate rule-based sequences of stimuli. Some of these can be used to investigate sequence-processing computations in non-human animals that might be related to, but not unique to, human language. Previous AG learning studies in non-human animals have used different AGs to separately test for specific sequence-processing abilities. However, given that natural language and certain animal communication systems (in particular, song) have multiple levels of complexity, mixed-complexity AGs are needed to simultaneously evaluate sensitivity to the different features of the AG. Here, we tested humans and Rhesus macaques using a mixed-complexity auditory AG, containing both adjacent (local) and non-adjacent (longer-distance) relationships. Following exposure to exemplary sequences generated by the AG, humans and macaques were individually tested with sequences that were either consistent with the AG or violated specific adjacent or non-adjacent relationships. We observed a considerable level of cross-species correspondence in the sensitivity of both humans and macaques to the adjacent AG relationships and to the statistical properties of the sequences. We found no significant sensitivity to the non-adjacent AG relationships in the macaques. A subset of humans was sensitive to this non-adjacent relationship, revealing interesting between- and within-species differences in AG learning strategies. The results suggest that humans and macaques are largely comparably sensitive to the adjacent AG relationships and their statistical properties. However, in the presence of multiple cues to grammaticality, the non-adjacent relationships are less salient to the macaques and many of the humans. © 2015 The Authors. European Journal of Neuroscience published by Federation of European Neuroscience Societies and John Wiley & Sons Ltd.

Hydrothermal synthesis, photoluminescence and photocatalytic properties of two silver(I) complexes

NASA Astrophysics Data System (ADS)

Yang, Yuan-Yuan; Zhou, Lin-Xia; Zheng, Yue-Qing; Zhu, Hong-Lin; Li, Wen-Ying

2017-09-01

Two new dinuclear silver(I) coordination complexes [Ag(Hntph)(tpyz)2/2]n1 and [Ag2(dtrz)2(Hntph)2] 2 (H2ntph=2-nitroterephthalic acid, tpyz=2,3,5-trimethylpyrazine, dtrz=3,5-dimethyl-4H-1,2,4-triazol-4-amine) have been obtained by hydrothermal reactions of Ag(I) salts with H2ntph and various N-donor ligands. Complex 1 exhibits a 2D layer structure constructed by the binuclear Ag2(Hntph)2 units and tpyz ligands. Complex 2 also shows a different binuclear unit Ag2(dtrz)2, which was assembled via hydrogen bonds interactions to a 3D supramolecular architecture. The photocatalytic experiments showed that complex 2 is an excellent visible light candidate for degradation of RhB, and the degradation ratio of RhB reached 91.4% after 7 h under the light of 90 W white LED lamp. Moreover, the photoluminescent properties and the optical band gaps of 1-2 have also been investigated.

An ultrastable conjugate of silver nanoparticles and protein formed through weak interactions

NASA Astrophysics Data System (ADS)

Brahmkhatri, Varsha P.; Chandra, Kousik; Dubey, Abhinav; Atreya, Hanudatta S.

2015-07-01

In recent years, silver nanoparticles (AgNPs) have attracted significant attention owing to their unique physicochemical, optical, conductive and antimicrobial properties. One of the properties of AgNPs which is crucial for all applications is their stability. In the present study we unravel a mechanism through which silver nanoparticles are rendered ultrastable in an aqueous solution in complex with the protein ubiquitin (Ubq). This involves a dynamic and reversible association and dissociation of ubiquitin from the surface of AgNP. The exchange occurs at a rate much greater than 25 s-1 implying a residence time of <40 ms for the protein. The AgNP-Ubq complex remains stable for months due to steric stabilization over a wide pH range compared to unconjugated AgNPs. NMR studies reveal that the protein molecules bind reversibly to AgNP with an approximate dissociation constant of 55 μM and undergo fast exchange. At pH > 4 the positively charged surface of the protein comes in contact with the citrate capped AgNP surface. Further, NMR relaxation-based experiments suggest that in addition to the dynamic exchange, a conformational rearrangement of the protein takes place upon binding to AgNP. The ultrastability of the AgNP-Ubq complex was found to be useful for its anti-microbial activity, which allowed the recycling of this complex multiple times without the loss of stability. Altogether, the study provides new insights into the mechanism of protein-silver nanoparticle interactions and opens up new avenues for its application in a wide range of systems.In recent years, silver nanoparticles (AgNPs) have attracted significant attention owing to their unique physicochemical, optical, conductive and antimicrobial properties. One of the properties of AgNPs which is crucial for all applications is their stability. In the present study we unravel a mechanism through which silver nanoparticles are rendered ultrastable in an aqueous solution in complex with the protein ubiquitin (Ubq). This involves a dynamic and reversible association and dissociation of ubiquitin from the surface of AgNP. The exchange occurs at a rate much greater than 25 s-1 implying a residence time of <40 ms for the protein. The AgNP-Ubq complex remains stable for months due to steric stabilization over a wide pH range compared to unconjugated AgNPs. NMR studies reveal that the protein molecules bind reversibly to AgNP with an approximate dissociation constant of 55 μM and undergo fast exchange. At pH > 4 the positively charged surface of the protein comes in contact with the citrate capped AgNP surface. Further, NMR relaxation-based experiments suggest that in addition to the dynamic exchange, a conformational rearrangement of the protein takes place upon binding to AgNP. The ultrastability of the AgNP-Ubq complex was found to be useful for its anti-microbial activity, which allowed the recycling of this complex multiple times without the loss of stability. Altogether, the study provides new insights into the mechanism of protein-silver nanoparticle interactions and opens up new avenues for its application in a wide range of systems. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03047a

Photoelectron spectroscopic and computational study of (M-CO2)- anions, M = Cu, Ag, Au

NASA Astrophysics Data System (ADS)

Zhang, Xinxing; Lim, Eunhak; Kim, Seong K.; Bowen, Kit H.

2015-11-01

In a combined photoelectron spectroscopic and computational study of (M-CO2)-, M = Au, Ag, Cu, anionic complexes, we show that (Au-CO2)- forms both the chemisorbed and physisorbed isomers, AuCO 2- and Au-(CO2), respectively; that (Ag-CO2)- forms only the physisorbed isomer, Ag-(CO2); and that (Cu-CO2)- forms only the chemisorbed isomer, CuCO 2- . The two chemisorbed complexes, AuCO 2- and CuCO 2- , are covalently bound, formate-like anions, in which their CO2 moieties are significantly reduced. These two species are examples of electron-induced CO2 activation. The two physisorbed complexes, Au-(CO2) and Ag-(CO2), are electrostatically and thus weakly bound.

Preparation of LuAG Powders with Single Phase and Good Dispersion for Transparent Ceramics Using Co-Precipitation Method

PubMed Central

Pan, Liangjie; Jiang, Benxue; Fan, Jintai; Yang, Qiuhong; Zhou, Chunlin; Zhang, Pande; Mao, Xiaojian; Zhang, Long

2015-01-01

The synthesis of pure and well dispersed lutetium aluminum garnet (LuAG) powder is crucial and important for the preparation of LuAG transparent ceramics. In this paper, high purity and well dispersed LuAG powders have been synthesized via co-precipitation method with lutetium nitrate and aluminum nitrate as raw materials. Ammonium hydrogen carbonate (AHC) was used as the precipitant. The influence of aging time, pH value, and dripping speed on the prepared LuAG powders were investigated. It showed that long aging duration (>15 h) with high terminal pH value (>7.80) resulted in segregation of rhombus Lu precipitate and Al precipitate. By decreasing the initial pH value or accelerating the dripping speed, rhombus Lu precipitate was eliminated and pure LuAG nano powders were synthesized. High quality LuAG transparent ceramics with transmission >75% at 1064 nm were fabricated using these well dispersed nano LuAG powders. PMID:28793510

Preparation of LuAG Powders with Single Phase and Good Dispersion for Transparent Ceramics Using Co-Precipitation Method.

PubMed

Pan, Liangjie; Jiang, Benxue; Fan, Jintai; Yang, Qiuhong; Zhou, Chunlin; Zhang, Pande; Mao, Xiaojian; Zhang, Long

2015-08-19

The synthesis of pure and well dispersed lutetium aluminum garnet (LuAG) powder is crucial and important for the preparation of LuAG transparent ceramics. In this paper, high purity and well dispersed LuAG powders have been synthesized via co-precipitation method with lutetium nitrate and aluminum nitrate as raw materials. Ammonium hydrogen carbonate (AHC) was used as the precipitant. The influence of aging time, pH value, and dripping speed on the prepared LuAG powders were investigated. It showed that long aging duration (>15 h) with high terminal pH value (>7.80) resulted in segregation of rhombus Lu precipitate and Al precipitate. By decreasing the initial pH value or accelerating the dripping speed, rhombus Lu precipitate was eliminated and pure LuAG nano powders were synthesized. High quality LuAG transparent ceramics with transmission >75% at 1064 nm were fabricated using these well dispersed nano LuAG powders.

A Comparison of Experimental EPMA Data and Monte Carlo Simulations

NASA Technical Reports Server (NTRS)

Carpenter, P. K.

2004-01-01

Monte Carlo (MC) modeling shows excellent prospects for simulating electron scattering and x-ray emission from complex geometries, and can be compared to experimental measurements using electron-probe microanalysis (EPMA) and phi(rho z) correction algorithms. Experimental EPMA measurements made on NIST SRM 481 (AgAu) and 482 (CuAu) alloys, at a range of accelerating potential and instrument take-off angles, represent a formal microanalysis data set that has been used to develop phi(rho z) correction algorithms. The accuracy of MC calculations obtained using the NIST, WinCasino, WinXray, and Penelope MC packages will be evaluated relative to these experimental data. There is additional information contained in the extended abstract.

Heterobimetallic N-Heterocyclic Carbene Complexes: A Synthetic, Spectroscopic, and Theoretical Study.

PubMed

Pell, Thomas P; Wilson, David J D; Skelton, Brian W; Dutton, Jason L; Barnard, Peter J

2016-07-18

A new synthetic methodology has been developed for the preparation of heterobimetallic group 11 and group 12 complexes of a symmetrical bis-NHC "pincer" ligand. The synthetic route involved the initial preparation of a mononuclear [Au(NHC)2](+) complex with pendent imidazole moieties on the NHC ligands. Subsequent alkylation of the imidazole groups with Et3OBF4 and metalation with a second metal ion (Ag(I) or Hg(II)) provided two heterobimetallic complexes. Four homobimetallic (Cu(I)2, Ag(I)2, Au(I)2, and Hg(II)2) complexes of the same bis-NHC "pincer" ligand were also prepared. The homobimetallic Cu(I)2, Au(I)2, and Hg(II)2 complexes and heterobimetallic Au(I)-Ag(I) and Au(I)-Hg(II) complexes and the synthetic intermediates for the heterobimetallic complexes were characterized by X-ray crystallography. These X-ray structures show that the bimetallic complexes adopt "twisted" conformations in the solid state, supporting short M···M interactions. Crystalline samples of the homobimetallic Ag(I)2 and Au(I)2 and heterobimetallic Au(I)-Ag(I) and Au(I)-Hg(II) complexes were emissive at room temperature and at 77 K. The geometries of the synthesized complexes were optimized at the M06-L/def2-SVP level of theory, and the electronic nature of the M···M interactions for all synthesized complexes was investigated using natural bond orbital (NBO) calculations.

Analysis of argentinated peptide complexes using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry: Peptide = oxytocin, arg(8) -vasopressin, bradykinin, bombesin, somatostatin, neurotensin.

PubMed

Gupta, Shyam L; Dhiman, Vikas; Jayasekharan, T; Sahoo, N K

2016-06-15

The increased use of silver nanoparticles (AgNPs) for various biological applications, and over-expression of various peptide receptors in different tumors/cancer cells, necessitate the need for dedicated investigations on the intrinsic binding ability of Ag with various biologically important peptides for better understanding of AgNPs-peptide interactions and for the future development of contrasting agents as well as drugs for imaging/biomedical applications. The [M+(Ag)n ](+) complexes are prepared and characterized using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). Silver complexes of the peptides [M+(Ag)n ](+) , where M = oxytocin, arg(8) -vasopressin, bradykinin, bombesin, somatostatin, and neurotensin, have been investigated for their intrinsic Ag(+) -binding ability. Unusual binding of up to seven Ag(+) with these small peptides is observed. The mass spectra show n = 1-5 for bombesin and somatostatin, n = 1-6 for bradykinin and arg(8) -vasopressin, and n = 1-7 for oxytocin and neurotensin. In addition, oxytocin and arg(8) -vasopressin show the formation of dimers and their complexes [M2 +(Ag)n ](+) with n = 1-8 and n = 1-5, respectively. The possible amino acid residues responsible for Ag(+) binding in each peptide have been identified on the basis of density functional theory (DFT)-calculated binding energy values of Ag(+) towards individual amino acids. Mass spectrometric evidence indicates that the peptides, viz., oxytocin, arg(8) -vasopressin, bradykinin, bombesin, somatostatin, and neurotensin, show greater affinity for Ag(+) . Hence, they may be used as carriers for AgNPs in targeted drug delivery as well as an alternative for iodinated contrasting agents in dual energy X-ray imaging techniques. Radio-labeled Ag with these peptides can also be used in radio-pharmaceuticals for diagnostic and therapeutic applications. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Phenytoin silver: a new nanocompound for promoting dermal wound healing via comprehensive pharmacological action.

PubMed

Ai, Xiao-Yu; Liu, Hui-Juan; Lu, Cheng; Liang, Cai-Li; Sun, Yan; Chen, Shuang; Sun, Bo; Li, Yang; Liu, Yan-Rong; Zhang, Qiang; Liu, Xue-Qiang; Xiao, Ting; Jing, Xue-Shuang; Sun, Tao; Zhou, Hong-Gang; Yang, Cheng

2017-01-01

Phenytoin, an antiepileptic drug, has been widely used for wound healing. Inspired by previous studies, phenytoin silver (PnAg), a sparingly soluble silver nanocompound, was synthesized which exhibited good therapeutic efficacy in tissue repair with low toxicity (LD50 >5 g/kg). In vivo studies showed that PnAg could accelerate dermal wound healing and strong inflammation control in Sprague-Dawley rats (SD rat) and Bama minipigs. Due to its low solubility, PnAg led to low toxicity and blood enrichment in animals. Furthermore, PnAg could upregulate the promoter activity of Jak, Stat3, and Stat3 downstream proteins. Therefore, PnAg may serve as an effective therapeutic compound for wound healing through regulating the gp130/Jak/Stat3 signaling pathway.

Development of a complex of instrumental nuclear-physical methods to detect PGE, Re, Au, and Ag in hard-to-analyze rocks and complex ores

NASA Astrophysics Data System (ADS)

Kolmogorov, Yu. P.; Mezentsev, N. A.; Mironov, A. G.; Parkhomenko, V. S.; Spiridonov, A. M.; Shaporenko, A. D.; Yusupov, T. S.; Zhmodik, S. M.; Zolotarev, K. V.; Anoshin, G. N.

2009-05-01

A system of methods to detect platinum group elements (PGE): Re, Au, and Ag in hard-to-analyze rocks and complex ores has been developed. It applies the SRXRF for Ru, Rh, Pd, and Ag and the INAA method for Os, Ir, Pt and Ag and implies mechanoactivation of probes to study. The results of measurement of standard samples of carbonaceous rocks and ores in order to PGE, gold, and silver confirm the possibility of detecting some of the above-listed elements with a detection limit of 10 ppb.

An AgI@g-C3N4 hybrid core@shell structure: Stable and enhanced photocatalytic degradation

NASA Astrophysics Data System (ADS)

Liu, Li; Qi, Yuehong; Yang, Jinyi; Cui, Wenquan; Li, Xingang; Zhang, Zisheng

2015-12-01

A novel visible-light-active material AgI@g-C3N4 was prepared by ultrasonication/chemisorption method. The core@shell structure AgI@g-C3N4 catalyst showed high efficiency for the degradation of MB under visible light irradiation (λ > 420 nm). Nearly 96.5% of MB was degraded after 120 min of irradiation in the presence of the AgI@g-C3N4 photocatalyst. Superior stability was also observed in the cyclic runs indicating that the as prepared hybrid composite is highly desirable for the remediation of organic contaminated wastewaters. The improved photocatalytic performance is due to synergistic effects at the interface of AgI and g-C3N4 which can effectively accelerate the charge separation and reinforce the photostability of hybrid composite. The possible mechanism for the photocatalytic activity of AgI@g-C3N4 was tentatively proposed.

Size-tailored synthesis of silver quasi-nanospheres by kinetically controlled seeded growth.

PubMed

Liu, Xiaxia; Yin, Yadong; Gao, Chuanbo

2013-08-20

This paper describes a simple and convenient procedure to synthesize monodisperse silver (Ag) quasi-nanospheres with size tunable in a range of 19-140 nm through a one-step seeded growth strategy. Acetonitrile was employed as a coordinating ligand of a Ag(I) salt in order to achieve a low concentration of elemental Ag after reduction and thus suppression of new nucleation events. Since the addition of the seeds significantly accelerates the reduction reaction of Ag(I) by ascorbic acid, the reaction kinetics was further delicately balanced by tuning the reaction temperature, which proved to be critical in producing Ag quasi-nanospheres with uniform size and shape. This synthesis is highly scalable, so that it provides a simple yet very robust process for producing Ag quasi-nanospheres for many biological, analytical, and catalytic applications which often demand samples in large quantity and widely tunable particle sizes.

A family of silver(I) complexes built with 2-sulfoterephthalic acid monosodium salt and different aminopyridine ligands: Syntheses, structures and properties

NASA Astrophysics Data System (ADS)

Zhang, Jie; Tan, Gai-Xiu; Liu, Bao-Lin; Dai, Yu-Bei; Xu, Na; Wen, Wei-Fen; Cao, Chong; Xiao, Hong-Ping

2017-05-01

Five Ag(I) coordination complexes, namely, [Ag6(2-stp)2(3-methyl-2-apy)3·H2O]n (1), [Ag3(2-stp)(4-methyl-2-apy)3]n (2), [Na2Ag18(2-stp)4(2-Hstp)4(5-methyl-2-apy)16 (H2O)4·11H2O]n (3), Ag3(2-stp)(6-methy-2-apy)4·H2O (4), and [Ag6(2-stp)2(6-methyl-2-apy)8(H2O)2·H2O]n (5) (2-NaH2stp = 2-sulfoterephthalic acid monosodium salt, 3-methyl-2-apy = 3-methyl-2-aminopyridine, 4-methyl-2-apy = 4-methyl-2-aminopyridine, 5-methyl-2-apy = 5-methyl-2-aminopyridine, 6-methyl-2-apy = 6-methyl-2-aminopyridine), have been synthesized and structurally characterized. Complexes 1 and 2 show two-dimensional network. In complex 3, the adjacent Ag10 units are bridged by 5-methyl-2-apy ligands to form a 2D infinite undulated sheet. Adjacent 2D sheets are linked by coordinative bonds between carboxylic oxygen atoms and Na(I) ions to form a 3D coordination polymer. Complex 4 is a 0-D discrete trinuclear molecule, and the self-complementary the Osbnd H⋯O and Nsbnd H⋯O hydrogen bonds incorporating hydrogen bond motifs extend these molecules into a 2D supramolecular framework. Compound 5 exhibits 1D-chain structure. However, complex 5 shows 3D supramolecular structure results from the linkage of neighboring layers through a rich hydrogen-bonding between uncoordinated sulfonates, amino groups and coordinated carboxylates. The thermogravimetric analyses and photoluminescence of the complexes were also investigated.

Influence of salinity and organic matter on silver accumulation in Gulf toadfish (Opsanus beta).

PubMed

Nichols, Joel W; Brown, Stephanie; Wood, Chris M; Walsh, Patrick J; Playle, Richard C

2006-06-30

To help extend the freshwater based biotic ligand model for silver (Ag) into brackish and saltwater conditions, 50g Gulf toadfish (Opsanus beta) were acclimated to 2.5%, 5%, 10%, 20%, 40%, 80%, or 100% salt water and exposed for 6d to 1.0microM AgNO(3), with or without 10mg C/L organic matter. Suwannee River natural organic matter collected by reverse osmosis was used. Silver accumulation in toadfish gills and plasma decreased as salinity increased, indicating low bioavailability of AgCl complexes. Complexation of Ag by organic matter, normally important in freshwater conditions, was less important as salinity increased. Although relatively little intestinal Ag uptake was observed, both liver and bile accumulated Ag from water imbibed past the isosmotic salinity point ( approximately 1/3 salt water). Toadfish also produced intestinal carbonate pellets, minerals which did not influence Ag accumulation. Our results further stress the importance of Ag speciation, physiological mechanisms, and intestinal Ag uptake when modelling Ag uptake and toxicity beyond freshwater conditions.

Novel product ions of 2-aminoanilide and benzimidazole Ag(I) complexes using electrospray ionization with multi-stage tandem mass spectrometry.

PubMed

Johnson, Byron S; Burinsky, David J; Burova, Svetlana A; Davis, Roman; Fitzgerald, Russ N; Matsuoka, Richard T

2012-05-15

The 2-aminoaniline scaffold is of significant value to the pharmaceutical industry and is embedded in a number of pharmacophores including 2-aminoanilides and benzimidazoles. A novel application of coordination ion spray mass spectrometry (CIS-MS) for interrogating the silver ion (Ag(+)) complexes of a homologous series of these compounds using multi-stage tandem mass spectrometry is described. Unlike the ubiquitous alkali metal ion complexes, Ag(+) complexes of 2-aminoanilides and benzimidazoles were found to yield [M - H](+) ions in significant abundance via gas-phase elimination of the metal hydride (AgH) resulting in unique product ion cascades. Sample introduction was by liquid chromatography with mass spectrometry analysis performed on a hybrid linear ion trap/orbitrap instrument capable of high-resolution measurements. Rigorous structural characterization by multi-stage tandem mass spectrometry using [M +  H](+), [M - H](-) and [M - H](+) precursor ions derived from ESI and CIS experiments was performed for the homologous series of 2-aminoanilide and benzimidazole compounds. A full tabular comparison of structural information resulting from these product ion cascades was produced. Multi-stage tandem mass spectrometry of [M - H](+) ions resulting from Ag(+) complexes of 2-aminoanilides and benzimidazoles in CIS-MS experiments produced unique product ion cascades that exhibited complementary structural information to that obtained from tandem mass spectrometry of [M  +  H](+) and [M - H](-) ions by electrospray ionization (ESI). These observations may be broadly applicable to other compounds that are observed to form Ag(+) complexes and eliminate AgH. Copyright © 2012 John Wiley & Sons, Ltd.

Characterization of surface complexes in enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Roy, D.; Furtak, T. E.

1984-11-01

An indicator molecule, para-nitrosodimethylanaline (p-NDMA), has been used to study the chemical nature of surface complexes involving the active site for SERS in the electrochemical environment. We present evidence for positively charged Ag atoms stabilized by coadsorbed Cl- ions as the primary sites which are produced during the oxidation reduction cycle treatment of an Ag electrode. Depending on the relative number of Cl- ions which influence the Ag site the active site demonstrates a greater or lesser electron accepting character toward p-NDMA. This character is influenced by the applied voltage and by the presence of Tl+ ions in the bulk of the solution near the surface. As in previously studied systems p-NDMA/Cl-/Ag complexes demonstrate charge transfer excitation which in this case is from the p-NDMA to the Ag site. These results further solidify the importance of complex formation in electrochemical SERS and suggest that caution should be applied when using SERS as a quantitative measure of surface coverage.

Fate, bioavailability and toxicity of silver in estuarine environments

USGS Publications Warehouse

Luoma, S.N.; Ho, Y.B.; Bryan, G.W.

1995-01-01

The chemistry and bioavailability of Ag contribute to its high toxicity in marine and estuarine waters. Silver is unusual, in that both the dominant speciation reaction in seawater and the processes important in sorbing Ag in sediments favour enhanced bioavailability. Formation of a stable chloro complex favours dispersal of dissolved Ag, and the abundant chloro complex is available to biota. Sequestration by sediments also occurs, but with relatively slow kinetics. Amorphous aggregated coatings enhance Ag accumulation in sediments, as well as Ag uptake from sediments by deposit feeders. In estuaries, the bioaccumulation of Ag increases 56-fold with each unit of increased Ag concentration in sediments. Toxicity for sensitive marine species occurs at absolute concentrations as low as those observed for any nonalkylated metal, partly because bioaccumulation increases so steeply with contamination. The environmental window of tolerance to Ag in estuaries could be narrower than for many elements.

Facile synthesis of S-Ag nanocomposites and Ag2S short nanorods by the interaction of sulfur with AgNO3 in PEG400

NASA Astrophysics Data System (ADS)

Zhang, Yan-Li; Xie, Xin-Yuan; Liang, Ming; Xie, Shu-Ming; Chen, Jie-Mei; Zheng, Wen-Jie

2016-06-01

A facile, eco-friendly and inexpensive method to prepare Ag2S short nanorods and S-Ag nanocomposites using sublimed sulfur, AgNO3, PVP and PEG400 was studied. According to x-ray diffraction and scanning electron microscopy of the Ag2S, the products are highly crystalline and pure Ag2S nanorods with diameters of 70-160 nm and lengths of 200-360 nm. X-ray diffraction of the S-Ag nanocomposites shows that we obtained cubic Ag and S nanoparticles. Transmission electron microscopy shows that the molar ratio of PVP to Ag+ plays an important role in controlling the size and morphology of the S-Ag nanocomposites. When the molar ratio of PVP to Ag+ was 10:1, smaller sizes, better dispersibility and narrower distribution of S-Ag nanocomposites with diameters of 10-40 nm were obtained. The formation mechanism of the S-Ag nanocomposites was studied by designing a series of experiments using ultraviolet-visible measurement, and it was found that S nanoparticles are produced first and act as seed crystals; then Ag+ becomes Ag nanocrystals on the surfaces of the S nanoparticles by the reduction of PVP. PEG400 acts as a catalyzer, accelerating the reaction rate, and protects the S-Ag nanocomposites from reacting to produce Ag2S. The antimicrobial experiments show that the S-Ag nanocomposites have greater antimicrobial activity on Staphylococcus aureus, Aspergillus niger and blue mold than Ag nanoparticles.

Interactions of aqueous Ag+ with fulvic acids: mechanisms of silver nanoparticle formation and investigation of stability.

PubMed

Adegboyega, Nathaniel F; Sharma, Virender K; Siskova, Karolina; Zbořil, Radek; Sohn, Mary; Schultz, Brian J; Banerjee, Sarbajit

2013-01-15

This study investigated the possible natural formation of silver nanoparticles (AgNPs) in Ag(+)-fulvic acid (FA) solutions under various environmentally relevant conditions (temperature, pH, and UV light). Increase in temperature (24-90 °C) and pH (6.1-9.0) of Ag(+)-Suwannee River fulvic acid (SRFA) solutions accelerated the appearance of the characteristic surface plasmon resonance (SPR) of AgNPs. The rate of AgNP formation via reduction of Ag(+) in the presence of different FAs (SRFA, Pahokee Peat fulvic acid, PPFA, Nordic lake fulvic acid, NLFA) and Suwannee River humic acid (SRHA) followed the order NLFA > SRHA > PPFA > SRFA. This order was found to be related to the free radical content of the acids, which was consistent with the proposed mechanism. The same order of AgNP growth was seen upon UV light illumination of Ag(+)-FA and Ag(+)-HA mixtures in moderately hard reconstituted water (MHRW). Stability studies of AgNPs, formed from the interactions of Ag(+)-SRFA, over a period of several months showed that these AgNPs were highly stable with SPR peak reductions of only ~15%. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements revealed bimodal particle size distributions of aged AgNPs. The stable AgNPs formed through the reduction of Ag(+) by fulvic and humic acid fractions of natural organic matter in the environment may be transported over significant distances and might also influence the overall bioavailability and ecotoxicity of AgNPs.

TVDG Organization Page

Science.gov Websites

-Booster-AGS Coordinator John Benjamin Accelerator Development, Maintenance and Operation Chuck Carlson Hans Abendroth Ion Source Develoment and Maintenance John Benjamin Dannie Steski Electrical and

Accelerator Facilities for Radiation Research

NASA Technical Reports Server (NTRS)

Cucinotta, Francis A.

1999-01-01

HSRP Goals in Accelerator Use and Development are: 1.Need for ground-based heavy ion and proton facility to understand space radiation effects discussed most recently by NAS/NRC Report (1996). 2. Strategic Program Goals in facility usage and development: -(1) operation of AGS for approximately 600 beam hours/year; (2) operation of Loma Linda University (LLU) proton facility for approximately 400 beam hours/year; (3) construction of BAF facility; and (4) collaborative research at HIMAC in Japan and with other existing or potential international facilities. 3. MOA with LLU has been established to provide proton beams with energies of 40-250 important for trapped protons and solar proton events. 4. Limited number of beam hours available at Brookhaven National Laboratory's (BNL) Alternating Gradient Synchrotron (AGS).

Natural ageing process accelerates the release of Ag from functional textile in various exposure scenarios

PubMed Central

Ding, Dahu; Chen, Lulu; Dong, Shaowei; Cai, Hao; Chen, Jifei; Jiang, Canlan; Cai, Tianming

2016-01-01

Natural ageing process occurs throughout the life cycle of textile products, which may possess influences on the release behavior of additives such as silver nanoparticles (Ag NPs). In this study, we assessed the releasability of Ag NPs from a Ag NPs functionalized textile in five different exposure scenarios (i.e. tap water (TW), pond water (PW), rain water (RW), artificial sweat (AS), and detergent solution (DS) along with deionized water (DW) as reference), which were very likely to occur throughout the life cycle of the textile. For the pristine textile, although the most remarkable release was found in DW (6–15 μg Ag/g textile), the highest release rate was found in RW (around 7 μg Ag/(g textile·h)). After ageing treatment, the total released Ag could be increased by 75.7~386.0% in DW, AS and DS. Morphological analysis clearly showed that the Ag NPs were isolated from the surface of the textile fibre due to the ageing treatment. This study provides useful information for risk assessment of nano-enhanced textile products. PMID:27869136

Cell-autonomous excitation of midbrain dopamine neurons by endocannabinoid-dependent lipid signaling

PubMed Central

Gantz, Stephanie C.; Bean, Bruce P.

2017-01-01

SUMMARY The major endocannabinoid in the mammalian brain is the bioactive lipid 2-arachidonoylglycerol (2-AG). The best-known effects of 2-AG are mediated by G protein-coupled cannabinoid receptors. In principle, 2-AG could modify neuronal excitability by acting directly on ion channels, but such mechanisms are poorly understood. Using a preparation of dissociated mouse midbrain dopamine neurons to isolate effects on intrinsic excitability, we found that 100 nM 2-AG accelerated pacemaking and steepened the frequency-current relationship for burst-like firing. In voltage-clamp experiments, 2-AG reduced A-type potassium current (IA) through a cannabinoid receptor-independent mechanism mimicked by arachidonic acid, which has no activity on cannabinoid receptors. Activation of orexin, neurotensin, and metabotropic glutamate Gq/11-linked receptors mimicked the effects of exogenous 2-AG and their actions were prevented by inhibiting the 2-AG-synthesizing enzyme diacylglycerol lipase α. The results show that 2-AG and related lipid signaling molecules can directly tune neuronal excitability in a cell-autonomous manner by modulating IA. PMID:28262417

Natural ageing process accelerates the release of Ag from functional textile in various exposure scenarios

NASA Astrophysics Data System (ADS)

Ding, Dahu; Chen, Lulu; Dong, Shaowei; Cai, Hao; Chen, Jifei; Jiang, Canlan; Cai, Tianming

2016-11-01

Natural ageing process occurs throughout the life cycle of textile products, which may possess influences on the release behavior of additives such as silver nanoparticles (Ag NPs). In this study, we assessed the releasability of Ag NPs from a Ag NPs functionalized textile in five different exposure scenarios (i.e. tap water (TW), pond water (PW), rain water (RW), artificial sweat (AS), and detergent solution (DS) along with deionized water (DW) as reference), which were very likely to occur throughout the life cycle of the textile. For the pristine textile, although the most remarkable release was found in DW (6-15 μg Ag/g textile), the highest release rate was found in RW (around 7 μg Ag/(g textile·h)). After ageing treatment, the total released Ag could be increased by 75.7~386.0% in DW, AS and DS. Morphological analysis clearly showed that the Ag NPs were isolated from the surface of the textile fibre due to the ageing treatment. This study provides useful information for risk assessment of nano-enhanced textile products.

Kinetics of Spontaneous Bimetallization between Silver and Noble Metal Nanoparticles.

PubMed

Hirakawa, Kazutaka; Kaneko, Tetsuya; Toshima, Naoki

2018-06-05

A physical mixture of polymer-protected Ag nanoparticles and Rh, Pd, or Pt nanoparticles spontaneously forms Ag-core bimetallic nanoparticles. The formed nanoparticles were smaller than the parent Ag nanoparticles. In the initial process of this reaction, the surface plasmon absorption of Ag nanoparticles diminished and then almost ceased within one hour. Within several minutes, the decrease in Ag surface plasmon absorption could be analyzed by second-order reaction. This reaction was accelerated with an increase of temperature and the energy gap in the Fermi level between Ag and the other metals. The activation energy (E a ) of this reaction could be determined. An electron transfer reaction from Ag to other metal nanoparticles was proposed as the initial interaction between these metal nanoparticles because the Fermi level of Ag is relatively high, and the electron transfer is possible in terms of energy. The Marcus plot between the rate constant and the driving force, roughly estimated from the work function of metals, and the observed E a values reasonably explained the proposed electron transfer mechanism. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chiral SiO2 and Ag@SiO2 Materials Templated by Complexes Consisting of Comblike Polyethyleneimine and Tartaric Acid.

PubMed

Yao, Dong-Dong; Murata, Hiroki; Tsunega, Seiji; Jin, Ren-Hua

2015-10-26

A facile avenue to fabricate micrometer-sized chiral (L-, D-) and meso-like (dl-) SiO2 materials with unique structures by using crystalline complexes (cPEI/tart), composed of comblike polyethyleneimine (cPEI) and L-, D-, or dl-tartaric acid, respectively, as catalytic templates is reported. Interestingly, both chiral crystalline complexes appeared as regularly left- and right-twisted bundle structures about 10 μm in length and about 5 μm in diameter, whereas the dl-form occurred as circular structures with about 10 μm diameter. Subsequently, SiO2 @cPEI/tart hybrids with high silica content (>55.0 wt %) were prepared by stirring a mixture containing tetramethoxysilane (TMOS) and the aggregates of the crystalline complexes in water. The chiral SiO2 hybrids and calcined chiral SiO2 showed very strong CD signals and a nanofiber-based morphology on their surface, whereas dl-SiO2 showed no CD activity and a nanosheet-packed disklike shape. Furthermore, metallic silver nanoparticles (Ag NPs) were encapsulated in each silica hybrid to obtain chiral (D and L forms) and meso-like (dl form) Ag@SiO2 composites. Also, the reaction between L-cysteine (Lcys) and these Ag@SiO2 composites was preliminarily investigated. Only chiral L- and D-Ag@SiO2 composites promoted the reaction between Lcys and Ag NPs to produce a molecular [Ag-Lcys]n complex with remarkable exciton chirality, whereas the reaction hardly occurred in the case of meso-like (dl-) Ag@SiO2 composite. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal Fatigue Evaluation of Pb-Free Solder Joints: Results, Lessons Learned, and Future Trends

NASA Astrophysics Data System (ADS)

Coyle, Richard J.; Sweatman, Keith; Arfaei, Babak

2015-09-01

Thermal fatigue is a major source of failure of solder joints in surface mount electronic components and it is critically important in high reliability applications such as telecommunication, military, and aeronautics. The electronic packaging industry has seen an increase in the number of Pb-free solder alloy choices beyond the common near-eutectic Sn-Ag-Cu alloys first established as replacements for eutectic SnPb. This paper discusses the results from Pb-free solder joint reliability programs sponsored by two industry consortia. The characteristic life in accelerated thermal cycling is reported for 12 different Pb-free solder alloys and a SnPb control in 9 different accelerated thermal cycling test profiles in terms of the effects of component type, accelerated thermal cycling profile and dwell time. Microstructural analysis on assembled and failed samples was performed to investigate the effect of initial microstructure and its evolution during accelerated thermal cycling test. A significant finding from the study is that the beneficial effect of Ag on accelerated thermal cycling reliability (measured by characteristic lifetime) diminishes as the severity of the accelerated thermal cycling, defined by greater ΔT, higher peak temperature, and longer dwell time increases. The results also indicate that all the Pb-free solders are more reliable in accelerated thermal cycling than the SnPb alloy they have replaced. Suggestions are made for future work, particularly with respect to the continued evolution of alloy development for emerging application requirements and the value of using advanced analytical methods to provide a better understanding of the effect of microstructure and its evolution on accelerated thermal cycling performance.

Synthesis, characterization of Ag(I), Pd(II) and Pt(II) complexes of a triazine-3-thione and their interactions with bovine serum albumin

NASA Astrophysics Data System (ADS)

Zhang, Xiuying; Li, Shuyan; Yang, Lin; Fan, Changqing

2007-11-01

Ag(I), Pd(II) and Pt(II) complexes of 5-methoxy-5,6-diphenyl-4,5-dihydro-2H-[1,2,4]triazine-3-thione (LH 2OCH 3) have been synthesized and characterized by elemental analysis, molar conductance, 1H NMR, IR spectra, UV spectra and thermal analysis (TG-DTA). The components of the three complexes are [Ag(C 15H 10N 3S)] 6, Pd(C 15H 10N 3S) 2 and Pt(C 15H 10N 3S) 2·C 3H 6O·2H 2O, respectively. All the complexes are nonelectrolyte and have high thermodynamic stability. The ligand may act as bidentate NS donor for Pd(II) and Pt(II) complexes, while it seems to be bidentate NS bridging via sulphur atom for Ag(I) complex. A planar quadrangular structure is proposed for Pd(II) and Pt(II) complexes and Ag(I) complex may be a hexanuclear cluster. Their interactions with bovine serum albumin (BSA) are investigated using steady state fluorescence technology. It is observed that all of them can quench the intrinsic fluorescence of BSA through static quenching procedure. The binding constants ( KA) at different temperatures, thermodynamic parameters enthalpy changes (Δ H) and entropy changes (Δ S) between BSA and the compounds are calculated. Based on the values of Δ H and Δ S, it is judged that the main acting force of PtL 2·C 3H 6O·2H 2O with BSA may be electrostatic interaction, and for the LH 2OCH 3, Ag 6L 6 and PdL 2, hydrophobic and electrostatic interactions may be involved in their binding processes.

Interaction of d(10) metal ions with thioether ligands: a thermodynamic and theoretical study.

PubMed

Melchior, Andrea; Peralta, Elena; Valiente, Manuel; Tavagnacco, Claudio; Endrizzi, Francesco; Tolazzi, Marilena

2013-05-07

Thermodynamic parameters of complex formation between d(10) metal ions, such as Zn(2+), Cd(2+), Hg(2+) and Ag(+), and the macrocyclic thioether 1,4,7-trithiacyclononane ([9]AneS3) or the monodentate diethylsulfide (Et(2)S), in acetonitrile (AN) at 298.15 K, were studied by a systematic methodology including potentiometry, calorimetry and polarography. [9]AneS3 is able to form complexes with all the target cations, Et(2)S only reacts with Hg(2+) and Ag(+). Mononuclear ML(j) (j = 1, 2) complexes are formed with all the metal ions investigated, where the affinity order is Hg(2+) > Ag(+) > Cd(2+) ≈ Zn(2+) when L = [9]AneS3 and Hg(2+) > Ag(+) when L = Et(2)S. Enthalpy and entropy values are generally negative, as a consequence of both metal ion interactions with neutral ligands, the reagents' loss of degrees of freedom and the release of solvating molecules. DFT calculations on the complexes formed with [9]AneS3 in vacuum and in AN are also carried out, to correlate experimental and theoretical thermodynamic values and to highlight the interplay between the direct metal-thioether interaction and the solvation effects. Trends obtained for the stability constants and enthalpies of the 1 : 1 and 1 : 2 complexes in solvent well reproduce the experimental ones for all the divalent metal ion complexes with [9]AneS3 and indicate the release of 3 AN molecules in the formation of each consecutive octahedral complex. In addition, calculated and experimental values for Ag(+) complex formation in solution suggest that in AgL(2) species [9]AneS3 ligands are not both tridentate.

Silver(I) complexes with hydantoins and allantoin: synthesis, crystal and molecular structure, cytotoxicity and pharmacokinetics.

PubMed

Puszyńska-Tuszkanow, Mariola; Grabowski, Tomasz; Daszkiewicz, Marek; Wietrzyk, Joanna; Filip, Beata; Maciejewska, Gabriela; Cieślak-Golonka, Maria

2011-01-01

Coordination polymers [Ag(L(1,3))](n) (L(1)=hydantoin, L(3)=5,5-dimethylhydantoin), {[Ag(L(2))](.)0.5H(2)O}(n) (L(2)=1-methylhydantoin) and [Ag(NH(3))(L(4))](n) (L(4)=allantoin) were prepared and characterized by elemental analysis, spectroscopic (IR, FTIR and NMR), thermal and mass spectrometry methods. The crystal structure of {[Ag(1-methylhydantoin)]·0,5H(2)O}(n) was determined and analyzed. Three 1-methylhydantoinate ligands create a T-shape (CN=3) coordination sphere around the Ag(+) ion. Additionally, a short Ag⋯Ag distance of 2.997Å was found in the structure resulting in the expanded [3+2] environment of a distorted square shape. The [Ag(L(2))] entities are bound to each other by the bridging organic ligands. Thus a two-dimensional coordination polymer is created with water molecules located between the layers. In contrast to hydantoins, the allantoin complex contains an additional ammonia molecule in the coordination sphere. Moreover, in the Ag-alla complex the M-organic ligand binding site is shifted to the N-atom of the ureid chain. Free ligands are cytotoxically inactive against human MCF-7 and A549 cancer cell lines and mouse fibroblasts Balb/3T3. The silver hydantoin complexes exhibit a very strong activity against these lines. (The introduction of the methyl groups to the ring slightly increases resistance only against the A549 cell line.) In contrast, the silver complex of allantoin shows only a weak activity which may be related to the presence of the cytotoxic ammonia group in the composition of the compound and/or the different binding site of the ligand. Calculated in silico physiochemical parameters are promising for the future application of the complexes as drugs. Copyright © 2010 Elsevier Inc. All rights reserved.

Longitudinal emittance measurements in the Booster and AGS during the 2014 RHIC gold run

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

Zeno, K.

2014-08-18

This note describes longitudinal emittance measurements that were made in the Booster and AGS during the 2014 RHIC Gold run. It also contains an overview of the longitudinal aspects of their setup during this run. Each bunch intended for RHIC is composed of beam from 4 Booster cycles, and there are two of them per AGS cycle. For each of the 8 Booster cycles required to produce the 2 bunches in the AGS, a beam pulse from EVIS is injected into the Booster and captured in four h=4 buckets. Then those bunches are accelerated to a porch where they aremore » merged into 2 bunches and then into 1 bunch.« less

Improved scaling of temperature-accelerated dynamics using localization

NASA Astrophysics Data System (ADS)

Shim, Yunsic; Amar, Jacques G.

2016-07-01

While temperature-accelerated dynamics (TAD) is a powerful method for carrying out non-equilibrium simulations of systems over extended time scales, the computational cost of serial TAD increases approximately as N3 where N is the number of atoms. In addition, although a parallel TAD method based on domain decomposition [Y. Shim et al., Phys. Rev. B 76, 205439 (2007)] has been shown to provide significantly improved scaling, the dynamics in such an approach is only approximate while the size of activated events is limited by the spatial decomposition size. Accordingly, it is of interest to develop methods to improve the scaling of serial TAD. As a first step in understanding the factors which determine the scaling behavior, we first present results for the overall scaling of serial TAD and its components, which were obtained from simulations of Ag/Ag(100) growth and Ag/Ag(100) annealing, and compare with theoretical predictions. We then discuss two methods based on localization which may be used to address two of the primary "bottlenecks" to the scaling of serial TAD with system size. By implementing both of these methods, we find that for intermediate system-sizes, the scaling is improved by almost a factor of N1/2. Some additional possible methods to improve the scaling of TAD are also discussed.

Self-assembled 1D infinite inorganic [2]catenane and 2D sheet framework with calix[8]phenylazoimidazole and [4+4]metallomacrocyclic motifs based on silver and ditopic bis(imidazolyl)methane ligands

NASA Astrophysics Data System (ADS)

Jin, Tianqi; Zhou, Junqiang; Pan, Yangyang; Huang, Yu; Jin, Chuanming

2018-05-01

Three novel supramolecular complexes, [Ag4(2-mBIM)4](ClO4)4(H2O) (1), [Ag2(2-mBIM)2](PF6)2 (2) and [Ag2(PA-BIM)2](ClO4)2(CH2Cl2) (3) (2-mBIM = bis(2-methyl- imidazol-1-yl)methane; PA-BIM = 1,1-bis[(2-phenylazo)imidazol-1-yl]methane), have been prepared and structurally characterized. The reported complexes bear [4+4]metallomacrocyclic motifs comprising four silver atoms and four ditopic bis(imidazolyl)methane ligands. Complex 1 exhibits a rare 1D infinite inorganic [2]catenane structure, which was self-assembled by the interlocking action of [4+4]metallomacrocyclic units. Complex 2 is a 2D layered supramolecular motif containing [4+4]macrometallacycle units with π-π interaction between imidazole rings. Complex 3 has a 2D sheet supramolecular framework through Ag-Ag interactions in [4+4]macrometallacyclic calix [8]phenylazoimidazole with a nanocavity. The results suggest that the bisimidazolium ligands and anions play crucial roles in the formation of the different host structures. The thermal stability and photoluminescence spectra of the synthesized complexes have also been discussed.

Spectroscopic characterization and biological studies in vitro of a new silver complex with furosemide: Prospective of application as an antimicrobial agent

NASA Astrophysics Data System (ADS)

Lustri, Wilton R.; Lazarini, Silmara C.; Lustri, Bruna Cardinali; Corbi, Pedro P.; Silva, Maria Aline C.; Resende Nogueira, Flávia Aparecida; Aquino, Renata; Amaral, André C.; Treu Filho, Oswaldo; Massabni, Antonio Carlos; da Silva Barud, Hernane

2017-04-01

The present article describes the synthesis and biological studies in vitro of a novel silver complex with furosemide (Ag-FSE). Elemental, thermal and mass spectrometric analysis indicated a 1:1 metal/ligand composition, with the molecular formula AgC12H10ClN2O5S. Infrared and nuclear magnetic resonance studies suggest coordination of the ligand to the silver ion by the oxygen atoms of the carboxylate group. Additional Density Functional Theory (DFT) studies led to the proposition of the structure of the Ag-FSE complex. The antibacterial activities of the complex were primarily evaluated by antibiogram assays using the disc diffusion method and minimum inhibitory concentrations (MIC). Moreover, the mutagenicity of the complex was also evaluated to ensure that it is safe for subsequent application. The Ag-FSE complex has shown a significant in vitro antibacterial activity against Gram-positive Staphylococcus aureus (ATCC 25923), Gram negative Escherichia coli (ATCC 25922) and Pseudomonas aeruginosa (ATCC 27853), and yeast Candida albicans (ATCC 90028). The absence of a mutagenic activity of Ag-FSE against Salmonella Typhimurium bacterial strains in the Ames assay is an extremely important finding for its future use as a drug in medicine.

Intermetallic Compounds Formed in Sn-20In-2.8Ag Solder BGA Packages with Ag/Cu Pads

NASA Astrophysics Data System (ADS)

Jain, C. C.; Wang, S. S.; Huang, K. W.; Chuang, T. H.

2009-03-01

The interfacial reactions in a Sn-20In-2.8Ag solder ball grid array (BGA) package with immersion Ag surface finish are investigated. After reflow, the Ag thin film dissolves quickly into the solder matrix, and scallop-shaped intermetallic layers, with compositions of (Cu0.98Ag0.02)6(In0.59Sn0.41)5, appear at the interfaces between Sn-20In-2.8Ag solder ball and Cu pad. No evident growth of the (Cu0.98Ag0.02)6(Sn0.59In0.41)5 intermetallic compounds was observed after prolonged aging at 100 °C. However, the growth accelerated at 150 °C, with more intermetallic scallops floating into the solder matrix. The intermetallic thickness versus the square root of reaction time ( t 1/2) shows a linear relation, indicating that the growth of intermetallic compounds is diffusion-controlled. Ball shear tests show that the strength of Sn-20In-2.8Ag solder joints after reflow is 4.4 N, which increases to 5.18 N and 5.14 N after aging at 100 and 150 °C, respectively.

Strontium (Sr) and silver (Ag) loaded nanotubular structures with combined osteoinductive and antimicrobial activities.

PubMed

Cheng, Hao; Xiong, Wei; Fang, Zhong; Guan, Hanfeng; Wu, Wei; Li, Yong; Zhang, Yong; Alvarez, Mario Moisés; Gao, Biao; Huo, Kaifu; Xu, Jiangwen; Xu, Na; Zhang, Chengcheng; Fu, Jijiang; Khademhosseini, Ali; Li, Feng

2016-02-01

Two frequent problems are associated with the titanium surfaces of bone/dental implants: lack of native tissue integration and associated infection. These problems have prompted a significant body of research regarding the modification of these surfaces. The present study describes a hydrothermal treatment for the fabrication of strontium (Sr) and silver (Ag) loaded nanotubular structures with different tube diameters on titanium surfaces. The Sr loading from a Sr(OH)2 solution was regulated by the size of the inner diameter of the titanium nanotubes (NT) (30nm or 80nm, formed at 10V or 40V, respectively). The quantity of Ag was adjusted by immersing the samples in 1.5 or 2.0M AgNO3 solutions. Sr and Ag were released in a controllable and prolonged matter from the NT-Ag.Sr samples, with negligible cytotoxicity. Prominent antibacterial activity was observed due to the release of Ag. Sr incorporation enhanced the initial cell adhesion, migration, and proliferation of preosteoblast MC3T3-E1 cells. Sr release also up-regulated the expression of osteogenic genes and induced mineralization, as suggested by the presence of more mineralized calcium nodules in cells cultured on NT-Ag.Sr surfaces. In vivo experiments showed that the Sr-loaded samples accelerated the formation of new bone in both osteoporosis and bone defect models, as confirmed by X-ray, Micro-CT evaluation, and histomorphometric analysis of rats implanted with NT-Ag.Sr samples. The antibacterial activity and outstanding osteogenic properties of NT-Ag.Sr samples highlight their excellent potential for use in clinical applications. Two frequent problems associated with Ti surfaces, widely used in orthopedic and dental arenas, are their lack of native tissue integration and risk of infection. We describe a novel approach for the fabrication of strontium (Sr) and silver (Ag) loaded nanotubular structures on titanium surfaces. A relevant aspect of this work is the demonstration of long-lasting and controllable Ag release, leading to excellent antibacterial and anti-adherent properties against methicillin-resistant Staphylococcus aureus (MRSA), and Gram-negative bacteria such as Escherichia coli. The extended release of Sr accelerates the filling of bone defects by improving the repair of damaged cortical bone and increasing trabecular bone microarchitecture. Our results highlight the potential of Sr and Ag loaded nanotubular structures for use in clinical applications. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Preclinical anti-cancer activity and multiple mechanisms of action of a cationic silver complex bearing N-heterocyclic carbene ligands.

PubMed

Allison, Simon J; Sadiq, Maria; Baronou, Efstathia; Cooper, Patricia A; Dunnill, Chris; Georgopoulos, Nikolaos T; Latif, Ayşe; Shepherd, Samantha; Shnyder, Steve D; Stratford, Ian J; Wheelhouse, Richard T; Willans, Charlotte E; Phillips, Roger M

2017-09-10

Organometallic complexes offer the prospect of targeting multiple pathways that are important in cancer biology. Here, the preclinical activity and mechanism(s) of action of a silver-bis(N-heterocyclic carbine) complex (Ag8) were evaluated. Ag8 induced DNA damage via several mechanisms including topoisomerase I/II and thioredoxin reductase inhibition and induction of reactive oxygen species. DNA damage induction was consistent with cytotoxicity observed against proliferating cells and Ag8 induced cell death by apoptosis. Ag8 also inhibited DNA repair enzyme PARP1, showed preferential activity against cisplatin resistant A2780 cells and potentiated the activity of temozolomide. Ag8 was substantially less active against non-proliferating non-cancer cells and selectively inhibited glycolysis in cancer cells. Ag8 also induced significant anti-tumour effects against cells implanted intraperitoneally in hollow fibres but lacked activity against hollow fibres implanted subcutaneously. Thus, Ag8 targets multiple pathways of importance in cancer biology, is less active against non-cancer cells and shows activity in vivo in a loco-regional setting. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

Silver(I) coordination polymers assembled from flexible cyclotriphosphazene ligand: structures, topologies and investigation of the counteranion effects.

PubMed

Davarcı, Derya; Gür, Rüştü; Beşli, Serap; Şenkuytu, Elif; Zorlu, Yunus

2016-06-01

The reactions of a flexible ligand hexakis(3-pyridyloxy)cyclotriphosphazene (HPCP) with a variety of silver(I) salts (AgX; X = NO3(-), PF6(-), ClO4(-), CH3PhSO3(-), BF4(-) and CF3SO3(-)) afforded six silver(I) coordination polymers, namely {[Ag2(HPCP)]·(NO3)2·H2O}n (1), {[Ag2(HPCP)(CH3CN)]·(PF6)2}n (2), {[Ag2(HPCP)(CH3CN)]·(ClO4)2}n (3), [Ag3(HPCP)(CH3PhSO3)3]n (4), [Ag2(HPCP)(CH3CN)(BF4)2]n (5) and {[Ag(HPCP)]·(CF3SO3)}n (6). All of the isolated crystalline compounds were structurally determined by X-ray crystallography. Changing the counteranions in the reactions, which were conducted under similar conditions of M/L ratio (1:1), temperature and solvent, resulted in structures with different types of topologies. In complexes (1)-(6), the ligand HPCP shows different coordination modes with Ag(I) ions giving two-dimensional layered structures and three-dimensional frameworks with different topologies. Complex (1) displays a new three-dimensional framework adopting a (3,3,6)-connected 3-nodal net with point symbol {4.6(2)}2{4(2).6(10).8(3)}. Complexes (2) and (3) are isomorphous and have a two-dimensional layered structure showing the same 3,6L60 topology with point symbol {4.2(6)}2{4(8).6(6).8}. Complex (4) is a two-dimensional structure incorporating short Ag...Ag argentophilic interactions and has a uninodal 4-connected sql/Shubnikov tetragonal plane net with {4(4).6(2)} topology. Complex (5) exhibits a novel three-dimensional framework and more suprisingly contains twofold interpenetrated honeycomb-like networks, in which the single net has a trinodal (2,3,5)-connected 3-nodal net with point symbol {6(3).8(6).12}{6(3)}{8}. Complex (6) crystallizes in a trigonal crystal system with the space group R\\bar 3 and possesses a three-dimensional polymeric structure showing a binodal (4,6)-connected fsh net with the point symbol (4(3).6(3))2.(4(6).6(6).8(3)). The effect of the counteranions on the formation of coordination polymers is discussed in this study.

Ag[Fe(CO)5]2(+) : a bare silver complex with Fe(CO)5 as a ligand.

PubMed

Malinowski, Przemysław J; Krossing, Ingo

2014-12-01

Attempts to prepare Fe(CO)5 (+) from Ag[Al(OR(F) )4 ] (R(F) =C(CF3 )3 ) and Fe(CO)5 in CH2 Cl2 yielded the first complex of a neutral metal carbonyl bound to a simple metal cation. The Ag[Fe(CO)5 ]2 (+) cation consists of two Fe(CO)5 molecules coordinating Ag(+) in an almost linear fashion. The ν(CO) modes are blue-shifted compared to Fe(CO)5 , with one band above 2143 cm(-1) indicating that back-bonding is heavily decreased in the Ag[Fe(CO)5 ]2 (+) cation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of Ag addition on solid–state interfacial reactions between Sn–Ag–Cu solder and Cu substrate

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

Yang, Ming

Low–Ag–content Sn–Ag–Cu (SAC) solders have attracted much recent attention in electronic packaging for their low cost. To reasonably reduce the Ag content in Pb–free solders, a deep understanding of the basic influence of Ag on the SAC solder/Cu substrate interfacial reaction is essential. Previous studies have discussed the influence of Ag on the interfacial intermetallic compound (IMC) thickness. However, because IMC growth is the joint result of multiple factors, such characterizations do not reveal the actual role of Ag. In this study, changes in interfacial IMCs after Ag introduction were systemically and quantitatively characterized in terms of coarsening behaviors, orientationmore » evolution, and growth kinetics. The results show that Ag in the solder alloy affects the coarsening behavior, accelerates the orientation concentration, and inhibits the growth of interfacial IMCs during solid–state aging. The inhibition mechanism was quantitatively discussed considering the individual diffusion behaviors of Cu and Sn atoms, revealing that Ag inhibits interfacial IMC growth primarily by slowing the diffusion of Cu atoms through the interface. - Highlights: •Role of Ag in IMC formation during Sn–Ag–Cu soldering was investigated. •Ag affects coarsening, crystallographic orientation, and IMC growth. •Diffusion pathways of Sn and Cu are affected differently by Ag. •Ag slows Cu diffusion to inhibit IMC growth at solder/substrate interface.« less

Comparison of secondary ion intensity enhancement from polymers on silicon and silver substrates by using Au-TOF-SIMS

NASA Astrophysics Data System (ADS)

Kudo, M.; Aimoto, K.; Sunagawa, Y.; Kato, N.; Aoyagi, S.; Iida, S.; Sanada, N.

2008-12-01

The usefulness of the usage of cluster primary ion source together with an Ag substrate and detection of Ag cationized molecular ions was studied from the standpoint to realize high sensitivity TOF-SIMS analysis of organic materials. Although secondary ions from polymer thin films on a Si substrate can be detected in a higher sensitivity with Au 3+ cluster primary ion compared with Ga + ion bombardment, it was clearly observed that the secondary ion intensities from samples on an Ag substrate showed quite a different tendency from that on Si. When monoatomic primary ions, e.g., Au + and Ga +, were used for the measurement of the sample on an Ag substrate, [M+Ag] + ions (M corresponds to polyethylene glycol molecule) were detected in a high sensitivity. On the contrary, when Au 3+ was used, no intensity enhancement of [M+Ag] + ions was observed. The acceleration energy dependence of the detected secondary ions implies the different ionization mechanisms on the different substrates.

Dry-growth of silver single-crystal nanowires from porous Ag structure

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

Chen, Chuantong, E-mail: chenchuantong@sanken.osaka-u.ac.jp; Nagao, Shijo; Jiu, Jinting

A fabrication method of single crystal Ag nanowires in large scale is introduced without any chemical synthesis in wet processes, which usually generates fivefold twinned nanowires of fcc metals. Dense single-crystal nanowires grow on a mechanically polished surface of micro-porous Ag structure, which is created from Ag micro-particles. The diameter and the length of the nanowires can be controlled simply by changing the temperature and the time of the heating during the nanowire growth in air. Unique growth mechanism is described in detail, based on stress-induced migration accelerated by the micro-porous structure where the origin of Ag nanowires growth ismore » incubated. Transmission electron microscopy analysis on the single crystal nanowires is also presented. This simple method offered an alternative preparation for metallic nanowires, especially with the single crystal structure in numerous applications.« less

Density functional theory study on Herzberg-Teller contribution in Raman scattering from 4-aminothiophenol-metal complex and metal-4-aminothiophenol-metal junction

NASA Astrophysics Data System (ADS)

Liu, Shasha; Zhao, Xiuming; Li, Yuanzuo; Zhao, Xiaohong; Chen, Maodu

2009-06-01

Density functional theory (DFT) and time-dependent DFT calculations have been performed to investigate the Raman scattering spectra of metal-molecule complex and metal-molecule-metal junction architectures interconnected with 4-aminothiophenol (PATP) molecule. The simulated profiles of normal Raman scattering (NRS) spectra for the two complexes (Ag2-PATP and PATP-Au2) and the two junctions (Ag2-PATP-Au2 and Au2-PATP-Ag2) are similar to each other, but exhibit obviously different Raman intensities. Due to the lager static polarizabilities of the two junctions, which directly influence the ground state chemical enhancement in NRS spectra, the calculated normal Raman intensities of them are stronger than those of two complexes by the factor of 102. We calculate preresonance Raman scattering (RRS) spectra with incident light at 1064 nm, which is much lower than the S1 electronic transition energy of complexes and junctions. Ag2-PATP-Au2 and Au2-PATP-Ag2 junctions yield higher Raman intensities than those of Ag2-PATP and PATP-Au2 complexes, especially for b2 modes. This effect is mainly attributed to charge transfer (CT) between the metal gap and the PAPT molecule which results in the occurrence of CT resonance enhancement. The calculated pre-RRS spectra strongly depend on the electronic transition state produced by new structures. With excitation at 514.5 nm, the calculated pre-RRS spectra of two complexes and two junctions are stronger than those of with excitation at 1064 nm. A charge difference densities methodology has been used to visually describe chemical enhancement mechanism of RRS spectrum. This methodology aims at visualizing intermolecular CT which provides direct evidence of the Herzberg-Teller mechanism.

Role of Dispersion in Metallophilic Hg···M Interactions (M = Cu, Ag, Au) within Coinage Metal Complexes of Bis(6-diphenylphosphinoacenaphth-5-yl)mercury.

PubMed

Hupf, Emanuel; Kather, Ralf; Vogt, Matthias; Lork, Enno; Mebs, Stefan; Beckmann, Jens

2016-11-07

The previously reported bis(6-diphenylphosphinoacenaphth-5-yl)mercury (1) was used as ligand for the preparation of the copper(I) complexes, 1·CuCl and [1·Cu(NCMe)]BF 4 , which were characterized by multinuclear NMR spectroscopy and X-ray crystallography. DFT calculations employing topological analysis of the electron and electron pair densities within the AIM and ELI-D space-partitioning schemes revealed significant metallophilic Hg···Cu interactions. Evaluation of noncovalent bonding aspects according to the noncovalent interaction (NCI) index was applied not only for the Cu complexes 1·CuCl and [1·Cu(NCMe)]BF 4 but also for the previously reported Ag and Au complexes, namely, [1·MCl] (M = Ag, Au) and [1·M(NCMe) n ] + (M = Ag, n = 2; M = Au, n = 0), and facilitated the assignment of attractive dispersive Hg···M interactions with the Hg···Cu contacts being comparable to the Hg···Ag but weaker than the Hg···Au interactions. The localization of the attractive noncovalent bonding regions increases in the order Cu < Ag < Au.

Complexation and phase evolution at dimethylformamide-Ag(111) interfaces

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

Song, Wentao; Leung, Kevin; Shao, Qian

The interaction of solvent molecules with metallic surfaces impacts many interfacial chemical processes. We investigate the chemical and structure evolution that follows adsorption of the polar solvent dimethylformamide (DMF) on Ag(111). An Ag(DMF) 2 coordination complex forms spontaneously by DMF etching of Ag(111), yielding mixed films of the complexes and DMF. Utilizing ultrahigh vacuum scanning tunneling microscopy (UHV-STM), in combination with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) computations, we map monolayer phases from the 2-D gas regime, consisting of a binary mixture of DMF and Ag(DMF) 2, through the saturation monolayer limit, in which these two chemicalmore » species phase separate into ordered islands. Structural models for the near-square DMF phase and the chain-like Ag(DMF) 2 phase are presented and supported by DFT computation. Interface evolution is summarized in a surface pressure-composition phase diagram, which allows structure prediction over arbitrary experimental conditions. In conclusion, this work reveals new surface coordination chemistry for an important electrolyte-electrode system, and illustrates how surface pressure can be used to tune monolayer phases.« less

Complexation and phase evolution at dimethylformamide-Ag(111) interfaces

DOE PAGES

Song, Wentao; Leung, Kevin; Shao, Qian; ...

2016-09-15

The interaction of solvent molecules with metallic surfaces impacts many interfacial chemical processes. We investigate the chemical and structure evolution that follows adsorption of the polar solvent dimethylformamide (DMF) on Ag(111). An Ag(DMF) 2 coordination complex forms spontaneously by DMF etching of Ag(111), yielding mixed films of the complexes and DMF. Utilizing ultrahigh vacuum scanning tunneling microscopy (UHV-STM), in combination with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) computations, we map monolayer phases from the 2-D gas regime, consisting of a binary mixture of DMF and Ag(DMF) 2, through the saturation monolayer limit, in which these two chemicalmore » species phase separate into ordered islands. Structural models for the near-square DMF phase and the chain-like Ag(DMF) 2 phase are presented and supported by DFT computation. Interface evolution is summarized in a surface pressure-composition phase diagram, which allows structure prediction over arbitrary experimental conditions. In conclusion, this work reveals new surface coordination chemistry for an important electrolyte-electrode system, and illustrates how surface pressure can be used to tune monolayer phases.« less

Structural modulation of silver complexes and their distinctive catalytic properties.

PubMed

Zhao, Yue; Chen, Kai; Fan, Jian; Okamura, Taka-aki; Lu, Yi; Luo, Li; Sun, Wei-Yin

2014-02-07

A family of silver(I) complexes, [Ag2(L)2(OOCCF3)2] (1), [Ag(L)0.5(OOCCF3)] (2), [Ag(L)2](OOCCF3)(H2O)2 (3), was obtained by reactions of 4,4'-di(2-oxazolinyl)biphenyl (L) and AgOOCCF3 in different reaction media. Compound 1 has a 1D chain structure with alternative connections between the Ag(I) and L ligand. When the crystal nucleation inductor, pyrazine, was added into the reaction system, complex 2 was isolated with no pyrazine observed in its structure. In 2, the 1D inorganic chains formed by Ag(I) cations and OOCCF3(-) anions were connected by the L ligand to produce a 2D network. When a different inductor, imidazole, was added into the reaction system, 3 with (4,4) topology was synthesized, and again no imidazole was found in 3. When 1-3 were used as catalysts for cycloaddition reactions between imino esters and methyl acrylate, 3 affords the highest yield, in which the particular size of the channels in 3 led to its selective catalytic performance.

Bioleaching of chalcopyrite and bornite by moderately thermophilic bacteria: an emphasis on their interactions

NASA Astrophysics Data System (ADS)

Zhao, Hong-bo; Wang, Jun; Gan, Xiao-wen; Qin, Wen-qing; Hu, Ming-hao; Qiu, Guan-zhou

2015-08-01

Interactions between chalcopyrite and bornite during bioleaching by moderately thermophilic bacteria were investigated mainly by X-ray diffraction, scanning electron microscopy, and electrochemical measurements performed in conjunction with bioleaching experiments. The results showed that a synergistic effect existed between chalcopyrite and bornite during bioleaching by both Acidithiobacillus caldus and Leptospirillum ferriphilum and that extremely high copper extraction could be achieved when chalcopyrite and bornite coexisted in a bioleaching system. Bornite dissolved preferentially because of its lower corrosion potential, and its dissolution was accelerated by the galvanic current during the initial stage of bioleaching. The galvanic current and optimum redox potential of 390-480 mV vs. Ag/AgCl promoted the reduction of chalcopyrite to chalcocite (Cu2S), thus accelerating its dissolution.

Ag@AgHPW as a plasmonic catalyst for visible-light photocatalytic degradation of environmentally harmful organic pollutants

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

Zhou, Wenhui; Cao, Minhua, E-mail: caomh@bit.edu.cn; Li, Na

2013-06-01

Graphical abstract: Ag@Ag{sub x}H{sub 3−x}PW12O40 (Ag@AgHPW) nanoparticles (NPs), a new visible-light driven plasmonic photocatalyst, are prepared by a green photoreduction strategy without the addition of any surfactant, which show a high activity and stability for the degradation of methyl blue (MB) under visible light irradiation. - Highlights: • A new visible-light driven photocatalyst Ag@Ag{sub x}H{sub 3−x}PW{sub 12}O{sub 40} was designed. • The photocatalyst shows a high activity for the degradation of methyl blue. • The high activity can be ascribed to the synergy of photoexcited AgHPW and Ag. - Abstract: Ag@Ag{sub x}H{sub 3−x}PW{sub 12}O{sub 40} (Ag@AgHPW) nanoparticles (NPs), a newmore » visible-light driven plasmonic photocatalyst, are prepared by a green photoreduction strategy without the addition of any surfactant. They show strong absorption in the visible region because of the localized surface plasmon resonance (LSPR) of Ag NPs. This plasmonic photocatalyst shows a high activity and stability for the degradation of methyl blue (MB) under visible light irradiation, which could be attributed to the highly synergy of photoexcited Ag{sub x}H{sub 3−x}PW{sub 12}O{sub 40} (AgHPW) and plasmon-excited Ag NPs and the confinement effects at interfaces between polyoxometalates (POMs) and silver. POM anions have redox ability and high photocatalytic activity, whereas Ag NPs could effectively accelerate the separation of electrons and holes, both of which contribute to their high activity.« less

Growth and characterization of AgGa0.5In0.5Se2 single crystals by modified vertical Bridgman method

NASA Astrophysics Data System (ADS)

Vijayakumar, P.; Ramasamy, P.

2016-05-01

AgGa0.5In0.5Se2 single crystal was grown using a double wall quartz ampoule with accelerated crucible rotation technique by modified vertical Bridgman method. The structural perfection was measured using HRXRD. The grown single crystal composition was measured using ICP-OES analysis and compositional uniformities were measured using Raman spectroscopy analysis. Photoconductivity measurements confirm the positive photoconducting nature.

Complexes of DNA bases and Watson-Crick base pairs interaction with neutral silver Agn (n = 8, 10, 12) clusters: a DFT and TDDFT study.

PubMed

Srivastava, Ruby

2018-03-01

We study the binding of the neutral Ag n (n = 8, 10, 12) to the DNA base-adenine (A), guanine (G) and Watson-Crick -adenine-thymine, guanine-cytosine pairs. Geometries of complexes were optimized at the DFT level using the hybrid B3LYP functional. LANL2DZ effective core potential was used for silver and 6-31 + G ** was used for all other atoms. NBO charges were analyzed using the Natural population analysis. The absorption properties of Ag n -A,G/WC complexes were also studied using time-dependent density functional theory. The absorption spectra for these complexes show wavelength in the visible region. It was revealed that silver clusters interact more strongly with WC pairs than with isolated DNA complexes. Furthermore, it was found that the electronic charge transferred from silver to isolated DNA clusters are less than the electronic charge transferred from silver to the Ag n -WC complexes. The vertical ionization potential, vertical electron affinity, hardness, and electrophilicity index of Ag n -DNA/WC complexes have also been discussed.

Electromagnetic and geometric characterization of accelerated ion beams by laser ablation

NASA Astrophysics Data System (ADS)

Nassisi, V.; Velardi, L.; Side, D. Delle

2013-05-01

Laser ion sources offer the possibility to get ion beam useful to improve particle accelerators. Pulsed lasers at intensities of the order of 108 W/cm2 and of ns pulse duration, interacting with solid matter in vacuum, produce plasma of high temperature and density. The charge state distribution of the plasma generates high electric fields which accelerate ions along the normal to the target surface. The energy of emitted ions has a Maxwell-Boltzmann distribution which depends on the ion charge state. To increase the ion energy, a post-acceleration system can be employed by means of high voltage power supplies of about 100 kV. The post acceleration system results to be a good method to obtain high ion currents by a not expensive system and the final ion beams find interesting applications in the field of the ion implantation, scientific applications and industrial use. In this work we compare the electromagnetic and geometric properties, like emittance, of the beams delivered by pure Cu, Y and Ag targets. The characterization of the plasma was performed by a Faraday cup for the electromagnetic characteristics, whereas a pepper pot system was used for the geometric ones. At 60 kV accelerating voltage the three examined ion bunches get a current peak of 5.5, 7.3 and 15 mA, with a normalized beam emittance of 0.22, 0.12 and 0.09 π mm mrad for the targets of Cu, Y, and Ag, respectively.

Effect of cysteine and humic acids on bioavailability of Ag from Ag nanoparticles to a freshwater snail

USGS Publications Warehouse

Luoma, Samuel N.; Tasha Stoiber,; Croteau, Marie-Noele; Isabelle Romer,; Ruth Merrifeild,; Lead, Jamie

2016-01-01

Metal-based engineered nanoparticles (NPs) will undergo transformations that will affect their bioavailability, toxicity and ecological risk when released to the environment, including interactions with dissolved organic material. The purpose of this paper is to determine how interactions with two different types of organic material affect the bioavailability of silver nanoparticles (AgNPs). Silver uptake rates by the pond snail Lymnaea stagnalis were determined after exposure to 25 nmol l-1 of Ag as PVP AgNPs, PEG AgNPs or AgNO3, in the presence of either Suwannee River humic acid or cysteine, a high-affinity thiol-rich organic ligand. Total uptake rate of Ag from the two NPs was either increased or not strongly affected in the presence of 1 – 10 mg 1-1 humic acid. Humic substances contain relatively few strong ligands for Ag explaining their limited effects on Ag uptake rate. In contrast, Ag uptake rate was substantially reduced by cysteine. Three components of uptake from the AgNPs were quantified in the presence of cysteine using a biodynamic modeling approach: uptake of dissolved Ag released by the AgNPs, uptake of a polymer or large (>3kD) Ag-cysteine complex and uptake of the nanoparticle itself. Addition of 1:1 Ag:cysteine reduced concentrations of dissolved Ag, which contributed to, but did not fully explain the reductions in uptake. A bioavailable Ag-cysteine complex (> 3kD) appeared to be the dominant avenue of uptake from both PVP AgNPs and PEG AgNPs in the presence of cysteine. Quantifying the different avenues of uptake sets the stage for studies to assess toxicity unique to NPs.

Agent planning in AgScala

NASA Astrophysics Data System (ADS)

Tošić, Saša; Mitrović, Dejan; Ivanović, Mirjana

2013-10-01

Agent-oriented programming languages are designed to simplify the development of software agents, especially those that exhibit complex, intelligent behavior. This paper presents recent improvements of AgScala, an agent-oriented programming language based on Scala. AgScala includes declarative constructs for managing beliefs, actions and goals of intelligent agents. Combined with object-oriented and functional programming paradigms offered by Scala, it aims to be an efficient framework for developing both purely reactive, and more complex, deliberate agents. Instead of the Prolog back-end used initially, the new version of AgScala relies on Agent Planning Package, a more advanced system for automated planning and reasoning.

Multispectroscopic DNA-Binding studies and antimicrobial evaluation of new mixed-ligand Silver(I) complex and nanocomplex: A comparative study

NASA Astrophysics Data System (ADS)

Movahedi, Elaheh; Rezvani, Ali Reza

2018-05-01

A novel mixed-ligand Ag(I) complex, , has been synthesized and characterized by the elemental analysis, IR spectroscopy and 1HNMR. In the formula, dian and phen are N-(4,5-diazafluoren-9-ylidene)aniline and 1,10-phenanthroline, respectively. This complex also has been prepared at nano size by sonochemical technique and characterized by the FTIR and scanning electron microscopy (SEM). To evaluate the biological preferences of the Ag(I) complex and nanocomplex and verify the relationships between the structure and biological function, in vitro DNA binding and antibacterial experiments have been carried out. DNA-complex interaction has been pursued by electronic absorption titration, luminescence titration, competitive binding experiment, effect of ionic strength, thermodynamic studies, viscometric evaluation and circular dichroism spectroscopy in the physiological pH. Each compound displays significant binding trend to the CT-DNA. The mode of binding to the CT-DNA probably is a moderate intercalation mode with the partial insertion of the planar ligands between the base stacks of double-stranded DNA. The relative viscosities and circular dichroism spectra of the CT-DNA with the complex solutions, confirm the intense interactions of the Ag(I) complex and nanocomplex with DNA. An in vitro antibacterial test of the complex and nanocomplex on a series of the Gram-positive bacteria (Staphylococcus aureus, Enterococcus faecalis) and the Gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa) shows a remarkable antibacterial feature of the Ag(I) complex. The MIC values (minimum inhibitory concentration) of the compounds compare with silver nitrate and silver sulfadiazine. The bacterial inhibitions of the Ag(I) complex and nanocomplex are agreed to their DNA binding affinities.

Dynamic Multivariate Accelerated Corrosion Test Protocol

DTIC Science & Technology

2014-10-01

atmospheric, accelerated, AA2024-T3, AA6061-T6, AA7075-T3, 1010 steel, AgCl, rare earth conversion coat, magnesium rich primer, polyurethane , Eyring, Monte...morphology and elemental analysis by scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and electrochemical determinations of...in the FT-IR analysis; degradation of the components of the high performance polyurethane coatings exposed in the UV/ozone chamber were more

Natural inorganic nanoparticles--formation, fate, and toxicity in the environment.

PubMed

Sharma, Virender K; Filip, Jan; Zboril, Radek; Varma, Rajender S

2015-12-07

The synthesis, stability, and toxicity of engineered metal nanoparticles (ENPs) have been extensively studied during the past two decades. In contrast, research on the formation, fate, and ecological effects of naturally-occurring nanoparticles (NNPs) has become a focus of attention only recently. The natural existence of metal nanoparticles and their oxides/sulfides in waters, wastewaters, ore deposits, mining regions, and hydrothermal vents, as exemplified by the formation of nanoparticles containing silver and gold (AgNPs and AuNPs), Fe, Mn, pyrite (FeS2), Ag2S, CuS, CdS, and ZnS, is dictated largely by environmental conditions (temperature, pH, oxic/anoxic, light, and concentration and characteristics of natural organic matter (NOM)). Examples include the formation of nanoparticles containing pyrite, Cu and Zn-containing pyrite, and iron in hydrothermal vent black smoker emissions. Metal sulfide nanoparticles can be formed directly from their precursor ions or indirectly by sulfide ion-assisted transformation of the corresponding metal oxides under anaerobic conditions. This tutorial focuses on the formation mechanisms, fate, and toxicity of natural metal nanoparticles. Natural waters containing Ag(I) and Au(III) ions in the presence of NOM generate AgNPs and AuNPs under thermal, non-thermal, and photochemical conditions. These processes are significantly accelerated by existing redox species of iron (Fe(II)/Fe(III)). NOM, metal-NOM complexes, and reactive oxygen species (ROS) such as O2˙(-), ˙OH, and H2O2 are largely responsible for the natural occurrence of nanoparticles. AgNPs and AuNPs emanating from Ag(I)/Au(III)-NOM reactions are stable for several months, thus indicating their potential to be transported over long distances from their point of origin. However, endogenous cations present in natural waters can destabilize the nanoparticles, with divalent cations (e.g., Ca(2+), Mg(2+)) being more influential than their monovalent equivalents (e.g., Na(+), K(+)). The toxicity of NNPs may differ from that of ENPs because of differences in the coatings on the nanoparticle surfaces. An example of this phenomenon is presented and is briefly discussed.

The Cellular and Molecular Mechanisms Underlying Silver Nanoparticle/Chitosan Oligosaccharide/Poly(vinyl alcohol) Nanofiber-Mediated Wound Healing.

PubMed

Zi-Wei, Li; Li, Chen-Wen; Wang, Qing; Shi, San-Jun; Hu, Min; Zhang, Qian; Cui, Huan-Huan; Sun, Jian-Bin; Zhou, Min; Wu, Guo-Lin; Dang, Ji-Zheng; Lu, Lai-Chun

2017-01-01

Wound healing is a complex pathophysiological process that occurs frequently in everyday pathology and remains a challenge during the treatment of trauma. Previously, we prepared silver nanoparticle/chitosan oligosaccharide/poly(vinyl alcohol) (PVA/COS-AgNP) nanofibers via an electrospinning technique. These nanofibers promoted the proliferation of human skin fibroblasts (HSFs) and the expression of transforming growth factor TGF-β1 in the early stage of wound repair, although the specific mechanisms remain unclear. Therefore, considering that TGF-β1 has emerged as a major modulator of wound healing, the objective of this study was to further understand whether the molecular mechanisms responsible for PVA/COS-AgNP nanofiber-mediated wound healing include the TGF-β1/Smad signal transduction pathway. In this study, we used human skin fibroblasts (HSFs) to investigate the molecular and cellular mechanisms underlying PVA/COSAgNP nanofiber-mediated wound healing. Cell adhesion and proliferation experiments, immunofluorescence staining, hydroxyproline content measurements, flow cytometry, quantitative real-time PCR (qRT-PCR), and western blotting (WB) were used to analyze the wound healing mechanisms of human skin fibroblasts treated with various concentrations of PVA/COS-AgNP nanofibers and the combined application of silver nanofibers and SB431542 (an inhibitor of the TGF-β1 receptor kinase). Our study showed that PVA/COS-AgNP nanofibers markedly promoted fibroblast proliferation, collagen synthesis, and cell adherence. We also found that treating fibroblasts with PVA/COS-AgNP nanofibers stimulated cell cycle progression from G1 into the S and G2 phases, reducing the proportion of cells in the G0/G1 phase and inducing S and G2/M arrest. Importantly, the cell factors associated with the TGF-β1/Smad signal transduction pathway, such as TGF-β1, TGFβRI, TGFβRII, pSmad2, pSmad3, collagen I, collagen III, and fibronectin were also up-regulated. Moreover, this enhancing effect was markedly inhibited by the TGFβRI receptor inhibitor, SB431542. Therefore, the PVA/COS-AgNP nanofibers used to accelerate wound healing do so by activating the TGF-β1/Smad signal transduction pathway.

MECHANISTIC PATHWAYS AND BIOLOGICAL ROLES FOR RECEPTOR-INDEPENDENT ACTIVATORS OF G-PROTEIN SIGNALING

PubMed Central

Blumer, Joe B.; Smrcka, Alan V.; Lanier, S.M.

2007-01-01

Signal processing via heterotrimeric G-proteins in response to cell surface receptors is a central and much investigated aspect of how cells integrate cellular stimuli to produce coordinated biological responses. The system is a target of numerous therapeutic agents, plays an important role in adaptive processes of organs, and aberrant processing of signals through these transducing systems is a component of various disease states. In addition to GPCR-mediated activation of G-protein signaling, nature has evolved creative ways to manipulate and utilize the Gαβγ heterotrimer or Gα and Gαβγ subunits independent of the cell surface receptor stimuli. In such situations, the G-protein subunits (Gα and Gαβγ) may actually be complexed with alternative binding partners independent of the typical heterotrimeric Gαβγ. Such regulatory accessory proteins include the family of RGS proteins that accelerate the GTPase activity of Gα and various entities that influence nucleotide binding properties and/or subunit interaction. The latter group of proteins includes receptor independent activators of G-protein signaling or AGS proteins that play surprising roles in signal processing. This review provides an overview of our current knowledge regarding AGS proteins. AGS proteins are indicative of a growing number of accessory proteins that influence signal propagation, facilitate cross talk between various types of signaling pathways and provide a platform for diverse functions of both the heterotrimeric Gαβγ and the individual Gα and Gαβγ subunits. PMID:17240454

Water chemistry controlled aggregation and photo-transformation of silver nanoparticles in environmental waters.

PubMed

Yin, Yongguang; Yang, Xiaoya; Zhou, Xiaoxia; Wang, Weidong; Yu, Sujuan; Liu, Jingfu; Jiang, Guibin

2015-08-01

The inevitable release of engineered silver nanoparticles (AgNPs) into aquatic environments has drawn great concerns about its environmental toxicity and safety. Although aggregation and transformation play crucial roles in the transport and toxicity of AgNPs, how the water chemistry of environmental waters influences the aggregation and transformation of engineered AgNPs is still not well understood. In this study, the aggregation of polyvinylpyrrolidone (PVP) coated AgNPs was investigated in eight typical environmental water samples (with different ionic strengths, hardness, and dissolved organic matter (DOM) concentrations) by using UV-visible spectroscopy and dynamic light scattering. Raman spectroscopy was applied to probe the interaction of DOM with the surface of AgNPs. Further, the photo-transformation and morphology changes of AgNPs in environmental waters were studied by UV-visible spectroscopy, inductively coupled plasma mass spectrometry, and transmission electron microscopy. The results suggested that both electrolytes (especially Ca(2+) and Mg(2+)) and DOM in the surface waters are key parameters for AgNP aggregation, and sunlight could accelerate the morphology change, aggregation, and further sedimentation of AgNPs. This water chemistry controlled aggregation and photo-transformation should have significant environmental impacts on the transport and toxicity of AgNPs in the aquatic environments. Copyright © 2015. Published by Elsevier B.V.

Metal release and speciation of released chromium from a biomedical CoCrMo alloy into simulated physiologically relevant solutions.

PubMed

Hedberg, Yolanda; Odnevall Wallinder, Inger

2014-05-01

The objective of this study was to investigate the extent of released Co, Cr(III), Cr(VI), and Mo from a biomedical high-carbon CoCrMo alloy exposed in phosphate-buffered saline (PBS), without and with the addition of 10 µM H2 O2 (PBS + H2 O2 ), and 10 g L(-1) bovine serum albumin (PBS + BSA) for time periods up to 28 days. Comparative studies were made on AISI 316L for the longest time period. No Cr(VI) release was observed for any of the alloys in either PBS or PBS + H2 O2 at open-circuit potential (no applied potential). However, at applied potentials (0.7 V vs. Ag/AgCl), Cr was primarily released as Cr(VI). Co was preferentially released from the CoCrMo alloy at no applied potential. As a consequence, Cr was enriched in the utmost surface oxide reducing the extent of metal release over time. This passivation effect was accelerated in PBS + H2 O2 . As previously reported for 316L, BSA may also enhance metal release from CoCrMo. However, this was not possible to verify due to the precipitation of metal-protein complexes with reduced metal concentrations in solution as a consequence. This was particularly important for Co-BSA complexes after sufficient time and resulted in an underestimation of metals in solution. Copyright © 2013 Wiley Periodicals, Inc.

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

Zeno, K.

There were only a few differences in the setup between this year’s Polarized Proton run and the previous one (Run 15). Consequently, this note will focus on these differences as well as a few more notable studies done during the course of the run. This year, the Booster input intensity was kept around 7e11 for the majority of the run whereas in Run 15 it was kept around 9e11. It was lowered because there was some indication that the source polarization was higher with this lower input. Some of the polarization measurements that motivated this change will be discussed. Bothmore » the emittance and polarization on the AGS flattop show intensity dependence, thought to be related to the peak current, especially early in the AGS acceleration ramp. In Run 15, the AGS Rf was configured for h=8, but in this run h=6 was used to reduce the peak current and also to allow for the possibility of using a dual harmonic to reduce it further. Eventually, a dual harmonic configuration was used for the first 100 ms or so of the AGS acceleration cycle. Two cavities were set to h=12 and phased differently than the other 8 to accomplish this. Quad pumping was also used at Booster extraction to make the bunch injected into the AGS wider in order to match the dual harmonic bucket right at injection. This configuration, which was used for the majority of the run, will be described. Measurements of the intensity dependence of the transverse emittance and polarization with and without it will be compared.« less

Influence of biocompatible metal ions (Ag, Fe, Y) on the surface chemistry, corrosion behavior and cytocompatibility of Mg-1Ca alloy treated with MEVVA.

PubMed

Liu, Yang; Bian, Dong; Wu, Yuanhao; Li, Nan; Qiu, Kejin; Zheng, Yufeng; Han, Yong

2015-09-01

Mg-1Ca samples were implanted with biocompatible alloy ions Ag, Fe and Y respectively with a dose of 2×10(17)ionscm(-2) by metal vapor vacuum arc technique (MEVVA). The surface morphologies and surface chemistry were investigated by SEM, AES and XPS. Surface changes were observed after all three kinds of elemental ion implantation. The results revealed that the modified layer was composed of two sublayers, including an outer oxidized layer with mixture of oxides and an inner implanted layer, after Ag and Fe ion implantation. Y ion implantation induced an Mg/Ca-deficient outer oxidized layer and the distribution of Y along with depth was more homogeneous. Both electrochemical test and immersion test revealed accelerated corrosion rate of Ag-implanted Mg-1Ca and Fe-implanted Mg-1Ca, whereas Y ion implantation showed a short period of protection since enhanced corrosion resistance was obtained by electrochemical test, but accelerated corrosion rate was found by long period immersion test. Indirect cytotoxicity assay indicated good cytocompatibility of Y-implanted Mg-1Ca. Moreover, the corresponding corrosion mechanisms involving implanting ions into magnesium alloys were proposed, which might provide guidance for further application of plasma ion implantation to biodegradable Mg alloys. Copyright © 2015 Elsevier B.V. All rights reserved.

Effects of Ag addition on FePt L1{sub 0} ordering transition: A direct observation of ordering transition and Ag segregation in FePtAg alloy films

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

Wang, Lei; Yu, Youxing, E-mail: yuyouxing@buaa.edu.cn; Gao, Tenghua

FePt and (FePt){sub 91.2}Ag{sub 8.8} alloy films were deposited by magnetron sputtering. The average coercivity of (FePt){sub 91.2}Ag{sub 8.8} films reaches 8.51 × 10{sup 5} A/m, which is 0.63 × 10{sup 5} A/m higher than that of the corresponding FePt films. Ag addition effectively promotes the FePt L1{sub 0} ordering transition at a relatively low annealing temperature of 400 °C. The promotion mechanism was investigated by using in situ high-resolution transmission electron microscopy (HRTEM) and ex situ X-ray absorption fine structure (XAFS). The concurrence of ordering transition and Ag segregation in FePtAg alloy films was first observed by using in situ heating HRTEM. The time-resolved evolution revealsmore » more details on the role of Ag addition in FePt low-temperature ordering. Ex situ XAFS results further confirm that Ag replaces Fe sites in the as-deposited films and segregates from FePt-Ag solid solution phase through annealing at elevated temperatures. The segregation of Ag atoms leaves vacancies in the grain. The vacancy formation is believed to accelerate the diffusion of Fe and Pt atoms, which is critical for the L1{sub 0} ordering transition.« less

Green synthesis of silver nanoparticles as antibacterial agent using Rhodomyrtus tomentosa acetone extract

NASA Astrophysics Data System (ADS)

Voravuthikunchai, Supayang P.; Chorachoo, Julalak; Jaiswal, Lily; Shankar, Shiv

2013-12-01

The capability of Rhodomyrtus tomentosa acetone extract (RAE) for the production of silver nanoparticles (AgNPs) has been explored for the first time. Silver nanoparticles with a surface plasmon resonance band centered at 420-430 nm were synthesized by reacting RAE with AgNO3. Reaction time, temperature, concentration of AgNO3 and RAE could accelerate the reduction rate of Ag+ and affect AgNPs size. The nanoparticles were found to be 10-30 nm in size and spherical in shape. XRD data demonstrated crystalline nature of AgNPs dominated by (200) facets. FTIR results showed decrease in intensity of peaks at 3394, 1716 and 1618 cm-1 indicating the involvement of O-H, carbonyl group and C=C stretching with the formation of AgNPs with RAE, respectively. The C-O-C and C-N stretching suggested the presence of many phytochemicals on the surface of the nanoparticles. High negative zeta potential values confirmed the stability of AgNPs in water. In vitro antibacterial activity of AgNPs was tested against Staphylococcus aureus using broth microdilution method. AgNPs capped with RAE demonstrated profound antibacterial activity against the organisms with minimum inhibitory concentration and minimum bactericidal concentration in the range between 3.1-6.2 and 6.2-50 μgmL-1, respectively. The synthesized nanoparticles could be applied as an effective antimicrobial agent against staphylococcal infections.

αA-Crystallin–Derived Mini-Chaperone Modulates Stability and Function of Cataract Causing αAG98R-Crystallin

PubMed Central

Raju, Murugesan; Santhoshkumar, Puttur; Sharma, K. Krishna

2012-01-01

Background A substitution mutation in human αA-crystallin (αAG98R) is associated with autosomal dominant cataract. The recombinant mutant αAG98R protein exhibits altered structure, substrate-dependent chaperone activity, impaired oligomer stability and aggregation on prolonged incubation at 37°C. Our previous studies have shown that αA-crystallin–derived mini-chaperone (DFVIFLDVKHFSPEDLTVK) functions like a molecular chaperone by suppressing the aggregation of denaturing proteins. The present study was undertaken to determine the effect of αA-crystallin–derived mini-chaperone on the stability and chaperone activity of αAG98R-crystallin. Methodology/Principal Findings Recombinant αAG98R was incubated in presence and absence of mini-chaperone and analyzed by chromatographic and spectrometric methods. Transmission electron microscope was used to examine the effect of mini-chaperone on the aggregation propensity of mutant protein. Mini-chaperone containing photoactive benzoylphenylalanine was used to confirm the interaction of mini-chaperone with αAG98R. The rescuing of chaperone activity in mutantα-crystallin (αAG98R) by mini-chaperone was confirmed by chaperone assays. We found that the addition of the mini-chaperone during incubation of αAG98R protected the mutant crystallin from forming larger aggregates that precipitate with time. The mini-chaperone-stabilized αAG98R displayed chaperone activity comparable to that of wild-type αA-crystallin. The complexes formed between mini-αA–αAG98R complex and ADH were more stable than the complexes formed between αAG98R and ADH. Western-blotting and mass spectrometry confirmed the binding of mini-chaperone to mutant crystallin. Conclusion/Significance These results demonstrate that mini-chaperone stabilizes the mutant αA-crystallin and modulates the chaperone activity of αAG98R. These findings aid in our understanding of how to design peptide chaperones that can be used to stabilize mutant αA-crystallins and preserve the chaperone function. PMID:22970163

Enhanced extraction of astragalosides from Radix Astragali by negative pressure cavitation-accelerated enzyme pretreatment.

PubMed

Yan, Ming-Ming; Chen, Cai-Yun; Zhao, Bao-Shan; Zu, Yuan-Gang; Fu, Yu-Jie; Liu, Wei; Efferth, Thomas

2010-10-01

The optimal conditions for extraction of astragalosides III and IV (AGs III and IV) in Radix Astragali by negative pressure cavitation-accelerated enzyme pretreatment were studied on the basis of a Box-Behnken design and response surface methodology. Experimental results showed that negative pressure, amount of enzyme and incubation temperature were the main factors governing the enzyme pretreatment of Radix Astragali. The optimum parameters were obtained as follows: negative pressure -0.08 Mpa, amount of enzyme 1.48% (w/w of materials) and incubation temperature 45 degrees C. Under the optimal conditions, the maximal extraction yields of AGs III and IV were 0.103 and 0.325 mg/g, which were 41.67% and 65.31% increased as compared to those without enzyme pretreatment, respectively. The effect of negative pressure cavitation and enzyme pretreatment on the structural changes of plant cells was observed by scanning electron microscopy. In conclusion, negative pressure cavitation-accelerated enzyme pretreatment was proved to be environment-friendly and economical, and could be used in secondary metabolites production. Copyright 2010 Elsevier Ltd. All rights reserved.

A theoretical investigation on Cu/Ag/Au bonding in XH2P⋯MY(X = H, CH3, F, CN, NO2; M = Cu, Ag, Au; Y = F, Cl, Br, I) complexes

NASA Astrophysics Data System (ADS)

Wang, Zhaoxu; Liu, Yi; Zheng, Baishu; Zhou, Fengxiang; Jiao, Yinchun; Liu, Yuan; Ding, XunLei; Lu, Tian

2018-05-01

Intermolecular interaction of XH2P...MY (X = H, CH3, F, CN, NO2; M = Cu, Ag, Au; Y = F, Cl, Br, I) complexes was investigated by means of an ab initio method. The molecular interaction energies are in the order Ag < Cu < Au and increased with the decrease of RP...M. Interaction energies are strengthened when electron-donating substituents X connected to XH2P, while electron-withdrawing substituents produce the opposite effect. The strongest P...M bond was found in CH3H2P...AuF with -70.95 kcal/mol, while the weakest one was found in NO2H2P...AgI with -20.45 kcal/mol. The three-center/four-electron (3c/4e) resonance-type of P:-M-:Y hyperbond was recognized by the natural resonance theory and the natural bond orbital analysis. The competition of P:M-Y ↔ P-M:Y resonance structures mainly arises from hyperconjugation interactions; the bond order of bP-M and bM-Y is in line with the conservation of the idealized relationship bP-M + bM-Y ≈ 1. In all MF-containing complexes, P-M:F resonance accounted for a larger proportion which leads to the covalent characters for partial ionicity of MF. The interaction energies of these Cu/Ag/Au complexes are basically above the characteristic values of the halogen-bond complexes and close to the observed strong hydrogen bonds in ionic hydrogen-bonded species.

Strong polarization-dependent terahertz modulation of aligned Ag nanowires on Si substrate.

PubMed

Lee, Gyuseok; Maeng, Inhee; Kang, Chul; Oh, Myoung-Kyu; Kee, Chul-Sik

2018-05-14

Optically tunable, strong polarization-dependent transmission of terahertz pulses through aligned Ag nanowires on a Si substrate is demonstrated. Terahertz pulses primarily pass through the Ag nanowires and the transmittance is weakly dependent on the angle between the direction of polarization of the terahertz pulse and the direction of nanowire alignment. However, the transmission of a terahertz pulse through optically excited materials strongly depends on the polarization direction. The extinction ratio increases as the power of the pumping laser increases. The enhanced polarization dependency is explained by the redistribution of photocarriers, which accelerates the sintering effect along the direction of alignment of the Ag nanowires. The photocarrier redistribution effect is examined by the enhancement of terahertz emission from the sample. Oblique metal nanowires on Si could be utilized for designing optically tunable terahertz polarization modulators.

Generation of attosecond electron packets via conical surface plasmon electron acceleration

PubMed Central

Greig, S. R.; Elezzabi, A. Y.

2016-01-01

We present a method for the generation of high kinetic energy attosecond electron packets via magnetostatic and aperture filtering of conical surface plasmon (SP) accelerated electrons. The conical SP waves are excited by coupling an ultrafast radially polarized laser beam to a conical silica lens coated with an Ag film. Electromagnetic and particle tracking models are employed to characterize the ultrafast electron packets. PMID:26764129

A model of polarized-beam AGS in the ray-tracing code Zgoubi

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

Meot, F.; Ahrens, L.; Brown, K.

A model of the Alternating Gradient Synchrotron, based on the AGS snapramps, has been developed in the stepwise ray-tracing code Zgoubi. It has been used over the past 5 years in a number of accelerator studies aimed at enhancing RHIC proton beam polarization. It is also used to study and optimize proton and Helion beam polarization in view of future RHIC and eRHIC programs. The AGS model in Zgoubi is operational on-line via three different applications, ’ZgoubiFromSnaprampCmd’, ’AgsZgoubiModel’ and ’AgsModelViewer’, with the latter two essentially interfaces to the former which is the actual model ’engine’. All three commands are availablemore » from the controls system application launcher in the AGS ’StartUp’ menu, or from eponymous commands on shell terminals. Main aspects of the model and of its operation are presented in this technical note, brief excerpts from various studies performed so far are given for illustration, means and methods entering in ZgoubiFromSnaprampCmd are developed further in appendix.« less

Ultrasound-accelerated synthesis of biphenyl compounds using novel Pd(0) nanoparticles immobilized on bio-composite.

PubMed

Baran, Talat

2018-07-01

This study describes (i) an eco-friendly approach for design of Pd(0) nanoparticles on a natural composite, which is composed of carboxymethyl cellulose/agar polysaccharides (CMC/AG), without using any toxic reducing agents and (ii) development of ultrasound assisted simple protocol for synthesis of biphenyl compounds. Chemical characterization studies of Pd(0) nanoparticles (Pd NPs@CMC/AG) revealed that size of the particles were in the range of 37-55 nm. Catalytic performance of Pd NPs@CMC/AG was evaluated in synthesis of various biphenyl compounds by using the ultrasound-assisted method that was developed in this study. Pd NPs@CMC/AG exhibited excellent catalytic performance by producing high reaction yields. In addition, Pd NPs@CMC/AG was successfully used up to six reaction cycles without losing its catalytic activity, indicating high reproducibility of Pd NPs@CMC/AG. Additionally, compared to conventional the methods, new ultrasound-assisted synthesis technique that was followed in this study exhibited some advantages such as shorter reaction time, greener reaction conditions, higher yields and easier work-up. Copyright © 2018 Elsevier B.V. All rights reserved.

Nanosized silver (II) pyridoxine complex to cause greater inflammatory response and less cytotoxicity to RAW264.7 macrophage cells

NASA Astrophysics Data System (ADS)

Paul, Avijit; Ju, Hee; Rangasamy, Sabarinathan; Shim, Yumi; Song, Joon Myong

2015-03-01

With advancements in nanotechnology, silver has been engineered into a nanometre size and has attracted great research interest for use in the treatment of wounds. Silver nanoparticles (AgNPs) have emerged as a potential alternative to conventional antibiotics because of their potential antimicrobial property. However, AgNPs also induce cytotoxicity, generate reactive oxygen species (ROS), and cause mitochondrial damage to human cells. Pyridoxine possesses antioxidant and cell proliferation activity. Therefore, in the present investigation, a nanosilver-pyridoxine complex (AgPyNP) was synthesized, and its cytotoxicity and immune response was compared with AgNPs in macrophage RAW264.7 cells. Results revealed that AgPyNPs showed less cytotoxicity compared with AgNPs by producing a smaller amount of ROS in RAW264.7 cells. Surprisingly, however, AgPyNPs caused macrophage RAW264.7 cells to secrete a larger amount of interleukin-8 (IL-8) and generate a more active inflammatory response compared to AgNPs. It activated TNF-α, NF-κB p65, and NF-κB p50 to generate a more vigorous immune protection that produces a greater amount of IL-8 compared to AgNPs. Overall findings indicate that AgPyNPs exhibited less cytotoxicity and evoked a greater immune response in macrophage RAW264.7 cells. Thus, it can be used as a better wound-healing agent than AgNPs.

Thermal and chemical decomposition of di(pyrazine)silver(II) peroxydisulfate and unusual crystal structure of a Ag(I) by-product.

PubMed

Leszczyński, Piotr J; Budzianowski, Armand; Dobrzycki, Lukasz; Cyrański, Michał K; Derzsi, Mariana; Grochala, Wojciech

2012-01-14

High purity samples of a [Ag(pyrazine)(2)]S(2)O(8) complex were obtained using modified synthetic pathways. Di(pyrazine)silver(II) peroxydisulfate is sensitive to moisture forming [Ag(pyrazine)(2)](S(2)O(8))(H(2)O) hydrate which degrades over time yielding HSO(4)(-) derivatives and releasing oxygen. One polymorphic form of pyrazinium hydrogensulfate, β-(pyrazineH(+))(HSO(4)(-)), is found among the products of chemical decomposition together with unique [Ag(i)(pyrazine)](5)(H(2)O)(2)(HSO(4))(2)[H(SO(4))(2)]. Chemical degradation of [Ag(pyrazine)(2)]S(2)O(8) in the presence of trace amounts of moisture can explain the very low yield of wet synthesis (11-15%). Attempts have failed to obtain a mixed valence Ag(II)/Ag(I) pyrazine complex via partial chemical reduction of the [Ag(pyrazine)(2)]S(2)O(8) precursor with a variety of inorganic and organic reducing agents, or via controlled thermal decomposition. Thermal degradation of [Ag(pyrazine)(2)]S(2)O(8) containing occluded water proceeds at T > 90 °C via evolution of O(2); simultaneous release of pyrazine and SO(3) is observed during the next stages of thermal decomposition (120-285 °C), while Ag(2)SO(4) and Ag are obtained upon heating to 400-450 °C.

Artificial gravity considerations for a mars exploration mission

NASA Technical Reports Server (NTRS)

Young, L. R.

1999-01-01

Artificial gravity (AG), as a means of preventing physiological deconditioning of astronauts during long-duration space flights, presents certain special challenges to the otolith organs and the adaptive capabilities of the CNS. The key issues regarding the choice of AG acceleration, radius, and rotation rate are reviewed from the viewpoints of physiological requirements and human factors disturbances. Head movements and resultant Coriolis forces on the rotating platform may limit the usefulness of economical short centrifuges for other than brief periods of intermittent stimulation.

Accelerated Modeling and New Ferroelectric Materials for Naval SONAR

DTIC Science & Technology

2004-06-01

AN other platforms was achieved. As expected, proper into BZ leads to a development of small polarization, vectorization and optimal memory usage were...polarization is due to a combination code was fully vectorized , a speed-up of 9.2 times over of large Ag off-centering and small displacements by the Pentium 4... Xeon and 6.6 times over the SGI 03K was other cations. The large Ag displacements are due to a achieved. We are currently using the X1 in production

NASA's Agricultural Program: A USDA/Grower Partnership

NASA Technical Reports Server (NTRS)

McKellip, Rodney; Thomas, Michael

2002-01-01

Ag20/20 is a partnership between USDA, NASA, and four national commodity associations. It is driven by the information needs of U.S. farmers. Ag20/20 is focused on utilization of earth science and remote sensing for decision-making and oriented toward economically viable operational solutions. Its purpose is to accelerate the use of remote sensing and other geospatial technologies on the farm to: 1) Increase the production efficiency of the American farmer; 2) Reduce crop production risks; 3) Improve environmental stewardship tools for agricultural production.

THE BIOLOGICAL ACTIVITY OF SOLUBLE ANTIGEN-ANTIBODY COMPLEXES

PubMed Central

Ishizaka, Kimishige; Ishizaka, Teruko; Campbell, Dan H.

1959-01-01

Soluble BSA-anti-BSA complexes, formed in antigen excess, give immediate skin reactions in normal guinea pigs. The mechanism of the reaction is not that of passive or reversed passive anaphylaxis. The complex itself is toxic. Skin activity of the complex depends on its composition. It has become obvious that the complex composed of two antigen molecules and one antibody molecule, (Ag2Ab), does not have the activity, whereas, Ag3Ab2 and more complicated complexes do. The role of complement as well as speculation on the structural changes of antibody-antigen complexes is presented. PMID:13620844

Fermilab | Tevatron | Accelerator

Science.gov Websites

Leading accelerator technology Accelerator complex Illinois Accelerator Research Center Fermilab temperature. They were used to transfer particles from one part of the Fermilab accelerator complex to another center ring of Fermilab's accelerator complex. Before the Tevatron shut down, it had three primary

Enhancement of plasmon-induced charge separation efficiency by coupling silver nanocubes with a thin gold film

NASA Astrophysics Data System (ADS)

Akiyoshi, Kazutaka; Saito, Koichiro; Tatsuma, Tetsu

2016-10-01

Plasmon-induced charge separation (PICS), in which an energetic electron is injected from a plasmonic nanoparticle (NP) to a semiconductor on contact, is often inhibited by a protecting agent adsorbed on the NP. We addressed this issue for an Ag nanocube-TiO2 system by coating it with a thin Au layer or by inserting the Au layer between the nanocubes (NCs) and TiO2. Both of the electrodes exhibit much higher photocurrents due to PICS than the electrodes without the Au film or the Ag NCs. These photocurrent enhancements can be explained in terms of PICS with accelerated electron transfer, in which electron injection from the Ag NCs or Ag@Au core-shell NCs to TiO2 is promoted by the Au film, or PICS enhanced by a nanoantenna effect, in which the electron injection from the Au film to TiO2 is enhanced by optical near field generated by the Ag NC.

Spectroscopic and phosphorescent modulation in triphosphine-supported PtAg2 heterotrinuclear alkynyl complexes.

PubMed

Zhang, Li-Yi; Xu, Liang-Jin; Zhang, Xu; Wang, Jin-Yun; Li, Jia; Chen, Zhong-Ning

2013-05-06

A series of highly phosphorescent PtAg2 heterotrinuclear alkynyl complexes with bis(diphenylphosphinomethyl)phenylphosphine (dpmp) were prepared and characterized structurally. The solution phosphorescence with various emitting colors is systematically modulated by modifying substituents as well as π-conjugated systems in aromatic acetylides. The crystals, powders, or films exhibit reversible stimuli-responsive phosphorescence changes upon exposure to vapor of MeCN, pyridine, DMF, etc., resulting from perturbation of d(8)-d(10) metallophilic interaction in the excited states as a consequence of the formation/disruption of Ag-solvent bonds. Both experimental and time-dependent density functional theory (TD-DFT) studies demonstrate that d(8)-d(10) metallophilic interaction exerts a crucial role on phosphorescent characteristics due to the PtAg2 cluster-based (3)[d → p] state. This study affords a paradigm for phosphorescence modulation in d(8)-d(10) heteronuclear complexes.

Coinage metal complexes of 2-diphenylphosphino-3-methylindole.

PubMed

Koshevoy, Igor O; Shakirova, Julia R; Melnikov, Alexei S; Haukka, Matti; Tunik, Sergey P; Pakkanen, Tapani A

2011-08-21

Coordination of P,N indolyl-phosphine ligands to Au(I), Ag(I) and Cu(I) metal ions under weakly basic conditions results in easy deprotonation of the indolyl N-H function and effective formation of a family of homo- and heterobimetallic complexes MM'(PPh(2)C(9)H(7)N)(2) (M = M' = Au (2), Ag (5); M = Au, M' = Cu (3), Ag (4)). The latter (4) exists as an inseparable mixture of four different complexes, which are in equilibrium driven by slow dynamics. The reaction of silver(I) and copper(I) ions with PPh(2)(C(9)H(8)N) affords a rare tetranuclear Z-shaped cluster Ag(2)Cu(2)(PPh(2)C(9)H(7)N)(4) (6), which exhibits red luminescence in solid state (650 nm) and a weak dual emission in solution with the main component in the near-IR region (746 nm). This journal is © The Royal Society of Chemistry 2011

Comparative toxicity of silver nanoparticles and silver ions to Escherichia coli.

PubMed

Choi, Yoojin; Kim, Hyun-A; Kim, Kyoung-Woong; Lee, Byung-Tae

2018-04-01

With the increase in silver (Ag)-based products in our lives, it is essential to test the potential toxicity of silver nanoparticles (AgNPs) and silver ions (Ag ions) on living organisms under various conditions. Here, we investigated the toxicity of AgNPs with Ag ions to Escherichia coli K-12 strain under various conditions. We observed that both AgNPs and Ag ions display antibacterial activities, and that Ag ions had higher toxicity to E. coli K-12 strain than AgNPs under the same concentrations. To understand the toxicity of AgNPs at a cellular level, reactive oxygen species (ROS) enzymes were detected for use as antioxidant enzymatic biomarkers. We have also studied the toxicity of AgNPs and Ag ions under various coexistence conditions including: fixed total concentration, with a varied the ratio of AgNPs to Ag ions; fixed the AgNPs concentration and then increased the Ag ions concentration; fixed Ag ions concentration and then increasing the AgNPs concentration. Exposure to AgNPs and Ag ions clearly had synergistic toxicity; however, decreased toxicity (for a fixed AgNPs concentration of 5mg/L, after increasing the Ag ions concentration) to E. coli K-12 strain. AgNPs and Ag ions in the presence of L-cysteine accelerated the bacterial cell growth rate, thereby reducing the bioavailability of Ag ions released from AgNPs under the single and coexistence conditions. Further works are needed to consider this potential for AgNPs and Ag ions toxicity across a range of environmental conditions. As silver nanoparticles (AgNPs)-based products are being broadly used in commercial industries, an ecotoxicological understanding of the AgNPs being released into the environment should be further considered. Here, we investigate the comparative toxicity of AgNPs and silver ions (Ag ions) to Escherichia coli K-12 strain, a representative ecotoxicological bioreporter. This study showed that toxicities of AgNPs and Ag ions to E. coli K-12 strain display different relationships when existing individually or when coexisting, and in the presence of L-cysteine materials. These findings suggest that the toxicology research of nanomaterials should consider conditions when NPs coexist with and without their bioavailable ions. Copyright © 2017. Published by Elsevier B.V.

Novel types of tetra-, hexa-, octa-, and dodecanuclear silver clusters containing (2,7-Di-tert-butylfluoren-9-ylidene)methanedithiolate.

PubMed

Vicente, José; González-Herrero, Pablo; García-Sánchez, Yolanda; Jones, Peter G

2009-03-02

The reaction of AgClO(4) with piperidinium 2,7-di-tert-butyl-9H-fluorene-9-carbodithioate (pipH)[S(2)C(t-Bu-Hfy)] (1) (t-Bu-Hfy = 2,7-di-tert-butylfluoren-9-yl) afforded [Ag(n){S(2)C(t-Bu-Hfy)}(n)] (2), which reacted with phosphines to give [Ag{S(2)C(t-Bu-Hfy)}L(2)] [L = PPh(3) (3a); L(2) = bis(diphenylphosphino)ethane (dppe, 3b), 1,1'-bis(diphenylphosphino)ferrocene (dppf, 3c). By reacting complex 2 with AgClO(4) and piperidine in a 1:1:1 molar ratio, the dodecanuclear cluster [Ag(12){S(2)C(t-Bu-fy)}(6)] (4) (t-Bu-fy = 2,7-di-tert-butylfluoren-9-ylidene) was obtained. Compound 4 can also be directly prepared from the reaction of 1 with AgClO(4) and piperidine in a 1:2:1 molar ratio. The reactions of 1 with AgClO(4), phosphines, and piperidine afforded the compounds [Ag(6){S(2)C(t-Bu-fy)}(3)L(5)] [1:2:2:1 molar ratio; L = PPh(3) (5a), P(p-To)(3) (5b)], [Ag(4){S(2)C(t-Bu-fy)}(2)(dppf)(2)] (6) (1:2:1:1 molar ratio), [Ag(n){S(2)C(t-Bu-fy)}(n/2){P(i-Pr)(3)}(n)] (7) (1:2:2:1 molar ratio), or [Ag(8){S(2)C(t-Bu-fy)}(4){P(i-Pr)(3)}(4)] (8) (1:2:1:1 molar ratio). Complexes 5a,b, 6, 7, and 8 can be also obtained by reacting 4 with the corresponding phosphine in the appropriate molar ratio. The crystal structures of 4, 5b, and 8 have been determined by X-ray diffraction studies. The nuclearity of complex 6 was established from its (31)P{(1)H} NMR data, which reveal a very fast dynamic process leading to an average coupling of each of the P atoms of the dppf ligands with four Ag atoms.

A Hexahomotrioxacalix[3]arene-Based Ditopic Receptor for Alkylammonium Ions Controlled by Ag + Ions

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

Jiang, Xue-Kai; Ikejiri, Yusuke; Wu, Chong

A receptor cone-1 based on a hexahomotrioxacalix[3]arene bearing three pyridyl groups was successfully synthesized, which has a C 3-symmetric conformation and is capable of binding alkylammonium and metal ions simultaneously in a cooperative fashion. It can bind alkylammonium ions through the π-cavity formed by three aryl rings. This behaviour is consistent with the cone-in/cone-out conformational rearrangement needed to reorganize the cavity for endo-complexation. As a C 3-symmetrical pyridyl-substituted calixarene, receptor cone-1 can also bind an Ag + ion, and the nitrogen atoms are turned towards the inside of the cavity and interact with Ag +. After complexation of tris(2-pyridylamide) derivativemore » receptor cone-1 with Ag +, the original C 3-symmetry was retained and higher complexation selectivity for n-BuNH 3 + versus t-BuNH 3 + was observed. Thus, it is believed that this receptor will have a role to play in the sensing, detection, and recognition of Ag + and n-BuNH 3 + ions.« less

A Hexahomotrioxacalix[3]arene-Based Ditopic Receptor for Alkylammonium Ions Controlled by Ag + Ions

DOE PAGES

Jiang, Xue-Kai; Ikejiri, Yusuke; Wu, Chong; ...

2018-02-21

A receptor cone-1 based on a hexahomotrioxacalix[3]arene bearing three pyridyl groups was successfully synthesized, which has a C 3-symmetric conformation and is capable of binding alkylammonium and metal ions simultaneously in a cooperative fashion. It can bind alkylammonium ions through the π-cavity formed by three aryl rings. This behaviour is consistent with the cone-in/cone-out conformational rearrangement needed to reorganize the cavity for endo-complexation. As a C 3-symmetrical pyridyl-substituted calixarene, receptor cone-1 can also bind an Ag + ion, and the nitrogen atoms are turned towards the inside of the cavity and interact with Ag +. After complexation of tris(2-pyridylamide) derivativemore » receptor cone-1 with Ag +, the original C 3-symmetry was retained and higher complexation selectivity for n-BuNH 3 + versus t-BuNH 3 + was observed. Thus, it is believed that this receptor will have a role to play in the sensing, detection, and recognition of Ag + and n-BuNH 3 + ions.« less

Spectroscopic exploration of interaction between PEG-functionalized Ag2S nanoparticles with bovine serum albumin

NASA Astrophysics Data System (ADS)

Prasanth, S.; RitheshRaj, D.; Vineeshkumar, T. V.; Sudarsanakumar, C.

2018-05-01

The introduction of nanoparticles into biological fluids often leads to the formation of biocorona over the surface of nanoparticles. For the effective use of nanoparticles in biological applications it is very essential to understand their interactions with proteins. Herein, we investigated the interactions of Poly ethylene glycol capped Ag2S nanoparticles with Bovine Serum Albumin by spectroscopic techniques. By the addition of Ag2S nanoparticles, a ground state complex is formed. The CD spectroscopy reveals that the secondary structure of BSA is altered by complexation with PEG-Ag2S nanoparticles, while the overall tertiary structure remains closer to that of native BSA.

Strategies for the Construction of Supramolecular Dimers versus Homoleptic 1D Coordination Polymers Starting from the Diphosphorus [Cp2Mo2(CO)4(η2‐P2)] Complex and Silver(I) Salts

PubMed Central

Elsayed Moussa, Mehdi; Fleischmann, Martin; Peresypkina, Eugenia V.; Dütsch, Luis; Seidl, Michael; Balázs, Gabor

2017-01-01

The reactions of the tetrahedral diphosphorus [Cp2Mo2(CO)4(η2‐P2)] (1; Cp = C5H5) complex with Ag[Al{OC(CF3)3}4] (AgTEF) (A) and Ag[FAl{OC(C6F5)(C6F10)}3] (AgFAl) (B) were studied. The first reaction led to the formation of the [Ag2(η2‐1)2(η1:η1‐1)2][TEF]2 (2) dimer and the [Ag2(η1:η1‐1)3]n[TEF]2n (3) coordination polymer, whereas the second reaction afforded the [Ag2(η1:η1‐1)2(η1‐CH2Cl2)2(η2‐C7H8)2][FAl]2 (4) or the [Ag2(η2‐1)2(η1:η1‐1)2][FAl]2 (5) dimer and the [Ag2(η1:η1‐1)4]n[FAl]2n (6) coordination polymer. In each case, the products obtained depended on the ratio of the reactants and/or the synthetic procedure. PMID:28943780

Aptamer and 5-fluorouracil dual-loading Ag2S quantum dots used as a sensitive label-free probe for near-infrared photoluminescence turn-on detection of CA125 antigen.

PubMed

Jin, Hui; Gui, Rijun; Gong, Jun; Huang, Wenxue

2017-06-15

In this article, Ag 2 S quantum dots (QDs) were prepared by a facile aqueous synthesis method, using thiourea as a new sulfur precursor. Based on electrostatic interactions, 5-fluorouracil (5-Fu) was combined with the aptamer of CA125 antigen to fabricate aptamer/5-Fu complex. The surface of as-prepared Ag 2 S QDs was modified with polyethylenimine, followed by combination with the aptamer/5-Fu complex to form Ag 2 S QDs/aptamer/5-Fu hybrids. During the combination of Ag 2 S QDs with aptamer/5-Fu complex, near-infrared (NIR) photoluminescence (PL) of QDs (peaked at 850nm) was markedly reduced under excitation at 625nm, attributed to photo-induced electron transfer from QDs to 5-Fu. However, the addition of CA125 induced obvious NIR PL recovery, which was ascribed to the strong binding affinity of CA125 with its aptamer, and the separation of aptamer/5-Fu complex from the surface of QDs. Hence, the Ag 2 S QDs/aptamer/5-Fu hybrids were developed as a novel NIR PL turn-on probe of CA125. In the concentration range of [CA125] from 0.1 to 10 6 ngmL -1 , there were a good linear relationship between NIR PL intensities of Ag 2 S QDs and Log[CA125], and a low limit of detection of 0.07ngmL -1 . Experimental results revealed the highly selective and sensitive NIR PL responses of this probe to CA125, over other potential interferences. In real human body fluids, this probe also exhibited superior analytical performance, together with high detection recoveries. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis, characterization and DFT studies of two new silver(I) complexes with 3,4-lutidine

NASA Astrophysics Data System (ADS)

Soliman, Saied M.; Assem, Rania; Abu-Youssef, Morsy A. M.; Kassem, Taher S.

2015-04-01

The synthesis, characterization and molecular structure of two new Ag(I) complexes with 3,4-lutidine (34lut) have been reported. The [Ag(34lut)3(OAC)]; 1 and [Ag(34lut)2(TFA)]; 2 complexes, where OAC and TFA are acetate and trifluoroacetate respectively, have been characterized using elemental analysis, FTIR, NMR and mass spectra. Their molecular structures were calculated using DFT quantum chemical calculations. Both 1 and 2 were found to have distorted tetrahedral geometry around the Ag(I). The spectroscopic properties of the studied complexes have been calculated using the same level of theory. The Infrared vibrational frequencies of the COO stretches confirmed that the OAC is monodentate in 1 while the TFA is bidentate in 2. The calculated polarizability (α0) and HOMO-LUMO energy gap (ΔE) values indicated that 1 has higher NLO activity than 2. The electronic spectra of these complexes are calculated using the TD-DFT calculations. The calculated 1H NMR chemical shift values using GIAO approach showed good correlations with the experimental data. The interaction energies using the second order perturbation theory have been used to study the different intramolecular charge transfer interactions in the studied complexes. The NBO calculations indicated that both the Agsbnd O bonds are almost identical in 2 but not in 1.

Evidence for complete epistasis of null mutations in murine Fanconi anemia genes Fanca and Fancg.

PubMed

van de Vrugt, Henri J; Koomen, Mireille; Bakker, Sietske; Berns, Mariska A D; Cheng, Ngan Ching; van der Valk, Martin A; de Vries, Yne; Rooimans, Martin A; Oostra, Anneke B; Hoatlin, Maureen E; Te Riele, Hein; Joenje, Hans; Arwert, Fré

2011-12-10

Fanconi anemia (FA) is a heritable disease characterized by bone marrow failure, congenital abnormalities, and cancer predisposition. The 15 identified FA genes operate in a molecular pathway to preserve genomic integrity. Within this pathway the FA core complex operates as an ubiquitin ligase that activates the complex of FANCD2 and FANCI to coordinate DNA repair. The FA core complex is formed by at least 12 proteins. However, only the FANCL subunit displays ubiquitin ligase activity. FANCA and FANCG are members of the FA core complex for which no other functions have been described than to participate in protein interactions. In this study we generated mice with combined null alleles for Fanca and Fancg to identify extended functions for these genes by characterizing the double mutant mice and cells. Double mutant a(-/-)/g(-/-) mice were born at near Mendelian frequencies without apparent developmental abnormalities. Histological analysis of a(-/-)/g(-/-) mice revealed a Leydig cell hyperplasia and frequent vacuolization of Sertoli cells in testes, while ovaries were depleted from developing follicles and displayed an interstitial cell hyperplasia. These gonadal aberrations were associated with a compromised fertility of a(-/-)/g(-/-) males and females. During the first year of life a(-/-)/g(-/-) did not develop malignancies or bone marrow failure. At the cellular level a(-/-)/g(-/-), Fanca(-/-), and Fancg(-/-) cells proved equally compromised in DNA crosslink and homology-directed repair. Overall the phenotype of a(-/-)/g(-/-) double knockout mice and cells appeared highly similar to the phenotype of Fanca or Fancg single knockouts. The lack of an augmented phenotype suggest that null mutations in Fanca or Fancg are fully epistatic, making additional important functions outside of the FA core complex highly unlikely. 2011 Elsevier B.V. All rights reserved.

Brookhaven highlights, October 1978-September 1979. [October 1978 to September 1979

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

Not Available

1979-01-01

These highlights present an overview of the major research and development achievements at Brookhaven National Laboratory from October 1978 to September 1979. Specific areas covered include: accelerator and high energy physics programs; high energy physics research; the AGS and improvements to the AGS; neutral beam development; heavy ion fusion; superconducting power cables; ISABELLE storage rings; the BNL Tandem accelerator; heavy ion experiments at the Tandem; the High Flux Beam Reactor; medium energy physics; nuclear theory; atomic and applied physics; solid state physics; neutron scattering studies; x-ray scattering studies; solid state theory; defects and disorder in solids; surface physics; the Nationalmore » Synchrotron Light Source ; Chemistry Department; Biology Department; Medical Department; energy sciences; environmental sciences; energy technology programs; National Center for Analysis of Energy Systems; advanced reactor systems; nuclear safety; National Nuclear Data Center; nuclear materials safeguards; Applied Mathematics Department; and support activities. (GHT)« less

On-the-fly transition search and applications to temperature-accelerated dynamics

NASA Astrophysics Data System (ADS)

Shim, Yunsic; Amar, Jacques

2015-03-01

Temperature-accelerated dynamics (TAD) is a powerful method to study non-equilibrium processes and has been providing surprising insights for a variety of systems. While serial TAD simulations have been limited by the roughly N3 increase in the computational cost as a function of the number of atoms N in the system, recently we have shown that by carrying out parallel TAD simulations which combine spatial decomposition with our semi-rigorous synchronous sublattice algorithm, significantly improved scaling is possible. However, in this approach the size of activated events is limited by the processor size while the dynamics is not exact. Here we discuss progress in improving the scaling of serial TAD by combining the use of on-the-fly transition searching with our previously developed localized saddle-point method. We demonstrate improved performance for the cases of Ag/Ag(100) annealing and Cu/Cu(100) growth. Supported by NSF DMR-1410840.

A novel biliary stent coated with silver nanoparticles prolongs the unobstructed period and survival via anti-bacterial activity

PubMed Central

Yang, Fuchun; Ren, Zhigang; Chai, Qinming; Cui, Guangying; Jiang, Li; Chen, Hanjian; Feng, Zhiying; Chen, Xinhua; Ji, Jian; Zhou, Lin; Wang, Weilin; Zheng, Shusen

2016-01-01

Symptomatic biliary stricture causes life-threatening complications, such as jaundice, recurrent cholangitis and secondary biliary cirrhosis. Fully covered self-expanding metal stents (FCSEMSs) are gaining acceptance for treatments of benign biliary stricture and palliative management of malignant biliary obstructions. However, the high rate of FCSEMS obstruction limits their clinic use. In this study, we developed a novel biliary stent coated with silver nanoparticles (AgNPs) and investigated its efficacy both in vitro and in vivo. We first identified properties of the AgNP complex using ultraviolet detection. The AgNP complex was stable without AgNP agglomeration, and Ag abundance was correspondingly increased with an increased bilayer number. The AgNP biliary stent demonstrated good performance in the spin-assembly method based on topographic observation. The AgNP biliary stent also exhibited a long-term anti-coagulation effect and a slow process of Ag+ release. In vitro anti-bacteria experiments indicated that the AgNP biliary stent exhibited high-efficiency anti-bacterial activity for both short- and long-term periods. Importantly, application of the AgNP biliary stent significantly prolonged the unobstructed period of the biliary system and improved survival in preclinical studies as a result of its anti-microbial activity and decreased granular tissue formation on the surface of the anastomotic biliary, providing a novel and effective treatment strategy for symptomatic biliary strictures. PMID:26883081

Effect of toxicity of Ag nanoparticles on SERS spectral variance of bacteria

NASA Astrophysics Data System (ADS)

Cui, Li; Chen, Shaode; Zhang, Kaisong

2015-02-01

Ag nanoparticles (NPs) have been extensively utilized in surface-enhanced Raman scattering (SERS) spectroscopy for bacterial identification. However, Ag NPs are toxic to bacteria. Whether such toxicity can affect SERS features of bacteria and interfere with bacterial identification is still unknown and needed to explore. Here, by carrying out a comparative study on non-toxic Au NPs with that on toxic Ag NPs, we investigated the influence of nanoparticle concentration and incubation time on bacterial SERS spectral variance, both of which were demonstrated to be closely related to the toxicity of Ag NPs. Sensitive spectral alterations were observed on Ag NPs with increase of NPs concentration or incubation time, accompanied with an obvious decrease in number of viable bacteria. In contrast, SERS spectra and viable bacterial number on Au NPs were rather constant under the same conditions. A further analysis on spectral changes demonstrated that it was cell response (i.e. metabolic activity or death) to the toxicity of Ag NPs causing spectral variance. However, biochemical responses to the toxicity of Ag were very different in different bacteria, indicating the complex toxic mechanism of Ag NPs. Ag NPs are toxic to a great variety of organisms, including bacteria, fungi, algae, protozoa etc., therefore, this work will be helpful in guiding the future application of SERS technique in various complex biological systems.

HBeAg-induced miR-106b promotes cell growth by targeting the retinoblastoma gene.

PubMed

Samal, Jasmine; Kandpal, Manish; Vivekanandan, Perumal

2017-10-30

Chronic HBV infection is a major cause of hepatocellular carcinoma (HCC). The association between hepatitis B "e" antigen (HBeAg) and HCC is well-established by epidemiological studies. Nonetheless, the biological role of HBeAg in HCC remains enigmatic. We investigate the role of HBeAg in HBV-related HCC. Our findings suggest that HBeAg enhances cell proliferation and accelerates progression from G0/G1 phase to the S phase of the cell cycle in Huh7 cells. Examination of host gene expression and miRNA expression profiles reveals a total of 21 host genes and 12 host miRNAs that were differentially regulated in cells expressing HBeAg. Importantly, HBeAg induced the expression of miR-106b, an oncogenic miRNA. Interestingly, HBeAg-expression results in a significant reduction in the expression of retinoblastoma (Rb) gene, an experimentally validated target of miR-106b. Inhibition of miR-106b significantly increased the expression of the Rb gene, resulting in reduced cell proliferation and slowing of cell cycle progression from the G0/G1 phase to S phase. These observations suggest that the up-regulation of miR-106b by HBeAg contributes to the pathogenesis of HBV-related HCC by down-regulating the Rb gene. Our results highlight a role for HBeAg in HCC and provide a novel perspective on the molecular mechanisms underlying HBV-related HCC.

Environment-resistive coating for the thin-film-based superconducting fault-current limiter Ag/Au-Ag/YBa 2Cu 3O 7/CeO 2/Al 2O 3

NASA Astrophysics Data System (ADS)

Matsui, H.; Kondo, W.; Tsukada, K.; Sohma, M.; Yamaguchi, I.; Kumagai, T.; Manabe, T.; Arai, K.; Yamasaki, H.

2010-02-01

We have studied environment-resistive coatings (ERC) for the thin-film-based superconducting fault-current limiter (SFCL) Ag/Au-Ag/YBa 2Cu 3O 7/CeO 2/Al 2O 3. We evaluated nine candidate ERC materials by two accelerating-environment tests, and revealed that the shellac- and the fluorine-resin have a high environmental resistance. Especially, the shellac resin almost completely protected Jc of an element exposed to 60 °C saturated water vapor for 2 h (3.4->3.2 MA/cm 2). We also performed a practical operation test of SFCL using an element half covered by shellac, and found that the ERC does not diminish the current limiting properties similarly to the previous results of the Teflon-coated SFCL [1].

Colorimetric detection of trace copper ions based on catalytic leaching of silver-coated gold nanoparticles.

PubMed

Lou, Tingting; Chen, Lingxin; Chen, Zhaopeng; Wang, Yunqing; Chen, Ling; Li, Jinhua

2011-11-01

A colorimetric, label-free, and nonaggregation-based silver coated gold nanoparticles (Ag/Au NPs) probe has been developed for detection of trace Cu(2+) in aqueous solution, based on the fact that Cu(2+) can accelerate the leaching rate of Ag/Au NPs by thiosulfate (S(2)O(3)(2-)). The leaching of Ag/Au NPs would lead to dramatic decrease in the surface plasmon resonance (SPR) absorption as the size of Ag/Au NPs decreased. This colorimetric strategy based on size-dependence of nanoparticles during their leaching process provided a highly sensitive (1.0 nM) and selective detection toward Cu(2+), with a wide linear detection range (5-800 nM) over nearly 3 orders of magnitude. The cost-effective probe allows rapid and sensitive detection of trace Cu(2+) ions in water samples, indicating its potential applicability for the determination of copper in real samples.

Silver(I)-pyridinyl Schiff base complexes: Synthesis, characterisation and antimicrobial studies

NASA Astrophysics Data System (ADS)

Njogu, Eric M.; Omondi, Bernard; Nyamori, Vincent O.

2017-05-01

Fifteen new silver(I)-pyridinyl complexes of the general formula [AgL2]X, where X = ClO4-, OTf or NO3-, were synthesised by reacting (E)-N-(pyridinylmethylene)aniline ligands and the respective silver(I) salts namely AgClO4, AgOTf, or AgNO3. The ligands were obtained by neat grinding of 2- or 4-pyridincarboaxaldehyde together with aniline, 2,6-dimethylaniline or 2,6-diisopropylaniline. The obtained (E)-N-(pyridinylmethylene)aniline ligands were further reacted with respective silver(I) salts in a 2:1 ratio in anhydrous ethanol at room temperature under inert atmosphere using the Schlenk techniques. Chemical structures of complexes were identified by nuclear magnetic resonance, electrospray ionization mass spectrometry, elemental analysis, infrared spectroscopy and some by single-crystal X-ray diffraction analysis. Reactions involving the 2-pyridinyl derivatives resulted in cationic complexes in which two ligands chelate silver(I) centres through the pyridinyl N and imine N atoms, with the counter anion out of the coordination sphere. The 4-pyridinyl derivatives conversely gave complexes in which two ligands coordinate to the silver(I) centre through their pyridinyl N atoms only, most likely a linear fashion. The newly synthesised silver(I) complexes and the free ligands were evaluated for their in vitro antimicrobial activity against Escherichia coli, Salmonella typhimirium, Staphylococcus aureus and Candida albicans. The complexes showed varied growth inhibitory activity against the test organisms.

Silver sulfadoxinate: Synthesis, structural and spectroscopic characterizations, and preliminary antibacterial assays in vitro

NASA Astrophysics Data System (ADS)

Zanvettor, Nina T.; Abbehausen, Camilla; Lustri, Wilton R.; Cuin, Alexandre; Masciocchi, Norberto; Corbi, Pedro P.

2015-02-01

The sulfa drug sulfadoxine (SFX) reacted with Ag+ ions in aqueous solution, affording a new silver(I) complex (AgSFX), which was fully characterized by chemical, spectroscopic and structural methods. Elemental, ESI-TOF mass spectrometric and thermal analyses of AgSFX suggested a [Ag(C12H13N4O2S)] empirical formula. Infrared spectroscopic measurements indicated ligand coordination to Ag(I) through the nitrogen atoms of the (deprotonated) sulfonamide group and by the pyrimidine ring, as well as through oxygen atom(s) of the sulfonamide group. These hypotheses were corroborated by 13C and 15N SS-NMR spectroscopy and by an unconventional structural characterization based on X-ray powder diffraction data. The latter showed that AgSFX crystallizes as centrosymmetric dimers with a strong Ag⋯Ag interaction of 2.7435(6) Å, induced by the presence of exo-bidentate N,N‧ bridging ligands and the formation of an eight-membered ring of [AgNCN]2 sequence, nearly planar. Participation of oxygen atoms of the sulfonamide residues generates in the crystal a 1D coordination polymer, likely responsible for its very limited solubility in all common solvents. Besides the analytical, spectroscopic and structural description, the antibacterial properties of AgSFX were assayed using disc diffusion methods against Escherichia coli and Pseudomonas aeruginosa (Gram-negative), and Staphylococcus aureus (Gram-positive) bacterial strains. The AgSFX complex showed to be active against Gram-positive and Gram-negative bacterial strains, being comparable to the activities of silver sulfadiazine.

Multifunctional triblock co-polymer mP3/4HB-b-PEG-b-lPEI for efficient intracellular siRNA delivery and gene silencing.

PubMed

Zhou, Li; Chen, Zhifei; Wang, Feifei; Yang, Xiuqun; Zhang, Biliang

2013-04-01

A non-viral siRNA carrier composed of mono-methoxy-poly (3-hydroxybutyrate-co-4-hydroxybutyrate)-block-polyethylene glycol-block-linear polyethyleneimine (mP3/4HB-b-PEG-b-lPEI) was synthesized using 1800 Da linear polyethyleneimine and evaluated for siRNA delivery. Our study demonstrated that siRNA could be efficiently combined with mP3/4HB-b-PEG-b-lPEI (mAG) co-polymer and was protected from nuclease degradation. The combined siRNA were released from the complexes easily under heparin competition. The particle size of the mAG/siRNA complexes was 158 nm, with a ζ-potential of around 28 mV. Atomic force microscopy images displayed spherical and homogeneously distributed complexes. The mAG block co-polymer displayed low cytotoxicity and efficient cellular uptake of Cy3-siRNA in A549 cells by flow cytometry and confocal microscopy. In vitro transfection efficiency of the block co-polymer was assessed using siRNA against luciferase in cultured A549-Luc, HeLa-Luc, HLF-Luc, A375-Luc and MCF-7-Luc cells. A higher transfection efficiency and lower cytotoxicity was obtained by mAG block co-polymer in five cell lines. Furthermore, a remarkable improvement in luciferase gene silencing efficiency of the mAG complex (up to 90-95%) over that of Lipofectamine™ 2000 (70-82%) was observed in HLF-Luc and A375-Luc cells. Additionally, a mAG/p65-siRNA complex also showed a better capability than Lipofectamine™ 2000/p65-siRNA complex to drastically reduce the p65 mRNA level down to 10-16% in HeLa, U251 and HUVEC cells at an N/P ratio of 70. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Two-stage DNA compaction induced by silver ions suggests a cooperative binding mechanism

NASA Astrophysics Data System (ADS)

Jiang, Wen-Yan; Ran, Shi-Yong

2018-05-01

The interaction between silver ions and DNA plays an important role in the therapeutic use of silver ions and in related technologies such as DNA sensors. However, the underlying mechanism has not been fully understood. In this study, the dynamics of Ag+-DNA interaction at a single-molecule level was studied using magnetic tweezers. AgNO3 solutions with concentrations ranging from 1 μM to 20 μM led to a 1.4-1.8 μm decrease in length of a single λ-DNA molecule, indicating that Ag+ has a strong binding with DNA, causing the DNA conformational change. The compaction process comprises one linear declining stage and another sigmoid-shaped stage, which can be attributed to the interaction mechanism. Considering the cooperative effect, the sigmoid trend was well explained using a phenomenological model. By contrast, addition of silver nanoparticle solution induced no detectable transition of DNA. The dependence of the interaction on ionic strength and DNA concentration was examined via morphology characterization and particle size distribution measurement. The size of the Ag+-DNA complex decreased with an increase in Ag+ ionic strength ranging from 1 μM to 1 mM. Morphology characterization confirmed that silver ions induced DNA to adopt a compacted globular conformation. At a fixed [AgNO3]:[DNA base pairs] ratio, increasing DNA concentration led to increased sizes of the complexes. Intermolecular interaction is believed to affect the Ag+-DNA complex formation to a large extent.

Fluorescence enhancement of quercetin complexes by silver nanoparticles and its analytical application

NASA Astrophysics Data System (ADS)

Liu, Ping; Zhao, Liangliang; Wu, Xia; Huang, Fei; Wang, Minqin; Liu, Xiaodan

2014-03-01

It is found that the plasmon effect of silver nanoparticles (AgNPs) helps to enhance the fluorescence intensity of the quercetin (Qu) and nucleic acids system. Qu exhibited strong fluorescence enhancement when it bound to nucleic acids in the presence of AgNPs. Based on this, a sensitive method for the determination of nucleic acids was developed. The detection limits for the nucleic acids (S/N = 3) were reduced to the ng mL-1 level. The interaction mechanism of the AgNPs-fish sperm DNA (fsDNA)-Qu system was also investigated in this paper. This complex system of Qu and AgNPs was also successfully used for the detection of nucleic acids in agarose gel electrophoresis analysis. Preliminary results indicated that AgNPs also helped to improve sensitivity in the fluorescence image analysis of Qu combined with cellular contents in Arabidopsis thaliana protoplasts.

Mitochondrial electron transport is inhibited by disappearance of metallothionein in human bronchial epithelial cells following exposure to silver nitrate.

PubMed

Miyayama, Takamitsu; Arai, Yuta; Suzuki, Noriyuki; Hirano, Seishiro

2013-03-08

Silver (Ag) possesses antibacterial activity and has been used in wound dressings and deodorant powders worldwide. However, the metabolic behavior and biological roles of Ag in mammals have not been well characterized. In the present study, we exposed human bronchial epithelial cells (BEAS-2B) to AgNO3 and investigated uptake and intracellular distribution of Ag, expression of metallothionein (MT), generation of reactive oxygen species (ROS), and changes in mitochondrial respiration. The culture medium concentration of Ag decreased with time and stabilized at 12h. The concentration of both Ag and MT in the soluble cellular fraction increased up to 3h and then decreased, indicating that cytosolic Ag relocated to the insoluble fraction of the cells. The levels of mRNAs for the major human MT isoforms MT-I and MT-II paralleled with the protein levels of Ag-MT. The intensity of fluorescence derived from ROS was elevated in the mitochondrial region at 24h. Ag decreased mitochondrial oxygen consumption in a dose-dependent manner and the activity of mitochondrial complex I-IV enzymes was significantly inhibited following exposure to Ag. In a separate experiment, we found that hydrogen peroxide (H2O2) at concentrations as low as 0.001% (equivalent to the concentration of H2O2 in Ag-exposed cells) removed Ag from MT. These results suggest MT was decomposed by cytosolic H2O2, and then Ag released from MT relocated to insoluble cellular fractions and inhibited electron chain transfer of mitochondrial complexes, which eventually led to cell damage. Crown Copyright © 2013. Published by Elsevier Ireland Ltd. All rights reserved.

Direct evidence and enhancement of surface plasmon resonance effect on Ag-loaded TiO2 nanotube arrays for photocatalytic CO2 reduction

NASA Astrophysics Data System (ADS)

Low, Jingxiang; Qiu, Shuoqi; Xu, Difa; Jiang, Chuanjia; Cheng, Bei

2018-03-01

Surface plasmon resonance (SPR) effect has been utilized in many solar conversion applications because of its ability to convert visible photons into "hot electron" energy. However, the direct evidence and enhancement of this unique effect are still great challenges, limiting its practical applications. Here we present the direct evidence and enhancement of SPR effect using TiO2 nanotube arrays (TNTAs) loaded with Ag nanoparticles (NPs) as a proof-of-concept example. Particularly, electrochemical deposition method is applied to deposit Ag NPs into the inner space of TNTAs for enhancing SPR effect of Ag NPs, as demonstrated by Raman and light absorption spectroscopies. This enhanced SPR effect is because multi-scattered light within TNTAs can be effectively utilized by Ag NPs in the inner space of TNTAs. Moreover, combining synchronous-illumination X-ray photoelectron and electrochemical impedance spectroscopy characterization, we confirm that the SPR effect of Ag NPs can enhance photocatalytic performance of TNTAs mainly from two aspects: (i) injection of "hot electrons" from Ag NPs to TNTAs and (ii) acceleration of charge carrier migration on the TNTAs through a unique near field effect. The direct evidence and enhancement of SPR effect open new perspectives in design of functional plasmonic nanomaterials with high solar conversion efficiency.

Proceeding of the 1999 Particle Accelerator Conference. Volume 3

DTIC Science & Technology

1999-04-02

conditioning, a laser pulse was irradiated on a copper cath- ode and the photo-emitted beam was accelerated up to 2.9 MeV. An effective quantum...dipole magnet and a vacuum Nd:YAG laser pulse irradiation . As a result, the pumping unit. The gun cavity has two s-band cells made maximu ensergy andlthe...Optimizing beam intensity in the AGS involves a correctors at strategic locations are pulsed to minimize the compromise between conflicting needs to

Microwave-assisted hydrothermal synthesis of Ag₂(W(1-x)Mox)O₄ heterostructures: Nucleation of Ag, morphology, and photoluminescence properties.

PubMed

Silva, M D P; Gonçalves, R F; Nogueira, I C; Longo, V M; Mondoni, L; Moron, M G; Santana, Y V; Longo, E

2016-01-15

Ag2W(1-x)MoxO4 (x=0.0 and 0.50) powders were synthesized by the co-precipitation (drop-by-drop) method and processed using a microwave-assisted hydrothermal method. We report the real-time in situ formation and growth of Ag filaments on the Ag2W(1-x)MoxO4 crystals using an accelerated electron beam under high vacuum. Various techniques were used to evaluate the influence of the network-former substitution on the structural and optical properties, including photoluminescence (PL) emission, of these materials. X-ray diffraction results confirmed the phases obtained by the synthesis methods. Raman spectroscopy revealed significant changes in local order-disorder as a function of the network-former substitution. Field-emission scanning electron microscopy was used to determine the shape as well as dimensions of the Ag2W(1-x)MoxO4 heterostructures. The PL spectra showed that the PL-emission intensities of Ag2W(1-x)MoxO4 were greater than those of pure Ag2WO4, probably because of the increase of intermediary energy levels within the band gap of the Ag2W(1-x)MoxO4 heterostructures, as evidenced by the decrease in the band-gap values measured by ultraviolet-visible spectroscopy. Copyright © 2015 Elsevier B.V. All rights reserved.

Reaching extended length-scales with temperature-accelerated dynamics

NASA Astrophysics Data System (ADS)

Amar, Jacques G.; Shim, Yunsic

2013-03-01

In temperature-accelerated dynamics (TAD) a high-temperature molecular dynamics (MD) simulation is used to accelerate the search for the next low-temperature activated event. While TAD has been quite successful in extending the time-scales of simulations of non-equilibrium processes, due to the fact that the computational work scales approximately as the cube of the number of atoms, until recently only simulations of relatively small systems have been carried out. Recently, we have shown that by combining spatial decomposition with our synchronous sublattice algorithm, significantly improved scaling is possible. However, in this approach the size of activated events is limited by the processor size while the dynamics is not exact. Here we discuss progress in developing an alternate approach in which high-temperature parallel MD along with localized saddle-point (LSAD) calculations, are used to carry out TAD simulations without restricting the size of activated events while keeping the dynamics ``exact'' within the context of harmonic transition-state theory. In tests of our LSAD method applied to Ag/Ag(100) annealing and Cu/Cu(100) growth simulations we find significantly improved scaling of TAD, while maintaining a negligibly small error in the energy barriers. Supported by NSF DMR-0907399.

Characterisation of Antigen B Protein Species Present in the Hydatid Cyst Fluid of Echinococcus canadensis G7 Genotype

PubMed Central

Folle, Ana Maite; Kitano, Eduardo S.; Lima, Analía; Gil, Magdalena; Cucher, Marcela; Mourglia-Ettlin, Gustavo; Iwai, Leo K.; Rosenzvit, Mara; Batthyány, Carlos

2017-01-01

The larva of cestodes belonging to the Echinococcus granulosus sensu lato (s.l.) complex causes cystic echinococcosis (CE). It is a globally distributed zoonosis with significant economic and public health impact. The most immunogenic and specific Echinococcus-genus antigen for human CE diagnosis is antigen B (AgB), an abundant lipoprotein of the hydatid cyst fluid (HF). The AgB protein moiety (apolipoprotein) is encoded by five genes (AgB1-AgB5), which generate mature 8 kDa proteins (AgB8/1-AgB8/5). These genes seem to be differentially expressed among Echinococcus species. Since AgB immunogenicity lies on its protein moiety, differences in AgB expression within E. granulosus s.l. complex might have diagnostic and epidemiological relevance for discriminating the contribution of distinct species to human CE. Interestingly, AgB2 was proposed as a pseudogene in E. canadensis, which is the second most common cause of human CE, but proteomic studies for verifying it have not been performed yet. Herein, we analysed the protein and lipid composition of AgB obtained from fertile HF of swine origin (E. canadensis G7 genotype). AgB apolipoproteins were identified and quantified using mass spectrometry tools. Results showed that AgB8/1 was the major protein component, representing 71% of total AgB apolipoproteins, followed by AgB8/4 (15.5%), AgB8/3 (13.2%) and AgB8/5 (0.3%). AgB8/2 was not detected. As a methodological control, a parallel analysis detected all AgB apolipoproteins in bovine fertile HF (G1/3/5 genotypes). Overall, E. canadensis AgB comprised mostly AgB8/1 together with a heterogeneous mixture of lipids, and AgB8/2 was not detected despite using high sensitivity proteomic techniques. This endorses genomic data supporting that AgB2 behaves as a pseudogene in G7 genotype. Since recombinant AgB8/2 has been found to be diagnostically valuable for human CE, our findings indicate that its use as antigen in immunoassays could contribute to false negative results in areas where E. canadensis circulates. Furthermore, the presence of anti-AgB8/2 antibodies in serum may represent a useful parameter to rule out E. canadensis infection when human CE is diagnosed. PMID:28045899

Characterisation of Antigen B Protein Species Present in the Hydatid Cyst Fluid of Echinococcus canadensis G7 Genotype.

PubMed

Folle, Ana Maite; Kitano, Eduardo S; Lima, Analía; Gil, Magdalena; Cucher, Marcela; Mourglia-Ettlin, Gustavo; Iwai, Leo K; Rosenzvit, Mara; Batthyány, Carlos; Ferreira, Ana María

2017-01-01

The larva of cestodes belonging to the Echinococcus granulosus sensu lato (s.l.) complex causes cystic echinococcosis (CE). It is a globally distributed zoonosis with significant economic and public health impact. The most immunogenic and specific Echinococcus-genus antigen for human CE diagnosis is antigen B (AgB), an abundant lipoprotein of the hydatid cyst fluid (HF). The AgB protein moiety (apolipoprotein) is encoded by five genes (AgB1-AgB5), which generate mature 8 kDa proteins (AgB8/1-AgB8/5). These genes seem to be differentially expressed among Echinococcus species. Since AgB immunogenicity lies on its protein moiety, differences in AgB expression within E. granulosus s.l. complex might have diagnostic and epidemiological relevance for discriminating the contribution of distinct species to human CE. Interestingly, AgB2 was proposed as a pseudogene in E. canadensis, which is the second most common cause of human CE, but proteomic studies for verifying it have not been performed yet. Herein, we analysed the protein and lipid composition of AgB obtained from fertile HF of swine origin (E. canadensis G7 genotype). AgB apolipoproteins were identified and quantified using mass spectrometry tools. Results showed that AgB8/1 was the major protein component, representing 71% of total AgB apolipoproteins, followed by AgB8/4 (15.5%), AgB8/3 (13.2%) and AgB8/5 (0.3%). AgB8/2 was not detected. As a methodological control, a parallel analysis detected all AgB apolipoproteins in bovine fertile HF (G1/3/5 genotypes). Overall, E. canadensis AgB comprised mostly AgB8/1 together with a heterogeneous mixture of lipids, and AgB8/2 was not detected despite using high sensitivity proteomic techniques. This endorses genomic data supporting that AgB2 behaves as a pseudogene in G7 genotype. Since recombinant AgB8/2 has been found to be diagnostically valuable for human CE, our findings indicate that its use as antigen in immunoassays could contribute to false negative results in areas where E. canadensis circulates. Furthermore, the presence of anti-AgB8/2 antibodies in serum may represent a useful parameter to rule out E. canadensis infection when human CE is diagnosed.

A new antibacterial silver(I) complex incorporating 2,5-dimethylpyrazine and the anti-inflammatory diclofenac.

PubMed

Hamamci Alisir, Sevim; Dege, Necmi

2016-12-01

Ag I -containing coordination complexes have attracted attention because of their photoluminescence properties and antimicrobial activities and, in principle, these properties depend on the nature of the structural topologies. A novel two-dimensional silver(I) complex with the anti-inflammatory diclofenac molecule, namely bis{μ-2-[2-(2,6-dichloroanilino)phenyl]acetato-κ 3 O,O':O}bis(μ-2,5-dimethylpyrazine-κ 2 N:N')silver(I), [Ag 2 (C 14 H 10 Cl 2 NO 2 ) 2 (C 6 H 8 N 2 )] n , (I), has been synthesized and characterized by single-crystal X-ray diffraction, revealing that the Ag I ions are chelated by the carboxylate groups of the anionic 2-[2-(2,6-dichloroanilino)phenyl]acetate (dicl) ligand in a μ 3 -η 1 :η 2 coordination mode. Each dicl ligand links three Ag I atoms to generate a one-dimensional infinite chain. Adjacent chains are connected through 2,5-dimethylpyrazine (dmpyz) ligands to form a two-dimensional layer structure parallel to the crystallographic bc plane. The layers are further connected by C-H...π interactions to generate a three-dimensional supramolecular structure. Additionally, the most striking feature is that the structure contains an intramolecular C-H ...Ag anagostic interaction. Furthermore, the title complex has been tested for its in vitro antibacterial activity and is determined to be highly effective on the studied microorganisms.

Highly Selective Adsorption of Ethylene over Ethane in a MOF Featuring the Combination of Open Metal Site and -Complexation

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

Zhang, Yiming; Li, Baiyan; Wu, Zili

The introduction of the combination of open metal site (OMS) and -complexation into MOF has led to very high ethylene/ethane adsorption selectivity at 318K, as illustrated in the context of MIL-101-Cr-SO 3Ag. The interactions with ethylene from both OMS and -complexation in MIL-101-Cr-SO 3Ag have been investigated by in situ IR spectroscopic studies and computational calculations, which suggest -complexation contributes dominantly to the high ethylene/ethane adsorption selectivity.

Highly Selective Adsorption of Ethylene over Ethane in a MOF Featuring the Combination of Open Metal Site and -Complexation

DOE PAGES

Zhang, Yiming; Li, Baiyan; Wu, Zili; ...

2015-01-09

The introduction of the combination of open metal site (OMS) and -complexation into MOF has led to very high ethylene/ethane adsorption selectivity at 318K, as illustrated in the context of MIL-101-Cr-SO 3Ag. The interactions with ethylene from both OMS and -complexation in MIL-101-Cr-SO 3Ag have been investigated by in situ IR spectroscopic studies and computational calculations, which suggest -complexation contributes dominantly to the high ethylene/ethane adsorption selectivity.

Emotional Intelligence in Agenesis of the Corpus Callosum.

PubMed

Anderson, Luke B; Paul, Lynn K; Brown, Warren S

2017-05-01

People with agenesis of the corpus callosum (AgCC) with normal general intelligence have deficits in complex cognitive processing, as well as in social cognition. It is uncertain the extent to which impoverished processing of emotions may contribute to social processing deficiencies. We used the Mayer-Salovey-Caruso Emotional Intelligence Test to clarify the nature of emotional intelligence in 16 adults with AgCC. As hypothesized, persons with AgCC exhibited greater disparities from norms on tests involving more socially complex aspects of emotions. The AgCC group did not differ from norms on the Experiential subscale, but they were significantly below norms on the Strategic subscale. These findings suggest that the corpus callosum is not essential for experiencing and thinking about basic emotions in a "normal" way, but is necessary for more complex processes involving emotions in the context of social interactions. © The Author 2017. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Wound healing and antibacterial activities of chondroitin sulfate- and acharan sulfate-reduced silver nanoparticles

NASA Astrophysics Data System (ADS)

Im, A.-Rang; Kim, Jee Young; Kim, Hyun-Seok; Cho, Seonho; Park, Youmie; Kim, Yeong Shik

2013-10-01

For topical applications in wound healing, silver nanoparticles (AgNPs) have attracted much attention as antibacterial agents. Herein, we describe a green-synthetic route for the production of biocompatible and crystalline AgNPs using two glycosaminoglycans, chondroitin sulfate (CS) and acharan sulfate (AS), as reducing agents. The synthetic approach avoids the use of toxic chemicals, and the yield of AgNPs formation is found to be 98.1% and 91.1% for the chondroitin sulfate-reduced silver nanoparticles (CS-AgNPs) and the acharan sulfate-reduced silver nanoparticles (AS-AgNPs), respectively. Nanoparticles with mostly spherical and amorphous shapes were observed, with an average diameter of 6.16 ± 2.26 nm for CS-AgNPs and 5.79 ± 3.10 nm for AS-AgNPs. Images of the CS-AgNPs obtained from atomic force microscopy revealed the self-assembled structure of CS was similar to a densely packed woven mat with AgNPs sprinkled on the CS. These nanoparticles were stable under cell culture conditions without any noticeable aggregation. An approximately 128-fold enhancement of the antibacterial activities of the AgNPs was observed against Enterobacter cloacae and Escherichia coli when compared to CS and AS alone. In addition, an in vivo animal model of wound healing activity was tested using mice that were subjected to deep incision wounds. In comparison to the controls, the ointments containing CS-AgNPs and AS-AgNPs stimulated wound closure under histological examination and accelerated the deposition of granulation tissue and collagen in the wound area. The wound healing activity of the ointments containing CS-AgNPs and AS-AgNPs are comparable to that of a commercial formulation of silver sulfadiazine even though the newly prepared ointments contain a lower silver concentration. Therefore, the newly prepared AgNPs demonstrate potential for use as an attractive biocompatible nanocomposite for topical applications in the treatment of wounds.

Balancing Near-Field Enhancement, Absorption, and Scattering for Effective Antenna-Reactor Plasmonic Photocatalysis.

PubMed

Li, Kun; Hogan, Nathaniel J; Kale, Matthew J; Halas, Naomi J; Nordlander, Peter; Christopher, Phillip

2017-06-14

Efficient photocatalysis requires multifunctional materials that absorb photons and generate energetic charge carriers at catalytic active sites to facilitate a desired chemical reaction. Antenna-reactor complexes are an emerging multifunctional photocatalytic structure where the strong, localized near field of the plasmonic metal nanoparticle (e.g., Ag) is coupled to the catalytic properties of the nonplasmonic metal nanoparticle (e.g., Pt) to enable chemical transformations. With an eye toward sustainable solar driven photocatalysis, we investigate how the structure of antenna-reactor complexes governs their photocatalytic activity in the light-limited regime, where all photons need to be effectively utilized. By synthesizing core@shell/satellite (Ag@SiO 2 /Pt) antenna-reactor complexes with varying Ag nanoparticle diameters and performing photocatalytic CO oxidation, we observed plasmon-enhanced photocatalysis only for antenna-reactor complexes with antenna components of intermediate sizes (25 and 50 nm). Optimal photocatalytic performance was shown to be determined by a balance between maximized local field enhancements at the catalytically active Pt surface, minimized collective scattering of photons out of the catalyst bed by the complexes, and minimal light absorption in the Ag nanoparticle antenna. These results elucidate the critical aspects of local field enhancement, light scattering, and absorption in plasmonic photocatalyst design, especially under light-limited illumination conditions.

Laser Desorption/Ionization Mass Spectrometric Imaging of Endogenous Lipids from Rat Brain Tissue Implanted with Silver Nanoparticles

NASA Astrophysics Data System (ADS)

Muller, Ludovic; Baldwin, Kathrine; Barbacci, Damon C.; Jackson, Shelley N.; Roux, Aurélie; Balaban, Carey D.; Brinson, Bruce E.; McCully, Michael I.; Lewis, Ernest K.; Schultz, J. Albert; Woods, Amina S.

2017-08-01

Mass spectrometry imaging (MSI) of tissue implanted with silver nanoparticulate (AgNP) matrix generates reproducible imaging of lipids in rodent models of disease and injury. Gas-phase production and acceleration of size-selected 8 nm AgNP is followed by controlled ion beam rastering and soft landing implantation of 500 eV AgNP into tissue. Focused 337 nm laser desorption produces high quality images for most lipid classes in rat brain tissue (in positive mode: galactoceramides, diacylglycerols, ceramides, phosphatidylcholines, cholesteryl ester, and cholesterol, and in negative ion mode: phosphatidylethanolamides, sulfatides, phosphatidylinositol, and sphingomyelins). Image reproducibility in serial sections of brain tissue is achieved within <10% tolerance by selecting argentated instead of alkali cationized ions. The imaging of brain tissues spotted with pure standards was used to demonstrate that Ag cationized ceramide and diacylglycerol ions are from intact, endogenous species. In contrast, almost all Ag cationized fatty acid ions are a result of fragmentations of numerous lipid types having the fatty acid as a subunit. Almost no argentated intact fatty acid ions come from the pure fatty acid standard on tissue.

Synthesis of High Valence Silver-Loaded Mesoporous Silica with Strong Antibacterial Properties

PubMed Central

Chen, Chun-Chi; Wu, Hsin-Hsien; Huang, Hsin-Yi; Liu, Chen-Wei; Chen, Yi-Ning

2016-01-01

A simple chemical method was developed for preparing high valence silver (Ag)-loaded mesoporous silica (Ag-ethylenediaminetetraacetic acid (EDTA)-SBA-15), which showed strong antibacterial activity. Ag-EDTA-SBA-15 exhibited stronger and more effective antibacterial activity than commercial Ag nanoparticles did, and it offered high stability of high valence silver in the porous matrix and long-lasting antibacterial activity. The synthesized materials were characterized using Fourier transform infrared spectroscopy, powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) analysis, and transmission electron microscopy (TEM). Ag existed in both surface complexation and Ag particles. EDTA anchored within a porous structure chelated Ag ions in higher oxidation states and prevented their agglomeration and oxidation reduction. The XRD results showed that most Ag in the Ag-EDTA-SBA-15 existed in higher oxidation states such as Ag(II) and Ag(III). However, the XPS and TEM results showed that Ag easily reduced in lower oxidation states and agglomerated as Ag particles on the exterior layer of the SBA-15. PMID:26742050

Persistence of Circulating Hepatitis C Virus Antigens-Specific Immune Complexes in Patients with Resolved HCV Infection.

PubMed

Hu, Ke-Qin; Cui, Wei

2018-05-01

Our recent study indicated the possible presence of detectable hepatitis C virus antigens (HCV-Ags) after denaturation of sera with resolved HCV (R-HCV) infection. The present study determined and characterized persistent HCV-Ags-specific immune complexes (ICs) in these patients. Sixty-eight sera with R-HCV and 34 with viremic HCV (V-HCV) infection were tested for free and IC-bound HCV-Ags using HCV-Ags enzyme immunoassay (EIA), the presence of HCV-Ags-specific ICs by immunoprecipitation and Western blot (IP-WB), HCV ICs containing HCV virions using IP and HCV RNA RT-PCR, and correlation of HCV ICs with clinical presentation in these patients. Using HCV-Ags EIA, we found 57.4% of sera with R-HCV infection were tested positive for bound, but not free HCV-Ags. Using pooled or individual anti-HCV E1/E2, cAg, NS3, NS4b, and/or NS5a to precipitate HCV-specific-Ags, we confirmed persistent HCV-Ags ICs specific to various HCV structural and non-structural proteins not only in V-HCV infection, but also in R-HCV infection. Using IP and HCV RNA PCR, we then confirmed the presence of HCV virions within circulating ICs in V-HCV, but not in R-HCV sera. Multivariable analysis indicated significant and independent associations of persistent circulating HCV-Ags-specific ICs with both age and the presence of cirrhosis in patients with R-HCV infection. Various HCV-Ag-specific ICs, but not virions, persist in 57.4% of patients who had spontaneous or treatment-induced HCV clearance for 6 months to 20 years. These findings enriched our knowledge on HCV pathogenesis and support further study on its long-term clinical relevance, such as extrahepatic manifestation, transfusion medicine, and hepatocarcinogenesis.

Silver nanoparticles with 4,4‧-dicyanamidobiphenyl ligand: Synthesis, photoluminescent and electroluminescent properties and DFT calculations

NASA Astrophysics Data System (ADS)

Chiniforoshan, Hossein; Khalesi, Sara Bahmanpour; Tabrizi, Leila; Hajipour, Abdol R.; Chermahini, Alireza Najafi; Karimzadeh, Morteza

2015-02-01

In this research, a new complex of 4,4‧-dicyanamidobiphenyl (bpH2) ligand, Ag(bpH) has been synthesized and characterized by FT-IR, UV-Vis spectroscopies, and elemental analysis. The morphology and size of complex were determined by the scanning electron microscopy (SEM) image. The diameter of the complex was about 61 nm and the nanoparticles were spherical. TGA result indicated that this complex was thermally stable. Also, photoluminescent and electroluminescent properties of Ag(bpH) were reported. The blue-green light emission was observed by fabricating double-layer devices using Ag(bpH) as electron-transport and NPB as hole-transport material. In addition, this complex was optimized by B3LYP/LANL2DZ method. The calculated FT-IR and UV-Vis data are in better agreement with the experimental results. In addition to DFT calculations, natural bond orbital (NBO) was also performed at the same level of theory.

Aniline chlorination by in situ formed Ag-Cl complexes under simulated solar light irradiation.

PubMed

Hu, Xuefeng; Wang, Xiaowen; Dong, Liuliu; Chang, Fei; Luo, Yongming

2015-01-01

Ag speciation in a chloride medium was dependent upon the Cl/Ag ratio after releasing into surface water. In this study, the photoreaction of in situ formed Ag-Cl species and their effects on aniline photochlorination were systematically investigated. Our results suggested that formation of chloroaniline was strongly relevant to the Cl/Ag ratio and could be interpreted using the thermodynamically expected speciation of Ag in the presence of Cl-. AgCl was the main species responsible for the photochlorination of aniline. Both photoinduced hole and •OH drove the oxidation of Cl- to radical •Cl, which promoted the chlorination of aniline. Ag0 formation was observed from the surface plasmon resonance absorption during AgCl photoreaction. This study revealed that Ag+ released into Cl--containing water may result in the formation of chlorinated intermediates of organic compounds under solar light irradiation.

Charge Transfer Between Quantum Dots and Peptide-Coupled Redox Complexes

DTIC Science & Technology

2009-01-01

labeled with reactive metal complexes includ- ing a ruthenium chelate (Ru), a bis-bipyridine ruthe- nium chelate (ruthenium-bpy), and a ferrocene metal...of unconjugated QDs and the metal complex–labeled peptides immobilized on indium tin oxide (ITO) electrodes. The ruthenium and ferrocene peptide...Ag/AgCI E v s. N H E E v s. v ac uu m (e V ) Ruthenium Ferrocene Ruthenium-bpy DHLA QDs DHLA-PEG QDs Quantum dot Metal complex CB VB E0X of QDs Fe

Spectrally selective fluorescence imaging of Chlorobaculum tepidum reaction centers conjugated to chelator-modified silver nanowires.

PubMed

Kowalska, Dorota; Szalkowski, Marcin; Ashraf, Khuram; Grzelak, Justyna; Lokstein, Heiko; Niedziolka-Jonsson, Joanna; Cogdell, Richard; Mackowski, Sebastian

2018-03-01

A polyhistidine tag (His-tag) present on Chlorobaculum tepidum reaction centers (RCs) was used to immobilize photosynthetic complexes on a silver nanowire (AgNW) modified with nickel-chelating nitrilo-triacetic acid (Ni-NTA). The optical properties of conjugated nanostructures were studied using wide-field and confocal fluorescence microscopy. Plasmonic enhancement of RCs conjugated to AgNWs was observed as their fluorescence intensity dependence on the excitation wavelength does not follow the excitation spectrum of RC complexes in solution. The strongest effect of plasmonic interactions on the emission intensity of RCs coincides with the absorption spectrum of AgNWs and is observed for excitation into the carotenoid absorption. From the absence of fluorescence decay shortening, we attribute the emission enhancement to increase of absorption in RC complexes.

UHV-TEM/TED observation of Ag islands grown on Si( 1 1 1 ) 3× 3-Ag surface

NASA Astrophysics Data System (ADS)

Oshima, Yoshifumi; Nakade, Hiroyuki; Shigeki, Sinya; Hirayama, Hiroyuki; Takayanagi, Kunio

2001-11-01

Growths of Ag islands on Si(1 1 1)3×3-Ag surface at room temperature were observed by UHV transmission electron microscopy and diffraction. The Ag islands grown after six monolayer deposition had neither (1 0 0) nor (1 1 0) orientation, but had two complex epitaxial orientations dominantly. One was striped islands which gave rise to a diffraction pattern commensurate with the 3×3 lattice of the Si(1 1 1) surface. The other was the coagulated islands whose diffraction pattern indicated the Ag(1 -3 4) sheet grown parallel to the Si(1 1 1) surface.

Syntheses, crystal structures and properties of series of 4d–4f ln(III)–Ag(I) heterometallic coordination polymers

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

Ran, Xing-Rui; Wang, Ning; Xie, Wei-Ping

2015-05-15

By control of the experimental parameters such as ligands, pH value and reacting temperature, series of three-dimensional (3D) 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction, namely, ([Ln{sup III}Ag{sup I}(na)(ina)(ox)]·2(H{sub 2}O)){sub n} [Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5), Ho(6), Y(7), Yb(8)], have been successfully synthesized under hydrothermal conditions and structurally characterized. All the complexes are characterized by elemental analyses, FT-IR spectroscopy, Powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Furthermore, the luminescence properties of compounds 2 and 4 and the magsnetic properties of complexes 3 and 5 were also investigated in detail. - Graphical abstract: Series of three-dimensional (3D)more » 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction which are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. - Highlights: • Complexes 1–8 are first built by three kinds of organic ligands based on nicotinic acid and isonicotinic acid. • PCPs 1–8 are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. • The total solvent-accessible volume of PCP 2 comprises 11.6% of the crystal volume after dislodging the free water molecules. • Complexes 2 and 4 exhibit characteristic lanthanide-centered luminescence, while compounds 3 and 5 show antiferromagnetic behaviors.« less

Structures of M2(SO2)6B12F12 (M = Ag or K) and Ag2(H2O)4B12F12: Comparison of the Coordination of SO2 versus H2O and of B12F122- versus Other Weakly Coordinating Anions to Metal Ions in the Solid State.

PubMed

Malischewski, Moritz; Peryshkov, Dmitry V; Bukovsky, Eric V; Seppelt, Konrad; Strauss, Steven H

2016-12-05

The structures of three solvated monovalent cation salts of the superweak anion B 12 F 12 2- (Y 2- ), K 2 (SO 2 ) 6 Y, Ag 2 (SO 2 ) 6 Y, and Ag 2 (H 2 O) 4 Y, are reported and discussed with respect to previously reported structures of Ag + and K + with other weakly coordinating anions. The structures of K 2 (SO 2 ) 6 Y and Ag 2 (SO 2 ) 6 Y are isomorphous and are based on expanded cubic close-packed arrays of Y 2- anions with M(OSO) 6 + complexes centered in the trigonal holes of one expanded close-packed layer of B 12 centroids (⊙). The K + and Ag + ions have virtually identical bicapped trigonal prism MO 6 F 2 coordination spheres, with M-O distances of 2.735(1)-3.032(2) Å for the potassium salt and 2.526(5)-2.790(5) Å for the silver salt. Each M(OSO) 6 + complex is connected to three other cationic complexes through their six μ-SO 2 -κ 1 O,κ 2 O' ligands. The structure of Ag 2 (H 2 O) 4 Y is unique [different from that of K 2 (H 2 O) 4 Y]. Planes of close-packed arrays of anions are offset from neighboring planes along only one of the linear ⊙···⊙···⊙ directions of the close-packed arrays, with [Ag(μ-H 2 O) 2 Ag(μ-H 2 O) 2 )] ∞ infinite chains between the planes of anions. There are two nearly identical AgO 4 F 2 coordination spheres, with Ag-O distances of 2.371(5)-2.524(5) Å and Ag-F distances of 2.734(4)-2.751(4) Å. This is only the second structurally characterized compound with four H 2 O molecules coordinated to a Ag + ion in the solid state. Comparisons with crystalline H 2 O and SO 2 solvates of other Ag + and K + salts of weakly coordinating anions show that (i) N[(SO 2 ) 2 (1,2-C 6 H 4 )] - , BF 4 - , SbF 6 - , and Al(OC(CF 3 ) 3 ) 4 - coordinate much more strongly to Ag + than does Y 2- , (ii) SnF 6 2- coordinates somewhat more strongly to K + than does Y 2- , and (iii) B 12 Cl 12 2- coordinates to K + about the same as, if not slightly weaker than, Y 2- .

Silver nanowire-carbon fiber cloth nanocomposites synthesized by UV curing adhesive for electrochemical point-of-use water disinfection.

PubMed

Hong, Xuesen; Wen, Junjie; Xiong, Xuhua; Hu, Yongyou

2016-07-01

Novel silver nanowire (AgNW) - carbon fiber cloth (CC) nanocomposites were synthesized by a rapid and facile method. Acting as filter in an electrical gravity filtration device, the AgNW-CC nanocomposites were applied to electrochemical point-of-use water disinfection. AgNW-CC nanocomposites were characterized by FESEM, XRD, and FTIR. Their disinfection performance toward Escherichia coli and bacteriophage MS2 was evaluated by inhibition zone tests, optical density growth curve tests, and flow tests. The results showed that complex 3D AgNW networks with controllable silver release (<100 ppb) were fabricated on CC by using UV curing adhesive. AgNW-CC nanocomposites exhibited excellent intrinsic antibacterial activities against E. coli. The concentration of AgNWs and UV adhesive controlled the released silver and hence led to the change in antibacterial activity. The external electric field significantly enhanced the disinfection efficiency of AgNW-CC nanocomposites. Over 99.999% removal of E. coli and MS2 could be achieved. More complex AgNW networks contributed to higher disinfection efficiency under 10 V and 10(6) CFU (PFU) mL(-1) of microorganism. UV adhesive could keep the disinfection performance from being affected by flow rate. The convenient synthesis and outstanding disinfection performance offer AgNW-CC nanocomposites opportunities in the application of electrochemical point-of-use drinking water disinfection. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ultrafast time-resolved carotenoid to-bacteriochlorophyll energy transfer in LH2 complexes from photosynthetic bacteria.

PubMed

Cong, Hong; Niedzwiedzki, Dariusz M; Gibson, George N; LaFountain, Amy M; Kelsh, Rhiannon M; Gardiner, Alastair T; Cogdell, Richard J; Frank, Harry A

2008-08-28

Steady-state and ultrafast time-resolved optical spectroscopic investigations have been carried out at 293 and 10 K on LH2 pigment-protein complexes isolated from three different strains of photosynthetic bacteria: Rhodobacter (Rb.) sphaeroides G1C, Rb. sphaeroides 2.4.1 (anaerobically and aerobically grown), and Rps. acidophila 10050. The LH2 complexes obtained from these strains contain the carotenoids, neurosporene, spheroidene, spheroidenone, and rhodopin glucoside, respectively. These molecules have a systematically increasing number of pi-electron conjugated carbon-carbon double bonds. Steady-state absorption and fluorescence excitation experiments have revealed that the total efficiency of energy transfer from the carotenoids to bacteriochlorophyll is independent of temperature and nearly constant at approximately 90% for the LH2 complexes containing neurosporene, spheroidene, spheroidenone, but drops to approximately 53% for the complex containing rhodopin glucoside. Ultrafast transient absorption spectra in the near-infrared (NIR) region of the purified carotenoids in solution have revealed the energies of the S1 (2(1)Ag-)-->S2 (1(1)Bu+) excited-state transitions which, when subtracted from the energies of the S0 (1(1)Ag-)-->S2 (1(1)Bu+) transitions determined by steady-state absorption measurements, give precise values for the positions of the S1 (2(1)Ag-) states of the carotenoids. Global fitting of the ultrafast spectral and temporal data sets have revealed the dynamics of the pathways of de-excitation of the carotenoid excited states. The pathways include energy transfer to bacteriochlorophyll, population of the so-called S* state of the carotenoids, and formation of carotenoid radical cations (Car*+). The investigation has found that excitation energy transfer to bacteriochlorophyll is partitioned through the S1 (1(1)Ag-), S2 (1(1)Bu+), and S* states of the different carotenoids to varying degrees. This is understood through a consideration of the energies of the states and the spectral profiles of the molecules. A significant finding is that, due to the low S1 (2(1)Ag-) energy of rhodopin glucoside, energy transfer from this state to the bacteriochlorophylls is significantly less probable compared to the other complexes. This work resolves a long-standing question regarding the cause of the precipitous drop in energy transfer efficiency when the extent of pi-electron conjugation of the carotenoid is extended from ten to eleven conjugated carbon-carbon double bonds in LH2 complexes from purple photosynthetic bacteria.

Synthesis and characterization of nitrile functionalized silver(I)-N-heterocyclic carbene complexes: DNA binding, cleavage studies, antibacterial properties and mosquitocidal activity against the dengue vector, Aedes albopictus.

PubMed

Asekunowo, Patrick O; Haque, Rosenani A; Razali, Mohd R; Avicor, Silas W; Wajidi, Mustafa F F

2018-04-25

A series of four benzimidazolium based nitrile-functionalized mononuclear-Ag(I)-N-heterocyclic carbene and binuclear-Ag(I)-N-heterocyclic carbene (Ag(I)-NHC) hexafluorophosphate complexes (5b-8b) were synthesized by reacting the corresponding hexafluorophosphate salts (1b-4b) with Ag 2 O in acetonitrile, respectively. These compounds were characterized by 1 H NMR, 13 C NMR, IR, UV-visible spectroscopic techniques, elemental analyses and molar conductivity. Additionally, 8b was structurally characterized by single crystal X-ray diffraction technique. Preliminary in vitro antibacterial evaluation was conducted for all the compounds against two standard bacteria; gram-positive (Staphylococcus aureus) and gram-negative (Escherichia coli) bacterial strains. Most of the Ag(I)-NHC complexes (5b-8b) showed moderate to good antibacterial activity with MIC values in the range of 12.5-100 μg/mL. Especially, compound 8b exhibited promising anti-Staphylococcus aureus activity with a low MIC value (12.5 μg/mL). However, all the hexafluorophosphate salts (1b-4b) were inactive against the bacteria strains. The preliminary interactive investigation revealed that the most active compound, 8b, could effectively intercalate into DNA to form 8b-DNA complex which shows a better binding ability for DNA (K b  = 3.627 × 10 6 ) than the complexes 5b-7b (2.177 × 10 6 , 8.672 × 10 5 and 6.665 × 10 5 , respectively). Nuclease activity of the complexes on plasmid DNA and Aedes albopictus genomic DNA was time-dependent, although minimal. The complexes were larvicidal to the mosquito, with 5b, 6b and 8b being highly active. Developmental progression from the larval to the adult stage was affected by the complexes, progressively being toxic to the insect's development with increasing concentration. These indicate the potential use of these complexes as control agents against bacteria and the dengue mosquito Ae. albopictus. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

The Effect of Cu:Ag Atomic Ratio on the Properties of Sputtered Cu–Ag Alloy Thin Films

PubMed Central

Hsieh, Janghsing; Hung, Shunyang

2016-01-01

Cu–Ag thin films with various atomic ratios were prepared using a co-sputtering technique, followed by rapid thermal annealing at various temperatures. The films’ structural, mechanical, and electrical properties were then characterized using X-ray diffractometry (XRD), atomic force microscopy (AFM), FESEM, nano-indentation, and TEM as functions of compositions and annealing conditions. In the as-deposited condition, the structure of these films transformed from a one-phase to a dual-phase state, and the resistivity shows a twin-peak pattern, which can be explained in part by Nordheim’s Rule and the miscibility gap of Cu–Ag alloy. After being annealed, the films’ resistivity followed the mixture rule in general, mainly due to the formation of a dual-phase structure containing Ag-rich and Cu-rich phases. The surface morphology and structure also varied as compositions and annealing conditions changed. The recrystallization of these films varied depending on Ag–Cu compositions. The annealed films composed of 40 at % to 60 at % Cu had higher hardness and lower roughness than those with other compositions. Particularly, the Cu50Ag50 film had the highest hardness after being annealed. From the dissolution testing, it was found that the Cu-ion concentration was about 40 times higher than that of Ag. The galvanic effect and over-saturated state could be the cause of the accelerated Cu dissolution and the reduced dissolution of the Ag. PMID:28774033

Green synthesis and antimicrobial activity of monodisperse silver nanoparticles synthesized using Ginkgo Biloba leaf extract

NASA Astrophysics Data System (ADS)

Ren, Yan-yu; Yang, Hui; Wang, Tao; Wang, Chuang

2016-11-01

Various parts of plants can be used as a raw material for the synthesis of nanoparticles, which is eco-friendly way and does not involve any harmful chemicals. In this project, Ginkgo biloba leaf, an abundantly available medicinal plant in China, was for the first time adopted as a reducing and stabilizing agent to synthesize smaller sized and stable silver nanoparticles (AgNPs). To improve the quality of AgNPs, the reduction was accelerated by changing the concentrations of initial Ag+ (0.02, 0.04, 0.06 and 0.08 mol/L) of the reaction mixture consisting of silver nitrate solution (AgNO3) and Ginkgo biloba leaf extract. At pH = 8 and lower AgNO3 concentration (0.02 mol/L), a colloid consisting of well-dispersed spherical nanoparticles was obtained. The synthesized nanocrystals were successfully characterized by UV-vis and XRD. TEM images revealed the size of the spherical AgNPs ranged between 10-16 nm. FTIR analysis revealed that biological macromolecules with groups of sbnd NH2, sbnd OH, and others were distributed on the surface of the nanoparticles. The biosynthesized AgNPs exhibited good antibacterial activities against gram-negative bacteria and gram-positive bacteria. Compared to traditional chemical methods, Ginkgo biloba leaf extract provides an easy green synthetical way. It is anticipated that the biosynthesized AgNPs can be used in areas such as cosmetics, foods and medical applications.

3D-printed bioceramic scaffolds with antibacterial and osteogenic activity.

PubMed

Zhang, Yongliang; Zhai, Dong; Xu, Mengchi; Yao, Qingqiang; Zhu, Huiying; Chang, Jiang; Wu, Chengtie

2017-06-20

Bacterial infection poses a significant risk with the wide application of bone graft materials. Designing bone grafts with good antibacterial performance and excellent bone-forming activity is of particular significance for bone tissue engineering. In our study, a 3D printing method was used to prepare β-tricalcium phosphate (β-TCP) bioceramic scaffolds. Silver (Ag) nanoparticles were uniformly dispersed on graphene oxide (GO) to form a homogeneous nanocomposite (named Ag@GO) with different Ag-to-graphene oxide mass ratios, with this being synthesized via the liquid chemical reduction approach. Ag@GO nanocomposites were successfully modified on the β-TCP scaffolds by a simple soaking method to achieve bifunctional biomaterials with antibacterial and osteogenic activity. The prepared scaffolds possessed a connected network with triangle pore morphology and the surfaces of the β-TCP scaffolds were uniformly modified by the Ag@GO nanocomposite layers. The Ag content in the scaffolds was controlled by changing the coating times and concentration of the Ag@GO nanocomposites. The antibacterial activity of the scaffolds was assessed with Gram-negative bacteria (Escherichia coli, E. coli). The results demonstrated that the scaffolds with Ag@GO nanocomposites presented excellent antibacterial activity. In addition, the scaffolds coated with Ag@GO nanocomposites conspicuously accelerated the osteogenic differentiation of rabbit bone marrow stromal cells by improving their alkaline phosphatase activity and bone-related gene expression (osteopontin, runt-related transcription factor 2, osteocalcin and bone sialoprotein). This study demonstrates that bifunctional scaffolds with a combination of antibacterial and osteogenic activity can be achieved for the reconstruction of large-bone defects while preventing or treating infections.

Silver clusters encapsulated in C{sub 60}: A density functional study

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

Dhiman, Shobhna; Kumar, Ranjan; Dharamvir, Keya

2015-08-28

We explore the possibility of formation of endohedral complexes of Ag{sub n} atoms (n=1-9) inside C{sub 60} molecule using density functional theory and molecular dynamics. The obtained results reveal that Ag{sub n} (n=8) atoms can form stable complexes with the C{sub 60} molecule. Encapsulation of large number of Ag{sub n} atoms (n>8) make C{sub 60} cage instable, showing distortion of cage. Binding energy/atom increases with the number of Ag atoms up to n=4, after that it increases. Ionization potential decreases till n=4 and then increases, electron affinity increases till n=4 and then shows oscillatory nature as a function of Agmore » atoms inside the cage. Homo –Lumo gap shows no systematic pattern. Our results agreed well with the data available.« less

Impact of the corrin framework of vitamin B12 on the electrochemical carbon-skeleton rearrangement in comparison to an imine/oxime planar ligand; tuning selectivity in 1,2-migration of a functional group by controlling electrolysis potential.

PubMed

Tahara, Keishiro; Pan, Ling; Yamaguchi, Ryoko; Shimakoshi, Hisashi; Abe, Masaaki; Hisaeda, Yoshio

2017-10-01

Among the coenzyme B 12 -dependent enzymes, methylmalonyl-CoA mutase (MMCM) catalyzes the carbon-skeleton rearrangement reaction between R-methylmalonyl-CoA and succinyl-CoA. Diethyl 2-bromomethyl-2-phenylmalonate, an alkyl bromide substrate having two different migrating groups (phenyl and carboxylic ester groups) on the β-carbon, was applied to the electrolysis mediated by a hydrophobic vitamin B 12 model complex, heptamethyl cobyrinate perchlorate in this study. The electrolysis of the substrate at -1.0V vs. Ag-AgCl by light irradiation afforded the simple reduced product (diethyl 2-methyl-2-phenylmalonate) and the phenyl migrated product (diethyl 2-benzyl-2-phenylmalonate), as well as the electrolysis of the substrate at -1.5V vs. Ag-AgCl in the dark. The electrolysis of the substrate at -2.0V vs. Ag-AgCl afforded the carboxylic ester migrated product (diethyl phenylsuccinate) as the major product. The selectivity for the migrating group was successfully tuned by controlling the electrolysis potential. We clarified that the cathodic chemistry of the Co(III) alkylated heptamethyl cobyrinate is critical for the selectivity of the migrating group through mechanistic investigations and comparisons to the simple vitamin B 12 model complex, an imine/oxime-type cobalt complex. Copyright © 2017 Elsevier Inc. All rights reserved.

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

Frampton, Gabriel; Coufal, Monique; Li, Huang

The endocannabinoids anandamide (AEA) and 2-arachidonylglycerol (2-AG) have opposing effects on cholangiocarcinoma growth. Implicated in cancer, Notch signaling requires the {gamma}-secretase complex for activation. The aims of this study were to determine if the opposing effects of endocannabinoids depend on the differential activation of the Notch receptors and to demonstrate that the differential activation of these receptors are due to presenilin 1 containing- and presenilin 2 containing-{gamma}-secretase complexes. Mz-ChA-1 cells were treated with AEA or 2-AG. Notch receptor expression, activation, and nuclear translocation were determined. Specific roles for Notch 1 and 2 on cannabinoid-induced effects were determined by transient transfectionmore » of Notch 1 or 2 shRNA vectors before stimulation with AEA or 2-AG. Expression of presenilin 1 and 2 was determined after AEA or 2-AG treatment, and the involvement of presenilin 1 and 2 in the cannabinoid-induced effects was demonstrated in cell lines with low presenilin 1 or 2 expression. Antiproliferative effects of AEA required increased Notch 1 mRNA, activation, and nuclear translocation, whereas the growth-promoting effects induced by 2-AG required increased Notch 2 mRNA expression, activation, and nuclear translocation. AEA increased presenilin 1 expression and recruitment into the {gamma}-secretase complex, whereas 2-AG increased expression and recruitment of presenilin 2. The development of novel therapeutic strategies aimed at modulating the endocannabinoid system or mimicking the mode of action of AEA on Notch signaling pathways would prove beneficial for cholangiocarcinoma management.« less

Surface-enhanced infrared spectroscopic studies of the catalytic behavior of silver nanoparticles on a germanium substrate.

PubMed

Liou, Yen-Chen Maggie; Yang, Jyisy; Fasasi, Ayuba; Griffiths, Peter R

2011-05-01

The catalytic activity of silver nanoparticles (AgNPs) on a germanium substrate is reported. Para-nitrothiophenol (pNTP) that had been adsorbed on this substrate is converted to p-aminothiophenol (pATP) under very mild reaction conditions, such as simply soaking in water. The AgNPs may be formed either by physical vapor deposition or by electroless deposition from a solution of silver nitrate. Analogous reactions were not observed on copper nanoparticles on germanium or AgNPs on silicon or zinc selenide even though very slow conversion of pNTP to pATP was observed with Au nanoparticles (AuNPs) on Ge under controlled reaction conditions. The effects of factors that could influence the catalytic reaction were examined; these included the particle size of the AgNPs, reaction temperature, concentration and chemical nature of other ions present in the solution, the pH of the water, and the nature of the substrate. The reaction rate was approximately independent of the particle size for AgNPs between 50 and 150 nm in diameter. Increasing the temperature accelerates the reaction significantly; at temperatures above 40 °C, the adsorbed pNTP is completely converted by water within five minutes. Not surprisingly, the reaction rate was increased as the pH of the solution was decreased, as the reduction of each nitro group to an amino group requires six protons. The presence of Br(-) and I(-) ions accelerated the reaction to the point that even at 4 °C, the conversion of the nitro group was still observable, while solutions containing chloride ions had to be heated to 40 °C before their effect became apparent. Apparently, Br(-) and I(-) ions remove the oxide layer from the surface of the germanium substrate, facilitating transfer of electrons from the germanium to the nitro group of the pNTP.

AgI -Induced Switching of DNA Binding Modes via Formation of a Supramolecular Metallacycle.

PubMed

Basak, Shibaji; Léon, J Christian; Ferranco, Annaleizle; Sharma, Renu; Hebenbrock, Marian; Lough, Alan; Müller, Jens; Kraatz, Heinz-Bernhard

2018-03-12

The histidine derivative L1 of the DNA intercalator naphthalenediimide (NDI) forms a triangular Ag I complex (C2). The interactions of L1 and of C2 with DNA were studied by circular dichroism (CD) and UV/Vis spectroscopy and by viscosity studies. Different binding modes were observed for L1 and for C2, as the Ag I complex C2 is too large in size to act as an intercalator. If Ag I is added to the NDI molecule that is already intercalated into a duplex, higher order complexes are formed within the DNA duplex and cause disruptions in the helical duplex structure, which leads to a significant decrease in the characteristic CD features of B-DNA. Thus, via addition of a metal we show how a classic and well-known organic intercalator unit can be turned into a partial metallo insertor. We also show how electrochemical impedance spectroscopy (EIS) can be used to probe DNA binding modes on DNA films that are immobilized on gold surfaces. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Silver nanoparticles: green synthesis using Phoenix dactylifera fruit extract, characterization, and anti-oxidant and anti-microbial activities

NASA Astrophysics Data System (ADS)

Shaikh, Anas Ejaz; Satardekar, Kshitij Vasant; Khan, Rummana Rehman; Tarte, Nanda Amit; Barve, Siddhivinayak Satyasandha

2018-03-01

Hydro-alcoholic (2:8 v/v) extract of the pulp of Phoenix dactylifera fruit pulp obtained using Soxhlet extraction (70 °C, 6 h) was found to contain alkaloids, sterols, tannins, flavonoids, cardiac glycosides, proteins, and carbohydrates. An aqueous solution (20% v/v) of the extract led to the synthesis of silver nanoparticles (AgNPs) from 0.01 M AgNO3 solution as confirmed by the surface plasmon resonance at 445 nm determined using UV-visible spectroscopy after 24 h. The synthesized AgNPs were found to be mostly spherical and complexed with phytochemicals from the extract. The size of AgNPs ranged from 12.2-140.2 nm with mean diameter of 47.0 nm as characterized by scanning electron microscopy (SEM). The elemental composition of the AgNPs complexed with the phytochemicals was found to be 80.49% silver (Ag), 15.21% carbon (C), and 4.30% oxygen (O) on a weight basis by energy-dispersive spectroscopy (EDS). Using the α,α-diphenyl-β-picrylhydrazyl (DPPH) assay, an anti-oxidant activity of 89.15% for 1 µg L-1 ultrasonically homogenized ethanolic solution of complexed AgNPs was obtained (equivalent to 0.20 mg mL-1 gallic acid solution), while methanolic solution of plant extract possessed an EC50 value of 3.45% (v/v) (equivalent to 0.11 mg mL-1 gallic acid solution). The plant-nanosilver broth was also found to possess effective anti-microbial activity against Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 6538, and Candida albicans ATCC 10231 as assessed by the disc diffusion assay. However, the plant extract showed negligible anti-microbial activity.

Inorganic anion-dependent assembly of zero-, one-, two- and three-dimensional Cu(II)/Ag(I) complexes under the guidance of the HSAB theory: Synthesis, structure, and magnetic property

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

Liu, Yaru; Xing, Zhiyan; Zhang, Xiao

To systematically explore the influence of inorganic anions on building coordination complexes, five novel complexes based on 1-(benzotriazole-1-methyl)−2-propylimidazole (bpmi), [Cu(bpmi){sub 2}(Ac){sub 2}]·H{sub 2}O (1), [Cu(bpmi){sub 2}(H{sub 2}O){sub 2}]·2NO{sub 3}·2H{sub 2}O (2), [Cu(bpmi)(N{sub 3}){sub 2}] (3), [Ag(bpmi)(NO{sub 3})] (4) and [Cu{sub 3}(bpmi){sub 2}(SCN){sub 4}(DMF)] (5) (Ac{sup −}=CH{sub 3}COO{sup −}, DMF=N,N-Dimethylformamide) are synthesized through rationally introducing Cu(II) salts and Ag(I) salt with different inorganic anions. X-ray single-crystal analyses reveal that these complexes show interesting structural features from mononuclear (1), one-dimensional (2 and 3), two-dimensional (4) to three-dimensional (5) under the influence of inorganic anions with different basicities. The structural variation can bemore » explained by the hard-soft-acid-base (HSAB) theory. Magnetic susceptibility measurement indicates that complex 3 exhibits an antiferromagnetic coupling between adjacent Cu(II) ions. - Graphical abstract: Five new Cu(II)/Ag(I) complexes show interesting structural features from mononuclear, one-dimension, two-dimension to three-dimension under the influence of inorganic anions. The structural variation can be explained by the HSAB theory. - Highlights: • Five inorganic anion-dependent complexes are synthesized. • Structural variation can be explained by the hard-soft-acid-base (HSAB) theory. • The magnetic property of complex has been studied.« less

The Electrodeposition of Silver from Supercritical Carbon Dioxide/Acetonitrile

PubMed Central

Bartlett, Philip N; Perdjon-Abel, Magdalena; Cook, David; Reid, Gillian; Levason, William; Cheng, Fei; Zhang, Wenjian; George, Michael W; Ke, Jie; Beanland, Richard; Sloan, Jeremy

2014-01-01

Cyclic voltammetry of silver coordination complexes in acetonitrile and in a single-phase supercritical carbon dioxide/acetonitrile (scCO2/CH3CN) system is reported. Five silver precursors are investigated: (1,5-cyclooctadiene)(hexafluoroacetylacetonato) silver(I) [Ag(hfac)(COD)], (hexafluoroacetylacetonato)(triphenylphosphine) silver(I) [Ag(hfac)(PPh3)], (perfluorooctanoato)bis(triphenylphosphine) silver(I) [Ag(CF3(CF2)6CO2)(PPh3)2], tetrakis(triphenylphosphine) silver(I) tetrafluoroborate [Ag(PPh3)4][BF4] and tetrakis(acetonitrile) silver(I) tetrafluoroborate [Ag(CH3CN)4][BF4]. Of these, [Ag(CH3CN)4][BF4] is found to be the most suitable for electrodeposition of silver from scCO2/CH3CN.

The AgroEcoSystem (AgES) response-function model simulates layered soil water dynamics in semi-arid Colorado: sensitivity and calibration

USDA-ARS?s Scientific Manuscript database

Simulation of vertical soil hydrology is a critical component of simulating even more complex soil water dynamics in space and time, including land-atmosphere and subsurface interactions. The AgroEcoSystem (AgES) model is defined here as a single land unit implementation of the full AgES-W (Watershe...

New vistas in transmetalation with discrete "AgCF₃" species: Implications in Pd-mediated trifluoromethylation reactions.

PubMed

Perez-Temprano, Monica Helvia; Martínez de Salinas, Sara; Mudarra, Angel Luis; Benet-Buchholz, Jordi; Parella, Teodor; Maseras, Feliu

2018-05-23

This work describes the employment of discrete "AgCF₃" complexes, including unique (Cat)[Ag(CF₃)₂] salts, as efficient transmetalating agents to PdII in order to tackle some of the usually overshadowed limitations related to this step within the trifluoromethylation area. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Membranous glomerulonephritis in a child asymptomatic for hepatitis B virus. Concomitant seropositivity for HBsAG and anti-HBs.

PubMed

Hirsch, H Z; Ainsworth, S K; DeBeukelaer, M; Brissie, R M; Hennigar, G R

1981-04-01

The presence of hepatitis B surface antigen (HBsAg) in association with immunoglobulins and complement components within the glomerular basement membranes of adults having chronic active hepatitis has been well documented. In addition, investigators in Poland have demonstrated HBsAg immune complexes in glomeruli of children who did not have clinical evidence of hepatitis. More recently, a single case of childhood membranous glomerulonephritis in an asymptomatic carrier of hepatitis B virus was cited by observers in Canada. Reported here is the deposition of HBsAg immune complexes in the glomerular basement membranes of a 13-year-old black boy who had membranous glomerulopathy but not clinical evidence of hepatitis. This may be the first reported case in the United States of HbsAg-associated membranous glomerulonephritis in a child asymptomatic for hepatitis B virus, and only the second such case in North America. However, unlike previous studies of childhood glomerulopathy in association with hepatitis B virus, this patient is seropositive for both HBsAg and anti-HBs (antibody for hepatitis B surface antigen). Similar "rare" serologic findings were found for the patient's eldest male sib.

Role of chemically and thermally induced crystal lattice distortion in enhancing the Seebeck coefficient in complex tellurides

DOE PAGES

Levin, E. M.; Iowa State Univ., Ames, IA; Kramer, M. J.; ...

2016-07-14

Composition and crystal structure of complex materials can significantly change the Seebeck effect, i.e., heat to electrical energy conversion, which is utilized in thermoelectric materials. Despite decades of studies of various thermoelectric materials and their application, the fundamental understanding of this effect still is limited. One of the most efficient groups of thermoelectric materials is based on GeTe, where Ge is replaced by [Ag + Sb], i.e., Ag xSb xGe 50-2xTe 50 alloys, traditionally shown as (GeTe) m(AgSbTe 2) 100-m (TAGS-m series). Here, in this article, we report on the discovery of two unique phenomena in TAGS materials attributed tomore » the effects from [Ag + Sb] atoms: (i) a linear relation between the Seebeck coefficient and rhombohedral lattice distortion, and (ii) resonance-like temperature-induced behavior of the contribution to the Seebeck coefficient produced by [Ag + Sb] atoms. Finally, our findings show that heat to electrical energy conversion strongly depends on the temperature- and compositionally-induced rhombohedral to cubic transformation where [Ag + Sb] atoms play a crucial mediating role.« less

Development of antibacterial paper coated with sodium hyaluronate stabilized curcumin-Ag nanohybrid and chitosan via polyelectrolyte complexation for medical applications

NASA Astrophysics Data System (ADS)

Rao Kummara, Madhusudana; Kumar, Anuj; Soo, Han Sung

2017-11-01

Sodium hyaluronate (HA) stabilized curcumin-Ag (Cur-Ag) hybrid nanoparticles were prepared in the water-ethanol mixture under constant mechanical stirring condition. The obtained HA stabilized Cur-Ag hybrid nanoparticles were characterized by fourier transform infrared spectroscopy, UV-visible spectroscopy, and x-ray diffraction to confirm the formation and structural interactions. The obtained Cur-Ag hybrid nanoparticles showed spherical shape with their size range 5-12 nm that was increased with the increasing a amount of silver ions as confirmed by transmission electron microscopic analysis. Further, a fibrous cellulose filter paper was impregnated with these hybrid nanoparticles and chitosan (CS) as biopolymer via polyelectrolyte complexation. The morphological analysis confirmed the uniform distribution of hybrid nanoparticle system onto the cellulose fibers of the fibrous filter paper. As per disc diffusion method, the Cur-Ag hybrid nanoparticles impregnated CS-coated filter paper exhibited excellent antibacterial properties against gram-negative Escherichia coli (E.coli) bacteria compared to HA stabilized Cur only. Moreover, as prepared hybrid nanoparticles impregnated biocomposite system is eco-friendly with efficient antibacterial property and have good potential to be used in medical applications.

Lanthanide-functionalized silver nanoparticles for detection of an anthrax biomarker and test paper fabrication

NASA Astrophysics Data System (ADS)

Tan, Hongliang; Li, Qian; Ma, Chanjiao; Song, Yonghai; Xu, Fugang; Chen, Shouhui; Wang, Li

2014-01-01

It is highly desirable to develop a simple and sensitive analytical method for detection of anthrax biomarker (dipicolinic acid, DPA) because of its dangerous nature. In this work, we developed a fluorescent sensor for DPA detection based on terbium ion-functionalized silver nanoparticles with an average size of 6.7 nm (AgNPs-Tb3+). The fluorescent intensity of Tb-DPA complex on the surface of AgNPs was two times higher than that of Tb-DPA complex alone in a solution phase due to the metal-enhanced fluorescence (MEF) effect of AgNPs. The proposed fluorescent sensor exhibits excellent selectivity and high sensitivity for DPA. Importantly, a test paper for DPA detection was fabricated for the first time by the integration of AgNPs-Tb3+ onto the nitrocellulose membrane. Owing to the MEF effect of AgNPs, the lowest detectable concentration of the test paper-integrated AgNPs-Tb3+ for DPA by naked eyes is 10 times lower than that of the test paper-integrated Tb3+ alone. We believe that the presented strategy may open up new avenues to the development of portable and robust-sensing platforms based on functional hybrid materials.

Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes

NASA Astrophysics Data System (ADS)

Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M. Arif

2016-05-01

We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica.

Synthesis of some transition metal complexes with new heterocyclic thiazolyl azo dye and their uses as sensitizers in photo reactions

NASA Astrophysics Data System (ADS)

AL-Adilee, Khalid J.; Abass, Ahmed K.; Taher, Ali M.

2016-03-01

A new heterocyclic thiazolylazo dye ligand, 2- [bar2-(4, 5- dimethyl thiazolyl) azo ] -4-Ethoxy Phenol (DMeTAEP), (LH) was synthesized by the diazotization of 4.5-dimethyl thiazolylazonium chloride and coupling with 4- Ethoxy phenol in alkaline alcoholic solution under suitable optimized experimental conditions to yield a new azo dye ligand. The structure of ligand and its complexes was prepared from Co(III), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II), Ag (I) and Au(III) ions. They confirmed by XRD, SEM, (TG-DTG) thermal analysis, 1H-NMR,UV-visb, mass and FT-IR spectroscopic methods, elemental analysis, atomic absorption, magnetic susceptibility and molar conductance. The mole ratio [M: L], it was also studied which was 1:1 for Ag (I) and Au (III) complexes and 1:2 The rest of the metal complexes. The isolated solid complexes are found to have the general formula [M (L)2 ] Cln.mH2O, where n = 1, m = 0 when M = Co (III) and n = 0, m = 1 when M = Ni (II), and Hg(II) while n = 0 and m = 0 when M = Cu (II), Zn (II), Cd (II) and ]ML (H2O)] of Ag(I) - complex but Au(III)-complex structural formula was [Au(L)Cl] Cl conductivity measurements for prepared complexes showed 1:1 electrolyte for Co(III(and Au(III) complexes and non - electrolyte the rest of complexes. The spectral and analytical data revealed that this ligand behaves as a tridentate chelating agent and coordination number of all metal ions were found to be six except for Ag (I) and Au (III) which was four. The activities of complexes were examined as sensitizers in the photocatalytic reaction of p-nitro aniline (PNA) which is used as a model of water pollutants.

Molecular structure and spectral properties of ethyl 3-quinolinecarboxylate (E3Q) and [Ag(E3Q)2(TCA)] complex (TCA = Trichloroacetate)

NASA Astrophysics Data System (ADS)

Soliman, Saied M.; Kassem, Taher S.; Badr, Ahmed M. A.; Abou Youssef, Morsy A.; Assem, Rania

2014-09-01

A new [Ag(E3Q)2(TCA)] complex; (E3Q = Ethyl 3-quinolinecarboxylate and TCA = Trichloroacetate) has been synthesized and characterized using elemental analysis, FTIR, NMR and mass spectroscopy. The molecular geometry and spectroscopic properties of the complex as well as the free ligand have been calculated using the hybrid B3LYP method. The calculations predicted a distorted tetrahedral arrangement around Ag(I) ion. The vibrational spectra of the studied compounds have been assigned using potential energy distribution (PED). TD-DFT method was used to predict the electronic absorption spectra. The most intense absorption band showed a bathochromic shift and lowering of intensity in case of the complex (233.7 nm, f = 0.5604) compared to E3Q (λmax = 228.0 nm, f = 0.9072). The calculated 1H NMR chemical shifts using GIAO method showed good correlations with the experimental data. The computed dipole moment, polarizability and HOMO-LUMO energy gap were used to predict the nonlinear optical (NLO) properties. It is found that Ag(I) enhances the NLO activity. The natural bond orbital (NBO) analyses were used to elucidate the intramolecular charge transfer interactions causing stabilization for the investigated systems.

Control of in vitro rooting and plant development in Corymbia maculata by silver nitrate, silver thiosulfate and thiosulfate ion.

PubMed

Steinitz, Benjamin; Barr, Nurit; Tabib, Yona; Vaknin, Yiftach; Bernstein, Nirit

2010-11-01

Plant regeneration and transformation in vitro is often improved by adding silver ion (Ag(+)) to the culture media as AgNO(3) or silver thiosulfate (STS). Ag(+) reacts with substances to form insoluble precipitates, while thiosulfate (S(2)O(3) (2-)) interferes with these reactions. We studied the implications of silver precipitation and S(2)O(3) (2-) in the medium for culture development by (1) examining formation of Ag(+) precipitates from AgNO(3) versus STS in agar gels and their possible dependence on agar type; (2) comparing Corymbia maculata culture responses to AgNO(3) and STS and determining which better suits control of culture development; (3) clarifying whether STS-dependent alterations in culture development are due to Ag(+) alone or also to a separate influence of S(2)O(3) (2-). Silver precipitates appeared in aqueous gels of four agar brands supplemented with AgNO(3), but not in Phytagel(™), which remained transparent. No precipitation was observed in gels with STS. Indole-3-butyric acid (IBA)-mediated adventitious root induction and shoot growth were higher in C. maculata shoot tips cultured on gels with STS versus AgNO(3) (6-25 μM Ag(+)). IBA-treated shoot tips exhibited enhanced adventitious root regeneration, accelerated root elongation, increased frequency of lateral root formation, and stimulated shoot growth mediated by 100-250 μM sodium thiosulfate (Na(2)S(2)O(3)) in medium without Ag(+). The potency of S(2)O(3) (2-) in facilitating culture development has never been recognized. It is inferred that superiority of STS in stimulating multiple responses of C. maculata culture results from sustained biological activity of Ag(+) through prevention of its precipitation, and from impact of S(2)O(3) (2-) on cell differentiation and growth.

Heteropolyhedral silver compounds containing the polydentate ligand N,N,O-E-[6-(hydroxyimino)ethyl]-1,3,7-trimethyllumazine. Preparation, spectral and XRD structural study and AIM calculations.

PubMed

Jiménez-Pulido, Sonia B; Hueso-Ureña, Francisco; Fernández-Liencres, M Paz; Fernández-Gómez, Manuel; Moreno-Carretero, Miguel N

2013-01-14

The oxime derived from 6-acetyl-1,3,7-trimethyllumazine (1) ((E-6-(hydroxyimino)ethyl)-1,3,7-trimethylpteridine-2,4(1H,3H)-dione, DLMAceMox) has been prepared and its molecular and crystal structure determined from spectral and XRD data. The oxime ligand was reacted with silver nitrate, perchlorate, thiocyanate, trifluoromethylsulfonate and tetrafluoroborate to give complexes with formulas [Ag(2)(DLMAceMox)(2)(NO(3))(2)](n) (2), [Ag(2)(DLMAceMox)(2)(ClO(4))(2)](n) (3), [Ag(2)(DLMAceMox)(2)(SCN)(2)] (4), [Ag(2)(DLMAceMox)(2)(CF(3)SO(3))(2)(CH(3)CH(2)OH)]·CH(3)CH(2)OH (5) and [Ag(DLMAceMox)(2)]BF(4) (6). Single-crystal XRD studies show that the asymmetrical residual unit of complexes 2, 3 and 5 contains two quite different but connected silver centers (Ag1-Ag2, 2.9-3.2 Å). In addition to this, the Ag1 ion displays coordination with the N5 and O4 atoms from both lumazine moieties and a ligand (nitrato, perchlorato or ethanol) bridging to another disilver unit. The Ag2 ion is coordinated to the N61 oxime nitrogens, a monodentate and a (O,O)-bridging nitrato/perchlorato or two monodentate O-trifluoromethylsulfonato anions. The coordination polyhedra can be best described as a strongly distorted octahedron (around Ag1) and a square-based pyramid (around Ag2). The Ag-N and Ag-O bond lengths range between 2.22-2.41 and 2.40-2.67 Å, respectively. Although the structure of 4 cannot be resolved by XRD, it is likely to be similar to those described for 2, 3 and 5, containing Ag-Ag units with S-thiocyanato terminal ligands. Finally, the structure of the tetrafluoroborate compound 6 is mononuclear with a strongly distorted tetrahedral AgN(4) core (Ag-N, 2.27-2.43 Å). Always, the different Ag-N distances found clearly point to the more basic character of the oxime N61 nitrogen atom when compared with the pyrazine N5 one. A topological analysis of the electron density within the framework provided by the quantum theory of atoms in molecules (QTAIM) using DFT(M06L) levels of theory has been performed. Every Ag-Ag and Ag-ligand interaction has been characterized in terms of Laplacian of the electron density, [nabla](2)ρ(r), and the total energy density, H(r).

Nano-Nucleation Characteristic of Cu-Ag Alloy Directly Electrodeposited on W Diffusion Barrier for Microelectronic Device Interconnect.

PubMed

Kim, Kang O; Kim, Sunjung

2016-05-01

Cu-Ag alloy interconnect is promising for ultra-large-scale integration (ULSI) microelectronic system of which device dimension keeps shrinking. In this study, seedless electrodeposition of Cu-Ag alloy directly on W diffusion barrier as interconnect technology is presented in respect of nano-nucleation control. Chemical equilibrium state of electrolyte was fundamentally investigated according to the pH of electrolyte because direct nano-nucleation of Cu-Ag alloy on W surface is challenging. Chelation behavior of Cu2+ and Ag+ ions with citrate (Cit) and ammonia ligands was dependent on the pH of electrolyte. The amount and kind of Cu- and Ag-based complexes determine the deposition rate, size, elemental composition, and surface morphology of Cu-Ag alloy nano-nuclei formed on W surface.

Synthesis, characterization, and chiral properties of CoIII2AgI3 pentanuclear, CoIII4ZnII4 octanuclear, and CoIII mononuclear complexes with aza-capped hexadentate-N3S3 thiolate ligands: crystal structures of.

PubMed

Tokuda, K; Okamoto, K; Konno, T

2000-01-24

The reaction of an S-bridged Co2(III)Ag3(I) pentanuclear complex, [Ag3[Co(aet)3]2][BF4]3 (aet = NH2CH2CH2S-), with paraformaldehyde in basic acetonitrile, followed by adding aqueous ammonia, produced an aza-capped Co2(III)-Ag3(I) complex, [Ag3[Co(L)]2]3+ ([1]3+) (L = N(CH2NHCH2CH2S-)3). The crystal structure of [1]3+ was determined by X-ray crystallography. [1][PF6]3 x H2O, empirical formula C18H44Ag3Co2F18N8OP3S6, crystallizes in the tetragonal space group 142m with a = 13.012(1) A, c = 24.707(2) A, and Z = 4. In [1]3+ the two aza-capped [Co(L)] units are linked by three Ag(I) atoms, such that the two Co(III) atoms are encapsulated in a macrobicyclic metallocage, [Ag3(I)(L)2]3-. [1]3+ was converted to an aza-capped Co4(III)Zn4(II) octanuclear complex, [Zn4O[Co(L)]4]6+ ([2]6+), by reaction with I- in the presence of Zn2+ and ZnO in water. The crystal structure of [2]6+ was also determined by X-ray crystallography. [2][PF6]6 x 8H2O, empirical formula C36H100Co4F36N16O9P6S12Zn4, crystallizes in the monoclinic space group P2(1/n) with a = 14.33(7) A, b = 25.67(10) A, c = 24.83(6) A, beta = 101.3(3) degrees , and Z = 4. In [2]6+ each of four [Co(L)] units is bound to each trigonal Zn3(II) face of the tetrahedral [Zn4(II)O]6+ core, such that each Co(III) atom is encapsulated in a macrobicyclic [Zn4(II)O(L)] fragment. Treatment of [2]6+ with a basic aqueous solution resulted in a cleavage of the Zn-S bonds to produce an aza-capped Co(III) mononuclear complex, [Co(L)] ([3]), from which [1]3+ is readily reproduced by the reaction with Ag+ in water. All the reactions were found to proceed with retention of the absolute configuration (delta or lambda) of the Co(III) chiral centers; deltadelta-[1]3+, deltadeltadeltadelta-[2]6+, and A-[3] were derived from deltadelta-[Ag3[Co(aet)3]2]3+. The contributions to circular dichroism (CD) from the triple helicity in [1]3+, besides from the asymmetric N and S donor atoms and the Co(III) chiral centers in [1]3+ and [2]6+, were estimated by comparing the CD spectra of deltadelta-[1]3+, deltadeltadeltadelta-[2]6+, and delta-[3].

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

Jones, L.W.; Krisch, A.D.

This report contains papers on the following topics: Kent M Terwilliger; Graduate School at Berkeley and Early Years at Michigan, 1949--1959; Terwilliger and the Group'': A Chronicle of MURA; Reflections on the MURA Years; The Evolution of High Energy Accelerators; Some Frontiers of Accelerator Physics; Reflections on the ZGS: Terwilliger's Contributions; Spark Chambers and Early Experiments; Strong Interaction Experiments at the ZGS; Polarized Beams at the ZGS and the AGS; Terwilliger and Spin Physics; Siberian Snakes and Future Polarized Beams; Washington and High Energy Physics; and Terwilliger in the Department and University. These papers have been cataloged separately. (LSP)

Microstructure and dielectric properties of silver-barium titanate nanocomplex materials by wet chemical approach

NASA Astrophysics Data System (ADS)

Ueno, Shintaro; Sakamoto, Yasunao; Nakashima, Kouichi; Wada, Satoshi

2014-09-01

To develop ceramic capacitors with a high effective dielectric constant, we attempted to fabricate BaTiO3 (BT) complexes with embedded Ag nanoparticles by wet chemical processes. Ag nanoparticle-adsorbed dendritic BT particles, Ag-BT hybrid particles, were synthesized from the sol-gel-derived precursor gel powders containing Ag, Ba, and Ti by hydrothermal treatment. These particles were pressed with BT fillers and TiO2 precursor nanoparticles into green compacts, and then, the green compacts were chemically converted into the Ag/BT nanocomplex compacts in Ba(OH)2 aqueous solution under the hydrothermal condition at 160 °C. The effective dielectric constant of the resultant Ag/BT nanocomplexes increases with an increase in Ag content. The maximal effective dielectric constant of approximately 900 was recorded for the nanocomplex with the Ag content of 10.7 vol %.

Silver in geological fluids from in situ X-ray absorption spectroscopy and first-principles molecular dynamics

NASA Astrophysics Data System (ADS)

Pokrovski, Gleb S.; Roux, Jacques; Ferlat, Guillaume; Jonchiere, Romain; Seitsonen, Ari P.; Vuilleumier, Rodolphe; Hazemann, Jean-Louis

2013-04-01

The molecular structure and stability of species formed by silver in aqueous saline solutions typical of hydrothermal settings were quantified using in situ X-ray absorption spectroscopy (XAS) measurements, quantum-chemical modeling of near-edge absorption spectra (XANES) and extended fine structure spectra (EXAFS), and first-principles molecular dynamics (FPMD). Results show that in nitrate-bearing acidic solutions to at least 200 °C, silver speciation is dominated by the hydrated Ag+ cation surrounded by 4-6 water molecules in its nearest coordination shell with mean Ag-O distances of 2.32 ± 0.02 Å. In NaCl-bearing acidic aqueous solutions of total Cl concentration from 0.7 to 5.9 mol/kg H2O (m) at temperatures from 200 to 450 °C and pressures to 750 bar, the dominant species are the di-chloride complex AgCl2- with Ag-Cl distances of 2.40 ± 0.02 Å and Cl-Ag-Cl angle of 160 ± 10°, and the tri-chloride complex AgCl32- of a triangular structure and mean Ag-Cl distances of 2.60 ± 0.05 Å. With increasing temperature, the contribution of the tri-chloride species decreases from ˜50% of total dissolved Ag in the most concentrated solution (5.9m Cl) at 200 °C to less than 10-20% at supercritical temperatures for all investigated solutions, so that AgCl2- becomes by far the dominant Ag-bearing species at conditions typical of hydrothermal-magmatic fluids. Both di- and tri-chloride species exhibit outer-sphere interactions with the solvent as shown by the detection, using FPMD modeling, of H2O, Cl-, and Na+ at distances of 3-4 Å from the silver atom. The species fractions derived from XAS and FPMD analyses, and total AgCl(s) solubilities, measured in situ in this work from the absorption edge height of XAS spectra, are in accord with thermodynamic predictions using the stability constants of AgCl2- and AgCl32- from Akinfiev and Zotov (2001) and Zotov et al. (1995), respectively, which are based on extensive previous AgCl(s) solubility measurements. These data are thus recommended for chemical equilibrium calculations in mineral-fluid systems above 200 °C. In contrast, our data disagree with SUPCRT-based datasets for Ag-Cl species, which predict large fractions of high-order chloride species, AgCl32- and AgCl43- in high-temperature saline fluids. Comparisons of the structural and stability data of Ag-Cl species derived in this study with those of their Au and Cu analogs suggest that molecular-level differences amongst the chloride complexes such as geometry, dipole moment, distances, and resulting outer-sphere interactions with the solvent may account, at least partly, for the observed partitioning of Au, Ag and Cu in vapor-brine and fluid-melt systems. In hydrothermal environments dominated by fluid-rock interactions, the contrasting affinity of these metals for sulfur ligands and the differences both in chemistry and stability of their main solid phases (Ag sulfides, Cu-Fe sulfides, and native Au) largely control the concentration and distribution of these metals in their economic deposits.

Discontinuous and continuous hardening processes in calcium and calcium—tin micro-alloyed lead: influence of 'secondary-lead' impurities

NASA Astrophysics Data System (ADS)

Bouirden, L.; Hilger, J. P.; Hertz, J.

Different transformations in leadcalcium and leadcaciumtin alloys are observed with various complementary techniques such as anisothermal microcalorimetry, optical and electronic microscopy, hardness measurements. Three alloy states are studied: as-cast, rehomogenised/water-quenched, rehomogenised/air-cooled. With binary leadcalcium alloys, three successive discontinuous transformations are observed, namely: an initial and complete discontinuous transformation with regular moving of the front of reaction; a second and incomplete discontinuous transformation (puzzle-shaped); a third and incomplete discontinuous transformation with precipitation of Pb 3Ca. The role of secondary-lead impurities is complex: Ag reduces and Bi accelerates the rate of the discontinuous reaction, while Al refines the grain size. Leadcalciumtin are characterized by the Sn/Ca ratio. For very small values of this ratio, the hardening is similar to that of leadcalcium alloys. For high ratio values, the hardening takes place after an incubation period and proceeds via a continuous micro-precipitation of the (PbSn) 3Ca Compound. For intermediate ratios, the different processes are able to operate separately in sequence. Ag increases the rate of the continuous precipitation and reduces the incubation time. No significant effects are observed with Bi or Al. The kinetic laws of the different transformations are presented and values for the energy of activation are determined.

Low-Cost, Disposable, Flexible and Highly Reproducible Screen Printed SERS Substrates for the Detection of Various Chemicals

PubMed Central

Wu, Wei; Liu, Li; Dai, Zhigao; Liu, Juhua; Yang, Shuanglei; Zhou, Li; Xiao, Xiangheng; Jiang, Changzhong; Roy, Vellaisamy A.L.

2015-01-01

Ideal SERS substrates for sensing applications should exhibit strong signal enhancement, generate a reproducible and uniform response, and should be able to fabricate in large-scale and low-cost. Herein, we demonstrate low-cost, highly sensitive, disposable and reproducible SERS substrates by means of screen printing Ag nanoparticles (NPs) on a plastic PET (Polyethylene terephthalate) substrates. While there are many complex methods for the fabrication of SERS substrates, screen printing is suitable for large-area fabrication and overcomes the uneven radial distribution. Using as-printed Ag substrates as the SERS platform, detection of various commonly known chemicals have been done. The SERS detection limit of Rhodamine 6G (R6G) is higher than the concentration of 1 × 10−10 M. The relative standard deviation (RSD) value for 784 points on the detection of R6G and Malachite green (MG) is less than 20% revealing a homogeneous SERS distribution and high reproducibility. Moreover, melamine (MA) is detected in fresh liquid-milk without additional pretreatment, which may accelerate the application of rapid on-line detection of MA in liquid milk. Our screen printing method highlights the use of large-scale printing strategies for the fabrication of well-defined functional nanostructures with applications well beyond the field of SERS sensing. PMID:25974125

Synthesis, characterization, and antimicrobial activity of silver(I) and copper(II) complexes of phosphate derivatives of pyridine and benzimidazole.

PubMed

Kalinowska-Lis, Urszula; Szewczyk, Eligia M; Chęcińska, Lilianna; Wojciechowski, Jakub M; Wolf, Wojciech M; Ochocki, Justyn

2014-01-01

Two silver(I) complexes--[Ag(4-pmOpe)]NO₃}(n) and [Ag(2-bimOpe)₂]NO₃--and three copper(II) complexes--[Cu₄Cl₆O(2-bimOpe)₄], [CuCl₂(4-pmOpe)₂], and [CuCl₂(2-bis(pm)Ope]--were synthesized by reaction of silver(I) nitrate or copper(II) chloride with phosphate derivatives of pyridine and benzimidazole, namely diethyl (pyridin-4-ylmethyl)phosphate (4-pmOpe), 1H-benzimidazol-2-ylmethyl diethyl phosphate (2-bimOpe), and ethyl bis(pyridin-2-ylmethyl)phosphate (2-bis(pm)Ope). These compounds were characterized by ¹H, ¹³C, and ³¹P NMR as well as IR spectroscopy, elemental analysis, and ESIMS spectrometry. Additionally, molecular and crystal structures of {[Ag(4-pmOpe)]NO₃}n and [Cu₄Cl₆O(2-bimOpe)₄] were determined by single-crystal X-ray diffraction analysis. The antimicrobial profiles of synthesized complexes and free ligands against test organisms from the ATCC and clinical sources were determined. Silver(I) complexes showed good antimicrobial activities against Candida albicans strains (MIC values of ∼19 μM). [Ag(2-bimOpe)₂]NO₃ was particularly active against Pseudomonas aeruginosa and methicillin-resistant Staphylococcus epidermidis, with MIC values of ∼5 and ∼10 μM, respectively. Neither copper(II) complexes nor the free ligands inhibited the growth of test organisms at concentrations below 500 μg mL⁻¹. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical DNA probe for Hg(2+) detection based on a triple-helix DNA and Multistage Signal Amplification Strategy.

PubMed

Wang, Huan; Zhang, Yihe; Ma, Hongmin; Ren, Xiang; Wang, Yaoguang; Zhang, Yong; Wei, Qin

2016-12-15

In this work, an ultrasensitive electrochemical sensor was developed for detection of Hg(2+). Gold nanoparticles decorated bovine serum albumin reduction of graphene oxide (AuNP-BSA-rGO) were used as subsurface material for the immobilization of triple-helix DNA. The triple-helix DNA containing a thiol labelled single-stranded DNA (sDNA) and a thymine-rich DNA (T-rich DNA), which could be unwinded in the present of Hg(2+) to form more stable thymine-Hg(2+)-thymine (T-Hg(2+)-T) complex. T-Hg(2+)-T complex was then removed and the sDNA was left on the electrode. At this time, gold nanoparticle carrying thiol labelled cytosine-rich complementary DNA (cDNA-AuNP) could bind with the free sDNA. Meanwhile, the other free cDNA on AuNP could bind with each other in the present of Ag(+) to form the stable cytosine-Ag(+)-cytosine (C-Ag(+)-C) complex and circle amplification. Plenty of C-Ag(+)-C could form silver nanoclusters by electrochemical reduction and the striping signal of Ag could be measured for purpose of the final electrochemical detection of Hg(2+). This sensor could detect Hg(2+) over a wide concentration range from 0.1 to 130nM with a detection limit of 0.03nM. Copyright © 2016 Elsevier B.V. All rights reserved.

A multi-frequency EPR and ENDOR study of Rh and Ir complexes in alkali and silver halides

NASA Astrophysics Data System (ADS)

Callens, F.; Vrielinck, H.; Matthys, P.

2003-01-01

Aliovalent Rh and Ir cations have been frequently used to influence the photographic properties of silver halide emulsions. The doping introduces several types of related defects with distinct trapping and recombination properties. EPR and ENDOR are, in principle, ideally suited for the determination of the microscopic structure of the individual centres but it will be demonstrated that well-chosen, sometimes sophisticated multi-frequency experiments are necessary in order to (partially) reach this goal. Model studies on single crystals of AgCl and NaCl also appeared indispensable for the unravelling of the spectra. In the review of Rh-centres in NaCl and AgCl special attention is paid to methods that allow to detect cation vacancies near Rh2+ complexes. An alternative explanation for the high temperature behaviour of the [RhCl6](4-) complexes in AgCl is presented.

Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes.

PubMed

Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M Arif

2016-05-15

We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica. Copyright © 2016 Elsevier B.V. All rights reserved.

Photochemical syntheses, transformations, and bioorthogonal chemistry of trans-cycloheptene and sila trans-cycloheptene Ag(i) complexes† †Electronic supplementary information (ESI) available: Full procedures, computational details and characterization data. CCDC 1583975 and 1583976. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04773h

PubMed Central

Fang, Yinzhi; Zhang, Han; Huang, Zhen; Scinto, Samuel L.; Yang, Jeffrey C.; am Ende, Christopher W.; Dmitrenko, Olga; Johnson, Douglas S.

2018-01-01

A photochemical synthesis of AgNO3 complexes of trans-cycloheptene (TCH) and trans-1-sila-4-cycloheptene (Si-TCH) derivatives is described. A low temperature flow photoreactor was designed to enable the synthesis of carbocyclic TCH derivatives due to their thermal sensitivity in the absence of metal coordination. Unlike the free carbocycles, TCH·AgNO3 complexes can be handled at rt and stored for weeks in the freezer (–18 °C). Si-TCH·AgNO3 complexes are especially robust, and are bench stable for days at rt, and for months in the freezer. X-ray crystallography was used to characterize a Si-TCH·AgNO3 complex for the first time. With decomplexation of AgNO3in situ, metal-free TCO and Si-TCH derivatives can engage in a range of cycloaddition reactions as well as dihydroxylation reactions. Computation was used to predict that Si-TCH would engage in bioorthogonal reactions that are more rapid than the most reactive trans-cyclooctenes. Metal-free Si-TCH derivatives were shown to display good stability in solution, and to engage in the fastest bioorthogonal reaction reported to date (k2 1.14 × 107 M–1 s–1 in 9 : 1 H2O : MeOH). Utility in bioorthogonal protein labeling in live cells is described, including labeling of GFP with an unnatural tetrazine-containing amino acid. The reactivity and specificity of the Si-TCH reagents with tetrazines in live mammalian cells was also evaluated using the HaloTag platform. The cell labeling experiments show that Si-TCH derivatives are best suited as probe molecules in the cellular environment. PMID:29675242

Quantum chemical study, spectroscopic investigations, NBO and HOMO-LUMO analyses of 3-aminoquinoline (3AQ) and [Ag(3AQ)2(TCA)] complex (TCA = Trichloroacetate)

NASA Astrophysics Data System (ADS)

Soliman, Saied M.; Kassem, Taher S.; Badr, Ahmed M. A.; Abu Youssef, Morsy A.; Assem, Rania

2014-09-01

The new [Ag(3AQ)2(TCA)]; (3AQ = 3-aminoquinoline and TCA = Trichloroacetate) complex is synthesized and characterized using elemental analysis, FTIR, NMR and mass spectroscopy. The molecular geometry, vibrational frequencies, gauge-including atomic orbital (GIAO) 1H chemical shift values of the free and coordinated 3AQ in the ground state have been calculated by using DFT/B3LYP method. The TD-DFT results of the [Ag(3AQ)2(TCA)] complex showed a π-π* transition band at 240.3-242.6 nm (f = 0.1334-0.1348) which has longer wavelength and lower absorption intensity than that for the free 3AQ (233.2 nm, f = 0.3958). Dipole moment, polarizability and HOMO-LUMO gap values predicted better nonlinear optical properties (NLO) for the [Ag(3AQ)2(TCA)] than the 3AQ ligand. NBO analysis has been used to predict the most accurate Lewis structure of the studied molecules. The energies of the different intramolecular charge transfer (ICT) interactions within the studied molecules were estimated using second order perturbation theory.

Synthesis and evaluation of α-Ag2WO4 as novel antifungal agent

NASA Astrophysics Data System (ADS)

Foggi, Camila C.; Fabbro, Maria T.; Santos, Luís P. S.; de Santana, Yuri V. B.; Vergani, Carlos E.; Machado, Ana L.; Cordoncillo, Eloisa; Andrés, Juan; Longo, Elson

2017-04-01

Because of the need for new antifungal materials with greater potency, microcrystals of α-Ag2WO4, a complex metal oxide, have been synthetized by a simple co-precipitation method, and their antifungal activity against Candida albicans has been investigated. A theoretical model based on clusters that are building blocks of α-Ag2WO4 has been proposed to explain the experimental results.

Developmental toxicity of Japanese medaka embryos by silver nanoparticles and released ions in the presence of humic acid.

PubMed

Kim, Jun Y; Kim, Ki-Tae; Lee, Byeong G; Lim, Byung J; Kim, Sang D

2013-06-01

The final destination point of nanoparticles is the environment, where they remain a long period; therefore, a deep understanding of the relationship between nanoparticles and the environmental factors is required. Japanese medaka embryos were exposed to two differently prepared AgNPs: freshly prepared AgNPs and aged AgNPs. With these two AgNP preparations, we studied the impacts of humic acid in terms of embryonic toxicity, as well as the behavior of AgNPs. Aged AgNPs exhibited a lower lethal concentration (LC50) value (1.44mg/L) compared to fresh AgNPs (3.53mg/L) through 96h acute toxicity tests, due to the release of silver ions, as confirmed by kinetic analysis. The presence of humic acids considerably reduced the toxicity of aged AgNPs due to complexation with silver ions. Agglomeration, induced by interactions with humic acid, might reduce the bioavailability of AgNPs to Japanese medaka embryos. This study demonstrates that aged AgNPs releasing more silver ions are more toxic than fresh AgNPs, and humic acids play a role in reducing the toxicity of aged AgNPs. Copyright © 2013 Elsevier Inc. All rights reserved.

A noncoding RNA transcribed from the AGAMOUS (AG) second intron binds to CURLY LEAF and represses AG expression in leaves.

PubMed

Wu, Hui-Wen; Deng, Shulin; Xu, Haiying; Mao, Hui-Zhu; Liu, Jun; Niu, Qi-Wen; Wang, Huan; Chua, Nam-Hai

2018-06-04

Dispersed H3K27 trimethylation (H3K27me3) of the AGAMOUS (AG) genomic locus is mediated by CURLY LEAF (CLF), a component of the Polycomb Repressive Complex (PRC) 2. Previous reports have shown that the AG second intron, which confers AG tissue-specific expression, harbors sequences targeted by several positive and negative regulators. Using RACE reverse transcription polymerase chain reaction, we found that the AG intron 2 encodes several noncoding RNAs. RNAi experiment showed that incRNA4 is needed for CLF repressive activity. AG-incRNA4RNAi lines showed increased leaf AG mRNA levels associated with a decrease of H3K27me3 levels; these plants displayed AG overexpression phenotypes. Genetic and biochemical analyses demonstrated that the AG-incRNA4 can associate with CLF to repress AG expression in leaf tissues through H3K27me3-mediated repression and to autoregulate its own expression level. The mechanism of AG-incRNA4-mediated repression may be relevant to investigations on tissue-specific expression of Arabidopsis MADS-box genes. © 2018 The Authors New Phytologist © 2018 New Phytologist Trust.

Biomolecule-assisted hydrothermal synthesis of silver bismuth sulfide with nanostructures

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

Kaowphong, Sulawan, E-mail: sulawank@gmail.com; Materials Science Research Center, Faculty of Science, Chiang Mai University, Chiang Mai 50200

2012-05-15

Silver bismuth sulfide (AgBiS{sub 2}) nanostructures were successfully prepared via a simple biomolecule-assisted hydrothermal synthesis at 200 Degree-Sign C for 12-72 h. Silver nitrate, bismuth nitrate and L-cysteine were used as starting materials. Here, the biomolecule, L-cysteine, was served as the sulfide source and a complexing agent. The products, characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), were cubic AgBiS{sub 2} nanoparticles with a diameter range of about 20-75 nm. It was found that their crystallinity and particle size increased with increasing reaction time. The energy dispersive X-ray spectroscopy (EDX) and inductively coupledmore » plasma optical emission spectrophotometry (ICP-OES) analyses were used to confirm the stoichiometry of AgBiS{sub 2}. The optical band gap of the AgBiS{sub 2} nanoparticles, calculated from UV-vis spectra, was 3.0 eV which indicated a strong blue shift because of the quantum confinement effect. A possible formation mechanism of the AgBiS{sub 2} nanoparticles was also discussed. - Graphical abstract: The optical band gap of the as-prepared AgBiS{sub 2} nanoparticles displays a strong blue shift comparing to the 2.46 eV of bulk AgBiS{sub 2} caused by the quantum confinement effects. Highlights: Black-Right-Pointing-Pointer A simple biomolecule-assisted hydrothermal method is developed to prepare AgBiS{sub 2}. Black-Right-Pointing-Pointer L-Cysteine is served as the sulfide source and a complexing agent. Black-Right-Pointing-Pointer Increase in band gap of the AgBiS{sub 2} nanoparticles attributes to the quantum confinement effects.« less

Hepatitis B surface antigen (HBsAg) expression in plant cell culture: Kinetics of antigen accumulation in batch culture and its intracellular form.

PubMed

Smith, Mark L; Mason, Hugh S; Shuler, Michael L

2002-12-30

The production of edible vaccines in transgenic plants and plant cell culture may be improved through a better understanding of antigen processing and assembly. The hepatitis B surface antigen (HBsAg) was chosen for study because it undergoes substantial and complex post-translational modifications, which are necessary for its immunogenicity. This antigen was expressed in soybean (Glycine max L. Merr. cv Williams 82) and tobacco NT1 (Nicotiana tabacum L.) cell suspension cultures, and HBsAg production in batch culture was characterized. The plant-derived antigen consisted predominantly of disulfide cross-linked HBsAg protein (p24(s)) dimers, which were all membrane associated. Similar to yeast, the plant-expressed HBsAg was retained intracellularly. The maximal HBsAg titers were obtained with soybean suspension cultures (20-22 mg/L) with titers in tobacco cultures being approximately 10-fold lower. For soybean cells, electron microscopy and immunolocalization demonstrated that all the HBsAg was localized to the endoplasmic reticulum (ER) and provoked dilation and proliferation of the ER network. Sucrose gradient analysis of crude extracts showed that HBsAg had a complex size distribution uncharacteristic of the antigen's normal structure of uniform 22-nm virus-like particles. The extent of authentic epitope formation was assessed by comparing total p24(s) synthesized to that reactive by polyclonal and monoclonal immunoassays. Depending on culture age, between 40% and 100% of total p24(s) was polyclonal antibody reactive whereas between 6% and 37% was recognized by a commercial monoclonal antibody assay. Possible strategies to increase HBsAg production and improve post-translational processing are discussed. Copyright 2002 Wiley Periodicals, Inc.

Interaction of flavonols with human serum albumin: a biophysical study showing structure-activity relationship and enhancement when coated on silver nanoparticles.

PubMed

Das, Pratyusa; Chaudhari, Sunil Kumar; Das, Asmita; Kundu, Somashree; Saha, Chabita

2018-04-24

Binding affinities of flavonols namely quercetin, myricetin, and kaempferol to human serum albumin (HSA) were determined fluorimetrically and the order was observed to be myricetin > quercetin > kaempferol demonstrating structure-activity relationship. Quercetin-coated silver nanoparticles (AgNPs) show higher binding affinity to HSA compared to free quercetin with binding constants 6.04 × 10 7  M -1 and 4.2 × 10 6  M -1 , respectively. Using site-specific markers it is concluded that free quercetin and that coated on AgNPs bind at different sites. Significant structural changes in circular dichroism (CD) spectra of HSA were recorded with quercetin-coated AgNPs compared to free quercetin. These results were further substantiated by time-resolved fluorescence spectroscopy where fluorescence life time of the tryptophan residue in HSA-quercetin-coated AgNPs complex decreased to 3.63 ns from 4.22 ns in HSA-quercetin complex. Isothermal calorimetric studies reveal two binding modes for quercetin-coated AgNPs and also higher binding constants compared to free quercetin. These higher binding affinities are attributed to altered properties of quercetin when coated on AgNPs enabling it to reach the binding sites other than site II where free quercetin mainly binds.

One-pot synthesis of monodisperse CoFe2O4@Ag core-shell nanoparticles and their characterization.

PubMed

Hara, Shuta; Aisu, Jumpei; Kato, Masahiro; Aono, Takashige; Sugawa, Kosuke; Takase, Kouichi; Otsuki, Joe; Shimizu, Shigeru; Ikake, Hiroki

2018-06-08

In recent years, monodispersed magnetic nanoparticles with a core/shell structure are expected for their wide applications including magnetic fluid, recoverable catalysts, and biological analysis. However, their synthesis method needs numerous processes such as solvent substitution, exchange of protective agents, and centrifugation. A simple and rapid method for the synthesis of monodispersed core-shell nanoparticles makes it possible to accelerate their further applications. This paper describes a simple and rapid one-pot synthesis of core (CoFe 2 O 4 )-shell (Ag) nanoparticles with high monodispersity. The synthesized nanoparticles showed plasmonic light absorption owing to the Ag shell. Moreover, the magnetic property of the nanoparticles had a soft magnetic behavior at room temperature and a hard magnetic behavior at 5 K. In addition, the nanoparticles showed high monodispersity with a low polydispersity index (PDI) value of 0.083 in hexane.

Silica nanoparticle stability in biological media revisited.

PubMed

Yang, Seon-Ah; Choi, Sungmoon; Jeon, Seon Mi; Yu, Junhua

2018-01-09

The stability of silica nanostructure in the core-silica shell nanomaterials is critical to understanding the activity of these nanomaterials since the exposure of core materials due to the poor stability of silica may cause misinterpretation of experiments, but unfortunately reports on the stability of silica have been inconsistent. Here, we show that luminescent silver nanodots (AgNDs) can be used to monitor the stability of silica nanostructures. Though relatively stable in water and phosphate buffered saline, silica nanoparticles are eroded by biological media, leading to the exposure of AgNDs from AgND@SiO 2 nanoparticles and the quenching of nanodot luminescence. Our results reveal that a synergistic effect of organic compounds, particularly the amino groups, accelerates the erosion. Our work indicates that silica nanostructures are vulnerable to cellular medium and it may be possible to tune the release of drug molecules from silica-based drug delivery vehicles through controlled erosion.

One-pot synthesis of monodisperse CoFe2O4@Ag core-shell nanoparticles and their characterization

NASA Astrophysics Data System (ADS)

Hara, Shuta; Aisu, Jumpei; Kato, Masahiro; Aono, Takashige; Sugawa, Kosuke; Takase, Kouichi; Otsuki, Joe; Shimizu, Shigeru; Ikake, Hiroki

2018-06-01

In recent years, monodispersed magnetic nanoparticles with a core/shell structure are expected for their wide applications including magnetic fluid, recoverable catalysts, and biological analysis. However, their synthesis method needs numerous processes such as solvent substitution, exchange of protective agents, and centrifugation. A simple and rapid method for the synthesis of monodispersed core-shell nanoparticles makes it possible to accelerate their further applications. This paper describes a simple and rapid one-pot synthesis of core (CoFe2O4)-shell (Ag) nanoparticles with high monodispersity. The synthesized nanoparticles showed plasmonic light absorption owing to the Ag shell. Moreover, the magnetic property of the nanoparticles had a soft magnetic behavior at room temperature and a hard magnetic behavior at 5 K. In addition, the nanoparticles showed high monodispersity with a low polydispersity index (PDI) value of 0.083 in hexane.

Rebamipide inhibits gastric cancer growth by targeting survivin and Aurora-B

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

Tarnawski, A.; University of California, Irvine, CA 92697; E-mail: andrzej.tarnawski@med.va.gov

Rebamipide accelerates healing of gastric ulcers and gastritis but its actions on gastric cancer are not known. Survivin, an anti-apoptosis protein, is overexpressed in stem, progenitor, and cancer cells. In gastric cancer, increased and sustained survivin expression provides survival advantage and facilitates tumor progression and resistance to anti-cancer drugs. Aurora-B kinase is essential for chromosome alignment and mitosis progression but surprisingly its role in gastric cancer has not been explored. We examined in human gastric cancer AGS cells: (1) survivin expression, (2) localization of survivin and Aurora-B (3) cell proliferation, and (4) effects of specific survivin siRNA and/or rebamipide (freemore » radical scavenging drug) on survivin and Aurora-B expression and cell proliferation. Survivin and Aurora-B are strongly expressed in human AGS gastric cancer cells and co-localize during mitosis. Survivin siRNA significantly reduces AGS cell viability. Rebamipide significantly downregulates in AGS cell survivin expression, its association with Aurora-B and cell proliferation. Rebamipide-induced downregulation of survivin is at the transcription level and does not involve ubiquitin-proteasome pathway.« less

Influence of Fluoride Ion on the Performance of Pb-Ag Anode During Long-Term Galvanostatic Electrolysis

NASA Astrophysics Data System (ADS)

Zhong, Xiaocong; Yu, Xiaoying; Jiang, Liangxing; Lv, Xiaojun; Liu, Fangyang; Lai, Yanqing; Li, Jie

2015-09-01

Anodic potential, morphology and phase composition of the anodic layer, corrosion morphology of the metallic substrate, and oxygen evolution behavior of Pb-Ag anode in H2SO4 solution without/with fluoride ion were investigated and compared. The results showed that the presence of fluoride ions contributed to a smoother anodic layer with lower PbO2 concentration, which resulted in lower double layer capacity and higher charge transfer resistance for the oxygen evolution reaction. Consequently, the Pb-Ag anode showed a higher anodic potential (about 35 mV) in the fluoride-containing electrolyte. In addition, the fluoride ions accelerated the detachment of loose flakes on the anodic layer. It was demonstrated that the anodic layer formed in the fluoride-containing H2SO4 solution was thinner. Furthermore, fluoride ions aggravated the corrosion of the metallic substrate at interdendritic boundary regions. Hence, the presence of fluoride ions is detrimental to oxygen evolution reactivity and increases the corrosion of the Pb-Ag anode, which may further increase the energy consumption and capital cost of zinc plants.

Flash-induced nanowelding of silver nanowire networks for transparent stretchable electrochromic devices.

PubMed

Lee, Chihak; Oh, Youngsu; Yoon, In Seon; Kim, Sun Hong; Ju, Byeong-Kwon; Hong, Jae-Min

2018-02-09

Electrochromic devices (ECDs) are emerging as a novel technology for various applications like commercialized smart window glasses, and auto-dimming rear-view mirrors. Recently, the development of low-power, lightweight, flexible, and stretchable devices has been accelerated to meet the growing demand in the new wearable devices market. Silver nanowires (AgNWs) can become new primary transparent conducting electrode (TCE) materials to replace indium tin oxide (ITO) for ECDs. However, issues such as substrate adhesion, delamination, and higher resistance still exist with AgNWs. Herein, we report a high-performance stretchable flash-induced AgNW-network-based TCE on surface-treated polydimethylsiloxane (PDMS) substrates. A Xe flash light method was used to create nanowelded networks of AgNWs. Surface silane treatments increased the adhesion and durability of the films as well. Finally, ECDs were fabricated under the optimal conditions and examined under strained conditions to demonstrate the resistance and mechanical behaviours of the devices. Results showed a flexible and durable film maintaining a high level of conductivity and reversible resistance behaviour, beyond those currently achievable with standard ITO/PET flexible TCEs.

Development of neutron-monitor detector using liquid organic scintillator coupled with 6Li + ZnS(Ag) Sheet.

PubMed

Sato, Tatsuhiko; Endo, Akira; Yamaguchi, Yasuhiro; Takahashi, Fumiaki

2004-01-01

A phoswitch-type detector has been developed for monitoring neutron doses in high-energy accelerator facilities. The detector is composed of a liquid organic scintillator (BC501A) coupled with ZnS(Ag) sheets doped with 6Li. The dose from neutrons with energies above 1 MeV is evaluated from the light output spectrum of the BC501A by applying the G-function, which relates the spectrum to the neutron dose directly. The dose from lower energy neutrons, on the other hand, is estimated from the number of scintillations emitted from the ZnS(Ag) sheets. Characteristics of the phoswitch-type detector were studied experimentally in some neutron fields. It was found from the experiments that the detector has an excellent property of pulse-shape discrimination between the scintillations of BC501A and the ZnS(Ag) sheets. The experimental results also indicate that the detector is capable of reproducing doses from thermal neutrons as well as neutrons with energies from one to several tens of megaelectronvolts (MeV).

Growth and structural evolution of Sn on Ag(001): Epitaxial monolayer to thick alloy film

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

Chakraborty, Suvankar; Menon, Krishnakumar S. R., E-mail: krishna.menon@saha.ac.in

The growth and structure of Sn on Ag(001), from submonolayer to thick film coverages at room temperature, are studied using low energy electron diffraction, x-ray photoemission spectroscopy and angle-resolved photoemission spectroscopy (ARPES) techniques. The authors observe different growth modes for submonolayer Sn coverages and for higher Sn coverages. Systematic surface structural evolution, consistent with the substitution of surface Ag atoms by Sn atoms, is observed for submonolayer Sn coverages while an ordered Ag-Sn bulk alloy film is formed for higher Sn coverages with an Ag overlayer. For monolayer coverage of Sn, a pseudomorphic growth of a Sn layer without alloyingmore » is determined. ARPES results also confirm the presence of an ordered Ag overlayer on the bulk Ag-Sn alloy film, suggesting the formation of an Ag/Ag{sub 3}Sn/Ag(001) sandwich structure at the surface for higher Sn coverages. The present results illustrate the complex interplay of atomic mobilities, surface free-energies, and alloy formation energies in determining the growth and structural properties of the system.« less

On the Dynamical Behavior of the Cysteine Dioxygenase-l-Cysteine Complex in the Presence of Free Dioxygen and l-Cysteine.

PubMed

Pietra, Francesco

2017-11-01

In this work, viable models of cysteine dioxygenase (CDO) and its complex with l-cysteine dianion were built for the first time, under strict adherence to the crystal structure from X-ray diffraction studies, for all atom molecular dynamics (MD). Based on the CHARMM36 FF, the active site, featuring an octahedral dummy Fe(II) model, allowed us observing water exchange, which would have escaped attention with the more popular bonded models. Free dioxygen (O 2 ) and l-cysteine, added at the active site, could be observed being expelled toward the solvating medium under Random Accelerated Molecular Dynamics (RAMD) along major and minor pathways. Correspondingly, free dioxygen (O 2 ), added to the solvating medium, could be observed to follow the same above pathways in getting to the active site under unbiased MD. For the bulky l-cysteine, 600 ns of trajectory were insufficient for protein penetration, and the molecule was stuck at the protein borders. These models pave the way to free energy studies of ligand associations, devised to better clarify how this cardinal enzyme behaves in human metabolism. © 2017 Wiley-VHCA AG, Zurich, Switzerland.

Structure of fluorescent metal clusters on a DNA template.

NASA Astrophysics Data System (ADS)

Vdovichev, A. A.; Sych, T. S.; Reveguk, Z. V.; Smirnova, A. A.; Maksimov, D. A.; Ramazanov, R. R.; Kononov, A. I.

2016-08-01

Luminescent metal clusters are a subject of growing interest in recent years due to their bright emission from visible to near infrared range. Detailed structure of the fluorescent complexes of Ag and other metal clusters with ligands still remains a challenging task. In this joint experimental and theoretical study we synthesized Ag-DNA complexes on a DNA oligonucleotide emitting in violet- green spectral range. The structure of DNA template was determined by means of various spectral measurements (CD, MS, XPS). Comparison of the experimental fluorescent excitation spectra and calculated absorption spectra for different QM/MM optimized structures allowed us to determine the detailed structure of the green cluster containing three silver atoms in the stem of the DNA hairpin structure stabilized by cytosine-Ag+-cytosine bonds.

Effect of Time Dependent Bending of Current Sheets in Response to Generation of Plasma Jets and Reverse Currents

NASA Astrophysics Data System (ADS)

Frank, Anna

Magnetic reconnection is a basis for many impulsive phenomena in space and laboratory plasmas accompanied by effective transformation of magnetic energy. Reconnection processes usually occur in relatively thin current sheets (CSs), which separate magnetic fields of different or opposite directions. We report on recent observations of time dependent bending of CSs, which results from plasma dynamics inside the sheet. The experiments are carried out with the CS-3D laboratory device (Institute of General Physics RAS, Moscow) [1]. The CS magnetic structure with an X line provides excitation of the Hall currents and plasma acceleration from the X line to both side edges [2]. In the presence of the guide field By the Hall currents give rise to bending of the sheet: the peripheral regions located away from the X line are deflected from CS middle plane (z=0) in the opposite directions ±z [3]. We have revealed generation of reverse currents jy near the CS edges, i.e. the currents flowing in the opposite direction to the main current in the sheet [4]. There are strong grounds to believe that reverse currents are generated by the outflow plasma jets [5], accelerated inside the sheet and penetrated into the regions with strong normal magnetic field component Bz [4]. An impressive effect of sudden change in the sign of the CS bend has been disclosed recently, when analyzing distributions of plasma density [6] and current away from the X line, in the presence of the guide field By. The CS configuration suddenly becomes opposite from that observed at the initial stage, and this effect correlates well with generation of reverse currents. Consequently this effect can be related to excitation of the reverse Hall currents owing to generation of reverse currents jy in the CS. Hence it may be concluded that CSs may exhibit time dependent vertical z-displacements, and the sheet geometry depends on excitation of the Hall currents, acceleration of plasma jets and generation of reverse currents. The work was supported in part by the Program (OFN-15) “Plasma Processes in Space and Laboratory” of the Division of Physical Sciences of the Russian Academy of Sciences. 1. Frank A.G., Bogdanov S.Yu., Markov V.S. et al. // Phys. Plasmas 2005. 12, 052316(1-11). 2. Frank A.G., Bugrov S.G., Markov V.S. // Phys. Plasmas 2008. 15, 092102 (1-10). 3. Frank A.G., Bogdanov S.Yu., Dreiden G.V. et al. // Phys. Lett. A 2006. 348, 318-325. 4. Frank A.G., Kyrie N.P., Satunin S.N. // Phys. Plasmas 2011. 18, 111209 (1-9). 5. Kyrie N.P., Markov V.S., Frank A.G. // Plasma Phys. Reports 2010. 36, 357-364; JETP Lett. 2012. 95, 14-19. 6. Ostrovskaya G.V., Frank A.G. // Plasma Phys. Reports 2014. 40, 21-33.

A luminescent silver-saccharinato complex with S, S-diphenylsulfimide: Synthesis, spectroscopic, thermal, structural and DFT computational studies

NASA Astrophysics Data System (ADS)

Gumus, Sedat; Hamamci, Sevim; Yilmaz, V. T.; Kazak, Canan

2007-02-01

A new silver(I)-saccharinato (sac) complex with S, S-diphenylsulfimide, [Ag(sac)(Ph 2SNH)], has been prepared and characterized by elemental analysis, IR spectroscopy, thermal analysis and single crystal X-ray diffraction. X-ray diffraction analyses show that the title complex has a monomeric structure containing linearly coordinated silver(I) ion with an N-Ag-N angle of 173.80(10)°. The individual molecules are linked by strong N-H⋯O hydrogen bonds and aromatic stacking π⋯π interactions and packing of the molecules is further reinforced by C-H⋯π interactions. Ph 2SNH and [Ag(sac)(Ph 2SNH)] in solution at room temperature display intense blue luminescence with emission maxima at 380 and 408 nm, respectively. The photoluminescence properties have been investigated by DFT calculations, showing that the luminescence properties of the Ph 2SNH are due to intraligand transitions, while for the silver(I) complex, the luminescence was originated from several transitions including intraligand transitions and metal-to-ligand charge transfer (MLCT).

Ligational behavior of clioquinol antifungal drug towards Ag(I), Hg(II), Cr(III) and Fe(III) metal ions: Synthesis, spectroscopic, thermal, morphological and antimicrobial studies

NASA Astrophysics Data System (ADS)

El-Megharbel, Samy M.; Refat, Moamen S.

2015-04-01

This article presents a synthesis, characterization, theoretical and biological (anti-bacterial, and anti-fugal) evaluation studies of Ag(I), Hg(II), Cr(III) and Fe(III) complexes of clioquinol (CQ) drug ligand. Structures of the titled complexes cited herein were discussed using elemental analyses and spectral measurements e.g., IR, 1H NMR, and electronic studies. The results confirmed the formation of the clioquinol complexes by three molar ratios (1:1) for Ag(I), (1:2) for Hg(II) and (1:3) for both Cr(III) and Fe(III) metal ions. The clioquinol reacts as a bidentate chelate bound to all respected metal ions through the oxygen and nitrogen of quinoline-8-ol. The metal(II) ions coordinated to clioquinol ligand through deprotonation of sbnd OH terminal group. Infrared and 1H NMR spectral data confirm that coordination is via the oxygen of phenolic group and nitrogen atom of quinoline moiety. The molar conductance measurements of the CQ complexes in DMSO correspond to be non-electrolyte nature. Thus, these complexes may be formulated as [Ag(CQ)(H2O)2] H2O, [Hg(CQ)2]ṡ2H2O, [Cr(CQ)3] and [Fe(CQ)3]H2O. The Coats-Redfern method, the kinetic thermodynamic parameters like activation energies (E∗), entropies (ΔS∗), enthalpies (ΔH∗), and Gibbs free energies (ΔG∗) of the thermal decomposition reactions have been deduced from thermogravimetric curves (TG) with helpful of differential thermo gravimetric (DTG) curves. The narrow size distribution in nano-scale range for the clioquinol complexes have been discussed using X-ray powder diffraction (XRD), scanning electron microscope (SEM), and X-ray energy dispersive spectrometer (EDX) analyzer.

Crystal structure of an antibody bound to an immunodominant peptide epitope: novel features in peptide-antibody recognition.

PubMed

Nair, D T; Singh, K; Sahu, N; Rao, K V; Salunke, D M

2000-12-15

The crystal structure of Fab of an Ab PC283 complexed with its corresponding peptide Ag, PS1 (HQLDPAFGANSTNPD), derived from the hepatitis B virus surface Ag was determined. The PS1 stretch Gln2P to Phe7P is present in the Ag binding site of the Ab, while the next three residues of the peptide are raised above the binding groove. The residues Ser11P, Thr12P, and Asn13P then loop back onto the Ag-binding site of the Ab. The last two residues, Pro14P and Asp15P, extend outside the binding site without forming any contacts with the Ab. The PC283-PS1 complex is among the few examples where the light chain complementarity-determining regions show more interactions than the heavy chain complementarity-determining regions, and a distal framework residue is involved in Ag binding. As seen from the crystal structure, most of the contacts between peptide and Ab are through the five residues, Leu3-Asp4-Pro5-Ala6-Phe7, of PS1. The paratope is predominantly hydrophobic with aromatic residues lining the binding pocket, although a salt bridge also contributes to stabilizing the Ag-Ab interaction. The molecular surface area buried upon PS1 binding is 756 A(2) for the peptide and 625 A(2) for the Fab, which is higher than what has been seen to date for Ab-peptide complexes. A comparison between PC283 structure and a homology model of its germline ancestor suggests that paratope optimization for PS1 occurs by improving both charge and shape complementarity.

1,1'-Bis(pyrazol-3-yl)ferrocene: A Clip Ligand That Forms Supramolecular Aggregates and Prismatic Hexanuclear Coinage Metal Complexes.

PubMed

Veronelli, Mattia; Dechert, Sebastian; Demeshko, Serhiy; Meyer, Franc

2015-07-20

Two ferrocene derivatives with appended pyrazole substituents, namely, 1,1'-bis(5-methyl-1H-pyrazol-3-yl)ferrocene (H2LH) and 1,1'-bis(5-trifluoromethyl-1H-pyrazol-3-yl)ferrocene (H2LF), were synthesized. In solid state they form distinct H-bonded dimers with orthogonal (H2LH, C2 symmetry) or antiparallel (H2LF, C2h symmetry) arrangement of the two ferrocene/pyrazole hybrid molecules. Supramolecular dimerization was also detected in solution at low temperatures, though diffusion-ordered spectroscopy and variable-temperature NMR spectroscopy revealed several dynamic processes. Redox potentials of the ferrocene derivatives are affected by the nature of the pyrazole substituent (Me, CF3). In their deprotonated form [LR]2-, both ferrocene/pyrazole hybrids serve as ligands and form oligonuclear CuI, AgI, and AuI complexes that were identified by matrix-assisted laser desorption ionization mass spectrometry. X-ray crystallography revealed the structures of Cu6L3H and Ag6L3F, which both contain two parallel and eclipsed [M(μ-pz)]3 metallamacrocycles (M = Cu, Ag) linked by three ferrocene units. MI···MI distances between the two triangular M3N6 decks are shorter in Ag6L3F (3.28-3.30 vs 3.44-3.51 Å in the case of Cu6L3H), indicating substantial intramolecular closed-shell Ag(d10)-Ag(d10) interactions. However, Cu6L3H features close intermolecular Cu···Cu contacts as short as 3.37 Å. Mössbauer data for both the ligands and complexes were collected, and electrochemical properties were measured; preliminary luminescence data are reported.

Simulation of 6 to 3 to 1 merge and squeeze of Au77+ bunches in AGS

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

Gardner, C. J.

2016-05-09

In order to increase the intensity per Au77+ bunch at AGS extraction, a 6 to 3 to 1 merge scheme was developed and implemented by K. Zeno during the 2016 RHIC run. For this scheme, 12 Booster loads, each consisting of a single bunch, are delivered to AGS per AGS magnetic cycle. The bunch from Booster is itself the result of a 4 to 2 to 1 merge which is carried out on a flat porch during the Booster magnetic cycle. Each Booster bunch is injected into a harmonic 24 bucket on the AGS injection porch. In order to fitmore » into the buckets and allow for the AGS injection kicker rise time, the bunch width must be reduced by exciting quadrupole oscillations just before extraction from Booster. The bunches are injected into two groups of six adjacent harmonic 24 buckets. In each group the 6 bunches are merged into 3 by bringing on RF harmonic 12 while reducing harmonic 24. This is a straightforward 2 to 1 merge (in which two adjacent bunches are merged into one). One ends up with two groups of three adjacent bunches sitting in harmonic 12 buckets. These bunches are accelerated to an intermediate porch for further merging. Doing the merge on a porch that sits above injection energy helps reduce losses that are believed to be due to the space-charge force acting on the bunched particles. (The 6 to 3 merge is done on the injection porch because the harmonic 24 frequency on the intermediate porch would be too high for the AGS RF cavities.) On the intermediate porch each group of 3 bunches is merged into one by bringing on RF harmonics 8 and 4 and then reducing harmonics 12 and 8. One ends up with 2 bunches, each the result of a 6 to 3 to 1 merge and each sitting in a harmonic 4 bucket. This puts 6 Booster loads into each bunch. Each merged bunch needs to be squeezed into a harmonic 12 bucket for subsequent acceleration. This is done by again bringing on harmonic 8 and then harmonic 12. Results of simulations of the 6 to 3 to 1 merge and the subsequent squeeze into harmonic 12 buckets are presented in this note. In particular, they provide a benchmark for what can be achieved with the available RF voltages.« less

Silica-Silver Nanocomposites as Regenerable Sorbents for Hg0 Removal from Flue Gases.

PubMed

Cao, Tiantian; Li, Zhen; Xiong, Yong; Yang, Yue; Xu, Shengming; Bisson, Teresa; Gupta, Rajender; Xu, Zhenghe

2017-10-17

Silica-silver nanocomposites (Ag-SBA-15) are a novel class of multifunctional materials with potential applications as sorbents, catalysts, sensors, and disinfectants. In this work, an innovative yet simple and robust method of depositing silver nanoparticles on a mesoporous silica (SBA-15) was developed. The synthesized Ag-SBA-15 was found to achieve a complete capture of Hg 0 at temperatures up to 200 °C. Silver nanoparticles on the SBA-15 were shown to be the critical active sites for the capture of Hg 0 by the Ag-Hg 0 amalgamation mechanism. An Hg 0 capture capacity as high as 13.2 mg·g -1 was achieved by Ag(10)-SBA-15, which is much higher than that achievable by existing Ag-based sorbents and comparable with that achieved by commercial activated carbon. Even after exposure to more complex simulated flue gas flow for 1 h, the Ag(10)-SBA-15 could still achieve an Hg 0 removal efficiency as high as 91.6% with a Hg 0 capture capacity of 457.3 μg·g -1 . More importantly, the spent sorbent could be effectively regenerated and reused without noticeable performance degradation over five cycles. The excellent Hg 0 removal efficiency combined with a simple synthesis procedure, strong tolerance to complex flue gas environment, great thermal stability, and outstanding regeneration capability make the Ag-SBA-15 a promising sorbent for practical applications to Hg 0 capture from coal-fired flue gases.

Copper(I), silver(I) and gold(I) halide complexes with the dithioformamidinium dihalides

NASA Astrophysics Data System (ADS)

Peyronel, Giorgio; Malavasi, Wanda; Pignedoli, Anna

Some copper(I), silver(I) and gold(I) halide complexes with the dithioformamidinium dihalides (Tu 2X 2) were prepared and studied by infrared spectroscopy and conductometry: 3CuX.2Tu 2X 2(XCl,I), CuBr.Tu 2Br 2, 4CuBr.3.5Tu 2Br 2.MeOH, 2CuBr.Tu 2Br 2.0.66EtOH, 3CuI.2Tu 2I 2, 2AgCl.2.5Tu 2Cl 2, 3AgCl.2Tu 2Cl 2.0.5EtOH, 3AgCl.Tu 2Cl 2, 2AgBr.2Tu 2Br 2.0.5Tu 2(NO 3) 2.H 2O, AgBr.Tu 2Br 2, 4AgBr.Tu 2Br 2, 4AgI.0.5Tu 2I 2.EtOH, AuCl.1.5Tu 2Cl 2, 4AuCl.3.5Tu 2Cl 2.2DMF, AuBr.4Tu 2Br 2, AuBr.2Tu 2Br 2.1.5DMF, AuI.5Tu 2I 2, AuI.Tu 2I 2. A decrease of the ν(NH), δ(NH 2) and ν(CN 2) frequencies and an increase of the ν(CS) frequencies indicate an N-coordination of the dithioformamidinium cation to the metal ions; ν(MN) and ν(MX) frequencies are tentatively assigned in the far-infrared spectra.

Silver nanoparticles enhance wound healing in zebrafish (Danio rerio).

PubMed

Seo, Seung Beom; Dananjaya, S H S; Nikapitiya, Chamilani; Park, Bae Keun; Gooneratne, Ravi; Kim, Tae-Yoon; Lee, Jehee; Kim, Cheol-Hee; De Zoysa, Mahanama

2017-09-01

Silver nanoparticles (AgNPs) were successfully synthesized by a chemical reduction method, physico-chemically characterized and their effect on wound-healing activity in zebrafish was investigated. The prepared AgNPs were circular-shaped, water soluble with average diameter and zeta potential of 72.66 nm and -0.45 mv, respectively. Following the creation of a laser skin wound on zebrafish, the effect of AgNPs on wound-healing activity was tested by two methods, direct skin application (2 μg/wound) and immersion in a solution of AgNPs and water (50 μg/L). The zebrafish were followed for 20 days post-wounding (dpw) by visual observation of wound size, calculating wound healing percentage (WHP), and histological examination. Visually, both direct skin application and immersion AgNPs treatments displayed clear and faster wound closure at 5, 10 and 20 dpw compared to the controls, which was confirmed by 5 dpw histology data. At 5 dpw, WHP was highest in the AgNPs immersion group (36.6%) > AgNPs direct application group (23.7%) > controls (18.2%), showing that WHP was most effective in fish immersed in AgNPs solution. In general, exposure to AgNPs induced gene expression of selected wound-healing-related genes, namely, transforming growth factor (TGF-β), matrix metalloproteinase (MMP) -9 and -13, pro-inflammatory cytokines (IL-1β and TNF-α) and antioxidant enzymes (superoxide dismutase and catalase), which observed differentiation at 12 and 24 h against the control; but the results were not consistently significant, and many either reached basal levels or were down regulated at 5 dpw in the wounded muscle. These results suggest that AgNPs are effective in acceleration of wound healing and altered the expression of some wound-healing-related genes. However, the detailed mechanism of enhanced wound healing remains to be investigated in fish. Copyright © 2017 Elsevier Ltd. All rights reserved.

Poly[mu2-(N-hydroxypyridine-2-carboxamidine)-mu2-nitrato-silver(I)].

PubMed

Cui, Ai-Li; Han, Peng; Yang, Hui-Juan; Wang, Ru-Ji; Kou, Hui-Zhong

2007-12-01

In the title complex, [Ag(NO3)(C6H7N3O)]n or [Ag(NO3)(pyaoxH2)] (pyaoxH2 is N-hydroxypyridine-2-carboxamidine), the Ag+ ion is bridged by the pyaoxH2 ligands and nitrate anions, giving rise to a two-dimensional molecular structure. Each pyaoxH2 ligand coordinates to two Ag+ ions using its pyridyl and carboxamidine N atoms, and the OH and the NH2 groups are uncoordinated. Each nitrate anion uses two O atoms to coordinate to two Ag+ ions. The Ag...Ag separation via the pyaoxH2 bridge is 2.869 (1) A, markedly shorter than that of 6.452 (1) A via the nitrate bridge. The two-dimensional structure is fishscale-like, and can be described as pyaoxH2-bridged Ag2 nodes that are further linked by nitrate anions. Hydrogen bonding between the amidine groups and the nitrate O atoms connects adjacent layers into a three-dimensional network.

Preparation of silver-chitosan nanocomposites and coating on bandage for antibacterial wound dressing application

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

Susilowati, Endang, E-mail: endwati@yahoo.co.id; Ashadi; Maryani

Bandage is a medical device that is essential for wound dressing. To improve the performance of the bandage, it has been coated by silver-chitosan nanocomposites (Ag/Chit) with pad-dry-cure method. The nanocomposites were performed by chemical reduction method at room temperature using glucose as reducing agent, sodium hydroxide (NaOH) as accelerator reagent, silver nitrate (AgNO{sub 3}) as metal precursor and chitosan as stabilizing agent. Localized surface plasmon resonance (LSPR) absorption band of silver nanoparticles was investigated using UV-Vis spectrophotometer. The bandage coated Ag/Chit nanocomposites (B-Ag/Chit) were characterized by fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscope (SEM).more » In addition, antibacterial activity of the bandage toward Gram positive (Staphylococcus aureus) and Gram negative (Escherichia coli) were also studied. The formation of silver nanoparticles was confirmed by the appearance of LSPR absorption peak at 412.2 – 423.2 nm. Coating of nanocomposite cause increasing rigidity of bandage and decreasing on crystallinity. The bandages of B-Ag/Chit demonstrated good activity against both Gram positive (S. aureus) and Gram negative (E.Coli). Thus the bandages have a potential to be used for antibacterial wound dressing application.« less

Development of chitosan oleate ionic micelles loaded with silver sulfadiazine to be associated with platelet lysate for application in wound healing.

PubMed

Dellera, Eleonora; Bonferoni, Maria Cristina; Sandri, Giuseppina; Rossi, Silvia; Ferrari, Franca; Del Fante, Claudia; Perotti, Cesare; Grisoli, Pietro; Caramella, Carla

2014-11-01

In the treatment of chronic wounds, topical application of anti-infective drugs such as silver sulfadiazine (AgSD) is of primary importance to avoid infections and accelerate wound repair. AgSD is used in burns and chronic wounds for its wide antibacterial spectrum, but presents limitations due to poor solubility and cytotoxicity. In the present work polymeric micelles obtained by self-assembling of chitosan ionically modified by interaction with oleic acid were developed as carriers for AgSD to overcome the drawbacks of the drug. The AgSD loaded micelles were intended to be associated in wound healing with platelet lysate (PL), a hemoderivative rich in growth factors. Unloaded micelles demonstrated good compatibility with both fibroblasts and PL. The relevance of chitosan concentration and of the ratio between chitosan and oleic acid to the drug loading and the particle size of nanoparticles was studied. A marked increase (up to 100 times with respect to saturated solution) of AgSD concentration in micelle dispersion was obtained. Moreover, the encapsulation reduced the cytotoxic effect of the drug towards fibroblasts and the drug incompatibility with PDGF-AB (platelet derived growth factor), chosen as representative of platelet growth factors. Copyright © 2014. Published by Elsevier B.V.

Effect of the SiO2 Support on the Catalytic Performance of Ag/ZrO2/SiO2 Catalysts for the Single-Bed Production of Butadiene from Ethanol

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

Dagle, Vanessa; Flake, Matthew D.; Lemmon, Teresa

2018-05-18

A ternary Ag/ZrO2/SiO2 catalyst system was studied for the single-step conversion of ethanol to butadiene by varying the catalyst composition (Ag, Ir, or Pt metal component, Ag/ZrO2 loading, and choice of SiO2 support) and operating conditions (space velocity and feed gas composition). Exceptional catalytic performance was achieved over a 1%Ag/4%ZrO2/SiO2-SBA-16 catalyst leading to 99% conversion and 71% butadiene selectivity while operating under mild conditions (325ºC, 1 atm, 0.23 hr-1). Several classes of silica (i.e., silica gels, fumed silicas, meoporous silicas) were evaluated as support, and SBA-16 was found to be the most promising. The nature of the SiO2 support wasmore » found to have a strong influence on both conversion and selectivity. Higher SiO2 catalyst surface areas lead to greater conversion due to increased Ag dispersion thus accelerating the initial ethanol dehydrogenation reaction. By independently varying Ag and ZrO2 loading, Ag was found to be the main component affecting ethanol conversion. Butadiene selectivity varied depending on the concentration of ZrO2 and acidic characteristics of the SiO2 support. A direct relationship between butadiene selectivity and concentration of Lewis acid sites was evidenced. Also, adding H2 to the feed had little effect on conversion while improving catalytic stability, however, selectivity to butadiene was decreased. Finally, catalyst regenerability was successfully demonstrated for several cycles.« less

Effect of the SiO 2 support on the catalytic performance of Ag/ZrO 2 /SiO 2 catalysts for the single-bed production of butadiene from ethanol

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

Dagle, Vanessa Lebarbier; Flake, Matthew D.; Lemmon, Teresa L.

A ternary Ag/ZrO2/SiO2 catalyst system was studied for the single-step conversion of ethanol to butadiene by varying the catalyst composition (Ag, Ir, or Pt metal component, Ag/ZrO2 loading, and choice of SiO2 support) and operating conditions (space velocity and feed gas composition). Exceptional catalytic performance was achieved over a 1%Ag/4%ZrO2/SiO2-SBA-16 catalyst leading to 99% conversion and 71% butadiene selectivity while operating under mild conditions (325ºC, 1 atm, 0.23 hr-1). Several classes of silica (i.e., silica gels, fumed silicas, meoporous silicas) were evaluated as support, and SBA-16 was found to be the most promising. The nature of the SiO2 support wasmore » found to have a strong influence on both conversion and selectivity. Higher SiO2 catalyst surface areas lead to greater conversion due to increased Ag dispersion thus accelerating the initial ethanol dehydrogenation reaction. By independently varying Ag and ZrO2 loading, Ag was found to be the main component affecting ethanol conversion. Butadiene selectivity varied depending on the concentration of ZrO2 and acidic characteristics of the SiO2 support. A direct relationship between butadiene selectivity and concentration of Lewis acid sites was evidenced. Also, adding H2 to the feed had little effect on conversion while improving catalytic stability, however, selectivity to butadiene was decreased. Finally, catalyst regenerability was successfully demonstrated for several cycles.« less

FFAGs: Front-end for neutrino factories and medical accelerators

NASA Astrophysics Data System (ADS)

Mori, Yoshiharu

The idea of Fixed Field Alternating Gradient (FFAG) accelerator was originated by different people and groups in the early 1950s. It was independently introduced by Ohkawa [Ohkawa (1953)], Symon et al. [Symon et al. (1956)], and Kolomensky [Kolomensky and Lebedev (1966)] when the strong Alternate Gradient (AG) focusing and the phase stability schemes were applied to particle acceleration. The first FFAG electron model was developed in the MURA accelerator project led by Kerst and Cole in the late 1950s. Since then, they have fabricated several electron models in the early 1960s [Symon et al. (1956)]. However, the studies did not lead to a single practical FFAG accelerator for the following 50 years. Because of the difficulties of treating non-linear magnetic field and RF acceleration for non-relativistic particles, the proton FFAG, especially, was not accomplished until recently. In 2000, the FFAG concept was revived with the world's first proton FFAG (POP) which was developed at KEK [Aiba (2000); Mori (1999)]. Since then, in many places [Berg (2004); Johnstone et al. (2004); Mori (2011); Ruggiero (2004); Trbojevic (2004)], FFAGs have been developed and constructed...

α-melanocyte stimulating hormone modulates the central acyl ghrelin-induced stimulation of feeding, gastrointestinal motility, and colonic secretion.

PubMed

Huang, Hsien-Hao; Chen, Liang-Yu; Doong, Ming-Luen; Chang, Shi-Chuan; Chen, Chih-Yen

2017-01-01

Acyl ghrelin-induced intake depends on hypothalamic neuropeptide Y and agouti-related protein (AgRP) neurotransmitters. Intracerebroventricular (ICV) injection of AgRP increases feeding through competitive antagonism at melanocortin receptors. ICV administration of α-melanocyte stimulating hormone (α-MSH), a natural antagonist of AgRP, may modulate the acyl ghrelin-induced orexigenic effect. This study aimed to investigate the modulating effect of α-MSH on the central acyl ghrelin-induced food intake, gastrointestinal motility, and colonic secretion in rats. We examined the effects of α-MSH and acyl ghrelin on food intake, gastric emptying, small intestinal transit, colonic motility, and secretion in conscious rats with a chronic implant of ICV catheters. ICV injection of O - n -octanoylated ghrelin (0.1 nmol/rat) significantly increased the cumulative food intake up to 8 h ( P <0.01), enhanced non-nutrient semi-liquid gastric emptying ( P <0.001), increased the geometric center and running percentage of small intestinal transit ( P <0.001), accelerated colonic transit time ( P <0.05), and increased fecal pellet output ( P <0.01) and total fecal weight ( P <0.01). Pretreatment with ICV injection of α-MSH (1.0 and 2.0 nmol/rat) attenuated the acyl ghrelin-induced hyperphagic effect, fecal pellet output, and total fecal weight, while higher dose of α-MSH (2.0 nmol/rat) attenuated the increase in the geometric center of small intestinal transit ( P <0.01). However, neither dose of α-MSH altered acyl ghrelin-stimulated gastroprokinetic effect, increase in the running percentage of small intestinal transit, nor accelerated colonic transit time. α-MSH is involved in central acyl ghrelin-elicited feeding, small intestinal transit, fecal pellet output, and fecal weight. α-MSH does not affect central acyl ghrelin-induced acceleration of gastric emptying and colonic transit time in rats.

Autoclave mediated one-pot-one-minute synthesis of AgNPs and Au-Ag nanocomposite from Melia azedarach bark extract with antimicrobial activity against food pathogens.

PubMed

Pani, Alok; Lee, Joong Hee; Yun, Soon-Ii

2016-01-01

The increasing use of nanoparticles and nanocomposite in pharmaceutical and processed food industry have increased the demand for nontoxic and inert metallic nanostructures. Chemical and physical method of synthesis of nanostructures is most popular in industrial production, despite the fact that these methods are labor intensive and/or generate toxic effluents. There has been an increasing demand for rapid, ecofriendly and relatively cheaper synthesis of nanostructures. Here, we propose a strategy, for one-minute green synthesis of AgNPs and a one-pot one-minute green synthesis of Au-Ag nanocomposite, using Melia azedarach bark aqueous extract as reducing agent. The hydrothermal mechanism of the autoclave technology has been successfully used in this study to accelerate the nucleation and growth of nano-crystals. The study also presents high antimicrobial potential of the synthesized nano solutions against common food and water born pathogens. The multistep characterization and analysis of the synthesized nanomaterial samples, using UV-visible spectroscopy, ICP-MS, FT-IR, EDX, XRD, HR-TEM and FE-SEM, also reveal the reaction dynamics of AgNO3, AuCl3 and plant extract in synthesis of the nanoparticles and nanocomposite. The antimicrobial effectiveness of the synthesized Au-Ag nanocomposite, with high gold to silver ratio, reduces the dependency on the AgNPs, which is considered to be environmentally more toxic than the gold counterpart. We hope that this new strategy will change the present course of green synthesis. The rapidity of synthesis will also help in industrial scale green production of nanostructures using Melia azedarach.

Toxicokinetics and toxicodynamics of differently coated silver nanoparticles and silver nitrate in Enchytraeus crypticus upon aqueous exposure in an inert sand medium.

PubMed

Topuz, Emel; van Gestel, Cornelis A M

2015-12-01

The aim of the present study was to evaluate the effect of silver nanoparticles (AgNPs) on Enchytraeus crypticus, applying a combined toxicokinetics and toxicodynamics approach to understand the relationship between survival and the development of internal Ag concentrations in the animals over time. Toxicity tests were conducted in medium composed of well-defined aqueous solutions added to inert quartz sand to avoid the complexity of soil conditions. Citrate-coated AgNPs (AgNP-Cit) and polyvinylpyrrolidone-coated AgNPs (AgNP-PVP) were tested and compared with silver nitrate (AgNO3), which was used as a positive control for Ag ion effects. The median lethal concentration (LC50) values based on Ag concentrations in the solution phase of the test medium decreased over time and reached steady state after 7 d, with AgNO3 and AgNP-PVP being more toxic than AgNP-Cit. Slow dissolution may explain the low uptake kinetics and lower toxicity of AgNP-Cit compared with the other 2 Ag forms. The LC50 values based on internal Ag concentrations in the animals were almost stable over time, highlighting the importance of integrating toxicokinetics and toxicodynamics and relating survival with internal Ag concentrations. Neither survival-based elimination rates nor internal LC50s in the organisms showed any significant evidence of nano-specific effects for both AgNPs, although they suggested some uptake of particulate Ag for AgNP-Cit. The authors conclude that the toxicity of both types of AgNP probably is mainly attributable to the release of Ag ions. © 2015 SETAC.

Optimizing Water Exchange Rates and Rotational Mobility for High-Relaxivity of a Novel Gd-DO3A Derivative Complex Conjugated to Inulin as Macromolecular Contrast Agents for MRI.

PubMed

Granato, Luigi; Vander Elst, Luce; Henoumont, Celine; Muller, Robert N; Laurent, Sophie

2018-02-01

Thanks to the understanding of the relationships between the residence lifetime τ M of the coordinated water molecules to macrocyclic Gd-complexes and the rotational mobility τ R of these structures, and according to the theory for paramagnetic relaxation, it is now possible to design macromolecular contrast agents with enhanced relaxivities by optimizing these two parameters through ligand structural modification. We succeeded in accelerating the water exchange rate by inducing steric compression around the water binding site, and by removing the amide function from the DOTA-AA ligand [1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid mono(p-aminoanilide)] (L) previously designed. This new ligand 10[2(1-oxo-1-p-propylthioureidophenylpropyl]-1,4,7,10-tetraazacyclodecane-1,4,7-tetraacetic acid (L 1 ) was then covalently conjugated to API [O-(aminopropyl)inulin] to get the complex API-(GdL 1 )x with intent to slow down the rotational correlation time (τ R ) of the macromolecular complex. The evaluation of the longitudinal relaxivity at different magnetic fields and the study of the 17 O-NMR at variable temperature of the low-molecular-weight compound (GdL 1 ) showed a slight decrease of the τ M value (τM310 = 331 ns vs. τM310 = 450 ns for the GdL complex). Consequently to the increase of the size of the API-(GdL 1 )x complex, the rotational correlation time becomes about 360 times longer compared to the monomeric GdL 1 complex (τ R  = 33,700 ps), which results in an enhanced proton relaxivity. © 2018 Wiley-VHCA AG, Zurich, Switzerland.

Structural diversity of silver (I) azine complexes - Effect of substituents and counter anions

NASA Astrophysics Data System (ADS)

Patra, Goutam Kumar; Mukherjee, Anindita; Mitra, Partha; Adarsh, N. N.

2011-08-01

Three new Ag(I) complexes, 1, 2, and 3 of two azine ligands diacetyl dihydrazone ( L1) and benzil dihydrazone ( L2) have been synthesized and characterized by single crystal X-ray diffraction studies (for 2 and 3), X-ray powder diffraction studies( 1 and 2), elemental analyses, IR and UV-VIS spectroscopy and TGA analysis. They represent one-dimensional polymeric assemblies and discrete dinuclear Ag(I) complex depending on functionality of the ligands and the counter anions. Tetrahedral as well as square pyramidal coordination motifs of the silver (I) ions have been observed in the supramolecular designing of such hybrid organic-inorganic materials.

Adsorption behavior of Fe atoms on a naphthalocyanine monolayer on Ag(111) surface

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

Yan, Ling -Hao; Wu, Rong -Ting; Bao, De -Liang

2015-05-29

Adsorption behavior of Fe atoms on a metal-free naphthalocyanine (H 2Nc) monolayer on Ag(111) surface at room temperature has been investigated using scanning tunneling microscopy combined with density functional theory (DFT) based calculations. We found that the Fe atoms adsorbed at the centers of H 2Nc molecules and formed Fe-H 2Nc complexes at low coverage. DFT calculations show that the configuration of Fe at the center of a molecule is the most stable site, in good agreement with the experimental observations. After an Fe-H 2Nc complex monolayer was formed, the extra Fe atoms self-assembled to Fe clusters of uniform sizemore » and adsorbed dispersively at the interstitial positions of Fe-H 2Nc complex monolayer. Furthermore, the H 2Nc monolayer grown on Ag(111) could be a good template to grow dispersed magnetic metal atoms and clusters at room temperature for further investigation of their magnetism-related properties.« less

Multifunctional Ultra-High Vacuum Apparatus for Studies of the Interactions of Chemical Warfare Agents on Complex Surfaces

DTIC Science & Technology

2014-01-02

colleagues employed solid state NMR to study the decomposition of CWAs on MgO,36 AgY and NaY zeolites ,37 CaO,38 and Al2O3.39 More recently, the...37G. W. Wagner and P. W. Bartram, “Reactions of VX, HD, and their simu- lants with NaY and AgY zeolites . Desulfurization of VX on AgY,” Lang- muir 15

Surface morphological, structural, electrical and optical properties of GaN-based light-emitting diodes using submicron-scaled Ag islands and ITO thin films

NASA Astrophysics Data System (ADS)

Lee, Young-Woong; Reddy, M. Siva Pratap; Kim, Bo-Myung; Park, Chinho

2018-07-01

An ITO-Ag islands complex as a new transparent conducting electrode (TCE) structure (on the 5 nm-thick p-InGaN/90 nm-thick p-GaN) for achieving high-performance and more reliable GaN-based LEDs were fabricated. A normal LED with a conventional ITO TCE was also compared. The surface morphological, structural, electrical and optical properties of fabricated GaN-based light-emitting diodes using a complex electrode of submicron-scaled Ag islands and ITO thin films are explored by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), current-voltage (I-V) and output power-current (L-I) techniques. Surface morphology investigations revealed Ag islands formed uniformly on the p-InGaN/p-GaN surface during rapid thermal annealing at 400 °C for 1 min in N2 ambient. The ohmic properties and overall device-performance of the suggested contact and device structures were superior to those in the conventional ITO contact and normal ITO LED structures. Based on the results of XRD and XPS measurements, the formation of the intermetallic gallide phases (AgGa) is responsible for better performance characteristics of the ITO-Ag islands device. The significant improvements are described in terms of the conducting bridge influence, highly effective micro-mirror effect, and wider photon window via the roughened structure.

Colloidal complexed silver and silver nanoparticles in extrapallial fluid of Mytilus edulis.

PubMed

Zuykov, Michael; Pelletier, Emilien; Demers, Serge

2011-02-01

Metal transport in mollusk extrapallial fluid (EPF) that acts as a "bridge" between soft tissues and shell has surprisingly received little attention until now. Using ultrafiltration and radiotracer techniques we determined silver concentrations and speciation in the EPF of the blue mussel Mytilus edulis after short-term uptake and depuration laboratory experiments. Radiolabelled silver ((¹¹⁰m)Ag) was used in dissolved or nanoparticulate phases (AgNPs < 40 nm), with a similar low Ag concentration (total radioactive and cold Ag ~0.7 μg/L) in a way that mussels could uptake radiotracers only from seawater. Our results indicated that silver nanoparticles were transported to the EPF of blue mussels at a level similar to the Ag ionic form. Bulk activity of radiolabelled silver in the EPF represented only up to 7% of the bulk activity measured in the whole mussels. The EPF extracted from mussels exposed to both treatments exhibited an Ag colloidal complexed form based on EPF ultrafiltration through a 3 kDa filter. This original study brings new insights to internal circulation of nanoparticles in living organisms and contributes to the international effort in studying the potential impacts of engineered nanomaterials on marine bivalves which play an essential role in coastal ecosystems, and are important contributors to human food supply from the sea. © 2010 Elsevier Ltd. All rights reserved.

Silver baits for the "miraculous draught" of amphiphilic lanthanide helicates.

PubMed

Terazzi, Emmanuel; Guénée, Laure; Varin, Johan; Bocquet, Bernard; Lemonnier, Jean-François; Emery, Daniel; Mareda, Jiri; Piguet, Claude

2011-01-03

The axial connection of flexible thioalkyls chains of variable length (n=1-12) within the segmental bis-tridentate 2-benzimidazole-8-hydroxyquinoline ligands [L12(Cn) -2 H](2-) provides amphiphilic receptors designed for the synthesis of neutral dinuclear lanthanides helicates. However, the stoichiometric mixing of metals and ligands in basic media only yields intricate mixtures of poorly soluble aggregates. The addition of Ag(I) in solution restores classical helicate architectures for n=3, with the quantitative formation of the discrete D(3) -symmetrical [Ln(2) Ag2(L12(C3) -2 H)(3) ](2+) complexes at millimolar concentration (Ln=La, Eu, Lu). The X-ray crystal structure supports the formation of [La(2) Ag(2) (L12(C3) -2 H)(3) ][OTf](2) , which exists in the solid state as infinite linear polymers bridged by S-Ag-S bonds. In contrast, molecular dynamics (MD) simulations in the gas phase and in solution confirm the experimental diffusion measurements, which imply the formation of discrete molecular entities in these media, in which the sulfur atoms of each lipophilic ligand are rapidly exchanged within the Ag(I) coordination sphere. Turned as a predictive tool, MD suggests that this Ag(I) templating effect is efficient only for n=1-3, while for n>3 very loose interactions occur between Ag(I) and the thioalkyl residues. The subsequent experimental demonstration that only 25 % of the total ligand speciation contributes to the formation of [Ln(2) Ag(2) (L12(C12) -2 H)(3) ](2+) in solution puts the bases for a rational approach for the design of amphiphilic helical complexes with predetermined molecular interfaces. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

MICROWAVE SPECTRA AND GEOMETRIES OF C2H_{2\\cdots AgI} and C2H_{4\\cdots AgI}

NASA Astrophysics Data System (ADS)

Stephens, Susanna L.; Tew, David Peter; Walker, Nick; Legon, Anthony

2015-06-01

A chirped-pulse Fourier transform microwave spectrometer has been used to measure the microwave spectra of both C2H_{2\\cdots AgI} and C2H_{4\\cdots AgI}. These complexes are generated via laser ablation at 532 nm of a silver surface in the presence of CF3I and either C2H_{2} or C2H_{4} and argon and are stabilized by a supersonic expansion. Rotational (A0, B0, C0) and centrifugal distortion constants (ΔJ and ΔJK) of each molecule have been determined as well the nuclear electric quadrupole coupling constants the iodine atom (χaa(I) and χbb-χcc(I)). The spectrum of each molecule is consistent with a C2v structure in which the metal atom interacts with the π-orbital of the ethene or ethyne molecule. Isotopic substitutions of atoms within the C2H_{2} or C2H_{4} subunits are in progress and in conjunction with high level ab initio calculations will allow for accurate determination of the geometry of each molecule. These to complexes are put in the context of the recently studied H2S\\cdots AgI, OC\\cdotsAgI, H3N\\cdots AgI and (CH3)_{3N\\cdots AgI}. S.Z. Riaz, S.L. Stephens, W. Mizukami, D.P. Tew, N.R. Walker, A.C. Legon, Chem. Phys. Let., 531, 1-12 (2012) S.L. Stephens, W. Mizukami, D.P. Tew, N.R. Walker, A.C. Legon, J. Chem. Phys., 136(6), 064306 (2012) D.M. Bittner, D.P. Zaleski, S.L. Stephens, N.R. Walker, A.C. Legon, Study in progress.

Metallogel templated synthesis and stabilization of silver-particles and its application in catalytic reduction of nitro-arene.

PubMed

Sharma, Mukesh; Sarma, Plaban Jyoti; Goswami, Manash Jyoti; Bania, Kusum K

2017-03-15

Metallogel of iron-carboxylates was obtained from trans-1,2-cyclohexanedicarboxylic acid in dimethylformamide (DMF) at basic condition. Spectroscopic and SEM morphology study of the iron-metallogel revealed that the iron complex with dicarboxylic acid was linked together via carboxylates and led to a supramolecular helical like architecture. The synthesized metallogel served as an excellent template for in-situ reduction of silver ion to silver particles micro to nano scale range. Variation of AgNO 3 concentration shepherd to change the morphology of the Ag-particles. AgNO 3 concentration was found to affect the shape and size of silver particles. On going from lower to higher concentration shape of silver particles changed from spherical to large agglomerated particles. Cubic shape Ag-particles were found on treatment of 0.05M AgNO 3 solution with metallogel. Cubical shape silver particles were found to be effective catalyst for nitro-arene reduction in presence of NaBH 4 . Density functional theory (DFT) calculations were performed to rationalize the role of Ag-particles in catalytic reduction of 4-nitrophenol to 4-aminophenol. Based on DFT study, we proposed that catalytic reduction occurred via Ag-hydride complex formation. Since metallogels as well as the 4-aminophenol are finding large application in pharmaceuticals industries therefore the current work can provide an alternatives path in production of 4-aminophenols. In addition to this, the synthesis of Ag-nanomaterials using metallogel as template can pave a new direction in the development of nanotechnology and might find wide applications in catalytic industrial processes. Copyright © 2016 Elsevier Inc. All rights reserved.

The detection of hepatitis c virus core antigen using afm chips with immobolized aptamers.

PubMed

Pleshakova, T O; Kaysheva, A L; Bayzyanova, J М; Anashkina, А S; Uchaikin, V F; Ziborov, V S; Konev, V A; Archakov, A I; Ivanov, Y D

2018-01-01

In the present study, the possibility of hepatitis C virus core antigen (HCVcoreAg) detection in buffer solution, using atomic force microscope chip (AFM-chip) with immobilized aptamers, has been demonstrated. The target protein was detected in 1mL of solution at concentrations from 10 -10 М to 10 -13 М. The registration of aptamer/antigen complexes on the chip surface was carried out by atomic force microscopy (AFM). The further mass-spectrometric (MS) identification of AFM-registered objects on the chip surface allowed reliable identification of HCVcoreAg target protein in the complexes. Aptamers, which were designed for therapeutic purposes, have been shown to be effective in HCVcoreAg detection as probe molecules. Copyright © 2017 Elsevier B.V. All rights reserved.

Effects of water chemistry and surface contact on the toxicity of silver nanoparticles to Bacillus subtilis.

PubMed

Yi, Jun; Cheng, Jinping

2017-07-01

The growing use of silver nanoparticles (AgNPs) has created concerns about its potential impacts on natural microbial communities. In this study, the physicochemical properties of AgNPs and its toxicity on natural bacteria Bacillus subtilis (B. subtilis) were investigated in aqueous conditions. The characterization data showed that AgNPs highly aggregated in aqueous conditions, and the hydrodynamic diameter of AgNPs in aqueous conditions was larger than its primary size. The studied AgNPs was less toxic to B. subtilis in estuarine water as compared to that in Milli-Q water and artificial seawater, which might be due to the observed enhanced aggregation of AgNPs in estuarine water. The toxicity of AgNPs to B. subtilis was greatly reduced when their surface contact was blocked by a dialysis membrane. Scanning electron microscope images showed that exposure contact to AgNPs resulted in damage of the microbial cell wall and enhanced formation of fibrillar structures. These results suggest that particle-cell contact is largely responsible for the observed toxicity of AgNPs in B. subtilis. This study can help to understand the potential impacts of AgNPs to natural microbes, especially in the complex aquatic environments.

BNL accelerator-based radiobiology facilities

NASA Technical Reports Server (NTRS)

Lowenstein, D. I.

2001-01-01

For the past several years, the Alternating Gradient Synchrotron (AGS) at Brookhaven National Laboratory (USA) has provided ions of iron, silicon and gold, at energies from 600 MeV/nucleon to 10 GeV/nucleon, for the US National Aeronautics and Space Administration (NASA) radiobiology research program. NASA has recently funded the construction of a new dedicated ion facility, the Booster Applications Facility (BAF). The Booster synchrotron will supply ion beams ranging from protons to gold, in an energy range from 40-3000 MeV/nucleon with maximum beam intensities of 10(10) to 10(11) ions per pulse. The BAF Project will be described and the future AGS and BAF operation plans will be presented.

BNL accelerator-based radiobiology facilities.

PubMed

Lowenstein, D I

2001-01-01

For the past several years, the Alternating Gradient Synchrotron (AGS) at Brookhaven National Laboratory (USA) has provided ions of iron, silicon and gold, at energies from 600 MeV/nucleon to 10 GeV/nucleon, for the US National Aeronautics and Space Administration (NASA) radiobiology research program. NASA has recently funded the construction of a new dedicated ion facility, the Booster Applications Facility (BAF). The Booster synchrotron will supply ion beams ranging from protons to gold, in an energy range from 40-3000 MeV/nucleon with maximum beam intensities of 10(10) to 10(11) ions per pulse. The BAF Project will be described and the future AGS and BAF operation plans will be presented.

Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag(+) /X2 (X=Cl, Br, I) System.

PubMed

Malinowski, Przemysław J; Himmel, Daniel; Krossing, Ingo

2016-08-01

The synergistic Ag(+) /X2 system (X=Cl, Br, I) is a very strong, but ill-defined oxidant-more powerful than X2 or Ag(+) alone. Intermediates for its action may include [Agm (X2 )n ](m+) complexes. Here, we report on an unexpectedly variable coordination chemistry of diiodine towards this direction: (A)Ag-I2 -Ag(A), [Ag2 (I2 )4 ](2+) (A(-) )2 and [Ag2 (I2 )6 ](2+) (A(-) )2 ⋅(I2 )x≈0.65 form by reaction of Ag(A) (A=Al(OR(F) )4 ; R(F) =C(CF3 )3 ) with diiodine (single crystal/powder XRD, Raman spectra and quantum-mechanical calculations). The molecular (A)Ag-I2 -Ag(A) is ideally set up to act as a 2 e(-) oxidant with stoichiometric formation of 2 AgI and 2 A(-) . Preliminary reactivity tests proved this (A)Ag-I2 -Ag(A) starting material to oxidize n-C5 H12 , C3 H8 , CH2 Cl2 , P4 or S8 at room temperature. A rough estimate of its electron affinity places it amongst very strong oxidizers like MF6 (M=4d metals). This suggests that (A)Ag-I2 -Ag(A) will serve as an easily in bulk accessible, well-defined, and very potent oxidant with multiple applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gender specific changes in cortical activation patterns during exposure to artificial gravity

NASA Astrophysics Data System (ADS)

Schneider, Stefan; Robinson, Ryan; Smith, Craig; von der Wiesche, Melanie; Goswami, Nandu

2014-11-01

Keeping astronauts healthy during long duration spaceflight remains a challenge. Artificial gravity (AG) generated by a short arm human centrifuges (SAHC) is proposed as the next generation of integrated countermeasure devices that will allow human beings to safely spend extended durations in space, although comparatively little is known about any psychological side effects of AG on brain function. 16 participants (8 male and 8 female, GENDER) were exposed to 10 min at a baseline gravitational load (G-Load) of +.03 Gz, then 10 min at +.6 Gz for females and +.8 Gz for males, before being exposed to increasing levels of AG in a stepped manner by increasing the acceleration by +.1 Gz every 3 min until showing signs of pre-syncope. EEG recordings were taken of brain activity during 2 min time periods at each AG level. Analysing the results of the mixed total population of participants by two way ANOVA, a significant effect of centrifugation on alpha and beta activity was found (p<.01). Furthermore results revealed a significant interaction between G-LOAD and GENDER alpha-activity (p<.01), but not for beta-activity. Although the increase in alpha and beta activity with G-LOAD does not reflect a general model of cortical arousal and therefore cannot support previous findings reporting that AG may be a cognitively arousing environment, the gender specific responses identified in this study may have wider implications for EEG and AG research.

In vitro antifungal activity of silver nanoparticles against ocular pathogenic filamentous fungi.

PubMed

Xu, Yan; Gao, Chuanwen; Li, Xiaohua; He, Yi; Zhou, Lutan; Pang, Guangren; Sun, Shengtao

2013-03-01

Fungal keratitis is emerging as a major cause of vision loss in a developing country such as China because of higher incidence and the unavailability of effective antifungals. It is urgent to explore broad-spectrum antifungals to effectively suppress ocular fungal pathogens, and to develop new antifungal eye drops to combat this vision-threatening infection. The aim of this study is to investigate the antifungal activity of silver nanoparticles (nano-Ag) in comparison with that of natamycin against ocular pathogenic filamentous fungi in vitro. Susceptibility tests were performed against 216 strains of fungi isolated from patients with fungal keratitis from the Henan Eye Institute in China by broth dilution antifungal susceptibility test of filamentous fungi approved by the Clinical and Laboratory Standards Institute M38-A document. The isolates included 112 Fusarium isolates (82 Fusarium solani species complex, 20 Fusarium verticillioides species complex, and 10 Fusarium oxysporum species complex), 94 Aspergillus isolates (61 Aspergillus flavus species complex, 11 Aspergillus fumigatus species complex, 12 Aspergillus versicolor species complex, and 10 Aspergillus niger species complex), and 10 Alternaria alternata isolates. The minimum inhibitory concentration (MIC) range and mode, the MIC for 50% of the strains tested (MIC50 value), and the MIC90 value were provided for the isolates with the SPSS statistical package. MIC50 value of nano-Ag were 1, 0.5, and 0.5 μg/mL for Fusarium spp., Aspergillus spp., and Al. alternata, respectively. MIC90 values of nano-Ag were 1, 1, and 1 μg/mL for Fusarium spp., Aspergillus spp., and Al. alternata, respectively. MIC50 values of natamycin were 4, 32, and 4 μg/mL for Fusarium spp., Aspergillus spp., and Al. alternata, respectively. MIC90 values of natamycin were 8, 32, and 4 μg/mL for Fusarium spp., Aspergillus spp., and Al. alternata, respectively. Nano-Ag, relative to natamycin, exhibits potent in vitro activity against ocular pathogenic filamentous fungi.

New Rh 2 (II,II) Complexes for Solar Energy Applications: Panchromatic Absorption and Excited-State Reactivity

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

Whittemore, Tyler J.; Sayre, Hannah J.; Xue, Congcong

In this work, the new heteroleptic paddlewheel complexes cis-[Rh 2(μ-form) 2(μ-np) 2][BF 4] 2, where form = p-ditolylformamidinate (DTolF) or p-difluorobenzylformamidinate (F-form) and np = 1,8-napthyridyine, and cis-Rh 2(μ-form) 2(μ-npCOO) 2 (npCOO – = 1,8-naphthyridine-2-carboxylate), were synthesized and characterized. The complexes absorb strongly throughout the ultraviolet (λ max = 300 nm, ε = 20 300 M –1 cm –1) and visible regions (λ max = 640 nm ε = 3500 M –1 cm –1), making them potentially useful new dyes with panchromatic light absorption for solar energy conversion applications. Ultrafast and nanosecond transient absorption and time-resolved infrared spectroscopies were usedmore » to characterize the identity and dynamics of the excited states, where singlet and triplet Rh 2/form-to-naphthyridine, metal/ligand-to-ligand charge-transfer (ML-LCT) excited states were observed in all four complexes. The npCOO – complexes exhibit red-shifted absorption profiles extending into the near-IR and undergo photoinitiated electron transfer to generate reduced methyl viologen, a species that persists in the presence of a sacrificial donor. The energy of the triplet excited state of each complex was estimated from energy-transfer quenching experiments using a series of organic triplet donors (E( 3ππ*) from 1.83 to 0.78 eV). The singlet reduction (+0.6 V vs Ag/AgCl) potentials, and singlet and triplet oxidation potentials (-1.1 and -0.5 V vs Ag/AgCl, respectively) were determined. Finally, based on the excited-state lifetimes and redox properties, these complexes represent a new class of light absorbers with potential application as dyes for charge injection into semiconductor solar cells and in sensitizer-catalyst assemblies for photocatalysis that operate with irradiation from the ultraviolet to ~800 nm.« less

New Rh 2 (II,II) Complexes for Solar Energy Applications: Panchromatic Absorption and Excited-State Reactivity

DOE PAGES

Whittemore, Tyler J.; Sayre, Hannah J.; Xue, Congcong; ...

2017-10-04

In this work, the new heteroleptic paddlewheel complexes cis-[Rh 2(μ-form) 2(μ-np) 2][BF 4] 2, where form = p-ditolylformamidinate (DTolF) or p-difluorobenzylformamidinate (F-form) and np = 1,8-napthyridyine, and cis-Rh 2(μ-form) 2(μ-npCOO) 2 (npCOO – = 1,8-naphthyridine-2-carboxylate), were synthesized and characterized. The complexes absorb strongly throughout the ultraviolet (λ max = 300 nm, ε = 20 300 M –1 cm –1) and visible regions (λ max = 640 nm ε = 3500 M –1 cm –1), making them potentially useful new dyes with panchromatic light absorption for solar energy conversion applications. Ultrafast and nanosecond transient absorption and time-resolved infrared spectroscopies were usedmore » to characterize the identity and dynamics of the excited states, where singlet and triplet Rh 2/form-to-naphthyridine, metal/ligand-to-ligand charge-transfer (ML-LCT) excited states were observed in all four complexes. The npCOO – complexes exhibit red-shifted absorption profiles extending into the near-IR and undergo photoinitiated electron transfer to generate reduced methyl viologen, a species that persists in the presence of a sacrificial donor. The energy of the triplet excited state of each complex was estimated from energy-transfer quenching experiments using a series of organic triplet donors (E( 3ππ*) from 1.83 to 0.78 eV). The singlet reduction (+0.6 V vs Ag/AgCl) potentials, and singlet and triplet oxidation potentials (-1.1 and -0.5 V vs Ag/AgCl, respectively) were determined. Finally, based on the excited-state lifetimes and redox properties, these complexes represent a new class of light absorbers with potential application as dyes for charge injection into semiconductor solar cells and in sensitizer-catalyst assemblies for photocatalysis that operate with irradiation from the ultraviolet to ~800 nm.« less

The effect of chronic silver nanoparticles on aquatic system in microcosms.

PubMed

Jiang, Hong Sheng; Yin, Liyan; Ren, Na Na; Xian, Ling; Zhao, Suting; Li, Wei; Gontero, Brigitte

2017-04-01

Silver nanoparticles (AgNPs) inevitably discharge into aquatic environments due to their abundant use in antibacterial products. It was reported that in laboratory conditions, AgNPs display dose-dependent toxicity to aquatic organisms, such as bacteria, algae, macrophytes, snails and fishes. However, AgNPs could behave differently in natural complex environments. In the present study, a series of microcosms were established to investigate the distribution and toxicity of AgNPs at approximately 500 μg L -1 in aquatic systems. As a comparison, the distribution and toxicity of the same concentration of AgNO 3 were also determined. The results showed that the surface layer of sediment was the main sink of Ag element for both AgNPs and AgNO 3 . Both aquatic plant (Hydrilla verticillata) and animals (Gambusia affinis and Radix spp) significantly accumulated Ag. With short-term treatment, phytoplankton biomass was affected by AgNO 3 but not by AgNPs. Chlorophyll content of H. verticillata increased with both AgNPs and AgNO 3 short-term exposure. However, the biomass of phytoplankton, aquatic plant and animals was not significantly different between control and samples treated with AgNPs or AgNO 3 for 90 d. The communities, diversity and richness of microbes were not significantly affected by AgNPs and AgNO 3 ; in contrast, the nitrification rate and its related microbe (Nitrospira) abundance significantly decreased. AgNPs and AgNO 3 may affect the nitrogen cycle and affect the environment and, since they might be also transferred to food web, they represent a risk for health. Copyright © 2017 Elsevier Ltd. All rights reserved.

Potential of silver against human colon cancer: (synthesis, characterization and crystal structures of xylyl (Ortho, meta, &Para) linked bis-benzimidazolium salts and Ag(I)-NHC complexes: In vitro anticancer studies)

PubMed Central

2013-01-01

Background Since the first successful synthesis of Ag(I)-N-heterocyclic carbene complex in 1993, this class of compounds has been extensively used for transmetallation reactions where the direct synthesis using other metal ions was either difficult or impossible. Initially, silver(I)-NHC complexes were tested for their catalytic potential but could not get fame because of lower potential compare to other competent compounds in this field; however, these compounds proved to have vital antimicrobial activities. These encouraging biomedical applications further convinced researchers to test these compounds against cancer. The current work has been carried out with this aim. Results N-ipropylbenzimidazole was synthesized by reaction of benzimidazole with ipropyl bromide. The subsequent treatment of the resulting N-alkylbenzimidazole with ortho/meta/para-(bromomethylene) benzene afforded corresponding bis-benzimidazolium bromides (5-7). The counter anion (Br-) of each salt was replaced by hexaflourophosphate (PF6-) for the ease of handling and further purification (8-10). Each salt (Ligand), in halide form, was further allowed to react with Ag2O with stirring at room temperature for a period of two days to synthesize dinuclear Ag(I)-NHC complexes (11-13). All synthesized compounds were characterized by spectroscopic techniques and microanalysis. Molecular structures of compounds 5, 9 &10 were established through single crystal x-ray diffraction technique. All the compounds were assessed for their anti-proliferation test on human colorectal cancer cell line (HCT 116). Results showed that the ligands (5-10) showed mild to negligible cytotoxicity on HCT 116 cells whereas respective silver complexes (11-13) exhibited dose dependent cytotoxicity towards the colon cancer cells with IC50 ranges between 9.7 to 44.5 μM. Interestingly, the complex 13 having para-xylyl spacer was found the most active (IC50 9.7 μM) that verifies our previously reported results. Conclusions All the bis-benzimidazolium salts (8-10) were found inactive whereas after bonding with silver cations, the Ag(I)-NHC complexes (11-13) showed a dose dependent cytotoxic activity. This proved that silver practice an important role in death of cancer cells. Also, the N-alkyl/aryl substitutions and ortho/metal/para xylyl units regulate the cytotoxicity. PMID:23391345

The accelerating effect of chitosan-silica hybrid dressing materials on the early phase of wound healing.

PubMed

Park, Ji-Ung; Jung, Hyun-Do; Song, Eun-Ho; Choi, Tae-Hyun; Kim, Hyoun-Ee; Song, Juha; Kim, Sukwha

2017-10-01

Commercialized dressing materials with or without silver have played a passive role in early-phase wound healing, protecting the skin defects from infections, absorbing exudate, and preventing dehydration. Chitosan (CTS)-based sponges have been developed in pure or hybrid forms for accelerating wound healing, but their wound-healing capabilities have not been extensively compared with widely used commercial dressing materials, providing limited information in a practical aspect. In this study, we have developed CTS-silica (CTS-Si) hybrid sponges with water absorption, flexibility, and mechanical behavior similar to those of CTS sponges. In vitro and in vivo tests were performed to compare the CTS-Si sponges with three commercial dressing materials [gauze, polyurethane (PU), and silver-containing hydrofiber (HF-Ag)] in addition to CTS sponges. Both in vitro and in vivo tests showed that CTS-Si sponges promoted fibroblast proliferation, leading to accelerated collagen synthesis, whereas the CTS sponges did not exhibit significant differences in fibroblast proliferation and collagen synthesis from gauze, PU, and HF-Ag sponges. In case of CTS-Si, the inflammatory cells were actively recruited to the wound by the influence of the released silicon ions from CTS-Si sponges, which, in return, led to an enhanced secretion of growth factors, particularly TGF-β during the early stage. The higher level of TGF-β likely improved the proliferation of fibroblasts, and as a result, collagen synthesis by fibroblasts became remarkably productive, thereby increasing collagen density at the wound site. Therefore, the CTS-Si hybrid sponges have considerable potential as a wound-dressing material for accelerating wound healing. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1828-1839, 2017. © 2016 Wiley Periodicals, Inc.

Stability of M 3S 3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni

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

Liu, Da-Jiang; Lee, Jiyoung; Windus, Theresa L.

Density Functional Theory is utilized to assess the stability of metal (M)-sulfur (S) complexes adsorbed on fcc M(111) surfaces, specifically considering S-decorated planar M trimers, M 3S 3. Scanning Tunneling Microscopy studies have identified structures proposed to be Ni 3S 3 on Ni(111), and Au 3S 3 on Au(111). In addition, Cu 3S 3 on Cu(111) has been suggested to facilitate enhanced Cu surface mass transport. Our analysis considers M 3S 3 complexes for M = Au, Ag, Cu, and Ni, assessing key measures of stability on surfaces, and also comparing behavior with trends in gas-phase stability. These surface andmore » gas-phase analyses are systematically related within the framework of Hess’s law, which allows elucidation of various contributions to the overall energetics. In all cases, the adsorbed complex is stable relative to its separated constituents adsorbed on the terrace. However, only for Ag does one find a negative energy of formation from excess S on terraces and M extracted from kink sites along step edges, implying spontaneous complex formation for this pathway. We interpret various experimental observations in the context of our results for energetics.« less

H{sub 2}—AgCl: A spectroscopic study of a dihydrogen complex

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

Grubbs, G. S.; Obenchain, Daniel A.; Pickett, Herbert M.

2014-09-21

H{sub 2}—AgCl has been observed on a Fourier transform microwave spectrometer equipped with laser ablation source and determined to be a dihydrogen complex. Transitions up to J = 3–2 have been measured and analyzed for four isotopologues of the complex containing ortho and para H{sub 2}. The ortho and para spin states have been included in one fit, a deviation from the typical H{sub 2} complex. Rotational constants B and C, centrifugal distortion constants Δ{sub J} and Δ{sub JK}, nuclear electric quadrupole coupling constants χ{sub aa}, χ{sub bb}, and χ{sub cc} for {sup 35}Cl and {sup 37}Cl have been fitmore » for both spin states while nuclear spin-nuclear spin constants D{sub aa}, D{sub bb}, and D{sub cc}, and nuclear spin-rotation constant C{sub aa} have been reported for the ortho spin state. Quantum chemical calculations predict a strong bonding interaction and the strength of the complex has been related to reported χ{sub aa} and Δ{sub J} values amongst a host of comparable species, including the AgCl monomer itself. Bond lengths have been determined for Ag—Cl, Ag—H{sub 2} center-of-mass, and H—H and are reported.« less

Stability of M 3S 3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni

DOE PAGES

Liu, Da-Jiang; Lee, Jiyoung; Windus, Theresa L.; ...

2018-02-08

Density Functional Theory is utilized to assess the stability of metal (M)-sulfur (S) complexes adsorbed on fcc M(111) surfaces, specifically considering S-decorated planar M trimers, M 3S 3. Scanning Tunneling Microscopy studies have identified structures proposed to be Ni 3S 3 on Ni(111), and Au 3S 3 on Au(111). In addition, Cu 3S 3 on Cu(111) has been suggested to facilitate enhanced Cu surface mass transport. Our analysis considers M 3S 3 complexes for M = Au, Ag, Cu, and Ni, assessing key measures of stability on surfaces, and also comparing behavior with trends in gas-phase stability. These surface andmore » gas-phase analyses are systematically related within the framework of Hess’s law, which allows elucidation of various contributions to the overall energetics. In all cases, the adsorbed complex is stable relative to its separated constituents adsorbed on the terrace. However, only for Ag does one find a negative energy of formation from excess S on terraces and M extracted from kink sites along step edges, implying spontaneous complex formation for this pathway. We interpret various experimental observations in the context of our results for energetics.« less

Ftmw Observation and Analysis of the {p}-H_2-{AgCl} and {o}-H_2-{AgCl} Complex

NASA Astrophysics Data System (ADS)

Grubbs, G. S.; Obenchain, D. A.; Pickett, H. M.; Novick, S. E.

2013-06-01

The rotational spectrum of p-H_2-{AgCl} and o-H_2-{AgCl} has been measured for the first time using a Balle-Flygare type Fourier transform microwave (FTMW) spectrometer. {(B+C)}/{2}'s, nuclear quadrupole coupling constants, and centrifugal distortion constants have been determined for multiple isotopologues of both species while spin-spin coupling constants have also been determined for at least one isotopologue of the o-H_2 species. Substantial changes in the eQq value from the monomer occur at the Cl nucleus upon complexation with the H_2 and will be discussed. Experimental r_0's for the H_2 C.O.M. distance to Ag and Ag distance to Cl are 1.809(2)Å and 2.2656(2)Å , respectively, for the p-H_2 species and will be compared to theory. Quantum chemical calculations were performed with an APFD density functional and MP2 with an aug-cc-pVQZ basis set for the hydrogen and chlorine with the effective core potential ECP28MDF_AVQZ for the Ag and will be presented. K. D. Hensel, C. Styger, W. Jäger, A. J. Merer, and M. C. L. Gerry, J. Chem. Phys., 99(1993) 3320. A. Austin, G. A. Petersson, M. J. Frisch, F. J. Dobek, G. Scalmani, and K. J. Throsselll. Chem. Theor. Comp., 8(2012) 4989. D. Figgen, G. Rauhut, M. Dolg, and H. Stoll. Chem. Phys., 311(2005) 227. K. A. Peterson and C. Puzzarini. Theor. Chem. Acc., 114(2005) 283.

Synthesis, Crystal Structure, and Luminescent Properties of Ag(I) Coordination Polymer with Tricarboxylic Acid and Flexible N-donor Ligand

NASA Astrophysics Data System (ADS)

Lu, J. F.; Xu, Y. H.; Li, P. A.; Jin, L. X.; Zhao, C. B.; Guoand, X. H.; Ge, H. G.

2017-12-01

The reaction of AgNO3 with combinations of 1,3-bis(4-pyridyl)propane ( bpp) and 1,3,5-benzenetricarboxylic acid (H3btc) in aqueous alcohol/ammonia at room temperature produces crystals of {[Ag6(H2O)2( bpp)6] · ( btc)2 · 25H2O} n (Ι). Single crystal X-ray diffraction analysis reveals that the complex Ι consists of 1D infinite cationic chains of [Ag( bpp)] n n+ and [Ag(H2O)( bpp)] n n+ which are further linked into the cation layer of [Ag( bpp)] n n+ by Ag···π interactions. The noncoordinated btc 3- serves as template driving surrounding water molecules to aggregate into the anionic water layer. The neighboring anionic water layer and cationic layer were further alternately joined into a 3D sandwich-like framework by hydrogen bonding. In addition, the luminescent properties of Ι were investigated.

Ultrafast dynamics in atomic clusters: Analysis and control

PubMed Central

Bonačić-Koutecký, Vlasta; Mitrić, Roland; Werner, Ute; Wöste, Ludger; Berry, R. Stephen

2006-01-01

We present a study of dynamics and ultrafast observables in the frame of pump–probe negative-to-neutral-to-positive ion (NeNePo) spectroscopy illustrated by the examples of bimetallic trimers Ag2Au−/Ag2Au/Ag2Au+ and silver oxides Ag3O2−/Ag3O2/Ag3O2+ in the context of cluster reactivity. First principle multistate adiabatic dynamics allows us to determine time scales of different ultrafast processes and conditions under which these processes can be experimentally observed. Furthermore, we present a strategy for optimal pump–dump control in complex systems based on the ab initio Wigner distribution approach and apply it to tailor laser fields for selective control of the isomerization process in Na3F2. The shapes of pulses can be assigned to underlying processes, and therefore control can be used as a tool for analysis. PMID:16740664

Ultrafast dynamics in atomic clusters: analysis and control.

PubMed

Bonacić-Koutecký, Vlasta; Mitrić, Roland; Werner, Ute; Wöste, Ludger; Berry, R Stephen

2006-07-11

We present a study of dynamics and ultrafast observables in the frame of pump-probe negative-to-neutral-to-positive ion (NeNePo) spectroscopy illustrated by the examples of bimetallic trimers Ag2Au-/Ag2Au/Ag2Au+ and silver oxides Ag3O2-/Ag3O2/Ag3O2+ in the context of cluster reactivity. First principle multistate adiabatic dynamics allows us to determine time scales of different ultrafast processes and conditions under which these processes can be experimentally observed. Furthermore, we present a strategy for optimal pump-dump control in complex systems based on the ab initio Wigner distribution approach and apply it to tailor laser fields for selective control of the isomerization process in Na3F2. The shapes of pulses can be assigned to underlying processes, and therefore control can be used as a tool for analysis.

Integrative assessment of the effects produced by Ag nanoparticles at different levels of biological complexity in Eisenia fetida maintained in two standard soils (OECD and LUFA 2.3).

PubMed

Garcia-Velasco, N; Peña-Cearra, A; Bilbao, E; Zaldibar, B; Soto, M

2017-08-01

There is a potential risk to increase the release of silver nanoparticles (Ag NPs) into the environment: For instance. in soils receiving sludge models estimate 0.007 mg Ag NPs kg -1 that will annually increase due to sludge or sludge incineration residues land-disposal. Thus, the concern about the hazards of nanosilver to soils and soil invertebrates is growing. Studies performed up to now have been focused in traditional endpoints, used limit range concentrations and employed different soil types that differ in physico-chemical characteristics. Presently, effects of Ag NPs have been measured at different levels of biological complexity in Eisenia fetida, exposed for 3 and 14 d to high but sublethal (50 mg Ag NPs kg -1 ) and close to modeled environmental concentrations (0.05 mg Ag NPs kg -1 ). Since characteristics of the exposure matrix may limit the response of the organisms to these concentrations, experiments were carried out in OECD and LUFA soils, the most used standard soils. High concentrations of Ag NPs increased catalase activity and DNA damage in OECD soils after 14 d while in LUFA 2.3 soils produced earlier effects (weight loss, decrease in cell viability and increase in catalase activity at day 3). At day 14, LUFA 2.3 (low clay and organic matter-OM-) could have provoked starvation of earthworms, masking Ag NPs toxicity. The concentration close to modeled environmental concentrations produced effects uniquely in LUFA 2.3 soil. Accurate physico-chemical characteristics of the standard soils are crucial to assess the toxicity exerted by Ag NPs in E. fetida since low clay and OM contents can be considered toxicity enhancers. Copyright © 2017 Elsevier Ltd. All rights reserved.

Incorporation of a Theranostic "Two-Tone" Luminescent Silver Complex into Biocompatible Agar Hydrogel Composite for the Eradication of ESKAPE Pathogens in a Skin and Soft Tissue Infection Model.

PubMed

Pinto, Miguel N; Martinez-Gonzalez, Jorge; Chakraborty, Indranil; Mascharak, Pradip K

2018-06-04

Microbial invasion and colonization of the skin and underlying soft tissues are among the most common types of infections, becoming increasingly prevalent in hospital settings. Systemic antibiotic chemotherapies are now extremely limited due to emergence of drug-resistant Gram-positive and multidrug-resistant Gram-negative bacterial strains. Topical administration of antimicrobials provides an effective route for the treatment of skin and soft tissue infections (SSTIs). Therefore, the development of new and effective materials for the delivery of these agents is of paramount importance. Silver is a broad-spectrum antibiotic used for the treatment and prevention of infections since ancient times. However, the high reactivity of silver cation (Ag + ) makes its incorporation into delivery materials quite challenging. Herein we report a novel soft agar hydrogel composite for the delivery of Ag + into infected wound sites. This material incorporates a Ag(I) complex [Ag 2 (DSX) 2 (NO 3 ) 2 ] (1; DSX = 5-(dimethylamino)- N, N-bis(pyridin-2-ylmethyl) naphthalene-1-sulfonamide) that exhibits a change in fluorescence upon Ag + release and qualitatively indicates the end point of silver delivery. The antibacterial efficacy of the material was tested against several bacterial strains in an SSTI model. The complex 1-agar composite proved effective at eradicating the pathogens responsible for the majority of SSTIs. The theranostic (therapeutic/diagnostic) properties coupled with its stability, softness, ease of application, and removal make this material an attractive silver-delivery vehicle for the treatment and prevention of SSTIs.

Fundamental Factors Impacting the Stability of Phosphonate-Derivatized Ruthenium Polypyridyl Sensitizers Adsorbed on Metal Oxide Surfaces.

PubMed

Raber, McKenzie; Brady, Matthew David; Troian-Gautier, Ludovic; Dickenson, John; Marquard, Seth L; Hyde, Jacob; Lopez, Santiago; Meyer, Gerald J; Meyer, Thomas J; Harrison, Daniel P

2018-06-08

A series of 18 ruthenium(II) polypyridyl complexes were synthesized and evaluated under electrochemically oxidative conditions, which generates the Ru(III) oxidation state and mimics the harsh conditions experienced during the kinetically-limited regime that can occur in dye-sensitized solar cells (DSSCs) and dye-sensitized photoelectrosynthesis cells (DSPECs), to further develop fundamental insights into the factors governing molecular sensitizer surface stability in aqueous 0.1 M HClO4 (aq). Both desorption and oxidatively induced ligand substitution were observed on planar fluorine doped tin oxide, FTO, electrodes, with a dependence on the E1/2 Ru(III/II) redox potential dictating the comparative ratios of the processes. Complexes such as RuP4OMe (E1/2 = 0.91 vs Ag/AgCl) displayed virtually only desorption, while complexes such as RuPbpz (E1/2 > 1.62 V vs Ag/AgCl) displayed only chemical decomposition. Comparing isomers of 4,4'- and 5,5-disubstituted-2,2'-bipyridine ancillary polypyridyl ligands, a dramatic increase in the rate of desorption of the Ru(III) complexes was observed for the 5,5'-ligands. Nanoscopic indium doped tin oxide thin films, nanoITO, were also sensitized and analyzed with cyclic voltammetry, UV-Vis absorption spectroscopy, and XPS, allowing for further distinction of desorption versus ligand substitution processes. Desorption loss to bulk solution associated with the planar surface of FTO is essentially non-existent on nanoITO, where both desorption and ligand substitution are shut down with RuP4OMe. These results revealed that minimizing time spent in the oxidized form, incorporating electron donating groups, maximizing hydrophobicity, and minimizing molecular bulk near the adsorbed ligand are critical to optimizing the performance of ruthenium(II) polypyridyl complexes in dye-sensitized solar cell devices.

Synthesis and ion transport characterization of hot-pressed Ag+ ion conducting glass-polymer electrolytes

NASA Astrophysics Data System (ADS)

Chandra, A.

2013-07-01

Synthesis and ion transport characterization of a new Ag+ ion conducting glass-polymer electrolyte (GPE) films: (1- x) PEO: x [0.8(0.75AgI:0.25AgCl):0.2(Ag2O:V2O5)], where 0 < x < 50 wt%, are reported. The composition: 70PEO: 30[0.8(0.75AgI:0.25AgCl):0.2(Ag2O:V2O5)] with conductivity ( σ) 7.7 × 10-7 Ω-1 cm-1 is identified as highest conducting composition referred to as the optimum conducting composition (OCC). Approximately two and half orders of conductivity enhancement have been achieved in OCC from that of the pure polymer poly(ethylene oxide). The glass-polymer complexation is confirmed by the XRD, FTIR, DSC and TGA techniques. The ion transport behavior has been reported on the basis of experimental measurements on some basic ionic parameters. A solid state polymeric battery has been fabricated by using GPE OCC as an electrolyte and their important cell parameters have been also calculated from the discharge profiles.

Lawsonia inermis-mediated synthesis of silver nanoparticles: activity against human pathogenic fungi and bacteria with special reference to formulation of an antimicrobial nanogel.

PubMed

Gupta, Arpita; Bonde, Shital R; Gaikwad, Swapnil; Ingle, Avinash; Gade, Aniket K; Rai, Mahendra

2014-09-01

Lawsonia inermis mediated synthesis of silver nanoparticles (Ag-NPs) and its efficacy against Candida albicans, Microsporum canis, Propioniabacterium acne and Trichophyton mentagrophytes is reported. A two-step mechanism has been proposed for bioreduction and formation of an intermediate complex leading to the synthesis of capped nanoparticles was developed. In addition, antimicrobial gel for M. canis and T. mentagrophytes was also formulated. Ag-NPs were synthesized by challenging the leaft extract of L. inermis with 1 mM AgNO₃. The Ag-NPs were characterized by Ultraviolet-Visible (UV-Vis) spectrophotometer and Fourier transform infrared spectroscopy (FTIR). Transmission electron microscopy (TEM), nanoparticle tracking and analysis sytem (NTA) and zeta potential was measured to detect the size of Ag-NPs. The antimicrobial activity of Ag-NPs was evaluated by disc diffusion method against the test organisms. Thus these Ag-NPs may prove as a better candidate drug due to their biogenic nature. Moreover, Ag-NPs may be an answer to the drug-resistant microorganisms.

Nanosilver and the microbiological activity of the particulate solids versus the leached soluble silver.

PubMed

Faiz, Merisa B; Amal, Rose; Marquis, Christopher P; Harry, Elizabeth J; Sotiriou, Georgios A; Rice, Scott A; Gunawan, Cindy

2018-04-01

Nanosilver (Ag NPs) is currently one of the most commercialized antimicrobial nanoparticles with as yet, still unresolved cytotoxicity origins. To date, research efforts have mostly described the antimicrobial contribution from the leaching of soluble silver, while the undissolved solid Ag particulates are often considered as being microbiologically inert, serving only as source of the cytotoxic Ag ions. Here, we show the rapid stimulation of lethal cellular oxidative stress in bacteria by the presence of the undissolved Ag particulates. The cytotoxicity characteristics are distinct from those arising from the leached soluble Ag, the latter being locked in organic complexes. The work also highlights the unique oxidative stress-independent bacterial toxicity of silver salt. Taken together, the findings advocate that future enquiries on the antimicrobial potency and also importantly, the environmental and clinical impact of Ag NPs use, should pay attention to the potential bacterial toxicological responses to the undissolved Ag particulates, rather than just to the leaching of soluble silver. The findings also put into question the common use of silver salt as model material for evaluating bacterial toxicity of Ag NPs.

Highly Stable Graphene-Based Nanocomposite (GO-PEI-Ag) with Broad-Spectrum, Long-Term Antimicrobial Activity and Antibiofilm Effects.

PubMed

Zhao, Rongtao; Kong, Wen; Sun, Mingxuan; Yang, Yi; Liu, Wanying; Lv, Min; Song, Shiping; Wang, Lihua; Song, Hongbin; Hao, Rongzhang

2018-05-30

Various silver nanoparticle (AgNP)-decorated graphene oxide (GO) nanocomposites (GO-Ag) have received increasing attention owing to their antimicrobial activity and biocompatibility; however, their aggregation in physiological solutions and the generally complex synthesis methods warrant improvement. This study aimed to synthesize a polyethyleneimine (PEI)-modified and AgNP-decorated GO nanocomposite (GO-PEI-Ag) through a facile approach through microwave irradiation without any extra reductants and surfactants; its antimicrobial activity was investigated on Gram-negative/-positive bacteria (including drug-resistant bacteria) and fungi. Compared with GO-Ag, GO-PEI-Ag acquired excellent stability in physiological solutions and electropositivity, showing substantially higher antimicrobial efficacy. Moreover, GO-PEI-Ag exhibited particularly excellent long-term effects, presenting no obvious decline in antimicrobial activity after 1 week storage in physiological saline and repeated use for three times and the lasting inhibition of bacterial growth in nutrient-rich culture medium. In contrast, GO-Ag exhibited a >60% decline in antimicrobial activity after storage. Importantly, GO-PEI-Ag effectively eliminated adhered bacteria, thereby preventing biofilm formation. The primary antimicrobial mechanisms of GO-PEI-Ag were evidenced as physical damage to the pathogen structure, causing cytoplasmic leakage. Hence, stable GO-PEI-Ag with robust, long-term antimicrobial activity holds promise in combating public-health threats posed by drug-resistant bacteria and biofilms.

Synthesis of novel cellulose- based antibacterial composites of Ag nanoparticles@ metal-organic frameworks@ carboxymethylated fibers.

PubMed

Duan, Chao; Meng, Jingru; Wang, Xinqi; Meng, Xin; Sun, Xiaole; Xu, Yongjian; Zhao, Wei; Ni, Yonghao

2018-08-01

A novel cellulose-based antibacterial material, namely silver nanoparticles@ metal-organic frameworks@ carboxymethylated fibers composites (Ag NPs@ HKUST-1@ CFs), was synthesized. The results showed that the metal-organic frameworks (HKUST-1) were uniformly anchored on the fiber's surfaces by virtue of complexation between copper ions in HKUST-1 and carboxyl groups on the carboxymethylated fibers (CFs). The silver nanoparticles (Ag NPs) were immobilized and well-dispersed into the pores and/or onto the surfaces of HKUST-1 via in situ microwave reduction, resulting in the formation of novel Ag NPs@ HKUST-1@ CFs composites. The antibacterial assays showed that the as-prepared composites exhibited a much higher antibacterial activity than Ag NPs@ CFs or HKUST-1@ CFs samples. Copyright © 2018 Elsevier Ltd. All rights reserved.

Preparation of the antithrombotic and antimicrobial coating through layer-by-layer self-assembly of nattokinase-nanosilver complex and polyethylenimine.

PubMed

Wei, Xuetuan; Luo, Mingfang; Liu, Huizhou

2014-04-01

The bifunctional coating with antithrombotic and antimicrobial activity was developed using nattokinase (NK) and nanosilver (AgNPs). Firstly, the adsorption interactions between NK and AgNPs were confirmed, and the composite particles of NK-AgNPs were prepared by adsorption of NK with AgNPs. At 5FU/mL of NK concentration, the saturation adsorption capacity reached 24.35 FU/mg AgNPs with a high activity recovery of 97%, and adsorption by AgNPs also enhanced the heat stability and anticoagulant effect of NK. Based on the electrostatic force driven layer-by-layer self-assembly, the NK-AgNPs were further assembled with polyethylenimine (PEI) to form coating. UV-vis analysis showed that the self-assembly process was regular, and atom force microscopy analysis indicated that NK-AgNPs were uniformly embedded into the coating. The NK-AgNPs-PEI composite coating showed potent antithrombotic activity and antibacterial activity. This study developed a novel strategy to construct the bifunctional coating with antithrombotic and antimicrobial properties, and the coating material showed promising potential to be applied in the medical device. Copyright © 2014 Elsevier B.V. All rights reserved.

Sunlight mediated synthesis of silver nanoparticles using redox phytoprotein and their application in catalysis and colorimetric mercury sensing.

PubMed

Ahmed, Khan Behlol Ayaz; Senthilnathan, Rajendran; Megarajan, Sengan; Anbazhagan, Veerappan

2015-10-01

Owing to the benign nature, plant extracts mediated green synthesis of metal nanoparticles (NPs) is rapidly expanding. In this study, we demonstrated the successful green synthesis of silver nanoparticles (AgNPs) by utilizing natural sunlight and redox protein complex composed of ferredoxin-NADP(+) reductase (FNR) and ferredoxin (FD). The capping and stabilization of the AgNPs by the redox protein was confirmed by Fourier transform infrared spectroscopy. Light and redox protein is the prerequisite factor for the formation of AgNPs. The obtained result shows that the photo generated free radicals by the redox protein is responsible for the reduction of Ag(+) to Ag(0). Transmission electron microscopy revealed the formation of spherical AgNPs with size ranging from 10 to 15 nm. As-prepared AgNPs exhibit excellent catalytic activity toward the degradation of hazardous organic dyes, such as methylene blue, methyl orange and methyl red. These bio-inspired AgNPs is highly sensitive and selective in sensing hazardous mercury ions in the water at micromolar concentration. In addition, FNR/FD extract stabilized AgNPs showed good antimicrobial activity against gram positive and gram negative bacteria. Copyright © 2015 Elsevier B.V. All rights reserved.

Evaluation of Immunogenicity and Protective Efficacy Elicited by Mycobacterium bovis BCG Overexpressing Ag85A Protein against Mycobacterium tuberculosis Aerosol Infection.

PubMed

Xu, Zheng Zhong; Chen, Xiang; Hu, Ting; Meng, Chuang; Wang, Xiao Bo; Rao, Yan; Zhang, Xiao Ming; Yin, Yue Lan; Pan, Zhi Ming; Jiao, Xin An

2016-01-01

Mycobacterium bovis bacillus Calmette-Guérin (BCG) is currently the only vaccine available for preventing tuberculosis (TB), however, BCG has varying success in preventing pulmonary TB. In this study, a recombinant BCG (rBCG::Ag85A) strain overexpressing the immunodominant Ag85A antigen was constructed, and its immunogenicity and protective efficacy were evaluated. Our results indicated that the Ag85A protein was successfully overexpressed in rBCG::Ag85A, and the Ag85A peptide-MHC complexes on draining lymph node dendritic cells of C57BL/6 mice infected with rBCG::Ag85A were detectable 4 h post-infection. The C57BL/6 mice infected with this strain had stronger antigen-specific interferon-gamma (IFN-γ) responses and higher antibody titers than those immunized with BCG, and the protective experiments showed that rBCG::Ag85A can enhance protection against Mycobacterium tuberculosis (M. tuberculosis) H37Rv infection compared to the BCG vaccine alone. Our results demonstrate the potential of rBCG::Ag85A as a candidate vaccine against TB.

Discovery and characterization of two Nimrod superfamily members in Anopheles gambiae.

PubMed

Midega, Janet; Blight, Joshua; Lombardo, Fabrizio; Povelones, Michael; Kafatos, Fotis; Christophides, George K

2013-12-01

Anti-bacterial proteins in mosquitoes are known to play an important modulatory role on immune responses to infections with human pathogens including malaria parasites. In this study we characterized two members of the Anopheles gambiae Nimrod superfamily, namely AgNimB2 and AgEater. We confirm that current annotation of the An. gambiae genome incorrectly identifies AgNimB2 and AgEater as a single gene, AGAP009762. Through in silico and experimental approaches, it has been shown that AgNimB2 is a secreted protein that mediates phagocytosis of Staphylococcus aureus but not of Escherichia coli bacteria. We also reveal that this function does not involve a direct interaction of AgNimB2 with S. aureus. Therefore, AgNimB2 may act downstream of complement-like pathway activation, first requiring bacterial opsonization. In addition, it has been shown that AgNimB2 has an anti-Plasmodium effect. Conversely, AgEater is a membrane-bound protein that either functions redundantly or is dispensable for phagocytosis of E. coli or S. aureus. Our study provides insights into the role of members of the complex Nimrod superfamily in An. gambiae, the most important African vector of human malaria.

Discovery and characterization of two Nimrod superfamily members in Anopheles gambiae

PubMed Central

Midega, Janet; Blight, Joshua; Lombardo, Fabrizio; Povelones, Michael; Kafatos, Fotis; Christophides, George K

2013-01-01

Anti-bacterial proteins in mosquitoes are known to play an important modulatory role on immune responses to infections with human pathogens including malaria parasites. In this study we characterized two members of the Anopheles gambiae Nimrod superfamily, namely AgNimB2 and AgEater. We confirm that current annotation of the An. gambiae genome incorrectly identifies AgNimB2 and AgEater as a single gene, AGAP009762. Through in silico and experimental approaches, it has been shown that AgNimB2 is a secreted protein that mediates phagocytosis of Staphylococcus aureus but not of Escherichia coli bacteria. We also reveal that this function does not involve a direct interaction of AgNimB2 with S. aureus. Therefore, AgNimB2 may act downstream of complement-like pathway activation, first requiring bacterial opsonization. In addition, it has been shown that AgNimB2 has an anti-Plasmodium effect. Conversely, AgEater is a membrane-bound protein that either functions redundantly or is dispensable for phagocytosis of E. coli or S. aureus. Our study provides insights into the role of members of the complex Nimrod superfamily in An. gambiae, the most important African vector of human malaria. PMID:24428830

Silver ions-mediated conformational switch: facile design of structure-controllable nucleic acid probes.

PubMed

Wang, Yongxiang; Li, Jishan; Wang, Hao; Jin, Jianyu; Liu, Jinhua; Wang, Kemin; Tan, Weihong; Yang, Ronghua

2010-08-01

Conformationally constraint nucleic acid probes were usually designed by forming an intramolecular duplex based on Watson-Crick hydrogen bonds. The disadvantages of these approaches are the inflexibility and instability in complex environment of the Watson-Crick-based duplex. We report that this hydrogen bonding pattern can be replaced by metal-ligation between specific metal ions and the natural bases. To demonstrate the feasibility of this principle, two linear oligonucleotides and silver ions were examined as models for DNA hybridization assay and adenosine triphosphate detection. The both nucleic acids contain target binding sequences in the middle and cytosine (C)-rich sequences at the lateral portions. The strong interaction between Ag(+) ions and cytosines forms stable C-Ag(+)-C structures, which promises the oligonucleotides to form conformationally constraint formations. In the presence of its target, interaction between the loop sequences and the target unfolds the C-Ag(+)-C structures, and the corresponding probes unfolding can be detected by a change in their fluorescence emission. We discuss the thermodynamic and kinetic opportunities that are provided by using Ag(+) ion complexes instead of traditional Watson-Crick-based duplex. In particular, the intrinsic feature of the metal-ligation motif facilitates the design of functional nucleic acids probes by independently varying the concentration of Ag(+) ions in the medium.

Effects of Ag and Cu ions on the microbial corrosion of 316L stainless steel in the presence of Desulfovibrio sp.

PubMed

Unsal, Tuba; Ilhan-Sungur, Esra; Arkan, Simge; Cansever, Nurhan

2016-08-01

The utilization of Ag and Cu ions to prevent both microbial corrosion and biofilm formation has recently increased. The emphasis of this study lies on the effects of Ag and Cu ions on the microbial corrosion of 316L stainless steel (SS) induced by Desulfovibrio sp. Electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization were used to analyze the corrosion behavior. The biofilm formation, corrosion products and Ag and Cu ions on the surfaces were investigated using scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS) and elemental mapping. Through circuit modeling, EIS results were used to interpret the physicoelectric interactions between the electrode, biofilm and culture interfaces. EIS results indicated that the metabolic activity of Desulfovibrio sp. accelerated the corrosion rate of SS in both conditions with and without ions. However, due to the retardation in the growth of Desulfovibrio sp. in the presence of Ag and Cu ions, significant decrease in corrosion rate was observed in the culture with the ions. In addition, SEM and EIS analyses revealed that the presence of the ions leads to the formation on the SS of a biofilm with different structure and morphology. Elemental analysis with EDS detected mainly sulfide- and phosphorous-based corrosion products on the surfaces. Copyright © 2016 Elsevier B.V. All rights reserved.

Green synthesis of silver nanoparticles using Achillea biebersteinii flower extract and its anti-angiogenic properties in the rat aortic ring model.

PubMed

Baharara, Javad; Namvar, Farideh; Ramezani, Tayebe; Hosseini, Nasrin; Mohamad, Rosfarizan

2014-04-15

Silver nanoparticles display unique physical and biological properties which have attracted intensive research interest because of their important medical applications. In this study silver nanoparticles (Ab.Ag-NPs) were synthesized for biomedical applications using a completely green biosynthetic method using Achillea biebersteinii flowers extract. The structure and properties of Ab.Ag-NPs were investigated using UV-visible spectroscopic techniques, transmission electron microscopy (TEM), zeta potential and energy dispersive X-ray spectrometers (EDS). The UV-visible spectroscopic analysis showed the absorbance peak at 460 nm, which indicates the synthesis of silver nanoparticles. The average particle diameter as determined by TEM was found to be 12±2 nm. The zeta potential analysis indicated that Ab.Ag-NPs have good stability EDX analysis also exhibits presentation of silver element. As angiogenesis is an important phenomenon and as growth factors imbalance in this process causes the acceleration of several diseases including cancer, the anti-angiogenic properties of Ab.Ag-NPs were evaluated using the rat aortic ring model. The results showed that Ab.Ag-NPs (200 μg/mL) lead to a 50% reduction in the length and number of vessel-like structures. The synthesized silver nanoparticles from the Achillea biebersteinii flowers extract, which do not involve any harmful chemicals were well-dispersed and stabilized through this green method and showed potential therapeutic benefits against angiogenesis.

Effect of gelatin sponge with colloid silver on bone healing in infected cranial defects.

PubMed

Dong, Yuliang; Liu, Weiqing; Lei, Yiling; Wu, Tingxi; Zhang, Shiwen; Guo, Yuchen; Liu, Yuan; Chen, Demeng; Yuan, Quan; Wang, Yongyue

2017-01-01

Oral infectious diseases may lead to bone loss, which makes it difficult to achieve satisfactory restoration. The rise of multidrug resistant bacteria has put forward severe challenges to the use of antibiotics. Silver (Ag) has long been known as a strong antibacterial agent. In clinic, gelatin sponge with colloid silver is used to reduce tooth extraction complication. To investigate how this material affect infected bone defects, methicillin-resistant Staphylococcus aureus (MRSA) infected 3-mm-diameter cranial defects were created in adult female Sprague-Dawley rats. One week after infection, the defects were debrided of all nonviable tissue and then implanted with gelatin sponge with colloid silver (gelatin/Ag group) or gelatin alone (gelatin group). At 2 and 3days after debridement, significantly lower mRNA expression levels of IL-6 and TNF-α and lower plate colony count value were detected in gelatin/Ag group than control. Micro-CT analysis showed a significant increase of newly formed bone volume fraction (BV/TV) in gelatin/Ag treated defects. The HE stained cranium sections also showed a faster rate of defect closure in gelatin/Ag group than control. These findings demonstrated that gelatin sponge with colloid silver can effectively reduce the infection caused by MRSA in cranial defects and accelerate bone healing process. Copyright © 2016. Published by Elsevier B.V.

Insufficiency of the Young’s modulus for illustrating the mechanical behavior of GaN nanowires

NASA Astrophysics Data System (ADS)

Zamani Kouhpanji, Mohammad Reza; Behzadirad, Mahmoud; Feezell, Daniel; Busani, Tito

2018-05-01

We use a non-classical modified couple stress theory including the acceleration gradients (MCST-AG), to precisely demonstrate the size dependency of the mechanical properties of gallium nitride (GaN) nanowires (NWs). The fundamental elastic constants, Young’s modulus and length scales of the GaN NWs were estimated both experimentally, using a novel experimental technique applied to atomic force microscopy, and theoretically, using atomic simulations. The Young’s modulus, static and the dynamic length scales, calculated with the MCST-AG, were found to be 323 GPa, 13 and 14.5 nm, respectively, for GaN NWs from a few nanometers radii to bulk radii. Analyzing the experimental data using the classical continuum theory shows an improvement in the experimental results by introducing smaller error. Using the length scales determined in MCST-AG, we explain the inconsistency of the Young’s moduli reported in recent literature, and we prove the insufficiency of the Young’s modulus for predicting the mechanical behavior of GaN NWs.

Insufficiency of the Young's modulus for illustrating the mechanical behavior of GaN nanowires.

PubMed

Kouhpanji, Mohammad Reza Zamani; Behzadirad, Mahmoud; Feezell, Daniel; Busani, Tito

2018-05-18

We use a non-classical modified couple stress theory including the acceleration gradients (MCST-AG), to precisely demonstrate the size dependency of the mechanical properties of gallium nitride (GaN) nanowires (NWs). The fundamental elastic constants, Young's modulus and length scales of the GaN NWs were estimated both experimentally, using a novel experimental technique applied to atomic force microscopy, and theoretically, using atomic simulations. The Young's modulus, static and the dynamic length scales, calculated with the MCST-AG, were found to be 323 GPa, 13 and 14.5 nm, respectively, for GaN NWs from a few nanometers radii to bulk radii. Analyzing the experimental data using the classical continuum theory shows an improvement in the experimental results by introducing smaller error. Using the length scales determined in MCST-AG, we explain the inconsistency of the Young's moduli reported in recent literature, and we prove the insufficiency of the Young's modulus for predicting the mechanical behavior of GaN NWs.

Optical chirality in AgCl-Ag thin films through formation of laser-induced planar crossed-chain nanostructures

NASA Astrophysics Data System (ADS)

Nahal, Arashmid; Kashani, Somayeh

2017-09-01

Irradiation of AgCl-Ag thin films by a linearly polarized He-Ne laser beam results in the formation of self-organized periodic nanostructures. As a result of secondary irradiation of the initially exposed sample by the same linearly polarized He-Ne laser beam, but with different orientations of polarization, a complex crossed-chain nanostructure forms. We found that such a complex nanostructure has noticeable chirality and increased optical anisotropy, resulting in optical activity of the sample. Double exposure produces two gratings, crossing each other with angle α, which leads to the formation of crossed building blocks with chiroptical effects. It is established that the amount and the sign of the angle between the two laser-induced gratings (±α) determine the amount and the direction of rotation of the linearly polarized probe beam, respectively. We have also observed an induced anisotropy-dependent ellipticity for the probe light, which is passed through the sample. It is shown that the amount of ellipticity depends on the angle α.

DNA-dependent protein kinase modulates the anti-cancer properties of silver nanoparticles in human cancer cells.

PubMed

Lim, Hui Kheng; Gurung, Resham Lal; Hande, M Prakash

2017-12-01

Silver nanoparticles (Ag-np) were reported to be toxic to eukaryotic cells. These potentially detrimental effects of Ag-np can be advantageous in experimental therapeutics. They are currently being employed to enhance the therapeutic efficacy of cancer drugs. In this study, we demonstrate that Ag-np treatment trigger the activation of DNA-PKcs and JNK pathway at selected doses, presumably as a physiologic response to DNA damage and repair in normal and malignant cells. Ag-np altered the telomere dynamics by disrupting the shelterin complex located at the telomeres and telomere lengths. The genotoxic effect of Ag-np was not restricted to telomeres but the entire genome as Ag-np induced γ-H2AX foci formation, an indicator of global DNA damage. Inhibition of DNA-PKcs activity sensitised the cancer cells towards the cytotoxicity of Ag-np and substantiated the damaging effect of Ag-np at telomeres in human cancer cells. Abrogation of JNK mediated DNA repair and extensive damage of telomeres led to greater cell death following Ag-np treatment in DNA-PKcs inhibited cancer cells. Collectively, this study suggests that improved anti-proliferative and cytotoxic effects of Ag-np treatment in cancer cells can be achieved by the inhibition of DNA-PKcs. Copyright © 2017 Elsevier B.V. All rights reserved.

The successful incorporation of Ag into single grain, Y-Ba-Cu-O bulk superconductors

NASA Astrophysics Data System (ADS)

Congreve, Jasmin V. J.; Shi, Yunhua; Dennis, Anthony R.; Durrell, John H.; Cardwell, David A.

2018-07-01

The use of RE-Ba-Cu-O [(RE)BCO] bulk superconductors, where RE = Y, Gd, Sm, in practical applications is, at least in part, limited by their mechanical properties and brittle nature, in particular. Alloying these materials with silver, however, produces a significant improvement in strength without any detrimental impact on their superconducting properties. Unfortunately, the top seeded melt growth technique, used routinely to process bulk (RE)BCO superconductors in the form of large, single grains required for practical applications, is complex and has a large number of inter-related variables, so the addition of silver increases the complexity of the growth process even further. This can make successful growth of this system extremely challenging. Here we report measurements of the growth rate of YBCO-Ag fabricated using a new growth technique consisting of continuous cooling and isothermal hold process. The resulting data form the basis of a model that has been used to derive suitable heating profiles for the successful single grain growth of YBCO-Ag bulk superconductors of up to 26 mm in diameter. The microstructure and distribution of silver within these samples have been studied in detail. The maximum trapped field at the top surface of the bulk YBCO-Ag samples has been found to be comparable to that of standard YBCO processed without Ag. The YBCO-Ag samples also exhibit a much more uniform trapped field profile compared to that of YBCO.

Resorcarene-based receptor: versatile behavior in its interaction with heavy and soft metal cations.

PubMed

Danil de Namor, Angela F; Chaaban, Jinane K; Piro, Oscar E; Castellano, Eduardo E

2006-02-09

Standard solution Gibbs energies, DeltasG degrees, of the resorcarene-based receptor 5,11,17,23-ethylthiomethylated calix[4]resorcarene, (characterized by 1H NMR and X-ray diffraction studies) in its monomeric state (established through partition experiments) in various solvents are for the first time reported in the area of resorcarene chemistry. Transfer Gibbs energies of from hexane (reference solvent) to other medium are calculated. Agreement between DeltatG degrees (referred to the pure solvents) and standard partition Gibbs energies, DeltapG degrees (solvent mutually saturated) is found. Cation-ligand interactions were investigated through 1H NMR (CD3CN and CD3OD) and conductometric titrations in acetonitrile and methanol. 1H NMR data revealed the sites of interaction of with the metal cation. The composition of the metal-ion complexes (Ag+ and Pb2+ in acetonitrile and Ag+ and Cu2+ in methanol) was established through conductometric titrations. Thus, complexes of 1:1 stoichiometry were formed between and Ag+ and Pb2+ in acetonitrile and Cu2+ in methanol. However, in moving from acetonitrile to methanol, the composition of the silver complex was altered. Thus, two metal cations are hosted by a unit of the ligand. As far as Cu2+ and in acetonitrile is concerned, conductance data suggest that metalates are formed in which up to four units of Cu2+ are taken up per unit of resorcarene. The contrasting behavior of with Cu2+ in acetonitrile relative to methanol is discussed. As far as mercury (II) is concerned, the unusual jump in conductance observed in the titration of Hg2+ with in acetonitrile and methanol after the formation of a multicharged complex (undefined composition) is attributed to the presence of highly charged smaller units (higher mobility) resulting from the departure of pendant arms from the resorcarene backbone. Isolation of these species followed by X-ray diffraction studies corroborated this statement. The thermodynamic characterization of metal-ion complexes of Ag+ and Pb2+ in acetonitrile and Cu2+ and Ag+ in methanol is reported. Final conclusions are given.

A Mechanistic Thermal Fatigue Model for SnAgCu Solder Joints

NASA Astrophysics Data System (ADS)

Borgesen, Peter; Wentlent, Luke; Hamasha, Sa'd.; Khasawneh, Saif; Shirazi, Sam; Schmitz, Debora; Alghoul, Thaer; Greene, Chris; Yin, Liang

2018-02-01

The present work offers both a complete, quantitative model and a conservative acceleration factor expression for the life span of SnAgCu solder joints in thermal cycling. A broad range of thermal cycling experiments, conducted over many years, has revealed a series of systematic trends that are not compatible with common damage functions or constitutive relations. Complementary mechanical testing and systematic studies of the evolution of the microstructure and damage have led to a fundamental understanding of the progression of thermal fatigue and failure. A special experiment was developed to allow the effective deconstruction of conventional thermal cycling experiments and the finalization of our model. According to this model, the evolution of damage and failure in thermal cycling is controlled by a continuous recrystallization process which is dominated by the coalescence and rotation of dislocation cell structures continuously added to during the high-temperature dwell. The dominance of this dynamic recrystallization contribution is not consistent with the common assumption of a correlation between the number of cycles to failure and the total work done on the solder joint in question in each cycle. It is, however, consistent with an apparent dependence on the work done during the high-temperature dwell. Importantly, the onset of this recrystallization is delayed by pinning on the Ag3Sn precipitates until these have coarsened sufficiently, leading to a model with two terms where one tends to dominate in service and the other in accelerated thermal cycling tests. Accumulation of damage under realistic service conditions with varying dwell temperatures and times is also addressed.

Squat exercise biomechanics during short-radius centrifugation.

PubMed

Duda, Kevin R; Jarchow, Thomas; Young, Laurence R

2012-02-01

Centrifuge-induced artificial gravity (AG) with exercise is a promising comprehensive countermeasure against the physiological de-conditioning that results from exposure to weightlessness. However, body movements onboard a rotating centrifuge are affected by both the gravity gradient and Coriolis accelerations. The effect of centrifugation on squat exercise biomechanics was investigated, and differences between AG and upright squat biomechanics were quantified. There were 28 subjects (16 male) who participated in two separate experiments. Knee position, foot reaction forces, and motion sickness were recorded during the squats in a 1-G field while standing upright and while supine on a horizontally rotating 2 m radius centrifuge at 0, 23, or 30 rpm. No participants terminated the experiment due to motion sickness symptoms. Total mediolateral knee deflection increased by 1.0 to 2.0 cm during centrifugation, and did not result in any injuries. There was no evidence of an increased mediolateral knee travel "after-effect" during postrotation supine squats. Peak foot reaction forces increased with rotation rate up to approximately 200% bodyweight (iRED on ISS provides approximately 210% bodyweight resistance). The ratio of left-to-right foot force throughout the squat cycle on the centrifuge was nonconstant and approximately sinusoidal. Total foot reaction force versus knee flexion-extension angles differed between upright and AG squats due to centripetal acceleration on the centrifuge. A brief exercise protocol during centrifugation can be safely completed without significant after-effects in mediolateral knee position or motion sickness. Several recommendations are made for the design of future centrifuge-based exercise protocols for in-space applications.

Nature-Inspired, Highly Durable CO2 Reduction System Consisting of a Binuclear Ruthenium(II) Complex and an Organic Semiconductor Using Visible Light.

PubMed

Kuriki, Ryo; Matsunaga, Hironori; Nakashima, Takuya; Wada, Keisuke; Yamakata, Akira; Ishitani, Osamu; Maeda, Kazuhiko

2016-04-20

A metal-free organic semiconductor of mesoporous graphitic carbon nitride (C3N4) coupled with a Ru(II) binuclear complex (RuRu') containing photosensitizer and catalytic units selectively reduced CO2 into HCOOH under visible light (λ > 400 nm) in the presence of a suitable electron donor with high durability, even in aqueous solution. Modification of C3N4 with Ag nanoparticles resulted in a RuRu'/Ag/C3N4 photocatalyst that exhibited a very high turnover number (>33000 with respect to the amount of RuRu'), while maintaining high selectivity for HCOOH production (87-99%). This turnover number was 30 times greater than that reported previously using C3N4 modified with a mononuclear Ru(II) complex, and by far the highest among the metal-complex/semiconductor hybrid systems reported to date. The results of photocatalytic reactions, emission decay measurements, and time-resolved infrared spectroscopy indicated that Ag nanoparticles on C3N4 collected electrons having lifetimes of several milliseconds from the conduction band of C3N4, which were transferred to the excited state of RuRu', thereby promoting photocatalytic CO2 reduction driven by two-step photoexcitation of C3N4 and RuRu'. This study also revealed that the RuRu'/Ag/C3N4 hybrid photocatalyst worked efficiently in water containing a proper electron donor, despite the intrinsic hydrophobic nature of C3N4 and low solubility of CO2 in an aqueous environment.

Properties of Orange-Pupa-Inducing Factor (OPIF) in the swallowtail butterfly, Papilio xuthus L.

PubMed

Yamanaka, Akira; Adachi, Miwa; Imai, Hiroshi; Uchiyama, Terumasa; Inoue, Moeko; Islam, A T M Fayezul; Kitazawa, Chisato; Endo, Katsuhiko

2006-03-01

Diapause pupae of the swallowtail butterfly Papilio xuthus L. exhibit diapause-green, orange and brownish-orange color polymorphism. Development of orange pupae involves a neuroendocrine factor inducing orange pupa (Orange-Pupa-Inducing Factor, OPIF), which is secreted from the head-thoracic region during late pharate pupal stages, in particular from the ganglia of short-day animals located posteriorly from the second thoracic ganglion2 (TG2). This report describes certain properties of OPIF using bioassays involving ligated abdomens of short-day pharate pupae. Localization of OPIF in the central nervous system of short-day larvae indicated that it was present predominantly in TG2, thoracic ganglion3 (TG3) and abdominal ganglion1 (AG1) complexes. OPIF activity in TG(2,3)-AG1 complexes was over two times higher than in the more posteriorely located ganglia. The developmental profile of OPIF in last instar short-day larvae revealed that OPIF activity in larval ganglia posterior to TG2 became gradually higher as larval growth proceeded, suggesting that OPIF might be accumulated in TG(2,3)-AG(1-7) complexes as larvae prepare for pupal molting. Furthermore, ligated abdomens of short-day larvae developed into pupae of an orange type when a 2% NaCl extract containing OPIF prepared from TG(2,3)-AG(1-7) complexes of long-day larvae was injected into ligated abdomens of short-day pharate pupae, indicating that OPIF is also present in long-day larvae. Additionally, a biochemical investigation using gel filtration chromatography showed that the molecular weight of OPIF was about 10 kDa.

Binding Selectivity of Methanobactin from Methylosinus trichosporium OB3b for Copper(I), Silver(I), Zinc(II), Nickel(II), Cobalt(II), Manganese(II), Lead(II), and Iron(II)

NASA Astrophysics Data System (ADS)

McCabe, Jacob W.; Vangala, Rajpal; Angel, Laurence A.

2017-12-01

Methanobactin (Mb) from Methylosinus trichosporium OB3b is a member of a class of metal binding peptides identified in methanotrophic bacteria. Mb will selectively bind and reduce Cu(II) to Cu(I), and is thought to mediate the acquisition of the copper cofactor for the enzyme methane monooxygenase. These copper chelating properties of Mb make it potentially useful as a chelating agent for treatment of diseases where copper plays a role including Wilson's disease, cancers, and neurodegenerative diseases. Utilizing traveling wave ion mobility-mass spectrometry (TWIMS), the competition for the Mb copper binding site from Ag(I), Pb(II), Co(II), Fe(II), Mn(II), Ni(II), and Zn(II) has been determined by a series of metal ion titrations, pH titrations, and metal ion displacement titrations. The TWIMS analyses allowed for the explicit identification and quantification of all the individual Mb species present during the titrations and measured their collision cross-sections and collision-induced dissociation patterns. The results showed Ag(I) and Ni(II) could irreversibly bind to Mb and not be effectively displaced by Cu(I), whereas Ag(I) could also partially displace Cu(I) from the Mb complex. At pH ≈ 6.5, the Mb binding selectivity follows the order Ag(I)≈Cu(I)>Ni(II)≈Zn(II)>Co(II)>>Mn(II)≈Pb(II)>Fe(II), and at pH 7.5 to 10.4 the order is Ag(I)>Cu(I)>Ni(II)>Co(II)>Zn(II)>Mn(II)≈Pb(II)>Fe(II). Breakdown curves of the disulfide reduced Cu(I) and Ag(I) complexes showed a correlation existed between their relative stability and their compact folded structure indicated by their CCS. Fluorescence spectroscopy, which allowed the determination of the binding constant, compared well with the TWIMS analyses, with the exception of the Ni(II) complex. [Figure not available: see fulltext.

Binding Selectivity of Methanobactin from Methylosinus trichosporium OB3b for Copper(I), Silver(I), Zinc(II), Nickel(II), Cobalt(II), Manganese(II), Lead(II), and Iron(II).

PubMed

McCabe, Jacob W; Vangala, Rajpal; Angel, Laurence A

2017-12-01

Methanobactin (Mb) from Methylosinus trichosporium OB3b is a member of a class of metal binding peptides identified in methanotrophic bacteria. Mb will selectively bind and reduce Cu(II) to Cu(I), and is thought to mediate the acquisition of the copper cofactor for the enzyme methane monooxygenase. These copper chelating properties of Mb make it potentially useful as a chelating agent for treatment of diseases where copper plays a role including Wilson's disease, cancers, and neurodegenerative diseases. Utilizing traveling wave ion mobility-mass spectrometry (TWIMS), the competition for the Mb copper binding site from Ag(I), Pb(II), Co(II), Fe(II), Mn(II), Ni(II), and Zn(II) has been determined by a series of metal ion titrations, pH titrations, and metal ion displacement titrations. The TWIMS analyses allowed for the explicit identification and quantification of all the individual Mb species present during the titrations and measured their collision cross-sections and collision-induced dissociation patterns. The results showed Ag(I) and Ni(II) could irreversibly bind to Mb and not be effectively displaced by Cu(I), whereas Ag(I) could also partially displace Cu(I) from the Mb complex. At pH ≈ 6.5, the Mb binding selectivity follows the order Ag(I)≈Cu(I)>Ni(II)≈Zn(II)>Co(II)>Mn(II)≈Pb(II)>Fe(II), and at pH 7.5 to 10.4 the order is Ag(I)>Cu(I)>Ni(II)>Co(II)>Zn(II)>Mn(II)≈Pb(II)>Fe(II). Breakdown curves of the disulfide reduced Cu(I) and Ag(I) complexes showed a correlation existed between their relative stability and their compact folded structure indicated by their CCS. Fluorescence spectroscopy, which allowed the determination of the binding constant, compared well with the TWIMS analyses, with the exception of the Ni(II) complex. Graphical abstract ᅟ.

Synthesis and crystallographic characterization of a mononuclear cobalt(III) complex possessing both thiol­ate and thio­ether donors: reactivity of an thiol­ate-bridged penta­nuclear Co2Ag3 complex with iodo­methane

PubMed Central

Fukuda, Yosuke; Yoshinari, Nobuto; Konno, Takumi

2017-01-01

Treatment of an S-bridged penta­nuclear AgI 3CoIII 2 complex, [Ag3{Co(L)}2]3+ [L 3– = N(CH2NHCH2CH2S−)3], in which two tris­(thiol­ate)-type mononuclear CoIII units ([Co(L)]) are bridged by three AgI ions through S atoms, with iodo­methane (CH3I) gave a new CoIII mononuclear complex, [Co(LMe2)]2+ [LMe2 − = N(CH2NHCH2CH2S−)(CH2NHCH2CH2SCH3)2], systematic name: {2-[(bis{[2-(methylsulfanyl)ethyl]aminomethyl}aminomethyl)amino]ethanethiolato}cobalt(III) bis(hexafluoridophosphate). This cationic complex was crystallized with PF6 − anions to form the title compound, [Co(LMe2)](PF6)2. In the [Co(LMe2)]2+ cation, two of three thiol­ate groups in [Co(L)] are methyl­ated while one thiol­ate group remains unreacted. Although a total of eight stereoisomers are possible for [Co(LMe2)]2+, only a pair of enanti­omers {ΛRR- and ΔSS-[Co(LMe2)]2+} are selectively formed. In the crystal, the complex cations and the PF­6 − anions are connected through weak N—H⋯F, C—H⋯F and C—H⋯S hydrogen bonds into a three-dimensional structure. Two F atoms in one PF6 anion are disordered over two sets of sites with refined occupancies of 0.61 (4) and 0.39 (4) and two F atoms in the other PF6 − anion are disordered over two sets of sites with occupancies of 0.5. PMID:28529774

Vascular epiphytes and host trees of ant-gardens in an anthropic landscape in southeastern Mexico

NASA Astrophysics Data System (ADS)

Morales-Linares, Jonas; García-Franco, José G.; Flores-Palacios, Alejandro; Valenzuela-González, Jorge E.; Mata-Rosas, Martín; Díaz-Castelazo, Cecilia

2016-12-01

Ant-gardens (AGs) are considered one of the most complex mutualist systems between ants and plants, since interactions involving dispersal, protection, and nutrition occur simultaneously in them; however, little is known about the effects of the transformation of ecosystems on their diversity and interactions. In five environments with different land use within an anthropic landscape in southeastern Mexico, we investigated the diversity and composition of epiphytes and host trees of AGs built by Azteca gnava. A total of 10,871 individuals of 26 epiphytic species, associating with 859 AGs located in 161 host trees, were recorded. The diversity and composition of epiphytes tended to be different between environments; however, Aechmea tillandsioides and Codonanthe uleana were the most important species and considered true AG epiphytes, because they were the most frequent, abundant, and occurred exclusively in AGs. Other important species were the orchids Epidendrum flexuosum, Coryanthes picturata, and Epidendrum pachyrachis, and should also be considered true AG epiphytes, because they occurred almost exclusively in the AGs. The AG abundance in agroforestry plantations was similar or even greater than in riparian vegetation (natural habitat). The AGs were registered in 37 host species but were more frequent in Mangifera indica and Citrus sinensis. We conclude that true epiphytes of A. gnava AGs persist in different environments and host trees, and even these AGs could proliferate in agroforestry plantations of anthropic landscapes.

Vascular epiphytes and host trees of ant-gardens in an anthropic landscape in southeastern Mexico.

PubMed

Morales-Linares, Jonas; García-Franco, José G; Flores-Palacios, Alejandro; Valenzuela-González, Jorge E; Mata-Rosas, Martín; Díaz-Castelazo, Cecilia

2016-12-01

Ant-gardens (AGs) are considered one of the most complex mutualist systems between ants and plants, since interactions involving dispersal, protection, and nutrition occur simultaneously in them; however, little is known about the effects of the transformation of ecosystems on their diversity and interactions. In five environments with different land use within an anthropic landscape in southeastern Mexico, we investigated the diversity and composition of epiphytes and host trees of AGs built by Azteca gnava. A total of 10,871 individuals of 26 epiphytic species, associating with 859 AGs located in 161 host trees, were recorded. The diversity and composition of epiphytes tended to be different between environments; however, Aechmea tillandsioides and Codonanthe uleana were the most important species and considered true AG epiphytes, because they were the most frequent, abundant, and occurred exclusively in AGs. Other important species were the orchids Epidendrum flexuosum, Coryanthes picturata, and Epidendrum pachyrachis, and should also be considered true AG epiphytes, because they occurred almost exclusively in the AGs. The AG abundance in agroforestry plantations was similar or even greater than in riparian vegetation (natural habitat). The AGs were registered in 37 host species but were more frequent in Mangifera indica and Citrus sinensis. We conclude that true epiphytes of A. gnava AGs persist in different environments and host trees, and even these AGs could proliferate in agroforestry plantations of anthropic landscapes.

Experimental evidence for the participation of deep eutectic solvents in silver chloride crystal formation at low temperature

NASA Astrophysics Data System (ADS)

Bhatt, Jitkumar; Mondal, Dibyendu; Prasad, Kamalesh

2016-05-01

Deep eutectic solvents (DESs) obtained by the complexation of choline chloride (ChoCl) as hydrogen bond acceptor and hydrogen bond donors such as ethylene glycol (ChoCl-EG 1:2) and glycerol (ChoCl-Gly 1:2) were used as media for the formation of AgCl crystals. Although formation of AgCl crystals was observed in both the solvents but the rate of formation of crystals was faster in ChoCl-EG 1:2 at low temperature (4-5 °C). In the crystals, cholinium cations were found to be present with chloride ions bridged with Ag ions resulting generation of 1D network of AgCl2 anions.

Performance and measurements of the AGS and Booster beams

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

Weng, W.T.

1996-06-01

In May 1995, the AGS reached its upgrade intensity goal of 6{times}10{sup 13} ppp, the highest world intensity record for a proton synchrotron on a single pulse basis. At the same time, the Booster reached 2.2{times}10{sup 13} ppp surpassing the design goal of 1.5{times}10{sup 13} ppp due to the introduction of second harmonic cavity during injection. The critical accelerator manipulations, such as resonance stopband corrections, second harmonics cavity, direct rf feedback, gamma-transition jump, longitudinal phase space dilution, and transverse instability damping, will be described as well as some beam measurements. Possible future intensity and brightness upgrades will also be reported.more » {copyright} {ital 1996 American Institute of Physics.}« less

Twenty years of space radiation physics at the BNL AGS and NASA Space Radiation Laboratory.

PubMed

Miller, J; Zeitlin, C

2016-06-01

Highly ionizing atomic nuclei HZE in the GCR will be a significant source of radiation exposure for humans on extended missions outside low Earth orbit. Accelerators such as the LBNL Bevalac and the BNL AGS, designed decades ago for fundamental nuclear and particle physics research, subsequently found use as sources of GCR-like particles for ground-based physics and biology research relevant to space flight. The NASA Space Radiation Laboratory at BNL was constructed specifically for space radiation research. Here we review some of the space-related physics results obtained over the first 20 years of NASA-sponsored research at Brookhaven. Copyright © 2016 The Committee on Space Research (COSPAR). Published by Elsevier Ltd. All rights reserved.

Control of the axial coordination of a surface-confined manganese (III) porphyrin complex.

PubMed

Beggan, J P; Krasnikov, S A; Sergeeva, N N; Senge, M O; Cafolla, A A

2012-06-15

The organization and thermal lability of chloro(5,10,15,20-tetraphenyl porphyrinato)manganese(III) (Cl-MnTPP) molecules on the Ag(111) surface have been investigated under ultra-high vacuum conditions, using scanning tunnelling microscopy, low energy electron diffraction and x-ray photoelectron spectroscopy. The findings reveal the epitaxial nature of the molecule-substrate interface, and moreover, offer a valuable insight into the latent coordination properties of surface-confined metalloporphyrins. The Cl-MnTPP molecules are found to self-assemble on the Ag(111) surface at room temperature, forming an ordered molecular overlayer described by a square unit cell. In accordance with the threefold symmetry of the Ag(111) surface, three rotationally equivalent domains of the molecular overlayer are observed. The primitive lattice vectors of the Cl-MnTPP overlayer show an azimuthal rotation of ±15° relative to those of the Ag(111) surface, while the principal molecular axes of the individual molecules are found to be aligned with the substrate (0(-)11) and ((-)211) crystallographic directions. The axial chloride (Cl) ligand is found to be orientated away from the Ag(111) surface, whereby the average plane of the porphyrin macrocycle lies parallel to that of the substrate. When adsorbed on the Ag(111) surface, the Cl-MnTPP molecules display a latent thermal lability resulting in the dissociation of the axial Cl ligand at ~423 K. The thermally induced dissociation of the Cl ligand leaves the porphyrin complex otherwise intact, giving rise to the coordinatively unsaturated Mn(III) derivative. Consistent with the surface conformation of the Cl-MnTPP precursor, the resulting (5,10,15,20-tetraphenyl porphyrinato)manganese(III) (MnTPP) molecules display the same lattice structure and registry with the Ag(111) surface.

Multiple Condensation Reactions Involving Pt(II) /Pd(II) -OH2 , Pt-NH3 , and Cytosine-NH2 Groups: New Twists in Cisplatin-Nucleobase Chemistry.

PubMed

Yin-Bandur, Lu; Sanz Miguel, Pablo J; Rodríguez-Santiago, Luis; Sodupe, Mariona; Berghaus, Melanie; Lippert, Bernhard

2016-09-12

The coordination chemistry of the antitumor agent cisplatin and related complexes with DNA and its constituents, that is, the nucleobases, appears to be dominated by 1:1 and 1:2 adducts of the types cis-[Pta2 (nucleobase)X] and cis-[Pta2 (nucleobase)2 ] (a=NH3 or amine; a2 =diamine or diimine; X=Cl, OH or OH2 ). Here, we have studied the interactions of the putative 1:1 adducts cis-[Pta2 (1-MeC-N3)(OH2 )](2+) (with a=NH3 , a2 =2,2'-bpy (2,2'-bipyridine), 1-MeC=model nucleobase 1-methylcytosine) with additional cis-[Pt(NH3 )2 (OH2 )2 ](2+) or its kinetically superior analogues [Pd(en)(OH2 )2 ](2+) (en=ethylenediamine) and [Pd(2,2'-bpy)(OH2 )2 ](2+) . Depending upon the conditions applied different compounds of different nuclearity are formed. Without exception they represent condensation products of the components, containing μ-1-MeC-H , μ-OH(-) , as well as μ-NH2 (-) bridges. In the presence of Ag(+) ions, the isolated products in several cases display additionally Pt→Ag dative bonds. On the basis of the cytosine-containing structures established by X-ray crystallography, it is proposed that any of the feasible initial 1:1 nucleobase adducts of cisplatin could form dinuclear Pt complexes upon reaction with additional hydrolyzed cisplatin, thereby generating nucleobase adducts other than the presently established ones. Two findings appear to be of particular significance: First, hydrolyzed cisplatin can have a moderately accelerating effect on the formation of a secondary nucleobase product. Second, NH3 ligands of the cisplatin moiety can be converted into bridging amido ligands following condensation with the diaqua species of cisplatin. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ deposition of a personalized nanofibrous dressing via a handy electrospinning device for skin wound care

NASA Astrophysics Data System (ADS)

Dong, Rui-Hua; Jia, Yue-Xiao; Qin, Chong-Chong; Zhan, Lu; Yan, Xu; Cui, Lin; Zhou, Yu; Jiang, Xingyu; Long, Yun-Ze

2016-02-01

Current strategies for wound care provide limited relief to millions of patients who suffer from burns, chronic skin ulcers or surgical-related wounds. The goal of this work is to develop an in situ deposition of a personalized nanofibrous dressing via a handy electrospinning (e-spinning) device and evaluate its properties related to skin wound care. MCM-41 type mesoporous silica nanoparticles decorated with silver nanoparticles (Ag-MSNs) were prepared by a facile and environmentally friendly approach, which possessed long-term antibacterial activity and low cytotoxicity. Poly-ε-caprolactone (PCL) incorporated with Ag-MSNs was successfully electrospun (e-spun) into nanofibrous membranes. These in situ e-spun nanofibrous membranes allowed the continuous release of Ag ions and showed broad-spectrum antimicrobial activity against two common types of pathogens, Staphylococcus aureus and Escherichia coli. In addition, the in vivo studies revealed that these antibacterial nanofibrous membranes could reduce the inflammatory response and accelerate wound healing in Wistar rats. The above results strongly demonstrate that such patient-specific dressings could be broadly applied in emergency medical transport, hospitals, clinics and at the patients' home in the near future.Current strategies for wound care provide limited relief to millions of patients who suffer from burns, chronic skin ulcers or surgical-related wounds. The goal of this work is to develop an in situ deposition of a personalized nanofibrous dressing via a handy electrospinning (e-spinning) device and evaluate its properties related to skin wound care. MCM-41 type mesoporous silica nanoparticles decorated with silver nanoparticles (Ag-MSNs) were prepared by a facile and environmentally friendly approach, which possessed long-term antibacterial activity and low cytotoxicity. Poly-ε-caprolactone (PCL) incorporated with Ag-MSNs was successfully electrospun (e-spun) into nanofibrous membranes. These in situ e-spun nanofibrous membranes allowed the continuous release of Ag ions and showed broad-spectrum antimicrobial activity against two common types of pathogens, Staphylococcus aureus and Escherichia coli. In addition, the in vivo studies revealed that these antibacterial nanofibrous membranes could reduce the inflammatory response and accelerate wound healing in Wistar rats. The above results strongly demonstrate that such patient-specific dressings could be broadly applied in emergency medical transport, hospitals, clinics and at the patients' home in the near future. Electronic supplementary information (ESI) available: In situ electrospun antimicrobial nanofibrous dressing. See DOI: 10.1039/c5nr08367b

Genetic and biochemical findings in Chinese children with Leigh syndrome.

PubMed

Ma, Yan-Yan; Wu, Tong-Fei; Liu, Yu-Peng; Wang, Qiao; Song, Jin-Qing; Li, Xi-Yuan; Shi, Xiu-Yu; Zhang, Wei-Na; Zhao, Meng; Hu, Lin-Yan; Yang, Yan-Ling; Zou, Li-Ping

2013-11-01

This study investigated the genetic and enzymological features of Leigh syndrome due to respiratory chain complex deficiency in Chinese patients. The clinical features of 75 patients were recorded. Mitochondrial respiratory chain enzyme activities were determined via spectrophotometry. Mitochondrial gene sequence analysis was performed in 23 patients. Five core pedigrees were investigated via restriction fragment length polymorphism and gene sequencing. Psychomotor retardation (55%), motor regression (20%), weakness (29%), and epilepsy (25%) were the most frequent manifestations. Sixty-four patients (85.3%) had isolated respiratory complex deficiencies: complex I was seen in 28 patients (37.3%); complex II, seven (9.3%); complex III, six (8%); complex IV, ten (13.3%); and complex V, 13 patients (17.3%). Eleven patients (14.7%) had combined complex deficiencies. Mitochondrial DNA mutations were detected in 10 patients. Eight point mutations were found in mitochondrial structural genes: m.4833A>G in ND2, m.10191T>C in ND3, m.12338T>C and m.13513G>A in ND5, m.14502T>C and m.14487T>C in ND6, m.8108A>G in COXII, and m.8993T>G in ATPase6. Three mutations were found in tRNA genes: m.4395A>G in tRNA-Gln, m.10454T>C in tRNA-Arg, and m.5587T>C in tRNA-Ala. One patient and their mother both had the m.12338T>C and m.8993T>C mutations. In conclusion, mitochondrial respiratory chain complex I deficiency and structural gene mutations frequently occur in Chinese Leigh syndrome patients. Copyright © 2013 Elsevier Ltd. All rights reserved.

Analysis of silver nanoparticles in antimicrobial products using surface-enhanced Raman spectroscopy (SERS).

PubMed

Guo, Huiyuan; Zhang, Zhiyun; Xing, Baoshan; Mukherjee, Arnab; Musante, Craig; White, Jason C; He, Lili

2015-04-07

Silver nanoparticles (AgNPs) are the most commonly used nanoparticles in consumer products. Concerns over human exposure to and risk from these particles have resulted in increased interest in novel strategies to detect AgNPs. This study investigated the feasibility of surface-enhanced Raman spectroscopy (SERS) as a method for the detection and quantification of AgNPs in antimicrobial products. By using ferbam (ferric dimethyl-dithiocarbamate) as an indicator molecule that binds strongly onto the nanoparticles, AgNPs detection and discrimination were achieved based on the signature SERS response of AgNPs-ferbam complexes. SERS response with ferbam was distinct for silver ions, silver chloride, silver bulk particles, and AgNPs. Two types of AgNPs with different coatings, citrate and polyvinylpirrolidone (PVP), both showed strong interactions with ferbam and induced strong SERS signals. SERS was effectively applicable for detecting Ag particles ranging from 20 to 200 nm, with the highest signal intensity in the 60-100 nm range. A linear relationship (R(2) = 0.9804) between Raman intensity and citrate-AgNPs concentrations (60 nm; 0-20 mg/L) indicates the potential for particle quantification. We also evaluated SERS detection of AgNPs in four commercially available antimicrobial products. Combined with ICP-MS and TEM data, the results indicated that the SERS response is primarily dependent on size, but also affected by AgNPs concentration. The findings demonstrate that SERS is a promising analytical platform for studying environmentally relevant levels of AgNPs in consumer products and related matrices.

Complex structural behavior of oligopurine-oligopyrimidine sequence cloned within the supercoiled plasmid.

PubMed Central

Parniewski, P; Galazka, G; Wilk, A; Klysik, J

1989-01-01

Synthetic sequence GATCC(AG)7ATCG(AT)4CG(AG)7 was cloned into plasmid and its structural behavior under the influence of supercoiling was analysed by chemical modification at variety of experimental conditions. It was found that this sequence adopts at least two different non-B conformations depending on -delta and pH values. Moreover, 12 nucleotide long non-pur.pyr spacer region separating two identical (AG)7 blocks does not provide a significant energy barrier protecting against unusual structures formation. Images PMID:2644622

Effect of the SiO 2 support on the catalytic performance of Ag/ZrO 2/SiO 2 catalysts for the single-bed production of butadiene from ethanol

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

Dagle, Vanessa Lebarbier; Flake, Matthew D.; Lemmon, Teresa L.

A ternary Ag/ZrO 2/SiO 2 catalyst system was studied for single-step conversion of ethanol to butadiene by varying the catalyst composition (Ag, Ir, or Pt metal component, Ag/ZrO 2 loading, and choice of SiO 2 support) and operating conditions (space velocity and feed gas composition). Exceptional catalytic performance was achieved over a 1%Ag/4%ZrO 2/SiO 2-SBA-16 catalyst leading to 99% conversion and 71% butadiene selectivity while operating under mild conditions (325°C, 1 atm, and 0.23 h –1). Several classes of silica—silica gels, fumed silicas, mesoporous silicas)—were evaluated as catalyst supports, and SBA-16 was found to be the most promising choice. Themore » SiO 2 support was found to significantly influence both conversion and selectivity. A higher SiO 2 catalyst surface area facilitates increased Ag dispersion which leads to greater conversion due to the accelerated initial ethanol dehydrogenation reaction step. By independently varying Ag and ZrO 2 loading, Ag was found to be the main component that affects ethanol conversion. ZrO 2 loading and thus Lewis acid sites concentration was found to have little impact on the ethanol conversion. Butadiene selectivity depends on the concentration of Lewis acid site, which in turn differs depending on the choice of SiO 2 support material. We observed a direct relationship between butadiene selectivity and concentration of Lewis acid sites. Butadiene selectivity decreases as the concentration of Lewis acid sites increases, which corresponds to an increase in ethanol dehydration to ethylene and diethyl ether. Additionally, adding H 2 to the feed had little effect on conversion while improving catalytic stability; however, selectivity to butadiene decreased. Lastly, catalyst regenerability was successfully demonstrated for several cycles.« less

Effect of the SiO 2 support on the catalytic performance of Ag/ZrO 2/SiO 2 catalysts for the single-bed production of butadiene from ethanol

DOE PAGES

Dagle, Vanessa Lebarbier; Flake, Matthew D.; Lemmon, Teresa L.; ...

2018-05-19

A ternary Ag/ZrO 2/SiO 2 catalyst system was studied for single-step conversion of ethanol to butadiene by varying the catalyst composition (Ag, Ir, or Pt metal component, Ag/ZrO 2 loading, and choice of SiO 2 support) and operating conditions (space velocity and feed gas composition). Exceptional catalytic performance was achieved over a 1%Ag/4%ZrO 2/SiO 2-SBA-16 catalyst leading to 99% conversion and 71% butadiene selectivity while operating under mild conditions (325°C, 1 atm, and 0.23 h –1). Several classes of silica—silica gels, fumed silicas, mesoporous silicas)—were evaluated as catalyst supports, and SBA-16 was found to be the most promising choice. Themore » SiO 2 support was found to significantly influence both conversion and selectivity. A higher SiO 2 catalyst surface area facilitates increased Ag dispersion which leads to greater conversion due to the accelerated initial ethanol dehydrogenation reaction step. By independently varying Ag and ZrO 2 loading, Ag was found to be the main component that affects ethanol conversion. ZrO 2 loading and thus Lewis acid sites concentration was found to have little impact on the ethanol conversion. Butadiene selectivity depends on the concentration of Lewis acid site, which in turn differs depending on the choice of SiO 2 support material. We observed a direct relationship between butadiene selectivity and concentration of Lewis acid sites. Butadiene selectivity decreases as the concentration of Lewis acid sites increases, which corresponds to an increase in ethanol dehydration to ethylene and diethyl ether. Additionally, adding H 2 to the feed had little effect on conversion while improving catalytic stability; however, selectivity to butadiene decreased. Lastly, catalyst regenerability was successfully demonstrated for several cycles.« less

CD4/CD8/Dendritic cell complexes in the spleen: CD8+ T cells can directly bind CD4+ T cells and modulate their response

PubMed Central

Barinov, Aleksandr; Galgano, Alessia; Krenn, Gerald; Tanchot, Corinne; Vasseur, Florence

2017-01-01

CD4+ T cell help to CD8+ T cell responses requires that CD4+ and CD8+ T cells interact with the same antigen presenting dendritic cell (Ag+DC), but it remains controversial whether helper signals are delivered indirectly through a licensed DC and/or involve direct CD4+/CD8+ T cell contacts and/or the formation of ternary complexes. We here describe the first in vivo imaging of the intact spleen, aiming to evaluate the first interactions between antigen-specific CD4+, CD8+ T cells and Ag+DCs. We show that in contrast to CD4+ T cells which form transient contacts with Ag+DC, CD8+ T cells form immediate stable contacts and activate the Ag+DC, acquire fragments of the DC membranes by trogocytosis, leading to their acquisition of some of the DC properties. They express MHC class II, and become able to present the specific Marilyn peptide to naïve Marilyn CD4+ T cells, inducing their extensive division. In vivo, these CD8+ T cells form direct stable contacts with motile naïve CD4+ T cells, recruiting them to Ag+DC binding and to the formation of ternary complexes, where CD4+ and CD8+ T cells interact with the DC and with one another. The presence of CD8+ T cells during in vivo immune responses leads to the early activation and up-regulation of multiple functions by CD4+ T lymphocytes. Thus, while CD4+ T cell help is important to CD8+ T cell responses, CD8+ T cells can interact directly with naïve CD4+ T cells impacting their recruitment and differentiation. PMID:28686740

Particle size affects Brassica seed meal-induced pathogen suppression of Rhizoctonia solani AG-5

USDA-ARS?s Scientific Manuscript database

R. solani AG-5 is a component of the pathogen complex that incites apple replant disease, and is suppressed via multiple mechanisms in response to B. juncea seed meal (SM) amendment. Allyl isothiocyanate (AITC) functions in suppression of this pathogen during the initial 24 h period post-seed meal a...

Detection and Quantification of Silver Nanoparticles at Environmentally Relevant Concentrations Using Asymmetric Flow Field–Flow Fractionation Online with Single Particle Inductively Coupled Plasma Mass Spectrometry

EPA Science Inventory

The presence of silver nanoparticles (AgNPs) in aquatic environments could potentially cause adverse impacts on ecosystems and human health. However, current understanding of the environmental fate and transport of AgNPs is still limited because their properties in complex enviro...

Protein-silver nanoparticle interactions to colloidal stability in acidic environments.

PubMed

Tai, Jui-Ting; Lai, Chao-Shun; Ho, Hsin-Chia; Yeh, Yu-Shan; Wang, Hsiao-Fang; Ho, Rong-Ming; Tsai, De-Hao

2014-11-04

We report a kinetic study of Ag nanoparticles (AgNPs) under acidic environments (i.e., pH 2.3 to pH ≈7) and systematically investigate the impact of protein interactions [i.e., bovine serum albumin (BSA) as representative] to the colloidal stability of AgNPs. Electrospray-differential mobility analysis (ES-DMA) was used to characterize the particle size distributions and the number concentrations of AgNPs. Transmission electron microscopy was employed orthogonally to provide visualization of AgNPs. For unconjugated AgNPs, the extent of aggregation, or the average particle size, was shown to be increased significantly with an increase of acidity, where a partial coalescence was found between the primary particles of unconjugated AgNP clusters. Aggregation rate constant, kD, was also shown to be proportional to acidity, following a correlation of log(kD) = -1.627(pH)-9.3715. Using ES-DMA, we observe BSA had a strong binding affinity (equilibrium binding constant, ≈ 1.1 × 10(6) L/mol) to the surface of AgNPs, with an estimated maximum molecular surface density of ≈0.012 nm(-2). BSA-functionalized AgNPs exhibited highly-improved colloidal stability compared to the unconjugated AgNPs under acidic environments, where both the acid-induced interfacial dissolution and the particle aggregation became negligible. Results confirm a complex mechanism of colloidal stability of AgNPs: the aggregation process was shown to be dominant, and the formation of BSA corona on AgNPs suppressed both particle aggregation and interfacial dissolution of AgNP samples under acidic environments.

Silver Nanoparticles Entering Soils via the Wastewater-Sludge-Soil Pathway Pose Low Risk to Plants but Elevated Cl Concentrations Increase Ag Bioavailability.

PubMed

Wang, Peng; Menzies, Neal W; Dennis, Paul G; Guo, Jianhua; Forstner, Christian; Sekine, Ryo; Lombi, Enzo; Kappen, Peter; Bertsch, Paul M; Kopittke, Peter M

2016-08-02

The widespread use of silver nanoparticles (Ag-NPs) results in their movement into wastewater treatment facilities and subsequently to agricultural soils via application of contaminated sludge. On-route, the chemical properties of Ag may change, and further alterations are possible upon entry to soil. In the present study, we examined the long-term stability and (bio)availability of Ag along the "wastewater-sludge-soil" pathway. Synchrotron-based X-ray absorption spectroscopy (XAS) revealed that ca. 99% of Ag added to the sludge reactors as either Ag-NPs or AgNO3 was retained in sludge, with ≥79% of this being transformed to Ag2S, with the majority (≥87%) remaining in this form even after introduction to soils at various pH values and Cl concentrations for up to 400 days. Diffusive gradients in thin films (DGT), chemical extraction, and plant uptake experiments indicated that the potential (bio)availability of Ag in soil was low but increased markedly in soils with elevated Cl, likely due to the formation of soluble AgClx complexes in the soil solution. Although high Cl concentrations increased the bioavailability of Ag markedly, plant growth was not reduced in any treatment. Our results indicate that Ag-NPs entering soils through the wastewater-sludge-soil pathway pose low risk to plants due to their conversion to Ag2S in the wastewater treatment process, although bioavailability may increase in saline soils or when irrigated with high-Cl water.

Mechanistic Studies on the Galvanic Replacement Reaction between Multiply Twinned Particles of Ag and HAuCl4 in an Organic Medium

PubMed Central

Lu, Xianmao; Tuan, Hsing-Yu; Chen, Jingyi; Li, Zhi-Yuan; Korgel, Brian A; Xia, Younan

2008-01-01

This article presents a mechanistic study on the galvanic replacement reaction between 11- and 14-nm multiply twinned particles (MTPs) of Ag and HAuCl4 in chloroform. We monitored both morphological and spectral changes as the molar ratio of HAuCl4 to Ag was increased. The details of reaction were different from previous observations on single-crystal Ag nanocubes and cubooctahedrons. Because Au and Ag form alloys rapidly within small MTPs rich in vacancy and grain boundary defects, a complete Au shell did not form on the surface of each individual Ag template. Instead, the replacement reaction resulted in the formation of alloy nanorings and nanocages from Ag MTPs of decahedral or icosahedral shape. For the nanorings and nanocages derived from 11-nm Ag MTPs, the surface plasmon resonance (SPR) peak can be continuously shifted from 400 to 616 nm. When the size of Ag MTPs was increased to 14 nm, the SPR peak can be further shifted to 740 nm, a wavelength sought by biomedical applications. We have also investigated the effects of capping ligands and AgCl precipitate on the replacement reaction. While hollow structures were routinely generated from oleylamine-capped Ag MTPs, we obtained very few hollow structures by using a stronger capping ligand such as oleic acid or tri-n-octylphosphine oxide (TOPO). Addition of extra oleylamine was found to be critical to the formation of well-controlled, uniform hollow structures free of AgCl contamination thanks to the formation of a soluble complex between AgCl and oleylamine. PMID:17243691

Nucleation and characterization of hydroxyapatite on thioglycolic acid-capped reduced graphene oxide/silver nanoparticles in simplified simulated body fluid

NASA Astrophysics Data System (ADS)

Zhao, Jun; Zhang, Zhaochun; Yu, Zhenwei; He, Zhenni; Yang, Shanshan; Jiang, Huiyi

2014-01-01

Herein hydroxyapatite (HA) has been synthesized by the nucleation on the surfaces of reduced graphene oxide/silver nanoparticles (rGO/AgNPs) chemisorbed with thioglycolic acid (TGA). The self-assembled monolayer of TGA formed on rGO/AgNPs was immersed in simplified simulated body fluid under gentle growth conditions, forming rGO/AgNPs/TGA/HA biocomposite. The phase structures and functional groups of biocomposite were analyzed by X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy and Raman spectroscopy. Enhanced Raman spectrum of TGA on prepared rGO/AgNPs was obtained with excitation at 633 nm, showing that TGA was chemisorbed on AgNPs through S atom and TGA molecular plane exhibited a tilted orientation with respect to AgNPs. The morphologies of biocomposite were investigated by means of atomic force microscope and transmission electron microscope coupled with energy dispersive spectrum. Analysis shows that the AgNPs uniformly distributed on the rGO nanosheets with the size of about 15-20 nm and HA formation initiated through Ca2+-adsorption upon complexation with sbnd COO- groups of TGA on AgNPs. The results obtained indicated that the rGO/AgNPs/TGA/HA biocomposite may have immense potential application in bone tissue engineering fields for its outstanding and stable activities.

Preparation of bio-deep eutectic solvent triggered cephalopod shaped silver chloride-DNA hybrid material having antibacterial and bactericidal activity.

PubMed

Bhatt, Jitkumar; Mondal, Dibyendu; Bhojani, Gopal; Chatterjee, Shruti; Prasad, Kamalesh

2015-11-01

2.5% w/w DNA (Salmon testes) was solubilized in a bio-deep eutectic solvent [(bio-DES), obtained by the complexation of choline chloride and ethylene glycol at 1:2 molar ratio] containing 1% w/w of silver chloride (AgCl) to yield a AgCl decorated DNA based hybrid material. Concentration dependent formation of AgCl crystals in the DES was observed and upon interaction with DNA it gave formation of a cephalopod shaped hybrid material. DNA was found to maintain its chemical and structural stability in the material. Further, AgCl microstructures were found to have orderly self assembled on the DNA helices indicating the electrostatic interaction between Ag(+) and phosphate side chain of DNA as a driving force for the formation of the material with ordered microstructural distribution of AgCl. Furthermore, the functionalized material exhibited excellent antibacterial and bactericidal activity against both Gram negative and Gram positive pathogenic bacteria. Copyright © 2015 Elsevier B.V. All rights reserved.

Supramolecular assembly of group 11 phosphorescent metal complexes for chemosensors of alcohol derivatives

NASA Astrophysics Data System (ADS)

Lintang, H. O.; Ghazalli, N. F.; Yuliati, L.

2018-04-01

We report on systematic study on vapochromic sensing of ethanol by using phosphorescent trinuclear metal pyrazolate complexes with supramolecular assembly of weak intermolecular metal-metal interactions using 4-(3,5-dimethoxybenzyl)-3,5-dimethyl pyrazole ligand (1) and group 11 metal ions (Cu(I), Ag(I), Au(I)). Upon excitation at 284, the resulting complexes showed emission bands with a peak centered at 616, 473 and 612 nm for 2(Cu), 2(Ag) and 2(Au), respectively. Chemosensor 2(Cu) showed positive response to ethanol vapors in 5 mins by blue-shifting its emission band from 616 to 555 nm and emitting bright orange to green. Otherwise 2(Au) gave shifting from its emission band centered at 612 to 587 nm with Δλ of 25 nm (41%) and color changes from red-orange to light green-orange while 2(Ag) showed quenching in its original emission intensity at 473 nm in 40% with color changes from dark green to less emissive. These results demonstrate that sensing capability of chemosensor 2(Cu) with suitable molecular design of ligand and metal ion in the complex is due to the formation of a weak intermolecular hydrogen bonding interaction of O atom at the methoxy of the benzyl ring with the OH of the vapors at the outside of the molecules.

Synthesis and photoluminescence properties of silver(I) complexes based on N-benzoyl-L-glutamic acid and N-donor ligands with different flexibility

NASA Astrophysics Data System (ADS)

Yan, Ming-Jie; Feng, Qi; Song, Hui-Hua

2016-05-01

By changing the N-donor ancillary ligand, three novel silver (I) complexes {[Ag(HbzgluO) (4,4‧-bipy)]·H2O}n (1), {[Ag2(HbzgluO)2 (bpe)2]·2H2O}n (2) and {[Ag(HbzgluO)(bpp)]·2H2O}n (3) (H2bzgluO = N-benzoyl-L-glutamic acid, 4,4‧-bipy = 4,4ˊ-bipyridine, bpe = 1,2-di(4-pyridyl)ethane, bpp = 1,3-di(4-pyridyl)propane) were synthesized. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric analyses (TGA). In this study, the N-donor ligands are changed from rigidity (4,4‧-bipy), quasi-flexibility (bpe) to flexibility (bpp), the structures of complexes also change. Complex 1 features a 1D chain structure which is further linked together to construct a 2D supramolecular structure through hydrogen bonds. Complex 2 is a 1D double-chains configuration which eventually forms a 3D supramolecular network via hydrogen bonding interactions. Whereas, complex 3 exhibits a 2D pleated grid structure which is linked by hydrogen bonding interactions into a 3D supramolecular network. The present observations demonstrate that the modulation of coordination polymers with different structures can accomplish by changing the spacer length of N-donor ligands. In addition, the solid-state circular dichroism (CD) spectra indicated that compound 2 exhibited negative cotton effect which originated from the chiral ligands H2bzgluO and the solid-state fluorescence spectra of the three complexes demonstrated the auxiliary ligands have influence on the photoluminescence properties of the complexes.

The PP4R1 sub-unit of protein phosphatase PP4 is essential for inhibition of NF-κB by merkel polyomavirus small tumour antigen.

PubMed

Abdul-Sada, Hussein; Müller, Marietta; Mehta, Rajni; Toth, Rachel; Arthur, J Simon C; Whitehouse, Adrian; Macdonald, Andrew

2017-04-11

Merkel cell carcinoma (MCC) is a highly aggressive skin cancer with a high metastatic potential. The majority of MCC cases are caused by the Merkel cell polyomavirus (MCPyV), through expression of the virus-encoded tumour antigens. Whilst mechanisms attributing tumour antigen expression to transformation are being uncovered, little is known of the mechanisms by which MCPyV persists in the host. We previously identified the MCPyV small T antigen (tAg) as a novel inhibitor of nuclear factor kappa B (NF-kB) signalling and a modulator of the host anti-viral response. Here we demonstrate that regulation of NF-kB activation involves a previously undocumented interaction between tAg and regulatory sub-unit 1 of protein phosphatase 4 (PP4R1). Formation of a complex with PP4R1 and PP4c is required to bridge MCPyV tAg to the NEMO adaptor protein, allowing deactivation of the NF-kB pathway. Mutations in MCPyV tAg that fail to interact with components of this complex, or siRNA depletion of PP4R1, prevents tAg-mediated inhibition of NF-kB and pro-inflammatory cytokine production. Comparison of tAg binding partners from other human polyomavirus demonstrates that interactions with NEMO and PP4R1 are unique to MCPyV. Collectively, these data identify PP4R1 as a novel target for virus subversion of the host anti-viral response.

Comparison of Customized Abutments Made from Titanium and a Machinable Precious Alloy.

PubMed

Lee, Jee-Ho; Park, Ji-Man; Park, Eun-Jin; Koak, Jai-Young; Kim, Seong-Kyun; Heo, Seong-Joo

2016-01-01

To investigate the clinical usefulness, a customized abutment produced with the Pd-Ag-In alloy was compared with a customized abutment produced with the conventional titanium alloy for discoloration and mechanical accuracy. Discoloration and resistance to corrosion of the Pd-Ag-In alloy were evaluated using chemical solutions. Marginal adaptation of internal-type implants and abutments was compared using 10 titanium abutments and 10 Pd-Ag-In abutments using a surface measuring system. A detorque test was performed on 12 implant-abutment complexes of each control and experimental group to investigate screw joint stability. Cyclic loading simulating a human's mastication movement for 1 year was applied after 30 Ncm initial tightening, and the removal torque was measured using a digital torque gauge. The noninferiority test was conducted to compare the Pd-Ag-In alloy with a titanium abutment with a 10% margin. The Pd-Ag-In alloy had a warm yellow color and displayed stable resistance to discoloration and corrosion, resulting in an advantageous esthetic property. When compared to the titanium alloy, it did not show noninferiority with respect to the gap between the implant and the abutment; the gap was approximately 13.3 μm on average, which was not significantly different from those observed in previous studies. After long-term use, it displayed statistically significant noninferiority in the removal torque value compared to the titanium group. The Pd-Ag-In alloy-based customized abutment had good mechanical properties of the implant-abutment complex as well as a superior esthetic property, and can provide favorable outcomes in anterior implant restoration.

Brucella abortus Inhibits Major Histocompatibility Complex Class II Expression and Antigen Processing through Interleukin-6 Secretion via Toll-Like Receptor 2▿

PubMed Central

Barrionuevo, Paula; Cassataro, Juliana; Delpino, M. Victoria; Zwerdling, Astrid; Pasquevich, Karina A.; Samartino, Clara García; Wallach, Jorge C.; Fossati, Carlos A.; Giambartolomei, Guillermo H.

2008-01-01

The strategies that allow Brucella abortus to survive inside macrophages for prolonged periods and to avoid the immunological surveillance of major histocompatibility complex class II (MHC-II)-restricted gamma interferon (IFN-γ)-producing CD4+ T lymphocytes are poorly understood. We report here that infection of THP-1 cells with B. abortus inhibited expression of MHC-II molecules and antigen (Ag) processing. Heat-killed B. abortus (HKBA) also induced both these phenomena, indicating the independence of bacterial viability and involvement of a structural component of the bacterium. Accordingly, outer membrane protein 19 (Omp19), a prototypical B. abortus lipoprotein, inhibited both MHC-II expression and Ag processing to the same extent as HKBA. Moreover, a synthetic lipohexapeptide that mimics the structure of the protein lipid moiety also inhibited MHC-II expression, indicating that any Brucella lipoprotein could down-modulate MHC-II expression and Ag processing. Inhibition of MHC-II expression and Ag processing by either HKBA or lipidated Omp19 (L-Omp19) depended on Toll-like receptor 2 and was mediated by interleukin-6. HKBA or L-Omp19 also inhibited MHC-II expression and Ag processing of human monocytes. In addition, exposure to the synthetic lipohexapeptide inhibited Ag-specific T-cell proliferation and IFN-γ production of peripheral blood mononuclear cells from Brucella-infected patients. Together, these results indicate that there is a mechanism by which B. abortus may prevent recognition by T cells to evade host immunity and establish a chronic infection. PMID:17984211

Preparation of Polyethylene Composites Containing Silver(I) Acylpyrazolonato Additives and SAR Investigation of their Antibacterial Activity.

PubMed

Marchetti, Fabio; Palmucci, Jessica; Pettinari, Claudio; Pettinari, Riccardo; Marangoni, Mirko; Ferraro, Stefano; Giovannetti, Rita; Scuri, Stefania; Grappasonni, Iolanda; Cocchioni, Mario; Maldonado Hodar, Francisco José; Gunnella, Roberto

2016-11-02

Novel composite materials PEn (n = 1-9) have been prepared by an easily up-scalable embedding procedure of three different families of Ag(I) acylpyrazolonato complexes in polyethylene (PE) matrix. In details, PE1-PE3 composites contain polynuclear [Ag(Q R )] n complexes, PE4-PE6 contain mononuclear [Ag(Q R )(L) m ] complexes and PE7-PE9 are loaded with mononuclear [Ag(Q R ) (PPh 3 ) 2 ] complexes, respectively (where L = 1-methylimidazole or 2-ethylimidazole, m = 1 or 2, and HQ R = 1-phenyl-3-methyl-4-RC(═O)-5-pyrazolone, where in detail HQ fb , R = -CF 2 CF 2 CF 3 ; HQ cy , R = -cyclo-C 6 H 11 ; HQ be , R = -C(H)═C(CH 3 ) 2 ). The PEn composites, prepared by using a 1:1000 w/w silver additive/polyethylene ratio, have been characterized in bulk by IR spectroscopy and TGA analyses, which confirmed that the properties of polyethylene matrix are essentially unchanged. AFM, SEM, and EDX surface techniques show that silver additives form agglomerates with dimensions 10-100 μm on the polyethylene surface, with a slight increment of surface roughness of pristine plastic within 50 nm. However, the elastic properties of the composites are essentially the same of PE. The antibacterial activity of all composites has been tested against three bacterial strains (E. coli, P. aeruginosa and S. aureus) and results show that two classes of composites, PE1-PE3 and PE4-PE6, display high and persistent bactericidal and bacteriostatic activity, comparable to PE embedded with AgNO 3 . By contrast, composites PE7-PE9 exhibit a reduced antibacterial action. Contact and release tests in several conditions for specific migration of Ag + from plastics, indicate a very limited but time persistent release of silver ions from PE1-PE6 composites, thus suggesting that they are potential antibacterial materials for future applications. Instead, PE7-PE9 almost do not release silver, only trace levels of silver ions being detected, in accordance with their reduced antibacterial action. None of the composites is toxic against higher organisms, as confirmed by D. magna test of ecotoxicity.

Biotic and abiotic interactions in aquatic microcosms determine fate and toxicity of Ag nanoparticles. Part 1. Aggregation and dissolution.

PubMed

Unrine, Jason M; Colman, Benjamin P; Bone, Audrey J; Gondikas, Andreas P; Matson, Cole W

2012-07-03

To better understand their fate and toxicity in aquatic environments, we compared the aggregation and dissolution behavior of gum arabic (GA) and polyvinylpyrrolidone (PVP) coated Ag nanoparticles (NPs) in aquatic microcosms. There were four microcosm types: surface water; water and sediment; water and aquatic plants; or water, sediment, and aquatic plants. Dissolution and aggregation behavior of AgNPs were examined using ultracentrifugation, ultrafiltration, and asymmetrical flow field flow fractionation coupled to ultraviolet-visible spectroscopy, dynamic and static laser light scattering, and inductively coupled plasma mass spectrometry. Plants released dissolved organic matter (DOM) into the water column either through active or passive processes in response to Ag exposure. This organic matter fraction readily bound Ag ions. The plant-derived DOM had the effect of stabilizing PVP-AgNPs as primary particles, but caused GA-AgNPs to be removed from the water column, likely by dissolution and binding of released Ag ions on sediment and plant surfaces. The destabilization of the GA-AgNPs also corresponded with X-ray absorption near edge spectroscopy results which suggest that 22-28% of the particulate Ag was associated with thiols and 5-14% was present as oxides. The results highlight the potential complexities of nanomaterial behavior in response to biotic and abiotic modifications in ecosystems, and may help to explain differences in toxicity of Ag observed in realistic exposure media compared to simplified laboratory exposures.

Green synthesis of biogenic silver nanoparticles using Solanum tuberosum extract and their interaction with human serum albumin: Evidence of "corona" formation through a multi-spectroscopic and molecular docking analysis.

PubMed

Ali, Mohd Sajid; Altaf, Mohammad; Al-Lohedan, Hamad A

2017-08-01

Biogenic silver nanoparticles (AgNPs) have been synthesized by using Solanum tuberosum (potato) extract (PE) as a reducing as well as stabilizing agent which is reasonably cheaper, non-toxic and easily available material. The green synthesis of silver nanoparticles has been carried out by very simple method and the nanoparticles were characterized by surface plasmon band as well as TEM measurements. The PE-AgNPs were highly dispersed in the solution and found to be spherical with around 10nm in size. Interaction of these nanoparticles was studied with plasma protein HSA by means of various spectroscopies, such as, UV-visible, fluorescence, DLS, CD and FTIR spectroscopies. The HSA was found to form the protein "corona" around the starch-capped PE-AgNPs. Absorption spectroscopy revealed that the interaction between HSA and PE-AgNPs resulted in the ground state complex formation. Due to the strong absorption of PE-AgNPs, the inner filter effect was corrected for the fluorescence data. PE-AgNPs were found to quench the fluorescence of HSA with a small blue shift attributed to the increase in the hydrophobicity near tryptophan residue due to the presence of amylopectin and amylose units in the starch. The value of n, Hill's constant, was found to be >1 which determines the existence of a cooperative binding between nanoparticle and albumin. Several parameters such as Stern-Volmer and binding constants in addition to the thermodynamic parameters have been analyzed and discussed which established that the complex formation has taken place via static quenching mechanism and the corona formation between albumin and PE-AgNPs was entropy driven process. Binding of biogenic PE-AgNPs to the HSA slightly affected the secondary structure of latter with a small decrease in α-helical contents resulting in the partial unfolding of the protein, though the structural motif remained the same. Molecular docking simulations revealed various possible binding modes between PE-AgNPs and albumin. Copyright © 2017 Elsevier B.V. All rights reserved.

A novel polydentate ligand chromophore for simultaneously colorimetric detection of trace Ag + and Fe3 +

NASA Astrophysics Data System (ADS)

Yan, Zhengquan; Zhao, Qi; Wen, Meijun; Hu, Lei; Zhang, Xuezhong; You, Jinmao

2017-11-01

A novel polydentate ligand chromophore, 3,6-di-(N-ethyl-N-ethoxyl phenylazo) acridine (EEPA), was identified and synthesized. After its structure was characterized by FTIR, 1H NMR, mass spectra and element analyses, it was noted to find that there was a simultaneously colorimetric response to Ag+ and Fe3 + accompanying with different color changes, i.e., from brown to light purple for Ag+ and further to purple-red for Fe3 +, respectively. Their different action mechanisms, a 1:2 complex mode for EEPA-Ag+ and 1:1 for EEPA-Fe3 +, were investigated and confirmed by means of Job's plot and theoretical calculation. EEPA would be a potential colorimetric chemo-dosimeter for simultaneous detection of Ag+ and Fe3 + with the detection limits of 1.6 nmol·L- 1 and 69 nmol·L- 1, respectively.

A new Ti-5Ag alloy for customized prostheses by three-dimensional printing (3DP).

PubMed

Hong, S B; Eliaz, N; Leisk, G G; Sach, E M; Latanision, R M; Allen, S M

2001-03-01

Three important considerations in the fabrication of customized cranio-maxillofacial prostheses are geometric precision, material strength, and biocompatibility. Three-dimensional printing (3DP) is a rapid part-fabrication process that can produce complex parts with high precision. The aim of this study was to design, synthesize by 3DP, and characterize a new Ti-5Ag (wt%) alloy. Silver nitrate was found to be an appropriate inorganic binder for the Ti powder-based skeleton, and the optimum sintering parameters for full densification were determined. The hardness of the Ti-5Ag alloy was shown to be much higher than that of a pure titanium sample. Potentiodynamic measurements, carried out in saline solution at body temperature, showed that the Ti-5Ag alloy had good passivation behavior, similar to that of pure titanium. It is concluded that the Ti-Ag system may be suitable for fabrication of customized prostheses by 3DP.

Pediatric air gun shot injury.

PubMed

Khan, Ubaid U; Kamal, Naglaa M; Mirza, Shazia J; Sherief, Laila M

2014-12-01

Air guns (AGs) use air or another compressed gas to propel a projectile. Different injuries may occur in children due to their body structure, which is less-resistant with thin soft tissue coverage that can be easily penetrated by an AG shot. We present 3 cases of pediatric AG shot injury. The first-case had right lumber deep tissue penetration of AG pallet without internal damage, the second-case had a complex course of pellet into the perineum, and the third-case was shot in the left shoulder. All cases were accidentally shot. The shooters were all children, and relatives of the victims. All patients were generally stable on arrival. Two cases were operated, and one received conservative management. On follow up, no complications were noted.  At first sight, AGs and air rifles may appear relatively harmless, but they are potentially lethal and children should not be allowed to play with them. 

Facile fabrication of high-quality Ag/PS coaxial nanocables based on the mixed mode of soft/hard templates

NASA Astrophysics Data System (ADS)

Wan, Mimi; Zhao, Wenbo; Peng, Fang; Wang, Qi; Xu, Ping; Mao, Chun; Shen, Jian

2016-08-01

A new kind of high-quality Ag/PS coaxial nanocables can be facilely synthesized by using soft/hard templates method. In order to effectively introduce Ag sources into porous polystyrene (PS) nanotubes which were trapped in porous anodic aluminum oxide (AAO) hard template, Pluronic F127 (F127) was used as guiding agent, soft template and reductant. Meanwhile, ethylene glycol solution was also used as solvent and co-reducing agent to assist in the formation of silver nanowires. The influences of concentration of F127 and reducing reaction time on the formation of Ag/PS coaxial nanocables were discussed. Results indicated that the high-quality Ag/PS coaxial nanocables can be obtained by the mixed mode of soft/hard templates under optimized conditions. This strategy is expected to be extended to design more metal/polymer coaxial nanocables for the benefit of creation of complex and functional nanoarchitectures and components.

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

Shim, Yunsic; Amar, Jacques G.

While temperature-accelerated dynamics (TAD) is a powerful method for carrying out non-equilibrium simulations of systems over extended time scales, the computational cost of serial TAD increases approximately as N{sup 3} where N is the number of atoms. In addition, although a parallel TAD method based on domain decomposition [Y. Shim et al., Phys. Rev. B 76, 205439 (2007)] has been shown to provide significantly improved scaling, the dynamics in such an approach is only approximate while the size of activated events is limited by the spatial decomposition size. Accordingly, it is of interest to develop methods to improve the scalingmore » of serial TAD. As a first step in understanding the factors which determine the scaling behavior, we first present results for the overall scaling of serial TAD and its components, which were obtained from simulations of Ag/Ag(100) growth and Ag/Ag(100) annealing, and compare with theoretical predictions. We then discuss two methods based on localization which may be used to address two of the primary “bottlenecks” to the scaling of serial TAD with system size. By implementing both of these methods, we find that for intermediate system-sizes, the scaling is improved by almost a factor of N{sup 1/2}. Some additional possible methods to improve the scaling of TAD are also discussed.« less

Light insensitive silver(I) cyanoximates as antimicrobial agents for indwelling medical devices.

PubMed

Gerasimchuk, Nikolay; Gamian, Andrzej; Glover, Garrett; Szponar, Bogumila

2010-11-01

Ten silver(I) cyanoximates of AgL composition (L = NC-C(NO)-R, where R is electron withdrawing groups: -CN, -C(O)NR(2), -C(O)R' (alkyl), -C(O)OEt, 2-heteroaryl fragments such as 2-pyridyl, 2-benzimidazolyl, 2-benzoxazolyl, 2-benzthiazolyl) were synthesized and characterized using spectroscopic methods and X-ray analysis. Crystal structures of four complexes were determined and revealed the formation of two-dimensional (2D) coordination polymers of different complexity in which anions exhibit bridging or combined chelate and bridging binding modes. In these compounds, anions are in the nitroso form. All studied AgL complexes are sparingly soluble in water and are thermally stable to 150 °C. Synthesized compounds demonstrated remarkable insensitivity toward visible light and UV-radiation, which was explained based on their polymeric structures with multiple covalent bonds between bridging cyanoxime ligands and Ag(I) centers. All 10 silver(I) cyanoximates were tested in vitro on the subject of their antimicrobial activity against both Gram-positive and Gram-negative microorganisms such as Escherichia coli, Klebsiella pneumoniae, Proteus sp., Pseudomonas aeruginosa, Enterococcus hirae, Streptococcus mutans, Staphylococcus aureus, and Mycobacterium fortuitum as well as against Candida albicans in solutions, and in the solid state as pressed pellets and dried filter paper disks presoaked with solutions of AgL in DMF. Results showed pronounced antimicrobial activity for all investigated complexes. A combination of five factors: (1) light insensitivity, (2) poor water solubility, (3) high thermal stability, (4) lack of toxicity of organic ligands, and (5) in vitro antimicrobial activity allows development of silver(I) cyanoximates for medical applications. These include antimicrobial additives to acrylate glue, cured by UV-radiation, used in introduction of prosthetic joints and dental implants, and prevention of biofilm formation on several types of indwelling medical devices.

Design, fabrication, and testing of the BNL radio frequency quadrupole accelerator

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

Brown, H.; Clifford, T.; Giordano, S.

1984-01-01

The Brookhaven National Laboratory polarized H/sup -/ injection program for the AGS utilizes a Radio Frequency Quadrupole Accelerator for acceleration between the polarized source and the Alvarez Linac. Although operation has commenced with a few ..mu.. amperes of H/sup -/ beam, it is anticipated that future polarized H/sup -/ sources will have a considerably improved output. The RFQ will operate at 201.25 MHz and will be capable of handling a beam current of 0.02 amperes with a duty cycle of 0.25%. The resulting low average power has allowed novel solutions to the problems of vane alignment, rf current contacts, andmore » removal of heat from the vanes. The design philosophy, details of cavity fabrication, and vane machining will be discussed. Results of low and high power rf testing will be presented together with the initial results of operations in the polarized H/sup -/ beam line.« less

Synthesis and Characterization of Pt–Ag Alloy Nanocages with Enhanced Activity and Durability toward Oxygen Reduction

DOE PAGES

Yang, Xuan; Roling, Luke T.; Vara, Madeline; ...

2016-09-23

Engineering the elemental composition of metal nanocrystals offers an effective strategy for the development of catalysts or electrocatalysts with greatly enhanced activity. Herein, we report the synthesis of Pt–Ag alloy nanocages with an outer edge length of 18 nm and a wall thickness of about 3 nm. Such nanocages with a composition of Pt 19Ag 81 could be readily prepared in one step through the galvanic replacement reaction between Ag nanocubes and a Pt(II) precursor. Here, after 10 000 cycles of potential cycling in the range of 0.60–1.0 V as in an accelerated durability test, the composition of the nanocagesmore » changed to Pt 56Ag 44, together with a specific activity of 1.23 mA cm –2 toward oxygen reduction, which was 3.3 times that of a state-of-the-art commercial Pt/C catalyst (0.37 mA cm –2) prior to durability testing. Density functional theory calculations attributed the increased activity to the stabilization of the transition state for breaking the O–O bond in molecular oxygen. Even after 30 000 cycles of potential cycling, the mass activity of the nanocages only dropped from 0.64 to 0.33 A mg –1 Pt, which was still about two times that of the pristine Pt/C catalyst (0.19 A mg –1 Pt).« less

Synthesis and Characterization of Pt–Ag Alloy Nanocages with Enhanced Activity and Durability toward Oxygen Reduction

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

Yang, Xuan; Roling, Luke T.; Vara, Madeline

Engineering the elemental composition of metal nanocrystals offers an effective strategy for the development of catalysts or electrocatalysts with greatly enhanced activity. Herein, we report the synthesis of Pt–Ag alloy nanocages with an outer edge length of 18 nm and a wall thickness of about 3 nm. Such nanocages with a composition of Pt 19Ag 81 could be readily prepared in one step through the galvanic replacement reaction between Ag nanocubes and a Pt(II) precursor. Here, after 10 000 cycles of potential cycling in the range of 0.60–1.0 V as in an accelerated durability test, the composition of the nanocagesmore » changed to Pt 56Ag 44, together with a specific activity of 1.23 mA cm –2 toward oxygen reduction, which was 3.3 times that of a state-of-the-art commercial Pt/C catalyst (0.37 mA cm –2) prior to durability testing. Density functional theory calculations attributed the increased activity to the stabilization of the transition state for breaking the O–O bond in molecular oxygen. Even after 30 000 cycles of potential cycling, the mass activity of the nanocages only dropped from 0.64 to 0.33 A mg –1 Pt, which was still about two times that of the pristine Pt/C catalyst (0.19 A mg –1 Pt).« less

The Trans-Cis Isomerisation of Bis(dioxolene)bis(pyridine)Ruthenium Complexes

DTIC Science & Technology

1992-03-03

and counter electrodes, and a AgCl/Ag quasi-reference electrode with ferrocene (Fc) as an internal standard. The Fc/Fc + couple lies at + 0.425 V vs...species which isomerise in chloroform at from 500C (actual temperature depending upon the phosphine ) to the all * ccc-Ru(CO) 2CI2(PR 3)2 species which

Detection and Quantification of Silver Nanoparticles at ...

EPA Pesticide Factsheets

The presence of silver nanoparticles (AgNPs) in aquatic environments could potentially cause adverse impacts on ecosystems and human health. However, current understanding of the environmental fate and transport of AgNPs is still limited because their properties in complex environmental samples cannot be accurately determined. In this study, the feasibility of using asymmetric flow field-flow fractionation (AF4) connected online with single particle inductively coupled plasma mass spectrometry (spICPMS) to detect and quantify AgNPs at environmentally relevant concentrations was investigated. The AF4 channel had a thickness of 350 μm and its accumulation wall was a 10 kDa regenerated cellulose membrane. A 0.02% FL-70 surfactant solution was used as an AF4 carrier. With 1.2 mL/min AF4 cross-flow rate, 1.5 mL/min AF4 channel flow rate, and 5 ms spICPMS dwell time, the AF4-spICPMS can detect and quantify 40–80 nm AgNPs, as well as Ag-SiO2 core−shell nanoparticles (51.0 nm diameter Ag core and 21.6 nm SiO2 shell), with good recovery within 30 min. This system was not only effective in differentiating and quantifying different types of AgNPs with similar hydrodynamic diameters, such as in mixtures containing Ag-SiO2 core–shell nanoparticles and 40–80 nm AgNPs, but also suitable for differentiating between 40 nm AgNPs and elevated Ag+ content. The study results indicate that AF4-spICPMS is capable of detecting and quantifying AgNPs and other engineered metal n

Inputs, dynamics and potential impacts of silver (Ag) from urban wastewater to a highly turbid estuary (SW France).

PubMed

Deycard, Victoria N; Schäfer, Jörg; Petit, Jérôme C J; Coynel, Alexandra; Lanceleur, Laurent; Dutruch, Lionel; Bossy, Cécile; Ventura, Alexandre; Blanc, Gérard

2017-01-01

Although silver (Ag) has been listed as a priority pollutant for the aquatic environment by the European Union (Directive 2006/11/EC), the use of Ag-based products with antimicrobial effects is increasing in Europe, as well as North America and Asia. This study investigates personal care products (PCP) as a potential source of Ag in wastewater, as well as the dynamics and fate of Ag in the influent and effluent of a major urban wastewater treatment plant (WWTP) located on the fluvial part of the Gironde Estuary. Typical household PCPs marked as using Ag contained concentrations of up to 0.4 mg kg -1 making them likely contributors to urban Ag released into the aquatic environment. Silver concentrations in influent wastewater generally occurred during mid-week working hours and decreased during the night and on weekends clearly indicating the dominance of urban sources. Up to 90% of the total Ag in wastewater was bound to particles and efficiently (>80%) removed by the treatment process, whereas 20% of Ag was released into the fluvial estuary. Silver concentrations in wastewater effluents clearly exceeded estuarine concentrations and may strongly amplify the local Ag concentrations and fluxes, especially during summer rainstorms in low river discharge conditions. Further work should focus on environmental effects and fate of urban Ag release due to immediate localized outfall and/or the adsorption on estuarine particles and subsequent release as dissolved Ag chloro-complexes within the estuarine salinity gradient. Copyright © 2016 Elsevier Ltd. All rights reserved.

Structure and electrical properties of a one-dimensional polymeric silver thiosaccharinate complex with argentophilic interactions.

PubMed

Dennehy, Mariana; Amo-Ochoa, Pilar; Freire, Eleonora; Suárez, Sebastián; Halac, Emilia; Baggio, Ricardo

2018-02-01

Among the potential applications of coordination polymers, electrical conductivity ranks high in technological interest. We report the synthesis, crystal structure and spectroscopic analysis of an Ag I -thiosaccharinate one-dimensional coordination polymer {systematic name: catena-poly[[[aquatetrakis(μ 3 -1,1-dioxo-1,2-benzisothiazole-3-thiolato-κ 3 N:S 3 :S 3 )tetrasilver(I)]-μ 2 -4,4'-(propane-1,3-diyl)dipyridine-κ 2 N:N'] dimethyl sulfoxide hemisolvate]}, {[Ag 4 (C 7 H 4 NO 2 S 2 ) 4 (C 13 H 14 N 2 )(H 2 O)]·0.5C 2 H 6 OS} n , with the 4,4'-(propane-1,3-diyl)dipyridine ligand acting as a spacer. A relevant feature of the structure is the presence of an unusually short Ag...Ag distance of 2.8306 (9) Å, well within the range of argentophilic interactions, confirmed experimentally as such by a Raman study on the low-frequency spectrum, and corroborated theoretically by an Atoms in Molecules (AIM) analysis of the calculated electron density. Electrical conductivity measurements show that this complex can act as a semiconductor with moderate conductivity.

Variant Ionotropic Receptors in the Malaria Vector Mosquito Anopheles gambiae Tuned to Amines and Carboxylic Acids

PubMed Central

Pitts, R. Jason; Derryberry, Stephen L.; Zhang, Zhiwei; Zwiebel, Laurence J.

2017-01-01

The principal Afrotropical human malaria vector mosquito, Anopheles gambiae, remains a significant threat to global health. A critical component in the transmission of malaria is the ability of An. gambiae females to detect and respond to human-derived chemical kairomones in their search for blood meal hosts. The basis for host odor responses resides in olfactory receptor neurons (ORNs) that express chemoreceptors encoded by large gene families, including the odorant receptors (ORs) and the variant ionotropic receptors (IRs). While ORs have been the focus of extensive investigation, functional IR complexes and the chemical compounds that activate them have not been identified in An. gambiae. Here we report the transcriptional profiles and functional characterization of three An. gambiae IR (AgIr) complexes that specifically respond to amines or carboxylic acids - two classes of semiochemicals that have been implicated in mediating host-seeking by adult females but are not known to activate An. gambiae ORs (AgOrs). Our results suggest that AgIrs play critical roles in the detection and behavioral responses to important classes of host odors that are underrepresented in the AgOr chemical space. PMID:28067294

A tritopic carbanionic N-heterocyclic dicarbene and its homo- and heterometallic coinage metal complexes.

PubMed

Zhang, Fan; Cao, Xiao-Ming; Wang, Jiwei; Jiao, Jiajun; Huang, Yongming; Shi, Min; Braunstein, Pierre; Zhang, Jun

2018-05-21

Homo (Au3)- and heterotrinuclear coinage metal complexes (Au2Ag and Au2Cu) ligated by the first tritopic carbanionic N-heterocyclic carbene (NHC) have been prepared by deprotonation of ditopic NHC digold complexes and structurally characterized by single-crystal X-ray diffraction.

Metal-ligand bond directionality in the M2-NH3 complexes (M = Cu, Ag and Au)

NASA Astrophysics Data System (ADS)

Eskandari, K.; Ebadinejad, F.

2018-05-01

The metal-ligand bonds in the M2-NH3 complexes (M = Au, Ag and Cu) are directional and the M-M-N angles tend to be linear. Natural energy decomposition analysis (NEDA) and localised molecular orbital energy decomposition analysis (LMOEDA) approaches indicate that the metal-ligand bonds in these complexes are mainly electrostatic in nature, however, the electrostatic is not the cause of the linearity of M-M-N arrangements. Instead, NEDA shows that the charge transfer and core repulsion are mainly responsible for the directionality of these bonds. In the LMOEDA point of view, the repulsion term is the main reason for the linearity of these complexes. Interacting quantum atoms (IQA) analysis shows that inter-atomic and inter-fragment interactions favour the nonlinear arrangements; however, these terms are compensated by the atomic self-energies, which stabilise the linear structure.

A study of the feasibility of conducting the ELISE and EXL experiments at the ITEP accelerator complex

NASA Astrophysics Data System (ADS)

Bolshakov, A. E.; Golubev, A. A.; Zenkevich, P. R.; Kats, M. M.; Kolomiets, A. A.

2014-09-01

We report the results of a study into the feasibility of conducting the ELISE and EXL experiments on collisions of nuclei of radioactive fragments with electrons at the Institute for Theoretical and Experimental Physics (ITEP). A scheme for uranium ion acceleration in the ITEP accelerator complex is chosen, and it is shown that uranium ions may be accelerated with an intensity of ˜1 × 1011 ions/s as soon as the complex is modified and a new injector is constructed. The basic parameters of the modified complex are given, and a layout diagram indicating the positions of the target that serves to produce radioactive fragments, the separator, and the storage rings (CR, RESR, NESR, and ER) at the ITEP site is presented.

A spectroscopic and voltammetric study of the pH-dependent Cu(II) coordination to the peptide GGGTH: relevance to the fifth Cu(II) site in the prion protein.

PubMed

Hureau, Christelle; Charlet, Laurent; Dorlet, Pierre; Gonnet, Florence; Spadini, Lorenzo; Anxolabéhère-Mallart, Elodie; Girerd, Jean-Jacques

2006-09-01

The GGGTH sequence has been proposed to be the minimal sequence involved in the binding of a fifth Cu(II) ion in addition to the octarepeat region of the prion protein (PrP) which binds four Cu(II) ions. Coordination of Cu(II) by the N- and C-protected Ac-GGGTH-NH(2) pentapeptide (P(5)) was investigated by using potentiometric titration, electrospray ionization mass spectrometry, UV-vis spectroscopy, electron paramagnetic resonance (EPR) spectroscopy and cyclic voltammetry experiments. Four different Cu(II) complexes were identified and characterized as a function of pH. The Cu(II) binding mode switches from NO(3) to N(4) for pH values ranging from 6.0 to 10.0. Quasi-reversible reduction of the [Cu(II)(P(5))H(-2)] complex formed at pH 6.7 occurs at E (1/2)=0.04 V versus Ag/AgCl, whereas reversible oxidation of the [Cu(II)(P(5))H(-3)](-) complex formed at pH 10.0 occurs at E (1/2)=0.66 V versus Ag/AgCl. Comparison of our EPR data with those of the rSHaPrP(90-231) (Burns et al. in Biochemistry 42:6794-6803, 2003) strongly suggests an N(3)O binding mode at physiological pH for the fifth Cu(II) site in the protein.

Activator of G Protein Signaling 8 (AGS8) Is Required for Hypoxia-induced Apoptosis of Cardiomyocytes

PubMed Central

Sato, Motohiko; Jiao, Qibin; Honda, Takashi; Kurotani, Reiko; Toyota, Eiji; Okumura, Satoshi; Takeya, Tatsuo; Minamisawa, Susumu; Lanier, Stephen M.; Ishikawa, Yoshihiro

2009-01-01

Ischemic injury of the heart is associated with activation of multiple signal transduction systems including the heterotrimeric G-protein system. Here, we report a role of the ischemia-inducible regulator of Gβγ subunit, AGS8, in survival of cardiomyocytes under hypoxia. Cultured rat neonatal cardiomyocytes (NCM) were exposed to hypoxia or hypoxia/reoxygenation following transfection of AGS8siRNA or pcDNA::AGS8. Hypoxia-induced apoptosis of NCM was completely blocked by AGS8siRNA, whereas overexpression of AGS8 increased apoptosis. AGS8 formed complexes with G-proteins and channel protein connexin 43 (CX43), which regulates the permeability of small molecules under hypoxic stress. AGS8 initiated CX43 phosphorylation in a Gβγ-dependent manner by providing a scaffold composed of Gβγ and CX43. AGS8siRNA blocked internalization of CX43 following exposure of NCM to repetitive hypoxia; however it did not influence epidermal growth factor-mediated internalization of CX43. The decreased dye flux through CX43 that occurred with hypoxic stress was also prevented by AGS8siRNA. Interestingly, the Gβγ inhibitor Gallein mimicked the effect of AGS8 knockdown on both the CX43 internalization and the changes in cell permeability elicited by hypoxic stress. These data indicate that AGS8 is required for hypoxia-induced apoptosis of NCM, and that AGS8-Gβγ signal input increased the sensitivity of cells to hypoxic stress by influencing CX43 regulation and associated cell permeability. Under hypoxic stress, this unrecognized response program plays a critical role in the fate of NCM. PMID:19723622

Ice nucleation efficiency of AgI: review and new insights

NASA Astrophysics Data System (ADS)

Marcolli, Claudia; Nagare, Baban; Welti, André; Lohmann, Ulrike

2016-07-01

AgI is one of the best-investigated ice-nucleating substances. It has relevance for the atmosphere since it is used for glaciogenic cloud seeding. Theoretical and experimental studies over the last 60 years provide a complex picture of silver iodide as an ice-nucleating agent with conflicting and inconsistent results. This review compares experimental ice nucleation studies in order to analyze the factors that influence the ice nucleation ability of AgI. The following picture emerges from this analysis: the ice nucleation ability of AgI seems to be enhanced when the AgI particle is on the surface of a droplet, which is indeed the position that a particle takes when it can freely move in a droplet. The ice nucleation by particles with surfaces exposed to air depends on water adsorption. AgI surfaces seem to be most efficient at nucleating ice when they are exposed to relative humidity at or even above water saturation. For AgI particles that are completely immersed in water, the freezing temperature increases with increasing AgI surface area. Higher threshold freezing temperatures seem to correlate with improved lattice matches as can be seen for AgI-AgCl solid solutions and 3AgI·NH4I·6H2O, which have slightly better lattice matches with ice than AgI and also higher threshold freezing temperatures. However, the effect of a good lattice match is annihilated when the surfaces have charges. Also, the ice nucleation ability seems to decrease during dissolution of AgI particles. This introduces an additional history and time dependence for ice nucleation in cloud chambers with short residence times.

The MNS glycophorin variant GP.Mur affects differential erythroid expression of Rh/RhAG transcripts.

PubMed

Hsu, K; Kuo, M-S; Yao, C-C; Cheng, H-C; Lin, H-J; Chan, Y-S; Lin, M

2017-10-01

The band 3 macrocomplex (also known as the ankyrin-associated complex) on the red cell membrane comprises two interacting subcomplexes: a band 3/glycophorin A subcomplex, and a Rh/RhAG subcomplex. Glycophorin B (GPB) is a component of the Rh/RhAG subcomplex that is also structurally associated with glycophorin A (GPA). Expression of glycophorin B-A-B hybrid GP.Mur enhances band 3 expression and is associated with lower levels of Rh-associated glycoprotein (RhAG) and Rh polypeptides. The goal of this study was to determine whether GP.Mur influenced erythroid Rh/RhAG expression at the transcript level. GP.Mur was serologically determined in healthy participants from Taitung County, Taiwan. RNA was extracted from the reticulocyte-enriched fraction of peripheral blood, followed by reverse transcription and quantitative PCR for RhAG, RhD and RhCcEe. Quantification by real-time PCR revealed significantly fewer RhAG and RhCcEe transcripts in the reticulocytes from subjects with homozygous GYP*Mur. Independent from GYP.Mur, both RhAG and RhD transcript levels were threefold or higher than that of RhCcEe. Also, in GYP.Mur and the control samples alike, direct quantitative associations were observed between the transcript levels of RhAG and RhD, but not between that of RhAG and RhCcEe. Erythroid RhD and RhCcEe were differentially expressed at the transcript levels, which could be related to their different degrees of interaction or sensitivity to RhAG. Further, the reduction or absence of glycophorin B in GYP.Mur erythroid cells affected transcript expressions of RhAG and RhCcEe. Thus, GPB and GP.Mur differentially influenced Rh/RhAG expressions prior to protein translation. © 2017 International Society of Blood Transfusion.

Matrix Effects Originating from Coexisting Minerals and Accurate Determination of Stable Silver Isotopes in Silver Deposits.

PubMed

Guo, Qi; Wei, Hai-Zhen; Jiang, Shao-Yong; Hohl, Simon; Lin, Yi-Bo; Wang, Yi-Jing; Li, Yin-Chuan

2017-12-19

Except for extensive studies in core formation and volatile-element depletion processes using radiogenic Ag isotopes (i.e., the Pd-Ag chronometer), recent research has revealed that the mass fractionation of silver isotopes is in principle controlled by physicochemical processes (e.g., evaporation, diffusion, chemical exchange, etc.) during magmatic emplacement and hydrothermal alteration. As these geologic processes only produce very minor variations of δ 109 Ag from -0.5 to +1.1‰, more accurate and precise measurements are required. In this work, a robust linear relationship between instrumental mass discrimination of Ag and Pd isotopes was obtained at the Ag/Pd molar ratio of 1:20. In Au-Ag ore deposits, silver minerals have complex paragenetic relationships with other minerals (e.g., chalcopyrite, sphalerite, galena, pyrite, etc.). It is difficult to remove such abundant impurities completely because the other metals are tens to thousands of times richer than silver. Both quantitative evaluation of matrix effects and modification of chemical chromatography were carried out to deal with the problems. Isobaric inferences (e.g., 65 Cu 40 Ar + to 105 Pd, 208 Pb 2+ to 104 Pd, and 67 Zn 40 Ar + to 107 Ag + ) and space charge effects dramatically shift the measured δ 109 Ag values. The selection of alternative Pd isotope pairs is effective in eliminating spectral matrix effects so as to ensure accurate analysis under the largest possible ranges for metal impurities, which are Cu/Ag ≤ 50:1, Fe/Ag ≤ 600:1, Pb/Ag ≤ 10:1, and Zn/Ag ≤ 1:1, respectively. With the modified procedure, we reported silver isotope compositions (δ 109 Ag) in geological standard materials and typical Au-Ag ore deposit samples varying from -0.029 to +0.689 ‰ with external reproducibility of ±0.009-0.084 ‰. A systemic survey of δ 109 Ag (or ε 109 Ag) variations in rocks, ore deposits, and environmental materials in nature is discussed.

Impact of surface coating and environmental conditions on the fate and transport of silver nanoparticles in the aquatic environment.

PubMed

Ellis, Laura-Jayne A; Valsami-Jones, Eugenia; Lead, Jamie R; Baalousha, Mohammed

2016-10-15

The role of surface coating (polyvinylpyrrolidone (PVP) and citrate) and water chemistry on the fate and behavior of AgNPs in aquatic microcosms is reported in this study. The migration and transformation of the AgNPs was examined in low (ultrapure water-UPW) and high ionic strength (moderately hard water - MHW) preparations, and in the presence of modeled natural organic matter (NOM) of Suwannee River Fulvic Acid (SRFA). The migration and fate of the AgNPs in the microcosms was validated using a sedimentation-diffusion model and the aggregation behavior was monitored by UV-visible spectrometry (UV-vis). Dissolved and particulate Ag concentrations (% Ag) were analyzed by ultrafiltration methods. Imaging of the AgNPs was captured using transmission electron microscopy (TEM). Results indicate that PVP-coated AgNPs (PVP-AgNPs) remained stable for 28days with similarly distributed concentrations of the PVP-AgNPs throughout the columns in each of the water conditions after approximately 96h (4days). The sedimentation-diffusion model confirmed PVP-AgNP stability in each condition, by showing diffusion dominated transport by using the original unaltered AgNP sizes to fit the parameters. In comparison, citrate AgNPs were largely unstable in the more complex water preparations (MHW). In MHW, aggregation dominated behavior followed by sedimentation/dissolution controlled transport was observed. The addition of SRFA to MHW resulted in small stabilizing effects, to the citrate coated AgNPs, producing smaller sized AgNPs (TEM) and mixed sedimentation and diffusion migration compared the studies absent of SRFA. The results suggest that surface coating and solution chemistry has a major impact on AgNP stability, furthermore the corresponding modeling will support the experimental understanding of the overall fate of AgNPs in the environment. Copyright © 2016 Elsevier B.V. All rights reserved.

User’s Guide for an Optical Contrast Seeker Monte Carlo Terminal Homing Simulation

DTIC Science & Technology

1975-05-14

AG sin X ) Eq. 2.16 33 Acceleration Normal to Plane .. X (Boresignt) G. Plane containing mass unbalance centrotd ~YG FIGURE 3.28. Inner Gimbal View...ill# .L01 0.090 jNi FORM -1.000 1. CJ2 .315 C.0 3 0.000 UNICORN -1.0100 1. U000 2,4kp1 .12J C.GG0 JN.’FORM -1.000100 14L2 -. 4.8 0.00a .JKIFORM -1.000...fu 1. rj m N. I At1 -- c2 0 0* 4- 0 W uI-WL UL w I~ f :.VPI *4 *.* .. 4 C, : IV 1A ag oo ,- * I4 1, %An Q. cc Go coc oC cVCa: .ato to o 1 o I a

Modeling the benefits of an artificial gravity countermeasure coupled with exercise and vibration

NASA Astrophysics Data System (ADS)

Goel, Rahul; Kaderka, Justin; Newman, Dava

2012-01-01

The current, system-specific countermeasures to space deconditioning have limited success with the musculoskeletal system in long duration missions. Artificial gravity (AG) that is produced by short radius centrifugation has been hypothesized as an effective countermeasure because it reintroduces an acceleration field in space; however, AG alone might not be enough stimuli to preserve the musculoskeletal system. A novel combination of AG coupled with one-legged squats on a vibrating platform may preserve muscle and bone in the lower limbs to a greater extent than the current exercise paradigm. The benefits of the proposed countermeasure have been analyzed through the development of a simulation platform. Ground reaction force data and motion data were collected using a motion capture system while performing one-legged and two-legged squats in 1-G. The motion was modeled in OpenSim, an open-source software, and inverse dynamics were applied in order to determine the muscle and reaction forces of lower limb joints. Vibration stimulus was modeled by adding a 20 Hz sinusoidal force of 0.5 body weight to the force plate data. From the numerical model in a 1-G acceleration field, muscle forces for quadriceps femoris, plantar flexors and glutei increased substantially for one-legged squats with vibration compared to one- or two-legged squats without vibration. Additionally, joint reaction forces for one-legged squats with vibration also increased significantly compared to two-legged squats with or without vibration. Higher muscle forces and joint reaction forces might help to stimulate muscle activation and bone modeling and thus might reduce musculoskeletal deconditioning. These results indicate that the proposed countermeasure might surpass the performance of the current space countermeasures and should be further studied as a method of mitigating musculoskeletal deconditioning.

First cross-section measurements of the reactions Ag,109107(p ,γ )Cd,110108 at energies relevant to the p process

NASA Astrophysics Data System (ADS)

Khaliel, A.; Mertzimekis, T. J.; Asimakopoulou, E.-M.; Kanellakopoulos, A.; Lagaki, V.; Psaltis, A.; Psyrra, I.; Mavrommatis, E.

2017-09-01

Background: One of the primary objectives of the field of Nuclear Astrophysics is the study of the elemental and isotopic abundances in the universe. Although significant progress has been made in understanding the mechanisms behind the production of a large number of nuclides in the isotopic chart, there are still many open questions regarding a number of neutron-deficient nuclei, the p nuclei. To that end, experimentally deduced nuclear reaction cross sections can provide invaluable input to astrophysical models. Purpose: The reactions Ag,109107(p ,γ )Cd,110108 have been studied at energies inside the astrophysically relevant energy window in an attempt to provide experimental data required for the testing of reaction-rate predictions in terms of the statistical model of Hauser-Feshbach around the p nucleus 108Cd. Methods: The experiments were performed with in-beam γ -ray spectroscopy with proton beams accelerated by the Tandem Van de Graaff Accelerator at NCSR "Demokritos" impinging a target of natural silver. A set of high-purity germanium detectors was employed to record the emitted radiation. Results: A first set of total cross-section measurements in radiative proton-capture reactions involving Ag,109107, producing the p -nucleus 108Cd, inside the astrophysically relevant energy window is reported. The experimental results are compared to theoretical calculations, using talys. An overall good agreement between the data and the theoretical calculations has been found. Conclusions: The results reported in this work add new information to the relatively unexplored p process. The present measurements can serve as a reference point in understanding the nuclear parameters in the related astrophysical environments and for future theoretical modeling and experimental works.

Adaptive temperature-accelerated dynamics

NASA Astrophysics Data System (ADS)

Shim, Yunsic; Amar, Jacques G.

2011-02-01

We present three adaptive methods for optimizing the high temperature Thigh on-the-fly in temperature-accelerated dynamics (TAD) simulations. In all three methods, the high temperature is adjusted periodically in order to maximize the performance. While in the first two methods the adjustment depends on the number of observed events, the third method depends on the minimum activation barrier observed so far and requires an a priori knowledge of the optimal high temperature T^{opt}_{high}(E_a) as a function of the activation barrier Ea for each accepted event. In order to determine the functional form of T^{opt}_{high}(E_a), we have carried out extensive simulations of submonolayer annealing on the (100) surface for a variety of metals (Ag, Cu, Ni, Pd, and Au). While the results for all five metals are different, when they are scaled with the melting temperature Tm, we find that they all lie on a single scaling curve. Similar results have also been obtained for (111) surfaces although in this case the scaling function is slightly different. In order to test the performance of all three methods, we have also carried out adaptive TAD simulations of Ag/Ag(100) annealing and growth at T = 80 K and compared with fixed high-temperature TAD simulations for different values of Thigh. We find that the performance of all three adaptive methods is typically as good as or better than that obtained in fixed high-temperature TAD simulations carried out using the effective optimal fixed high temperature. In addition, we find that the final high temperatures obtained in our adaptive TAD simulations are very close to our results for T^{opt}_{high}(E_a). The applicability of the adaptive methods to a variety of TAD simulations is also briefly discussed.

[Pretreatment of Aluminum-Lithium Alloy Sample and Determination of Argentum and Lithium by Spectral Analysis].

PubMed

Zhou, Hui; Tan, Qian; Gao, Ya-ling; Sang, Shi-hua; Chen, Wen

2015-10-01

Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES), Flame Atomic Absorption Spectrometry (FAAS) and Visible Spectrometry (VS) was applied for determination of Ag and Li in lithium-aluminium alloy standard sample and test sample, their respective advantages and disadvantages were compared, the excellent selectivity of ICP-OES was confirmed by analyses of certified standard sample. Three different sample digestion methods were compared and discussed in this study. It was found that the better accuracy would be obtained by digesting sample with chloroazotic acid while the content of Li was measured by FAAS, and it was better to digest sample with hydrochloric acid and hydrogen peroxide while determining Ag and Li by ICP-OES simultaneously and determining Ag by FAAS and VS. The interference of co-existing elements and elimination methods was detailedly discussed. Ammonium hydroxide was added to adjust the sample solution into alkalescent and Al, Ti, Zr was precipitated by forming hydroxide precipitation, Mg and Cu was formed complex precipitation with 8-hydroxyquinoline in this condition, then the interference from matrix element to determinate Ag by FAAS was eliminated. In addition, phosphate was used to precipitate Ti to eliminate its interference for determination of Li by FAAS. The same treatment of determination for Ag by FAAS was used to eliminate the interference of matrix element for determination of Ag by VS, the excess of nitrate was added into sample and heated to release Ag+ from silver chloride complex, and the color of 8-hydroxyquinoline was eliminated because of decomposed by heating. The accuracy of analysis result for standard sample was conspicuously improved which confirms the efficient of the method to eliminate interference in this study. The optimal digestion method and eliminate interference method was applied to lithium-aluminium alloy samples. The recovery of samples was from 100.39% to 103.01% by ICP-OES determination for Ag, and from 100.42% to 103.01% by ICP-OES determination for Li. The recovery ranged from 95.91% to 99.98% by FAAS determination for Ag, and ranged from 98.04% to 99.98% for FAAS determination of Li. The recovery was from 98.00% to 101.00 by VS determination for Ag, the analysis results all meet the analysis requirement.

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

Liu, Yanhong; Gao, Ping; Bi, Kaifeng

Conducting pathway of percolation network was identified in resistive switching devices (RSDs) with the structure of silver/amorphous silicon/p-type silicon (Ag/a-Si/p-Si) based on its gradual RESET-process and the stochastic complex impedance spectroscopy characteristics (CIS). The formation of the percolation network is attributed to amounts of nanocrystalline Si particles as well as defect sites embedded in a-Si layer, in which the defect sites supply positions for Ag ions to nucleate and grow. The similar percolation network has been only observed in Ag-Ge-Se based RSD before. This report provides a better understanding for electric properties of RSD based on the percolation network.

Competitive cesium-133 NMR spectroscopic study of complexation of different metal ions with dibenzo-21-crown-7 in acetonitrile-dimethylsulfoxide and nitromethane-dimethylsulfoxide mixtures.

PubMed

Sahmsipur, Mojtaba; Dastjerdi, Leila Shafiee; Alizadeh, Nader; Bijanzadeh, Hamid Reza

2008-04-01

(133)Cs NMR spectroscopy was used to determine the stoichiometry and stability of the Cs(+) ion complex with dibenzo-21-crown-7 (DB21C7) in acetonitrile-dimethylsulfoxide (96.5:3.5, w/w) and nitromethane-dimethylsulfoxide (96.5:3.5, w/w) mixtures. A competitive (133)Cs NMR technique was also employed to probe the complexation of Na(+), K(+), Rb(+), Ag(+), Tl(+), NH(4)(+), Mg(2+), Ba(2+), Hg(2+), Pb(2+) and UO(2)(2+) ions with DB21C7 in the same solvent systems. All the resulting 1:1 complexes in nitromethane-dimethylsulfoxide were more stable than those in acetonitrile-dimethylsulfoxide solution. In both solvent systems, the stability of the resulting complexes was found to vary in the order Rb(+)>K(+) approximately Ba(2+)>Tl(+)>Cs(+)>NH(4)(+) approximately Pb(2+)>Ag(+)>UO(2)(2+)>Hg(2+)>Mg(2+)>Na(+).

Influence of complex impurity centres on radiation damage in wide-gap metal oxides

NASA Astrophysics Data System (ADS)

Lushchik, A.; Lushchik, Ch.; Popov, A. I.; Schwartz, K.; Shablonin, E.; Vasil'chenko, E.

2016-05-01

Different mechanisms of radiation damage of wide-gap metal oxides as well as a dual influence of impurity ions on the efficiency of radiation damage have been considered on the example of binary ionic MgO and complex ionic-covalent Lu3Al5O12 single crystals. Particular emphasis has been placed on irradiation with ∼2 GeV heavy ions (197Au, 209Bi, 238U, fluence of 1012 ions/cm2) providing extremely high density of electronic excitations within ion tracks. Besides knock-out mechanism for Frenkel pair formation, the additional mechanism through the collapse of mobile discrete breathers at certain lattice places (e.g., complex impurity centres) leads to the creation of complex defects that involve a large number of host atoms. The experimental manifestations of the radiation creation of intrinsic and impurity antisite defects (Lu|Al or Ce|Al - a heavy ion in a wrong cation site) have been detected in LuAG and LuAG:Ce3+ single crystals. Light doping of LuAG causes a small enhancement of radiation resistance, while pair impurity centres (for instance, Ce|Lu-Ce|Al or Cr3+-Cr3+ in MgO) are formed with a rise of impurity concentration. These complex impurity centres as well as radiation-induced intrinsic antisite defects (Lu|Al strongly interacting with Lu in a regular site) tentatively serve as the places for breathers collapse, thus decreasing the material resistance against dense irradiation.

Highly stabilized gadolinium chelates functionalized on metal nanoparticles as magnetic resonance imaging contrast agent

NASA Astrophysics Data System (ADS)

Siddiqui, Talha S.

Magnetic resonance imaging (MRI) is a non-invasive method for imaging and diagnosing tissue damage, organ function and the vascular system. Magnevist(TM) a complex of diethylenetriaminepentaacetic acid (DTPA) and Gd3+ is a clinically approved contrast agent for MRI. A derivative of DTPA was formed by the addition of two cysteine groups (DTPA-L-Cys) through amide linkage. The Gd complex of this ligand bonds with the silver surfaces through the cysteine thiols. GdDTPA-L-Cys was bound to ˜10nm diameter Ag nanoparticles for use as a multifunctional MRI contrast agent. The ligand and complex were characterized by 1H and 13C NMR, ESI-MS and IR spectroscopy. The silver construct was characterized by TEM, TGA and UV-Vis absorption spectra. The per metal complex r1 relaxivity of GdDTPA-L-Cys{Ag} greater than that of Magnavist(TM) with the same molarity for both compounds. The synthesis of a DTPA derivative is described that allows it to bind to silver or gold nanoparticles through a single thiol linkage (DTPASH). The resulting Gd complex, GdDTPASH, was bound to Ag nanoparticles to create a single monolayer on the surface. The construct was further stabilized in buffered solution with the addition of a thiolated PEG chain. The highly stabilized nanoparticle construct delivers a high payload of Gd compelex and is an effective T1 brightening agent. The production of this type of construct opens the way for engineered multimodal MRI contrast agents.

Detection of a premature stop codon in the surface gene of hepatitis B virus from an HBsAg and antiHBc negative blood donor.

PubMed

Datta, Sibnarayan; Banerjee, Arup; Chandra, Partha K; Chakraborty, Subhasis; Basu, Subir Kumar; Chakravarty, Runu

2007-11-01

In blood donors, HBV infection is detected by the presence of serum hepatitis B surface antigen (HBsAg). However, some mutations in the surface gene region may result in altered or truncated HBsAg that can escape from immunoassay-based diagnosis. Such diagnostic escape mutants pose a potential risk for blood transfusion services. In the present study, we report a blood donor seronegative for HBsAg and antiHBc, but positive for antiHBs who was HBV DNA positive by PCR. Sequencing of the HBsAg gene revealed presence of a point mutation (T-A) at 207th nucleotide of the HBsAg ORF, which resulted in a premature stop codon at position 69. This results in a truncated HBsAg gene lacking the entire 'a' determinant region. However, follow-up of the donor after 2 years revealed clearance of HBV DNA from the serum. The case illustrates an unusual mutation, which causes HBsAg negativity. The finding emphasizes the importance of molecular assays in reducing the possibility of HBV transmission through blood transfusion. However, developing more sensitive serological assays, capable of detecting HBV mutants, is an alternative to expensive and complex amplification-based assays for developing countries.

On the nature of citrate-derived surface species on Ag nanoparticles: Insights from X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Mikhlin, Yuri L.; Vorobyev, Sergey A.; Saikova, Svetlana V.; Vishnyakova, Elena A.; Romanchenko, Alexander S.; Zharkov, Sergey M.; Larichev, Yurii V.

2018-01-01

Citrate is an important stabilizing, reducing, and complexing reagent in the wet chemical synthesis of nanoparticles of silver and other metals, however, the exact nature of adsorbates, and its mechanism of action are still uncertain. Here, we applied X-ray photoelectron spectroscopy, soft X-ray absorption near-edge spectroscopy, and other techniques in order to determine the surface composition and to specify the citrate-related species at Ag nanoparticles immobilized from the dense hydrosol prepared using room-temperature reduction of aqueous Ag+ ions with ferrous ions and citrate as stabilizer (Carey Lea method). It was found that, contrary to the common view, the species adsorbed on the Ag nanoparticles are, in large part, products of citrate decomposition comprising an alcohol group and one or two carboxylate bound to the surface Ag, and minor unbound carboxylate group; these may also be mixtures of citrate with lower molecular weight anions. No ketone groups were specified, and very minor surface Ag(I) and Fe (mainly, ferric oxyhydroxides) species were detected. Moreover, the adsorbates were different at AgNPs having various size and shape. The relation between the capping and the particle growth, colloidal stability of the high-concentration sol and properties of AgNPs is briefly considered.

Green Silver Nanoparticles Based Dual Sensor for Toxic Hg (II) Ions.

PubMed

Sebastian, Maria; Aravind, Archana; Mathew, Beena

2018-06-11

The present study focuses on the utilization of green silver nanoparticles as they are more preferred for sensing applications due to their environment friendly nature. We have examined the optical and electrochemical sensing behavior of silver nanoparticles from Agaricus Bispores (AgNP-AB) towards Hg(II) ions. AgNP-AB was prepared by microwave reactor. The synthesized AgNPs have been used for the sensing of Hg(II) ions without the use of modifiers or further sophisticated instrumentation. The synthesized nanoparticles were successfully characterized by different techniques. AgNP-AB leads to aggregation with addition of Hg(II) ions in aqueous medium and developed a color change from brown to black which leads to the formation of AgNP-AB-Hg(II) complex. Moreover, the metal sensing ability of AgNPs has been explored using electrochemical studies. AgNP-AB modified platinum electrode (AgNP-AB/PE) was developed for the fast sensing of toxic Hg(II) ions. The sensor exhibits good limit of detection at 2.1x10-6M. The sensitivity of AgNP-AB/PE towards Hg(II) ion was analyzed with various metal ions. The sensing skill of developed system was successfully checked with real water sample from Vembanade Lake, Kumarakom, Kerala. The silver nanoparticles from Agaricus Bispoes are highly versatile and promising for different environmental applications. © 2018 IOP Publishing Ltd.

Multifrequency electron paramagnetic resonance and electron-nuclear double-resonance studies of photo-hole processes in AgBr and AgCl emulsion grains

NASA Astrophysics Data System (ADS)

Eachus, R. S.; Pawlik, Th D.; Baetzold, R. C.

2000-10-01

By using a combination of multifrequency EPR spectroscopy, ENDOR spectroscopy and calculations of structure and energy, the reactivities of photo-generated holes in microcrystalline AgBr and AgCl dispersions (photographic emulsions) have been followed in detail. Progress has been facilitated by the use of both gelatin and polyvinyl alcohol (PVA) as peptizers. The initial trapped hole centres produced by band-gap excitation have been identified. In AgBr, this species is [(Br4)3-.V], a neutral complex formed from hole trapping by the four nearest neighbours of a surface Ag+ vacancy (=V). [(Br4)3-.V] reacts with gelatin to produce a transient organic radical at the grain's surface. It does not, however, react with PVA. The formation of the oxidized gelatin radical might involve atomic bromine as an intermediate. In AgCl, the well-known self-trapped hole centre (AgCl6)4- is the initial hole species. The hole diffuses by an electron exchange process until it is trapped by a silver ion on the grain's surface or within its penultimate layer of lattice ions. It is subsequently released from this Ag2+ site to be retrapped at a centre containing four equivalent Cl- ions. The precise identity of this defect has yet to be determined, but its decay also results in the oxidation of gelatin.

(C{H3})3N\\cdot\\cdot\\cdotAgI AND H3N\\cdot\\cdot\\cdotAgI STUDIED BY BROADBAND ROTATIONAL SPECTROSCOPY AND AB INITIO CALCULATIONS

NASA Astrophysics Data System (ADS)

Bittner, Dror M.; Zaleski, Daniel P.; Stephens, Susanna L.; Walker, Nick; Legon, Anthony

2015-06-01

The pure rotational spectra of 8 isotopologues of H3N\\cdot\\cdot\\cdotAgI and 6 isotopologues of (C{H3})3N\\cdot\\cdot\\cdotAgI were measured in a chirped pulse Fourier-transform microwave spectrometer. The complexes were synthesized in a molecular beam from a gas sample containing H3N or (C{H3})3N and CF3I precursors diluted in argon. Laser ablation was used to introduce silver atoms to the gas phase. The rotational constant B0, centrifugal distortion constants DJ and DJK, and the nuclear quadrupole coupling constant χaa(I) have been determined for (C{H3})314/15N\\cdot\\cdot\\cdot107/109AgI, (C{D3})3N\\cdot\\cdot\\cdot107/109AgI, H314/15N\\cdot\\cdot\\cdot107/109AgI and D3N\\cdot\\cdot\\cdot107/109AgI by fitting the measured transitions to a symmetric top Hamiltonian. The spectroscopic constants (B0+ C0), ΔJ and χaa(I) have been determined for D2HN\\cdot\\cdot\\cdot107/109AgI through fits that employed a Hamiltonian appropriate for a very near prolate asymmetric rotor. Partial effective (r0) and substitution (rs) structures have been determined.

Antibacterial activity and cytotoxicity of multi-walled carbon nanotubes decorated with silver nanoparticles

PubMed Central

Seo, Youngmin; Hwang, Jangsun; Kim, Jieun; Jeong, Yoon; Hwang, Mintai P; Choi, Jonghoon

2014-01-01

Recently, various nanoscale materials, including silver (Ag) nanoparticles, have been actively studied for their capacity to effectively prevent bacterial growth. A critical challenge is to enhance the antibacterial properties of nanomaterials while maintaining their biocompatibility. The conjugation of multiple nanomaterials with different dimensions, such as spherical nanoparticles and high-aspect-ratio nanotubes, may increase the target-specific antibacterial capacity of the consequent nanostructure while retaining an optimal biocompatibility. In this study, multi-walled carbon nanotubes (MWCNTs) were treated with a mixture of acids and decorated with Ag nanoparticles via a chemical reduction of Ag cations by ethanol solution. The synthesized Ag-MWCNT complexes were characterized by transmission electron microscopy, X-ray diffractometry, and energy-dispersive X-ray spectroscopy. The antibacterial function of Ag-MWCNTs was evaluated against Methylobacterium spp. and Sphingomonas spp. In addition, the biocompatibility of Ag-MWCNTs was evaluated using both mouse liver hepatocytes (AML 12) and human peripheral blood mononuclear cells. Finally, we determined the minimum amount of Ag-MWCNTs required for a biocompatible yet effective antibacterial treatment modality. We report that 30 μg/mL of Ag-MWCNTs confers antibacterial functionality while maintaining minimal cytotoxicity toward both human and animal cells. The results reported herein would be beneficial for researchers interested in the efficient preparation of hybrid nanostructures and in determining the minimum amount of Ag-MWCNTs necessary to effectively hinder the growth of bacteria. PMID:25336943

Plasmon-induced absorption of blind chlorophylls in photosynthetic proteins assembled on silver nanowires.

PubMed

Szalkowski, Marcin; Janna Olmos, Julian David; Buczyńska, Dorota; Maćkowski, Sebastian; Kowalska, Dorota; Kargul, Joanna

2017-07-27

We demonstrate that controlled assembly of eukaryotic photosystem I with its associated light harvesting antenna complex (PSI-LHCI) on plasmonically active silver nanowires (AgNWs) substantially improves the optical functionality of such a novel biohybrid nanostructure. By comparing fluorescence intensities measured for PSI-LHCI complex randomly oriented on AgNWs and the results obtained for the PSI-LHCI/cytochrome c 553 (cyt c 553 ) bioconjugate with AgNWs we conclude that the specific binding of photosynthetic complexes with defined uniform orientation yields selective excitation of a pool of chlorophyll (Chl) molecules that are otherwise almost non-absorbing. This is remarkable, as this study shows for the first time that plasmonic excitations in metallic nanostructures can not only be used to enhance native absorption of photosynthetic pigments, but also - by employing cyt c 553 as the conjugation cofactor - to activate the specific Chl pools as the absorbing sites only when the uniform and well-defined orientation of PSI-LHCI with respect to plasmonic nanostructures is achieved. As absorption of PSI alone is comparatively low, our approach lends itself as an innovative approach to outperform the reported-to-date biohybrid devices with respect to solar energy conversion.

Core-Shell Coating Silicon Anode Interfaces with Coordination Complex for Stable Lithium-Ion Batteries.

PubMed

Zhou, Jinqiu; Qian, Tao; Wang, Mengfan; Xu, Na; Zhang, Qi; Li, Qun; Yan, Chenglin

2016-03-02

In situ core-shell coating was used to improve the electrochemical performance of Si-based anodes with polypyrrole-Fe coordination complex. The vast functional groups in the organometallic coordination complex easily formed hydrogen bonds when in situ modifying commercial Si nanoparticles. The incorporation of polypyrrole-Fe resulted in the conformal conductive coating surrounding each Si nanoparticle, not only providing good electrical connection to the particles but also promoting the formation of a stable solid-electrolyte-interface layer on the Si electrode surface, enhancing the cycling properties. As an anode material for Li-ion batteries, modified silicon powders exhibited high reversible capacity (3567 mAh/g at 0.3 A/g), good rate property (549.12 mAh/g at 12 A/g), and excellent cycling performance (reversible capacity of 1500 mAh/g after 800 cycles at 1.2 A/g). The constructed novel concept of core-shell coating Si particles presented a promising route for facile and large-scale production of Si-based anodes for extremely durable Li-ion batteries, which provided a wide range of applications in the field of energy storage of the renewable energy derived from the solar energy, hydropower, tidal energy, and geothermal heat.

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

Yokosawa, A.

Spin physics activities at medium and high energies became significantly active when polarized targets and polarized beams became accessible for hadron-hadron scattering experiments. My overview of spin physics will be inclined to the study of strong interaction using facilities at Argonne ZGS, Brookhaven AGS (including RHIC), CERN, Fermilab, LAMPF, an SATURNE. In 1960 accelerator physicists had already been convinced that the ZGS could be unique in accelerating a polarized beam; polarized beams were being accelerated through linear accelerators elsewhere at that time. However, there was much concern about going ahead with the construction of a polarized beam because (i) themore » source intensity was not high enough to accelerate in the accelerator, (ii) the use of the accelerator would be limited to only polarized-beam physics, that is, proton-proton interaction, and (iii) p-p elastic scattering was not the most popular topic in high-energy physics. In fact, within spin physics, [pi]-nucleon physics looked attractive, since the determination of spin and parity of possible [pi]p resonances attracted much attention. To proceed we needed more data beside total cross sections and elastic differential cross sections; measurements of polarization and other parameters were urgently needed. Polarization measurements had traditionally been performed by analyzing the spin of recoil protons. The drawbacks of this technique are: (i) it involves double scattering, resulting in poor accuracy of the data, and (ii) a carbon analyzer can only be used for a limited region of energy.« less

Oxidation of free-standing and supported borophene

NASA Astrophysics Data System (ADS)

Alvarez-Quiceno, J. C.; Miwa, R. H.; Dalpian, G. M.; Fazzio, A.

2017-06-01

Crystalline 2D boron sheets, known as borophene, are the most recently-discovered type of 2D materials, and very little is known about them. Different configurations of borophene have been reported stable when grown on Ag(1 1 1) surface under well controlled conditions. One of this configurations is partially oxidized while the other one remains quite inert to oxidation when exposed to ambient conditions. In this work, the oxidation process of the free-standing and Ag(1 1 1)-supported borophene is modeled using first-principles calculations based on density functional theory (DFT). On the free-standing case, the oxygen molecule may go through a triplet to singlet transition, followed by a barrierless oxidation process. This transition is not observed upon the presence of the Ag(1 1 1) surface, what accelerates the oxidation process. We also propose that the different structures of borophene reported in the literature can be understood by this oxidation process. Oxidation of the buckled structure could induce the planar structure with an ordered distribution of vacancies.

Tracking the Fate of Surface Plasmon Resonance-Generated Hot Electrons by In Situ SERS Surveying of Catalyzed Reaction.

PubMed

Liu, Rui; He, Zuoliang; Sun, Jiefang; Liu, Jingfu; Jiang, Guibin

2016-12-01

Plasmonic catalysis is an emerging process that utilizes surface plasmon resonance (SPR) process to harnesses solar energy for the promotion of catalyzed reactions. In most cases, SPR generated hot electrons (HEs) play an indispensable role in this solar-chemical energy shift process. Therefore, understanding the effectiveness of the HEs in promoting chemical reactions, and identifying the key factors that contribute to this utilization efficiency is of profound importance. Herein, the authors outline an in situ surface enhanced Raman spectroscopy protocol to track the fate of HEs. This is based on the unheeded HEs-acceleration nature of the p-nitirothiophenol hydrogenation reaction. By this way, the authors discover that unlike Au@Pd nanostructures which experience a 20-fold increase in rate constant, HEs primary leak to surrounding H + /O species through Ag pinholes in Ag@Pd. This work sheds light on why Ag is seldom employed as a plasmonic cocatalyst, and provides a new viewpoint to design plasmonic nanocatalysts with efficient light utilization. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Failure of the Hume-Rothery stabilization mechanism in the Ag(5)Li(8) gamma-brass studied by first-principles FLAPW electronic structure calculations.

PubMed

Mizutani, U; Asahi, R; Sato, H; Noritake, T; Takeuchi, T

2008-07-09

The first-principles FLAPW (full potential linearized augmented plane wave) electronic structure calculations were performed for the Ag(5)Li(8) gamma-brass, which contains 52 atoms in a unit cell and has been known for many years as one of the most structurally complex alloy phases. The calculations were also made for its neighboring phase AgLi B2 compound. The main objective in the present work is to examine if the Ag(5)Li(8) gamma-brass is stabilized at the particular electrons per atom ratio e/a = 21/13 in the same way as some other gamma-brasses like Cu(5)Zn(8) and Cu(9)Al(4), obeying the Hume-Rothery electron concentration rule. For this purpose, the e/a value for the Ag(5)Li(8) gamma-brass as well as the AgLi B2 compound was first determined by means of the FLAPW-Fourier method we have developed. It proved that both the gamma-brass and the B2 compound possess an e/a value equal to unity instead of 21/13. Moreover, we could demonstrate why the Hume-Rothery stabilization mechanism fails for the Ag(5)Li(8) gamma-brass and proposed a new stability mechanism, in which the unique gamma-brass structure can effectively lower the band-structure energy by forming heavily populated bonding states near the bottom of the Ag-4d band.

Evaluation of Aminoglycoside and Carbapenem Resistance in a Collection of Drug-Resistant Pseudomonas aeruginosa Clinical Isolates.

PubMed

Holbrook, Selina Y L; Garneau-Tsodikova, Sylvie

2017-12-20

Pseudomonas aeruginosa, a Gram-negative bacterium, is a member of the ESKAPE pathogens and one of the leading causes of healthcare-associated infections worldwide. Aminoglycosides (AGs) are recognized for their efficacy against P. aeruginosa. The most common resistance mechanism against AGs is the acquisition of AG-modifying enzymes (AMEs) by the bacteria, including AG N-acetyltransferases (AACs), AG O-phosphotransferases (APHs), and AG O-nucleotidyltransferases (ANTs). In this study, we obtained 122 multidrug-resistant P. aeruginosa clinical isolates and evaluated the antibacterial effects of six AGs and two carbapenems alone against all clinical isolates, and in combination against eight selected strains. We further probed for four representatives of the most common AME genes [aac(6')-Ib, aac(3)-IV, ant(2")-Ia, and aph(3')-Ia] by polymerase chain reaction (PCR) and compared the AME patterns of these 122 clinical isolates to their antibiotic resistance profile. Among the diverse antibiotics resistance profile displayed by these clinical isolates, we found correlations between the resistance to various AGs as well as between the resistance to one AG and the resistance to carbapenems. PCR results revealed that the presence of aac(6')-Ib renders these isolates more resistant to a variety of antibiotics. The correlation between resistance to various AGs and carbapenems partially reflects the complex resistance strategies adapted in these pathogens and encourages the development of strategic treatment for each P. aeruginosa infection by considering the genetic information of each isolated bacteria.

Mechanism of light-dependent biosynthesis of silver nanoparticles mediated by cell extract of Neochloris oleoabundans.

PubMed

Bao, Zeqing; Lan, Christopher Q

2018-06-04

This study investigated the role of chlorophyll and light in the biosynthesis of silver nanoparticles (AgNPs) using disrupted cell aqueous extract of Neochloris oleoabundans. It was found that, while increasing sonication time increased the percentage of disrupted cells and efficiency of aqueous cell extraction, over-sonication reduced AgNPs production. AgNPs biosynthesis required illumination of white, blue, or purple light while AgNPs formation was undetectable under dark condition or illumination of orange or red light, indicating only photons of high energy levels among the photosynthetic active radiations are capable of exciting the electrons of chlorophylls to a state that is sufficient for Ag + reduction. Chlorophylls were demonstrated to be an essential component mediating the reduction of Ag + and results of mass balance suggest that chlorophylls need to be recycled for the reaction to complete. The ultimate electron donor was hypothesized to be water, which supplemented electrons through water splitting catalyzed by photosynthetic enzyme complexes such as photosystem II. A hypothetical reaction mechanism is proposed for the light-dependent biosynthesis of AgNPs based on systematic experimental results and literature data for the first time. Copyright © 2018 Elsevier B.V. All rights reserved.

Effects of citrate-coated silver nanoparticles on interactions between soil bacteria and the major crop plant Zea mays

NASA Astrophysics Data System (ADS)

Doody, Michael; Bais, Harsh; Jin, Yan

2014-05-01

The increasing use of silver nanoparticles (AgNPs) in commercial antimicrobial products presents an opportunity for increased environmental exposures. While the behavior of AgNPs in surface waters is becoming increasingly understood, little research has been conducted on the effects of these, or any nanoparticles, on soil-dwelling bacteria and major crop plants. Because of the importance of soil bacteria to the overall health of natural and agricultural soils, it is necessary to better understand how AgNPs interact with common bacterial species such as Bacillus subtilis and Escherichia coli. It is further necessary to quantify the effect of AgNPs on major crop plants, including Zea mays, a staple crop for much of the world. Finally, research is needed on how complex plant-microbe interactions that originate in the rhizosphere may be disrupted by AgNPs. Our preliminary data show highly statistically significant growth inhibition near 30% for both species of bacteria exposed to 1.0 mg L-1 citrate-coated AgNPs (c-AgNPs). Growth curves compiled from absorbance data show a similar dose-response for both species. Treatment with aqueous Ag as AgNO3 slightly inhibits E. coli (90 ± 5 %), but enhances growth of B. subtilis to 127 ± 23% of control. These results indicate that toxicity may be related to specific nano-scale properties of the c-AgNPs. On-going experiments measure potential growth inhibition, root development and morphology of Z. mays exposed to c-AgNPs, and resulting changes in plant-microbe interactions.

Detection of silver nanoparticles in seawater at ppb levels using UV-visible spectrophotometry with long path cells.

PubMed

Lodeiro, Pablo; Achterberg, Eric P; El-Shahawi, Mohammad S

2017-03-01

Silver nanoparticles (AgNPs) are emerging contaminants that are difficult to detect in natural waters. UV-visible spectrophotometry is a simple technique that allows detection of AgNPs through analysis of their characteristic surface plasmon resonance band. The detection limit for nanoparticles using up to 10cm path length cuvettes with UV-visible spectrophotometry is in the 0.1-10ppm range. This detection limit is insufficiently low to observe AgNPs in natural environments. Here we show how the use of capillary cells with an optical path length up to 200cm, forms an excellent technique for rapid detection and quantification of non-aggregated AgNPs at ppb concentrations in complex natural matrices such as seawater. Copyright © 2016 Elsevier B.V. All rights reserved.

Current-voltage characteristics of organic semiconductors: Interfacial control between organic layers and electrodes

NASA Astrophysics Data System (ADS)

Kondo, Takeshi

2007-12-01

Current-voltage (I-V) characteristics of organic molecular glasses and solution processable materials embedded between two electrodes were studied to find materials possessing high charge-carrier mobilities and to design organic memory devices. The comparison studies between TOF, FET and SCLC measurements confirm the validity of using analyses of I-V characteristics to determine the mobility of organic semiconductors. Hexaazatrinaphthylene derivatives tri-substituted by electron withdrawing groups were characterized as potential electron transporting molecular glasses. The presence of two isomers has important implications for film morphology and effective mobility. The statistical isomer mixture of hexaazatrinaphthylene derivatized with pentafluoro-phenylmethyl ester is able to form amorphous films, and electron mobilities with the range of 10--2 cm2/Vs are observed in their I-V characteristics. Single-layer organic memory devices consisting of a polymer layer embedded between an Al electrode and ITO modified with Ag nanodots (Ag-NDs) prepared by a solution-based surface assembly demonstrated a potential capability as nonvolatile organic memory device with high ON/OFF switching ratios of 10 4. This level of performance could be achieved by modifying the ITO electrodes with some Ag-NDs that act as trapping sites, reducing the current in the OFF state. Based upon the observed electrical characteristics, the currents of the low-resistance state can be attributed to a tunneling through low-resistance pathways of metal particles originating from the metal top electrode in the organic layer and that the high-resistance state is controlled by charge trapping by the metal particles including Ag-NDs. In an alternative approach, complex films of AgNO3: hexaazatrinaphthylene derivatives were studied as the active layers for all-solution processed and air-stable organic memory devices. Rewritable memory effects were observed in the devices comprised of a thin polymer dielectric layer deposited on the bottom electrode, the complex film, and a conducting polymer film as the top electrode. The electrical characteristics indicate that the accumulation of Ag+ ions at the interface of the complex film and the top electrode may contribute to the switching effect.

Cobalt dipicolinate complexes with nicotinamide and isonicotinamide ligands: Syntheses, crystal structures, spectroscopic, thermal and voltammetric studies

NASA Astrophysics Data System (ADS)

Uçar, İbrahim; Bulut, Ahmet; Karadağ, Ahmet; Kazak, Canan

2007-06-01

Two new dipicolinate complexes of cobalt, [Co(dpc)(na)(H 2O) 2]·H 2O ( 1) and [Co(dpc)(ina)(H 2O) 2] ( 2) [dpc is dipicolinate or pyridine-2,6-dicarboxylate, na is nicotinamide and ina is isonicotinamide], have been prepared and characterized by thermal analysis, IR spectroscopy and X-ray diffraction techniques. The complex ( 1) crystallizes in triclinic system, whereas the complex ( 2) crystallizes in monoclinic system. The Co(II) ion in both complexes is bonded to dpc ligand through pyridine N atom together with one O atom of each carboxylate group, two aqua ligands and N pyridine atom of na ( 1) or ina ( 2), forming the distorted octahedral geometry. The complex molecules ( 1) and ( 2) are connected via N sbnd H⋯O and O sbnd H⋯O hydrogen bonds. The voltammetric behaviour of complexes ( 1) and ( 2) was also investigated in DMSO (dimethylsulfoxide) solution by cyclic voltammetry using n-Bu 4NClO 4 supporting electrolyte. The complexes exhibit only metal centered electroactivity in the potential ±1.25 V versus Ag/AgCl reference electrode.

Baseline characteristics of HIV & hepatitis B virus (HIV/HBV) co-infected patients from Kolkata, India.

PubMed

Sarkar, Jayeeta; Saha, Debraj; Bandyopadhyay, Bhaswati; Saha, Bibhuti; Kedia, Deepika; Guha Mazumder, D N; Chakravarty, Runu; Guha, Subhasish Kamal

2016-05-01

Hepatitis B virus (HBV) and HIV co-infection has variable prevalence worldwide. In comparison to HBV mono-infection, the course of chronic HBV infection is accelerated in HIV/HBV co-infected patients. the present study was carried out to analyse the baseline characteristics (clinical, biochemical, serological and virological) of treatment naïve HIV/HBV co-infected and HIV mono-infected patients. Between July 2011 and January 2013, a total number of 1331 HIV-seropositive treatment naïve individuals, enrolled in the ART Centre of Calcutta School of Tropical Medicine, Kolkata, India, were screened for hepatitis B surface antigen (HBsAg). A total of 1253 HIV mono-infected and 78 HIV/HBV co-infected patients were characterized. The co-infected patients were evaluated for HBeAg and anti-HBe antibody by ELISA. HIV RNA was quantified for all co-infected patients. HBV DNA was detected and quantified by real time-PCR amplification followed by HBV genotype determination. HIV/HBV co-infected patients had proportionately more advanced HIV disease (WHO clinical stage 3 and 4) than HIV mono-infected individuals (37.1 vs. 19.9%). The co-infected patients had significantly higher serum bilirubin, alanine aminotransferase (ALT), alkaline phosphatase and ALT/platelet ratio index (APRI). CD4 count was non-significantly lower in co-infected patients. Majority (61.5%) were HBeAg positive with higher HIV RNA (P<0.05), HBV DNA (p<0.001) and APRI (p<0.05) compared to those who were HBeAg negative. HBV/D was the predominant genotype (73.2%) and D2 (43.7%) was the commonest subgenotype. HIV/HBV co-infected patients had significantly higher serum bilirubin, ALT, alkaline phosphatase and lower platelet count. HBeAg positive co-infected patients had higher HIV RNA and HBV DNA compared to HBeAg negative co-infected patients. Prior to initiation of antiretroviral treatment (ART) all patients should be screened for HBsAg to initiate appropriate ART regimen.

The Raman and SERS spectra of indigo and indigo-Ag2 complex: DFT calculation and comparison with experiment.

PubMed

Ricci, Marilena; Lofrumento, Cristiana; Becucci, Maurizio; Castellucci, Emilio M

2018-01-05

Using time-dependent density functional theory in conjunction with B3LYP functional and LANL2DZ/6-31+g(d,p) basis sets, static and pre-resonance Raman spectra of the indigo-Ag 2 complex have been calculated. Structure optimization, excitation energies and pre-resonance Raman spectra of the indigo molecule have been obtained at the same level of theory. The available experimental Raman spectra at 1064, 785 and 514nm and the SERS spectra at 785 and 514nm have been well reproduced by the calculation. Experimental SERS spectra are confronted with the calculated pre-resonance Raman spectra obtained for the indigo-Ag 2 complex. The Raman activities calculated under the infinite lifetime approximation show a strong dependence upon the proximity to the energy and the oscillator strength of the excitation electronic transition. The comparison of the integrated EFs for indigo and indigo-Ag 2 calculated Raman spectra, gave some hints as to the enhancement mechanisms acting for the different excitation wavelengths. Whereas for excitation at a wavelength corresponding to 785nm, the enhancement mechanism for the Raman spectrum of the metal complex seems the chemical one, the strong increment (ten times) of the integrated EF of the Raman spectra of the complex in the case of 514nm excitation, suggests the onset of other enhancement mechanisms. Assuming that intra-cluster transitions with high oscillator strength can be thought of as to mimic surface plasmons excitations, we suggest the onset of the electromagnetic mechanisms (EM) as the origin of the Raman spectrum enhancement. Nevertheless, other enhancement effects cannot be ruled out, as a new molecular transition gains strength in the proximity of the excitation wavelength, as a consequence of the symmetry lowering of the molecule in the complex. A large variation across vibrational modes, by a factor of at least 10 4 , was found for the EFs. This large variation in the EFs can indicate that B-term Herzberg-Teller scattering, due to metal and/or charge transfer states, can feed intensity to the inactive (in the molecule) and/or non totally symmetric modes. Copyright © 2017 Elsevier B.V. All rights reserved.

The Raman and SERS spectra of indigo and indigo-Ag2 complex: DFT calculation and comparison with experiment

NASA Astrophysics Data System (ADS)

Ricci, Marilena; Lofrumento, Cristiana; Becucci, Maurizio; Castellucci, Emilio M.

2018-01-01

Using time-dependent density functional theory in conjunction with B3LYP functional and LANL2DZ/6-31+g(d,p) basis sets, static and pre-resonance Raman spectra of the indigo-Ag2 complex have been calculated. Structure optimization, excitation energies and pre-resonance Raman spectra of the indigo molecule have been obtained at the same level of theory. The available experimental Raman spectra at 1064, 785 and 514 nm and the SERS spectra at 785 and 514 nm have been well reproduced by the calculation. Experimental SERS spectra are confronted with the calculated pre-resonance Raman spectra obtained for the indigo-Ag2 complex. The Raman activities calculated under the infinite lifetime approximation show a strong dependence upon the proximity to the energy and the oscillator strength of the excitation electronic transition. The comparison of the integrated EFs for indigo and indigo-Ag2 calculated Raman spectra, gave some hints as to the enhancement mechanisms acting for the different excitation wavelengths. Whereas for excitation at a wavelength corresponding to 785 nm, the enhancement mechanism for the Raman spectrum of the metal complex seems the chemical one, the strong increment (ten times) of the integrated EF of the Raman spectra of the complex in the case of 514 nm excitation, suggests the onset of other enhancement mechanisms. Assuming that intra-cluster transitions with high oscillator strength can be thought of as to mimic surface plasmons excitations, we suggest the onset of the electromagnetic mechanisms (EM) as the origin of the Raman spectrum enhancement. Nevertheless, other enhancement effects cannot be ruled out, as a new molecular transition gains strength in the proximity of the excitation wavelength, as a consequence of the symmetry lowering of the molecule in the complex. A large variation across vibrational modes, by a factor of at least 104, was found for the EFs. This large variation in the EFs can indicate that B-term Herzberg-Teller scattering, due to metal and/or charge transfer states, can feed intensity to the inactive (in the molecule) and/or non totally symmetric modes.

Detection and Quantification of Silver Nanoparticles at Environmentally Relevant Concentrations Using Asymmetric Flow Field??Flow Fractionation Online with Single Particle Inductively Coupled Plasma Mass Spectrometry

EPA Pesticide Factsheets

The presence of silver nanoparticles (AgNPs) in aquatic environments could potentially cause adverse impacts on ecosystems and human health. However, current understanding of the environmental fate and transport of AgNPs is still limited because their properties in complex environmental samples cannot be accurately determined. In this study, the feasibility of using asymmetric flow field-flow fractionation (AF4) connected online with single particle inductively coupled plasma mass spectrometry (spICPMS) to detect and quantify AgNPs at environmentally relevant concentrations was investigated. The AF4 channel had a thickness of 350 00b5m and its accumulation wall was a 10 kDa regenerated cellulose membrane. A 0.02 % FL-70 surfactant solution was used as an AF4 carrier. With 1.2 mL/min AF4 cross flow rate, 1.5 mL/min AF4 channel flow rate, and 5 ms spICPMS dwell time, the AF4??spICPMS can detect and quantify 40 ?? 80 nm AgNPs, as well as Ag-SiO2 nanoparticles (51.0 nm diameter Ag core and 21.6 nm SiO2 shell), with good recovery within 30 min. This system was not only effective in differentiating and quantifying different types of AgNPs with similar hydrodynamic diameters, such as in mixtures containing Ag-SiO2 core-shell nanoparticles and 40 ?? 80 nm AgNPs, but also suitable for differentiating between 40 nm AgNPs and elevated dissolved Ag content. The study results indicate that AF4??spICPMS is capable of detecting and quantifying AgNPs and other engineered

Silver nanoparticles and dissolved silver activate contrasting immune responses and stress-induced heat shock protein expression in sea urchin.

PubMed

Magesky, Adriano; de Oliveira Ribeiro, Ciro A; Beaulieu, Lucie; Pelletier, Émilien

2017-07-01

Using immune cells of sea urchin Strongylocentrotus droebachiensis in early development as a model, the cellular protective mechanisms against ionic and poly(allylamine)-coated silver nanoparticle (AgNPs; 14 ± 6 nm) treatments at 100 μg L -1 were investigated. Oxidative stress, heat shock protein expression, and pigment production by spherulocytes were determined as well as AgNP translocation pathways and their multiple effects on circulating coelomocytes. Sea urchins showed an increasing resilience to Ag over time because ionic Ag is accumulated in a steady way, although nanoAg levels dropped between 48 h and 96 h. A clotting reaction emerged on tissues injured by dissolved Ag (present as chloro-complexes in seawater) between 12 h and 48 h. Silver contamination and nutritional state influenced the production of reactive oxygen species. After passing through coelomic sinuses and gut, AgNPs were found in coelomocytes. Inside blood vessels, apoptosis-like processes appeared in coelomocytes highly contaminated by poly(allylamine)-coated AgNPs. Increasing levels of Ag accumulated by urchins once exposed to AgNPs pointed to a Trojan-horse mechanism operating over 12-d exposure. However, under short-term treatments, physical interactions of poly(allylamine)-coated AgNPs with cell structures might be, at some point, predominant and responsible for the highest levels of stress-related proteins detected. The present study is the first report detailing nano-translocation in a marine organism and multiple mechanisms by which sea urchin cells can deal with toxic AgNPs. Environ Toxicol Chem 2017;36:1872-1886. © 2016 SETAC. © 2016 SETAC.

Mimetic Ag nanoparticle/Zn-based MOF nanocomposite (AgNPs@ZnMOF) capped with molecularly imprinted polymer for the selective detection of patulin.

PubMed

Bagheri, Nafiseh; Khataee, Alireza; Habibi, Biuck; Hassanzadeh, Javad

2018-03-01

Here, Ag nanoparticle/flake-like Zn-based MOF nanocomposite (AgNPs@ZnMOF) with great peroxidase-like activity was applied as an efficient support for molecularly imprinted polymer (MIP) and successfully used for selective determination of patulin. AgNPs@ZnMOF was simply synthesized by creating Ag nanoparticles (Ag NPs) inside the nano-pores of flake-like (Zn)MOF. The high surface area of MOF remarkably improved the catalytic activity of Ag NPs which was assessed by fluorometric, colorimetric and electrochemical techniques. Furthermore, it was observed that patulin could strangely reduce the catalytic activity of AgNPs@ZnMOF, probably due to its electron capturing features. This outcome was the motivation to design an assay for patulin detection. In order to make a selective interaction with patulin molecules, MIP layer was created on the surface of AgNPs@ZnMOF by co-polymerization reaction of 3-aminopropyl triethoxysilane (APTES) and tetraethyl orthosilicate (TEOS) monomers wherein patulin was applied as template agent. Combination between the selective identifying feature of MIP and outstanding peroxidase-like activity of novel AgNPs@ZnMOF nanocomposite as well as the sensitive fluorescence detection system was led to the design of a reliable probe for patulin. The prepared MIP-capped AgNPs@ZnMOF catalyzed the H 2 O 2 -terephthalic acid reaction which produced a high florescent product. In the presence of patulin, the fluorescence intensity was decreased proportional to its concentration in the range of 0.1-10µmolL -1 with a detection limit of 0.06µmolL -1 . The proposed method was able to selectively measure patulin in a complex media without significant interfering effects from analogue compounds. Copyright © 2017 Elsevier B.V. All rights reserved.

Red light emitting nano-PVP fibers that hybrid with Ag@SiO2@Eu(tta)3phen-NPs by electrostatic spinning method

NASA Astrophysics Data System (ADS)

Zhang, Xiaolin; Tang, Jianguo; Li, Haidong; Wang, Yao; Wang, Xinzhi; Wang, Yanxin; Huang, Linjun; Belfiore, Laurence A.

2018-04-01

This work demonstrated red light emitting nano-PVP fibers that incorporated with novel three-layer nanostructure of Ag@SiO2@Eu(tta)3phen nanoparticles (Ag@SiO2@Eu(tta)3phen-NPs), and the hybrid nano-PVP fibers were fabricated via a remarkably simple electrostatic spinning method. For Ag@SiO2@Eu(tta)3phen-NPs, the thickness of SiO2 is optimized to obtain the maximum luminescent intensity, as results, the optimized thickness of SiO2 is 20 nm. And the corresponding luminescent intensity (612 nm) of the Ag@SiO2@Eu(tta)3phen-NPs is enhanced up to 10 times compared with the pure Eu(tta)3phen complex, which indicates that with 20 nm SiO2 thickness, the localized surface plasmon resonance (LSPR) effect of Ag@SiO2 exhibits highest performance for enhancing luminescence. Moreover, the luminescent PVP fibers emit bright red light under the fluorescence microscope, which definitely confirms that the microenvironment provided by PVP polymer is absolutely suitable for the fluorescent composites.

Comparison of Ball-And-Racket Impact Force in Two-Handed Backhand Stroke Stances for Different-Skill-Level Tennis Players.

PubMed

Lo, Kuo-Cheng; Hsieh, Yung-Chun

2016-06-01

This study compared the kinetic roles of the upper extremities in racket impact force generation between the open stance (OS) and square stance (SS) for tennis players with different skill levels in two-handed backhand strokes. Twelve male tennis players were divided into an advanced group (AG) (L3-L2 skill level) and intermediate group (IG) (L7-L6 skill level), and their data were used in a three-dimensional kinetic analysis. Their motions were captured using 21 reflective markers attached to anatomic landmarks for two-handed backhand stroke motion data collection. During the acceleration phase, significant differences were not observed between both stances, but they were observed between the groups with different skill levels for the force of the upper extremities (p = 0.027). The joint forces were significantly lower in the AG than in the IG. Players performing the SS had significantly larger pronation and supination of the wrist joint moment than those in the OS (p = 0.032) during the acceleration phase, irrespective of the playing level. Higher internal rotation moment after impact was observed at each joint, particularly among young intermediate tennis players, regardless of their stance. The AG demonstrated a higher joint force and moment at every joint compared with the IG at impact. Moreover, the AG demonstrated superior stroke efficiency and effectively reduced joint moment after impact and sports injury. Key pointsAdvanced players, regardless of open stance or square stance, have larger joint force and moment at each joint before ball impact resulting in better stroke efficiency and reduced chance of injury.Intermediate players, regardless of stance, have higher internal rotation moment at each joint instead of larger joint force as compared to advanced players before ball impact. The higher internal rotation moment will induce higher joint impact force which makes the player injury-prone.Young intermediate tennis players may want to avoid excessive follow-through movement after ball impact to prevent injury in their early career.

Cytotoxicity and Physiological Effects of Silver Nanoparticles on Marine Invertebrates.

PubMed

Magesky, Adriano; Pelletier, Émilien

2018-01-01

Silver nanoparticles (AgNPs) incorporation in commercial products is increasing due to their remarkable physical and chemical properties and their low cost on the market. Silver has been known for a long time to be highly toxic to bacterial communities, aquatic organisms, and particularly to marine biota. Strong chloro-complexes dominate Ag speciation in seawater and facilitate its persistence in dissolved form. It has a great impact on marine organisms because low concentration of silver can lead to strong bioaccumulation, partly because the neutral silver chloro complex (AgCl 0 ) is highly bioavailable. Owing to the fact that estuaries and coastal areas are considered as the ultimate fate for AgNPs, the study of their toxic effects on marine invertebrates can reveal some environmental risks related to nanosilver exposure. In an attempt to reach this goal, many invertebrate taxa including mollusks, crustaceans, echinoderms and polychaetes have been used as biological models. The main findings related to AgNP toxicity and marine invertebrates are summarized hereafter. Some cellular mechanisms involving nano-internalization (cellular uptake, distribution and elimination), DNA damaging, antioxidant cellular defenses and protein expression are discussed. Physiological effects on early stage development, silver metabolic speciation, immune response, tissue damaging, anti-oxidant effects and nano-depuration are also described. Finally, we paid attention to some recent interesting findings using sea urchin developmental stages and their cells as models for nanotoxicity investigation. Cellular and physiological processes characterizing sea urchin development revealed new and multiple toxicity mechanisms of both soluble and nano forms of silver.

Latex-protein complexes from an acute phase recombinant antigen of Toxoplasma gondii for the diagnosis of recently acquired toxoplasmosis.

PubMed

Peretti, Leandro E; Gonzalez, Verónica D G; Marcipar, Iván S; Gugliotta, Luis M

2014-08-01

The synthesis and characterization of latex-protein complexes (LPC), from the acute phase recombinant antigen P35 (P35Ag) of Toxoplasma gondii and "core-shell" carboxylated or polystyrene (PS) latexes (of different sizes and charge densities) are considered, with the aim of producing immunoagglutination reagents able to detect recently acquired toxoplasmosis. Physical adsorption (PA) and chemical coupling (CC) of P35Ag onto latex particles at different pH were investigated. Greater amounts of adsorbed protein were obtained on PS latexes than on carboxylated latexes, indicating that hydrophobic forces govern the interactions between the protein and the particle surface. In the CC experiments, the highest amount of bound protein was obtained at pH 6, near the isoelectric point of the protein (IP=6.27). At this pH, it decreased both the repulsion between particle surface and protein, and the repulsion between neighboring molecules. The LPC were characterized and the antigenicity of the P35Ag protein coupled on the particles surface was evaluated by Enzyme-Linked ImmunoSorbent Assay (ELISA). Results from ELISA showed that the P35Ag coupled to the latex particles surface was not affected during the particles sensitization by PA and CC and the produced LPC were able to recognize specific anti-P35Ag antibodies present in the acute phase of the disease. Copyright © 2014 Elsevier B.V. All rights reserved.

Preliminary characterization of Thy-1.1 and Ag-B antigens from rat tissues solubilized in detergents

PubMed Central

Letarte-Muirhead, Michelle; Acton, Ronald T.; Williams, Alan F.

1974-01-01

1. A radioactive binding assay for Thy-1.1 alloantigen which functions in the presence of detergents was established by using glutaraldehyde-fixed thymocytes as target cells. Thy-1.1 activity in detergent extracts was then assayed by measuring inhibition of the binding assay. 2. Solubilization of Thy-1.1 from whole thymocytes, and their membranes by a large number of non-ionic detergents and deoxycholate was studied. In the same extracts Ag-B(4) histocompatibility antigenic activities were measured. With the exception of Nonidet P-40, the detergents did not affect the antigenicity of Thy-1.1, but only Lubrol-PX and deoxycholate gave effective solubilization as measured by activity remaining in the supernatant after centrifugation at 200000g for 40min. With Ag-B(4) antigen, Triton X-100, Triton X-67 and Nonidet P-40 gave effective solubilization as well as Lubrol-PX and deoxycholate. Solubilization of Thy-1.1 activity from leukaemia cells and a brain homogenate was also studied, but none of the non-ionic detergents gave satisfactory results with these tissues. 3. Extracts from thymocyte membranes were further examined by gel filtration and sucrose gradient centrifugation. The Thy-1.1 activity behaved as a single component in deoxycholate with a density similar to that of a globular protein, but in Lubrol-PX the antigen was contained in a low-density complex. In Lubrol-PX extracts Ag-B(4) was also found in aggregates not observed in deoxycholate. 4. The s20,w values for Thy-1.1 and Ag-B(4) antigens in deoxycholate were 2.4 and 4.4, and v̄ values were 0.70 and 0.75 respectively. The Stokes radius observed for Thy-1.1 was 3.1nm and for Ag-B(4) 5.3nm. By using these values the molecular weights for the antigen–detergent complexes were calculated to be 28000 for Thy-1.1 and 100000 for Ag-B(4). PMID:4219284

Significant contribution of subtype G to HIV-1 genetic complexity in Nigeria identified by a newly developed subtyping assay specific for subtype G and CRF02_AG

PubMed Central

Heipertz, Richard A.; Ayemoba, Ojor; Sanders-Buell, Eric; Poltavee, Kultida; Pham, Phuc; Kijak, Gustavo H.; Lei, Esther; Bose, Meera; Howell, Shana; O'Sullivan, Anne Marie; Bates, Adam; Cervenka, Taylor; Kuroiwa, Janelle; Akintunde, Akindiran; Ibezim, Onyekachukwu; Alabi, Abraham; Okoye, Obumneke; Manak, Mark; Malia, Jennifer; Peel, Sheila; Maisaka, Mohammed; Singer, Darrell; O’Connell, Robert J.; Robb, Merlin L.; Kim, Jerome H.; Michael, Nelson L.; Njoku, Ogbonnaya; Tovanabutra, Sodsai

2016-01-01

Abstract While abundant sequence information is available from human immunodeficiency virus type 1 (HIV-1) subtypes A, B, C and CRF01_AE for HIV-1 vaccine design, sequences from West Africa are less represented. We sought to augment our understanding of HIV-1 variants circulating in 6 Nigerian cities as a step to subsequent HIV-1 vaccine development. The G/CRF02_AG multi-region hybridization assay (MHA) was developed to differentiate subtype G, CRF02_AG and their recombinants from other subtypes based on 7 HIV-1 segments. Plasma from 224 HIV-1 infected volunteers enrolled in a cohort examining HIV-1 prevalence, risk factor, and subtype from Makurdi (30), Abuja (18), Enugu (11), Kaduna (12), Tafa (95), and Ojo/Lagos (58) was analyzed using MHA. HIV-1 genomes from 42 samples were sequenced to validate the MHA and fully explore the recombinant structure of G and CRF02_AG variants. The sensitivity and specificity of MHA varied between 73–100% and 90–100%, respectively. The subtype distribution as identified by MHA among 224 samples revealed 38% CRF02_AG, 28% G, and 26% G/CRF02_AG recombinants while 8% remained nontypeable strains. In envelope (env) gp120, 38.84% of the samples reacted to a G probe while 31.25% reacted to a CRF02 (subtype A) probe. Full genome characterization of 42 sequences revealed the complexity of Nigerian HIV-1 variants. CRF02_AG, subtype G, and their recombinants were the major circulating HIV-1 variants in 6 Nigerian cities. High proportions of samples reacted to a G probe in env gp120 confirms that subtype G infections are abundant and should be considered in strategies for global HIV-1 vaccine development. PMID:27512845

The Spallation Neutron Source accelerator system design

NASA Astrophysics Data System (ADS)

Henderson, S.; Abraham, W.; Aleksandrov, A.; Allen, C.; Alonso, J.; Anderson, D.; Arenius, D.; Arthur, T.; Assadi, S.; Ayers, J.; Bach, P.; Badea, V.; Battle, R.; Beebe-Wang, J.; Bergmann, B.; Bernardin, J.; Bhatia, T.; Billen, J.; Birke, T.; Bjorklund, E.; Blaskiewicz, M.; Blind, B.; Blokland, W.; Bookwalter, V.; Borovina, D.; Bowling, S.; Bradley, J.; Brantley, C.; Brennan, J.; Brodowski, J.; Brown, S.; Brown, R.; Bruce, D.; Bultman, N.; Cameron, P.; Campisi, I.; Casagrande, F.; Catalan-Lasheras, N.; Champion, M.; Champion, M.; Chen, Z.; Cheng, D.; Cho, Y.; Christensen, K.; Chu, C.; Cleaves, J.; Connolly, R.; Cote, T.; Cousineau, S.; Crandall, K.; Creel, J.; Crofford, M.; Cull, P.; Cutler, R.; Dabney, R.; Dalesio, L.; Daly, E.; Damm, R.; Danilov, V.; Davino, D.; Davis, K.; Dawson, C.; Day, L.; Deibele, C.; Delayen, J.; DeLong, J.; Demello, A.; DeVan, W.; Digennaro, R.; Dixon, K.; Dodson, G.; Doleans, M.; Doolittle, L.; Doss, J.; Drury, M.; Elliot, T.; Ellis, S.; Error, J.; Fazekas, J.; Fedotov, A.; Feng, P.; Fischer, J.; Fox, W.; Fuja, R.; Funk, W.; Galambos, J.; Ganni, V.; Garnett, R.; Geng, X.; Gentzlinger, R.; Giannella, M.; Gibson, P.; Gillis, R.; Gioia, J.; Gordon, J.; Gough, R.; Greer, J.; Gregory, W.; Gribble, R.; Grice, W.; Gurd, D.; Gurd, P.; Guthrie, A.; Hahn, H.; Hardek, T.; Hardekopf, R.; Harrison, J.; Hatfield, D.; He, P.; Hechler, M.; Heistermann, F.; Helus, S.; Hiatt, T.; Hicks, S.; Hill, J.; Hill, J.; Hoff, L.; Hoff, M.; Hogan, J.; Holding, M.; Holik, P.; Holmes, J.; Holtkamp, N.; Hovater, C.; Howell, M.; Hseuh, H.; Huhn, A.; Hunter, T.; Ilg, T.; Jackson, J.; Jain, A.; Jason, A.; Jeon, D.; Johnson, G.; Jones, A.; Joseph, S.; Justice, A.; Kang, Y.; Kasemir, K.; Keller, R.; Kersevan, R.; Kerstiens, D.; Kesselman, M.; Kim, S.; Kneisel, P.; Kravchuk, L.; Kuneli, T.; Kurennoy, S.; Kustom, R.; Kwon, S.; Ladd, P.; Lambiase, R.; Lee, Y. Y.; Leitner, M.; Leung, K.-N.; Lewis, S.; Liaw, C.; Lionberger, C.; Lo, C. C.; Long, C.; Ludewig, H.; Ludvig, J.; Luft, P.; Lynch, M.; Ma, H.; MacGill, R.; Macha, K.; Madre, B.; Mahler, G.; Mahoney, K.; Maines, J.; Mammosser, J.; Mann, T.; Marneris, I.; Marroquin, P.; Martineau, R.; Matsumoto, K.; McCarthy, M.; McChesney, C.; McGahern, W.; McGehee, P.; Meng, W.; Merz, B.; Meyer, R.; Meyer, R.; Miller, B.; Mitchell, R.; Mize, J.; Monroy, M.; Munro, J.; Murdoch, G.; Musson, J.; Nath, S.; Nelson, R.; Nelson, R.; O`Hara, J.; Olsen, D.; Oren, W.; Oshatz, D.; Owens, T.; Pai, C.; Papaphilippou, I.; Patterson, N.; Patterson, J.; Pearson, C.; Pelaia, T.; Pieck, M.; Piller, C.; Plawski, T.; Plum, M.; Pogge, J.; Power, J.; Powers, T.; Preble, J.; Prokop, M.; Pruyn, J.; Purcell, D.; Rank, J.; Raparia, D.; Ratti, A.; Reass, W.; Reece, K.; Rees, D.; Regan, A.; Regis, M.; Reijonen, J.; Rej, D.; Richards, D.; Richied, D.; Rode, C.; Rodriguez, W.; Rodriguez, M.; Rohlev, A.; Rose, C.; Roseberry, T.; Rowton, L.; Roybal, W.; Rust, K.; Salazer, G.; Sandberg, J.; Saunders, J.; Schenkel, T.; Schneider, W.; Schrage, D.; Schubert, J.; Severino, F.; Shafer, R.; Shea, T.; Shishlo, A.; Shoaee, H.; Sibley, C.; Sims, J.; Smee, S.; Smith, J.; Smith, K.; Spitz, R.; Staples, J.; Stein, P.; Stettler, M.; Stirbet, M.; Stockli, M.; Stone, W.; Stout, D.; Stovall, J.; Strelo, W.; Strong, H.; Sundelin, R.; Syversrud, D.; Szajbler, M.; Takeda, H.; Tallerico, P.; Tang, J.; Tanke, E.; Tepikian, S.; Thomae, R.; Thompson, D.; Thomson, D.; Thuot, M.; Treml, C.; Tsoupas, N.; Tuozzolo, J.; Tuzel, W.; Vassioutchenko, A.; Virostek, S.; Wallig, J.; Wanderer, P.; Wang, Y.; Wang, J. G.; Wangler, T.; Warren, D.; Wei, J.; Weiss, D.; Welton, R.; Weng, J.; Weng, W.-T.; Wezensky, M.; White, M.; Whitlatch, T.; Williams, D.; Williams, E.; Wilson, K.; Wiseman, M.; Wood, R.; Wright, P.; Wu, A.; Ybarrolaza, N.; Young, K.; Young, L.; Yourd, R.; Zachoszcz, A.; Zaltsman, A.; Zhang, S.; Zhang, W.; Zhang, Y.; Zhukov, A.

2014-11-01

The Spallation Neutron Source (SNS) was designed and constructed by a collaboration of six U.S. Department of Energy national laboratories. The SNS accelerator system consists of a 1 GeV linear accelerator and an accumulator ring providing 1.4 MW of proton beam power in microsecond-long beam pulses to a liquid mercury target for neutron production. The accelerator complex consists of a front-end negative hydrogen-ion injector system, an 87 MeV drift tube linear accelerator, a 186 MeV side-coupled linear accelerator, a 1 GeV superconducting linear accelerator, a 248-m circumference accumulator ring and associated beam transport lines. The accelerator complex is supported by ~100 high-power RF power systems, a 2 K cryogenic plant, ~400 DC and pulsed power supply systems, ~400 beam diagnostic devices and a distributed control system handling ~100,000 I/O signals. The beam dynamics design of the SNS accelerator is presented, as is the engineering design of the major accelerator subsystems.

Hydrodynamic chromatography coupled to single-particle ICP-MS for the simultaneous characterization of AgNPs and determination of dissolved Ag in plasma and blood of burn patients.

PubMed

Roman, Marco; Rigo, Chiara; Castillo-Michel, Hiram; Munivrana, Ivan; Vindigni, Vincenzo; Mičetić, Ivan; Benetti, Federico; Manodori, Laura; Cairns, Warren R L

2016-07-01

Silver nanoparticles (AgNPs) are increasingly used in medical devices as innovative antibacterial agents, but no data are currently available on their chemical transformations and fate in vivo in the human body, particularly on their potential to reach the circulatory system. To study the processes involving AgNPs in human plasma and blood, we developed an analytical method based on hydrodynamic chromatography (HDC) coupled to inductively coupled plasma mass spectrometry (ICP-MS) in single-particle detection mode. An innovative algorithm was implemented to deconvolute the signals of dissolved Ag and AgNPs and to extrapolate a multiparametric characterization of the particles in the same chromatogram. From a single injection, the method provides the concentration of dissolved Ag and the distribution of AgNPs in terms of hydrodynamic diameter, mass-derived diameter, number and mass concentration. This analytical approach is robust and suitable to study quantitatively the dynamics and kinetics of AgNPs in complex biological fluids, including processes such as agglomeration, dissolution and formation of protein coronas. The method was applied to study the transformations of AgNP standards and an AgNP-coated dressing in human plasma, supported by micro X-ray fluorescence (μXRF) and micro X-ray absorption near-edge spectroscopy (μXANES) speciation analysis and imaging, and to investigate, for the first time, the possible presence of AgNPs in the blood of three burn patients treated with the same dressing. Together with our previous studies, the results strongly support the hypothesis that the systemic mobilization of the metal after topical administration of AgNPs is driven by their dissolution in situ. Graphical Abstract Simplified scheme of the combined analytical approach adopted for studying the chemical dynamics of AgNPs in human plasma/blood.

Selective interaction of AGS3 with G-proteins and the influence of AGS3 on the activation state of G-proteins.

PubMed

Bernard, M L; Peterson, Y K; Chung, P; Jourdan, J; Lanier, S M

2001-01-12

AGS3 (activator of G-protein signaling 3) was isolated in a yeast-based functional screen for receptor-independent activators of heterotrimeric G-proteins. As an initial approach to define the role of AGS3 in mammalian signal processing, we defined the AGS3 subdomains involved in G-protein interaction, its selectivity for G-proteins, and its influence on the activation state of G-protein. Immunoblot analysis with AGS3 antisera indicated expression in rat brain, the neuronal-like cell lines PC12 and NG108-15, as well as the smooth muscle cell line DDT(1)-MF2. Immunofluorescence studies and confocal imaging indicated that AGS3 was predominantly cytoplasmic and enriched in microdomains of the cell. AGS3 coimmunoprecipitated with Galpha(i3) from cell and tissue lysates, indicating that a subpopulation of AGS3 and Galpha(i) exist as a complex in the cell. The coimmunoprecipitation of AGS3 and Galpha(i) was dependent upon the conformation of Galpha(i3) (GDP GTPgammaS (guanosine 5'-3-O-(thio)triphosphate)). The regions of AGS3 that bound Galpha(i) were localized to four amino acid repeats (G-protein regulatory motif (GPR)) in the carboxyl terminus (Pro(463)-Ser(650)), each of which were capable of binding Galpha(i). AGS3-GPR domains selectively interacted with Galpha(i) in tissue and cell lysates and with purified Galpha(i)/Galpha(t). Subsequent experiments with purified Galpha(i2) and Galpha(i3) indicated that the carboxyl-terminal region containing the four GPR motifs actually bound more than one Galpha(i) subunit at the same time. The AGS3-GPR domains effectively competed with Gbetagamma for binding to Galpha(t(GDP)) and blocked GTPgammaS binding to Galpha(i1). AGS3 and related proteins provide unexpected mechanisms for coordination of G-protein signaling pathways.

Energies and excited-state dynamics of 1Bu+, 1Bu- and 3Ag- states of carotenoids bound to LH2 antenna complexes from purple photosynthetic bacteria

NASA Astrophysics Data System (ADS)

Christiana, Rebecca; Miki, Takeshi; Kakitani, Yoshinori; Aoyagi, Shiho; Koyama, Yasushi; Limantara, Leenawaty

2009-10-01

Time-resolved pump-probe stimulated-emission and transient-absorption spectra were recorded after excitation with ˜30 fs pulses to the 1Bu+(0) and optically-forbidden diabatic levels of carotenoids, neurosporene, spheroidene and lycopene having n = 9-11 double bonds, bound to LH2 antenna complexes from Rhodobacter sphaeroides G1C, 2.4.1 and Rhodospirillum molischianum. The low-energy shift of stimulated emission from the covalent 1Bu-(0) and 3Ag-(0) levels slightly larger than that from the ionic 1Bu+(0) state suggests the polarization, whereas more efficient triplet generation suggests the twisting of the conjugated chain in Cars bound to the LH2 complexes, when compared to Cars free in solution.

Code comparison for accelerator design and analysis

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

Parsa, Z.

1988-01-01

We present a comparison between results obtained from standard accelerator physics codes used for the design and analysis of synchrotrons and storage rings, with programs SYNCH, MAD, HARMON, PATRICIA, PATPET, BETA, DIMAD, MARYLIE and RACE-TRACK. In our analysis we have considered 5 (various size) lattices with large and small angles including AGS Booster (10/degree/ bend), RHIC (2.24/degree/), SXLS, XLS (XUV ring with 45/degree/ bend) and X-RAY rings. The differences in the integration methods used and the treatment of the fringe fields in these codes could lead to different results. The inclusion of nonlinear (e.g., dipole) terms may be necessary inmore » these calculations specially for a small ring. 12 refs., 6 figs., 10 tabs.« less

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

Huang, H.; Ahrens, L. A.; Bai, M.

Acceleration of polarized protons in the energy range of 5 to 25 GeV is challenging. In a medium energy accelerator, the depolarizing spin resonances are strong enough to cause significant polarization loss but full Siberian snakes cause intolerably large orbit excursions and are also not feasible since straight sections usually are too short. Recently, two helical partial Siberian snakes with double pitch design have been installed in the Brookhaven Alternating Gradient Synchrotron (AGS). With a careful setup of optics at injection and along the energy ramp, this combination can eliminate the intrinsic and imperfection depolarizing resonances otherwise encountered during accelerationmore » to maintain a high intensity polarized beam in medium energy synchrotrons. The observation of partial snake resonances of higher than second order will also be described.« less

Nickel-phendione complex covalently attached onto carbon nanotube/cross linked glucose dehydrogenase as bioanode for glucose/oxygen compartment-less biofuel cell

NASA Astrophysics Data System (ADS)

Korani, Aazam; Salimi, Abdollah; Hadadzadeh, Hasan

2015-05-01

Here, [Ni(phendion) (phen)]Cl2 complex, (phendion and phen are 1,10-phenanthroline-5,6-dione and 5-amino-1, 10-phenanthrolin) covalently attached onto carboxyl functionalized multi walls carbon nanotube modified glassy carbon electrode (GCE/MWCNTs-COOH) using solid phase interactions and combinatorial approaches.The attached [Ni(phendion) (phen)]Cl2 complex displays a surface controlled electrode process and it acts as an effective redox mediator for electrocatalytic oxidation of dihydronicotinamide adenine dinucleotide (NADH) at reduced overpotentials. With co-immobilization of glucose dehydrogenase enzyme (GDH) by crosslinking an effective biocatalyst for glucose oxidation designed. The onset potential and current density are -0.1 V versus Ag/AgCl electrode and 0.550 mA cm-2, which indicate the applicability of the proposed system as an efficient bioanode for biofuel cell (BFC) design. A GCE/MWCNTs modified with electrodeposited gold nanoparticles (AuNPs) as a platform for immobilization of bilirubin oxidase (BOD) and the prepared GCE/MWCNTs/AuNPs/BOD biocathode exhibits an onset potential of 0.56 V versus Ag/AgCl. The performance of the fabricated bioanode and biocathode in a membraneless enzyme based glucose/O2 biofuel cell is evaluated. The open circuit voltage of the cell and maximum current density are 520 mV and 0.233 mA cm-2, respectively, while maximum power density of 40 μWcm-2 achieves at voltage of 280 mV with stable output power after 24 h continues operation.

Adjustable coordination of a hybrid phosphine-phosphine oxide ligand in luminescent Cu, Ag and Au complexes.

PubMed

Dau, Thuy Minh; Asamoah, Benjamin Darko; Belyaev, Andrey; Chakkaradhari, Gomathy; Hirva, Pipsa; Jänis, Janne; Grachova, Elena V; Tunik, Sergey P; Koshevoy, Igor O

2016-09-28

A potentially tridentate hemilabile ligand, PPh2-C6H4-PPh(O)-C6H4-PPh2 (P(3)O), has been used for the construction of a family of bimetallic complexes [MM'(P(3)O)2](2+) (M = M' = Cu (1), Ag (2), Au (3); M = Au, M' = Cu (4)) and their mononuclear halide congeners M(P(3)O)Hal (M = Cu (5-7), Ag (8-10)). Compounds 1-10 have been characterized in the solid state by single-crystal X-ray diffraction analysis to reveal a variable coordination mode of the phosphine-oxide group of the P(3)O ligand depending on the preferable number of coordination vacancies on the metal center. According to the theoretical studies, the interaction of the hard donor P[double bond, length as m-dash]O moiety with d(10) ions becomes less effective in the order Cu > Ag > Au. 1-10 exhibit room temperature luminescence in the solid state, and the intensity and energy of emission are mostly determined by the nature of metal atoms. The photophysical characteristics of the monometallic species were compared with those of the related compounds M(P(3))Hal (11-16) with the non-oxidized ligand P(3). It was found that in the case of the copper complexes 5-7 the P(3)O hybrid ligand introduces effective non-radiative pathways of the excited state relaxation leading to poor emission, while for the silver luminophores the P[double bond, length as m-dash]O group leads mainly to the modulation of luminescence wavelength.

Payette River Basin Project: Improving Operational Forecasting in Complex Terrain through Chemistry

NASA Astrophysics Data System (ADS)

Blestrud, D.; Kunkel, M. L.; Parkinson, S.; Holbrook, V. P.; Benner, S. G.; Fisher, J.

2015-12-01

Idaho Power Company (IPC) is an investor owned hydroelectric based utility, serving customers throughout southern Idaho and eastern Oregon. The University of Arizona (UA) runs an operational 1.8-km resolution Weather and Research Forecast (WRF) model for IPC, which is incorporated into IPC near and real-time forecasts for hydro, solar and wind generation, load servicing and a large-scale wintertime cloud seeding operation to increase winter snowpack. Winter snowpack is critical to IPC, as hydropower provides ~50% of the company's generation needs. In efforts to improve IPC's near-term forecasts and operational guidance to its cloud seeding program, IPC is working extensively with UA and the National Center for Atmospheric Research (NCAR) to improve WRF performance in the complex terrain of central Idaho. As part of this project, NCAR has developed a WRF based cloud seeding module (WRF CS) to deliver high-resolution, tailored forecasts to provide accurate guidance for IPC's operations. Working with Boise State University (BSU), IPC is conducting a multiyear campaign to validate the WRF CS's ability to account for and disperse the cloud seeding agent (AgI) within the boundary layer. This improved understanding of how WRF handles the AgI dispersion and fate will improve the understanding and ultimately the performance of WRF to forecast other parameters. As part of this campaign, IPC has developed an extensive ground based monitoring network including a Remote Area Snow Sampling Device (RASSD) that provides spatially and temporally discrete snow samples during active cloud seeding periods. To quantify AgI dispersion in the complex terrain, BSU conducts trace element analysis using LA-ICP-MS on the RASSD sampled snow to provide measurements (at the 10-12 level) of incorporated AgI, measurements are compare directly with WRF CS's estimates of distributed AgI. Modeling and analysis results from previous year's research and plans for coming seasons will be presented.

Spectroscopic properties of Arx-Zn and Arx-Ag+ (x = 1,2) van der Waals complexes

NASA Astrophysics Data System (ADS)

Oyedepo, Gbenga A.; Peterson, Charles; Schoendorff, George; Wilson, Angela K.

2013-03-01

Potential energy curves have been constructed using coupled cluster with singles, doubles, and perturbative triple excitations (CCSD(T)) in combination with all-electron and pseudopotential-based multiply augmented correlation consistent basis sets [m-aug-cc-pV(n + d)Z; m = singly, doubly, triply, n = D,T,Q,5]. The effect of basis set superposition error on the spectroscopic properties of Ar-Zn, Ar2-Zn, Ar-Ag+, and Ar2-Ag+ van der Waals complexes was examined. The diffuse functions of the doubly and triply augmented basis sets have been constructed using the even-tempered expansion. The a posteriori counterpoise scheme of Boys and Bernardi and its generalized variant by Valiron and Mayer has been utilized to correct for basis set superposition error (BSSE) in the calculated spectroscopic properties for diatomic and triatomic species. It is found that even at the extrapolated complete basis set limit for the energetic properties, the pseudopotential-based calculations still suffer from significant BSSE effects unlike the all-electron basis sets. This indicates that the quality of the approximations used in the design of pseudopotentials could have major impact on a seemingly valence-exclusive effect like BSSE. We confirm the experimentally determined equilibrium internuclear distance (re), binding energy (De), harmonic vibrational frequency (ωe), and C1Π ← X1Σ transition energy for ArZn and also predict the spectroscopic properties for the low-lying excited states of linear Ar2-Zn (X1Σg, 3Πg, 1Πg), Ar-Ag+ (X1Σ, 3Σ, 3Π, 3Δ, 1Σ, 1Π, 1Δ), and Ar2-Ag+ (X1Σg, 3Σg, 3Πg, 3Δg, 1Σg, 1Πg, 1Δg) complexes, using the CCSD(T) and MR-CISD + Q methods, to aid in their experimental characterizations.

Observations of the Coronal Mass Ejection with a Complex Acceleration Profile

NASA Astrophysics Data System (ADS)

Reva, A. A.; Kirichenko, A. S.; Ulyanov, A. S.; Kuzin, S. V.

2017-12-01

We study the coronal mass ejection (CME) with a complex acceleration profile. The event occurred on 2009 April 23. It had an impulsive acceleration phase, an impulsive deceleration phase, and a second impulsive acceleration phase. During its evolution, the CME showed signatures of different acceleration mechanisms: kink instability, prominence drainage, flare reconnection, and a CME–CME collision. The special feature of the observations is the usage of the TESIS EUV telescope. The instrument could image the solar corona in the Fe 171 Å line up to a distance of 2 {R}ȯ from the center of the Sun. This allows us to trace the CME up to the LASCO/C2 field of view without losing the CME from sight. The onset of the CME was caused by kink instability. The mass drainage occurred after the kink instability. The mass drainage played only an auxiliary role: it decreased the CME mass, which helped to accelerate the CME. The first impulsive acceleration phase was caused by the flare reconnection. We observed the two-ribbon flare and an increase of the soft X-ray flux during the first impulsive acceleration phase. The impulsive deceleration and the second impulsive acceleration phases were caused by the CME–CME collision. The studied event shows that CMEs are complex phenomena that cannot be explained with only one acceleration mechanism. We should seek a combination of different mechanisms that accelerate CMEs at different stages of their evolution.

Structural and optical properties of DC magnetron sputtered ZnO films on glass substrate and their modification by Ag ions implantation

NASA Astrophysics Data System (ADS)

Ahmad, R.; Afzal, Naveed; Amjad, U.; Jabbar, S.; Hussain, T.; Hussnain, A.

2017-07-01

This work is focused on investigating the effects of deposition time and Ag ions implantation on structural and optical properties of ZnO film. The ZnO film was prepared on glass substrate by pulsed DC magnetron sputtering of pure Zn target in reactive oxygen environment for 2 h, 3 h, 4 h and 5 h respectively. X-ray diffraction results revealed polycrystalline ZnO film whose crystallinity was improved with increase of the deposition time. The morphological features indicated agglomeration of smaller grains into larger ones by increasing the deposition time. The UV-vis spectroscopy analysis depicted a small decrease in the band gap of ZnO from 3.36 eV to 3.27 eV with increase of deposition time. The Ag ions implantation in ZnO films deposited for 5 h on glass was carried out by using Pelletron Accelerator at different ions fluences ranging from 1  ×  1011 ions cm-2 to 2  ×  1012 ions cm-2. XRD patterns of Ag ions implanted ZnO did not show significant change in crystallite size by increasing ions fluence from 1  ×  1011 ions cm-2 to 5  ×  1011 ions cm-2. However, with further increase of the ions fluence, the crystallite size was decreased. The band gap of Ag ions implanted ZnO indicated anomalous variations with increase of the ions fluence.

Antimicrobial effect of an ultrasonic levitation washer disinfector with silver electrolysis and ozone oxidation on methicillin-resistant Staphylococcus aureus.

PubMed

Tamai, Mariko; Matsushita, Shigeto; Miyanohara, Hiroaki; Imuta, Naoko; Ikeda, Ryuji; Kawai, Kazuhiro; Nishi, Junichiro; Sakamoto, Akihiro; Shigihara, Takanori; Kanekura, Takuro

2013-12-01

Methicillin-resistant Staphylococcus aureus (MRSA) has rapidly emerged as a cause of severe and intractable skin infection. At present, there are no effective topical treatments, and infection or colonization by MRSA of the skin raises serious medical problems. We developed an ultrasonic levitation washer that generates silver ions (Ag(+)) and ozone (O3) to clean and sterilize medical devices. We report the effect of ultrasonic levitation (levitation) with Ag(+) and O3 on MRSA in vitro and in vivo. Antimicrobial effect against six MRSA strains of all agr types was examined under three in vitro conditions; cells floating in a water tank, cells infiltrating-, and cells forming a biofilm on an atelocollagen membrane. In the in vivo studies, we assayed the number of MRSA organisms that survived treatment on murine skin ulcers and evaluated the ulcer size. Levitation with Ag(+) dramatically decreased the survival of MRSA floating in a water tank. Levitation with Ag(+) and O3 significantly decreased the viability of MRSA that had infiltrated or formed a biofilm on atelocollagen membranes regardless of the level of biofilm production. In vivo studies showed that the number of MRSA on murine skin ulcers was significantly decreased when 15-min treatment was performed for 7 consecutive days and that the ulcer size was significantly decreased after the seventh treatment course. Levitation with Ag(+) and O3 may be a valuable tool for treating MRSA infestation of the skin and for accelerating wound healing. © 2013 Japanese Dermatological Association.

Facile fabrication of high-quality Ag/PS coaxial nanocables based on the mixed mode of soft/hard templates

PubMed Central

Wan, Mimi; Zhao, Wenbo; Peng, Fang; Wang, Qi; Xu, Ping; Mao, Chun; Shen, Jian

2016-01-01

A new kind of high-quality Ag/PS coaxial nanocables can be facilely synthesized by using soft/hard templates method. In order to effectively introduce Ag sources into porous polystyrene (PS) nanotubes which were trapped in porous anodic aluminum oxide (AAO) hard template, Pluronic F127 (F127) was used as guiding agent, soft template and reductant. Meanwhile, ethylene glycol solution was also used as solvent and co-reducing agent to assist in the formation of silver nanowires. The influences of concentration of F127 and reducing reaction time on the formation of Ag/PS coaxial nanocables were discussed. Results indicated that the high-quality Ag/PS coaxial nanocables can be obtained by the mixed mode of soft/hard templates under optimized conditions. This strategy is expected to be extended to design more metal/polymer coaxial nanocables for the benefit of creation of complex and functional nanoarchitectures and components. PMID:27477888

Phase diagram of Ag-Pd bimetallic nanoclusters by molecular dynamics simulations: solid-to-liquid transition and size-dependent behavior.

PubMed

Kim, Da Hye; Kim, Hyun You; Ryu, Ji Hoon; Lee, Hyuck Mo

2009-07-07

This report on the solid-to-liquid transition region of an Ag-Pd bimetallic nanocluster is based on a constant energy microcanonical ensemble molecular dynamics simulation combined with a collision method. By varying the size and composition of an Ag-Pd bimetallic cluster, we obtained a complete solid-solution type of binary phase diagram of the Ag-Pd system. Irrespective of the size and composition of the cluster, the melting temperature of Ag-Pd bimetallic clusters is lower than that of the bulk state and rises as the cluster size and the Pd composition increase. Additionally, the slope of the phase boundaries (even though not exactly linear) is lowered when the cluster size is reduced on account of the complex relations of the surface tension, the bulk melting temperature, and the heat of fusion. The melting of the cluster initially starts at the surface layer. The initiation and propagation of a five-fold icosahedron symmetry is related to the sequential melting of the cluster.

Formation and characterization of a multicomponent equilibrium system derived from cis- and trans-1-aminomethylcyclohexane-1,2-diol.

PubMed

Hetényi, Anasztázia; Szakonyi, Zsolt; Klika, Karel D; Pihlaja, Kalevi; Fülöp, Ferenc

2003-03-21

Both cis and trans isomers of amino diols 3-6 were prepared stereoselectively. In the reactions between 3-6 and phenyl isothiocyanate, the ring closure proceeded regioselectively and resulted only in spiro derivatives of 2-phenyliminooxazolidines 9, 10, 13, and 14. The reaction of cis- (or trans-)1-aminomethylcyclohexane-1,2-diol 4 (or 6) with 1 equiv of an aromatic aldehyde 15a-g in EtOH at room temperature resulted in a complex, multicomponent equilibrium mixture of 16a-g and 18a-g (or 17a-g and 19a-g), in each case consisting of a five-component, ring-chain tautomeric system 16A-E (or 17A-E), involving the Schiff base, two epimeric spirooxazolidines, two epimeric condensed 1,3-oxazines, and some of the four tricyclic compounds 18A-D (or 19A-D). The five-component, ring-chain equilibria were found to be adequately described by the Hammett-Brown linear free energy equation.

Synthesis and Properties of Chelating N-Heterocyclic Carbene Rhodium(I) Complexes: Synthetic Experiments in Current Organometallic Chemistry

ERIC Educational Resources Information Center

Mata, Jose A.; Poyatos, Macarena; Mas-Marza, Elena

2011-01-01

The preparation and characterization of two air-stable Rh(I) complexes bearing a chelating N-heterocyclic carbene (NHC) ligand is described. The synthesis involves the preparation of a Ag(I)-NHC complex and its use as carbene transfer agent to a Rh(I) precursor. The so obtained complex can be further reacted with carbon monoxide to give the…

VEGFR-3 signaling is regulated by a G-protein activator, activator of G-protein signaling 8, in lymphatic endothelial cells.

PubMed

Sakima, Miho; Hayashi, Hisaki; Mamun, Abdullah Al; Sato, Motohiko

2018-07-01

Vascular endothelial growth factor C (VEGFC) and its cognate receptor VEGFR-3 play a key role in lymphangiogenesis. We previously reported that an ischemia-inducible Gβγ signal regulator, activator of G-protein signaling 8 (AGS8), regulated the subcellular distribution of vascular endothelial growth factor receptor-2 (VEGFR-2) and influenced VEGFA-induced signaling in vascular endothelial cells. Here, we report that AGS8 regulates VEGFR-3, which is another subtype of the VEGF receptor family, and mediates VEGFC signaling in human dermal lymphatic endothelial cells (HDLECs). VEGFC stimulated the proliferation of HDLECs and tube formation by HDLECs, which were inhibited by knocking down AGS8 by small interfering RNA (siRNA). AGS8 siRNA inhibited VEGFC-mediated phosphorylation of VEGFR-3 and its downstream molecules, including ERK1/2 and AKT. Analysis of fluorescence-activated cell sorting and immunofluorescence staining demonstrated that AGS8 knockdown was associated with a reduction of VEGFR-3 at the cell surface. Endocytosis inhibitors did not rescue the decrease of cell-surface VEGFR-3, suggesting that AGS8 regulated the trafficking of VEGFR-3 to the plasma membrane. An immunoprecipitation assay indicated that VEGFR-3 formed a complex including AGS8 and Gβγ in cells. These data suggest the novel regulation of VEGFC-VEGFR-3 by AGS8 in HDLECs and a potential role for AGS8 in lymphangiogenesis. Copyright © 2018 Elsevier Inc. All rights reserved.

Effect of 120 MeV Ag9+ ion irradiation of YCOB single crystals

NASA Astrophysics Data System (ADS)

Arun Kumar, R.; Dhanasekaran, R.

2012-09-01

Single crystals of yttrium calcium oxy borate (YCOB) grown from boron-tri-oxide flux were subjected to swift heavy ion irradiation using silver Ag9+ ions from the 15 UD Pelletron facility at Inter University Accelerator Center, New Delhi. The crystals were irradiated at 1 × 1013, 5 × 1013 and 1 × 1014 ions/cm2 fluences at room temperature and with 5 × 1013 ions/cm2 fluence at liquid nitrogen temperature. The pristine and the irradiated samples were characterized by glancing angle X-ray diffraction, UV-Vis-NIR and photoluminescence studies. From the characterization studies performed on the samples, it is inferred that the crystals irradiated at liquid nitrogen temperature had fewer defects compared to the crystals irradiated at room temperature and the defects increased when the ion fluence was increased at room temperature.

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

Bauer, R.; Ebersberger, B.; Kupfer, C.

SnAg solder bump is one bump type which is used to replace eutectic SnPb bumps. In this work tests have been done to characterize the reliability properties of this bump type. Electromigration (EM) tests, which were accelerated by high current and high temperature and high temperature storage (HTS) tests were performed. It was found that the reliability properties are sensitive to the material combinations in the interconnect stack. The interconnect stack includes substrate pad, pad finish, bump, underbump metallization (UBM) and the chip pad. Therefore separate test groups for SnAg bumps on Cu substrate pads with organic solderability preservative (OSP)more » finish and the identical bumps on pads with Ni/Au finish were used. In this paper the reliability test results and the corresponding failure analysis are presented. Some explanations about the differences in formation of intermetallic compounds (IMCs) are given.« less

1,3-dialkyl- and 1,3-diaryl-3,4,5,6-tetrahydropyrimidin-2-ylidene rhodium(i) and palladium(II) complexes: synthesis, structure, and reactivity.

PubMed

Mayr, Monika; Wurst, Klaus; Ongania, Karl-Hans; Buchmeiser, Michael R

2004-03-05

The synthesis of novel 1,3-diaryl- and 1,3-dialkylpyrimidin-2-ylidene-based N-heterocyclic carbenes (NHCs) and their rhodium(i) and palladium(II) complexes is described. The rhodium compounds bromo(cod)[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (7), bromo(cod)(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (8) (cod=eta(4)-1,5-cyclooctadiene, mesityl=2,4,6-trimethylphenyl), chloro(cod)(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (9), and chloro(cod)[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (10) were prepared by reaction of [[Rh(cod)Cl](2)] with lithium tert-butoxide followed by addition of 1,3-dimesityl-3,4,5,6-tetrahydropyrimidinium bromide (3), 1,3-dimesityl-3,4,5,6-tetrahydropyrimidinium tetrafluoroborate (4), 1,3-di-2-propyl-3,4,5,6-tetrahydropyrimidinium bromide (6), and 1,3-di-2-propyl-3,4,5,6-tetrahydropyrimidinium tetrafluoroborate, respectively. Complex 7 crystallizes in the monoclinic space group P2(1)/n, and 8 in the monoclinic space group P2(1). Complexes 9 and 10 were used for the synthesis of the corresponding dicarbonyl complexes dicarbonylchloro(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (11), and dicarbonylchloro[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (12). The wavenumbers nu(CO I)/nu(CO II) for 11 and 12 were used as a quantitative measure for the basicity of the NHC ligand. The values of 2062/1976 and 2063/1982 cm(-1), respectively, indicate that the new NHCs are among the most basic cyclic ligands reported so far. Compounds 3 and 6 were additionally converted to the corresponding cationic silver(i) bis-NHC complexes [Ag(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2)]AgBr(2) (13) and [Ag[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene](2)]AgBr(2) (14), which were subsequently used in transmetalation reactions for the synthesis of the corresponding palladium(II) complexes Pd(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2) (2+)(Ag(2)Br(2)Cl(4) (4-))(1/2) (15) and Pd[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2)]Cl(2) (16). Complex 15 crystallizes in the monoclinic space group P2(1)/c, and 16 in the monoclinic space group C(2)/c. The catalytic activity of 15 and 16 in Heck-type reactions was studied in detail. Both compounds are highly active in the coupling of aliphatic and aromatic vinyl compounds with aryl bromides and chlorides with turnover numbers (TONs) up to 2000000. Stabilities of 15 and 16 under Heck-couplings conditions were correlated with their molecular structure. Finally, selected kinetic data for these couplings are presented.

Synthesis of phosphinoferrocene amides and thioamides from carbamoyl chlorides and the structural chemistry of Group 11 metal complexes with these mixed-donor ligands.

PubMed

Fernandes, Tiago A; Solařová, Hana; Císařová, Ivana; Uhlík, Filip; Štícha, Martin; Štěpnička, Petr

2015-02-21

The reaction of in situ generated 1'-(diphenylphosphino)-1-lithioferrocene with carbamoyl chlorides, ClC(E)NMe2, affords the corresponding (thio)amides, Ph2PfcC(E)NMe2 (E = O (), S (); fc = ferrocene-1,1'-diyl). These compounds as well as their analogues, Ph2PfcC(O)NHMe () and Ph2PfcC(O)NH2 (), prepared from 1'-(diphenylphosphino)ferrocene-1-carboxylic acid (Hdpf) were studied as ligands for the Group 11 metal ions. In the reactions with [Cu(MeCN)4][BF4], the amides give rise to bis-chelate complexes of the type [Cu(L-κ(2)O,P)2][BF4]. Similar products, [Ag(L-κ(2)O,P)2]ClO4, are obtained from silver(i) perchlorate and , or . In contrast, the reaction of AgClO4 with produces a unique molecular dimer [Ag()(ClO4-κO)]2, where the metal centres are bridged by the sulfur atoms of the P,S-chelating thioamides. The reactions of with [AuCl(tht)] (tht = tetrahydrothiophene) afford the expected gold(i)-phosphine complexes, [AuCl(L-κP)], containing uncoordinated (thio)amide moieties. Hemilabile coordination of the phosphinoamide ligands in complexes with the soft Group 11 metal ions is established by the crystal structure of a solvento complex, [Cu(-κ(2)O,P)(-κP)(CHCl3-κCl)][BF4], which was isolated serendipitously during an attempted crystallisation of [Cu(-κ(2)O,P)2][BF4]. All of the compounds are characterised by spectroscopic methods, and the structures of several representatives of both the free phosphinoamides and their complexes are determined by X-ray diffraction analysis and further studied by DFT calculations and cyclic voltammetry.

An investigation into the effects of silver nanoparticles on natural microbial communities in two freshwater sediments.

PubMed

Bao, Shaopan; Wang, Han; Zhang, Weicheng; Xie, Zhicai; Fang, Tao

2016-12-01

The expanding production and usage of commercial silver nanoparticles (AgNPs) will inevitably increase their environmental release, with sediments as a substantial sink. However, little knowledge is available about the potential impacts of AgNPs on freshwater sediment microbial communities, as well as the interactions between microbial communities and biogeochemical factors in AgNPs polluted sediment. To address these issues, two different sediments: a eutrophic freshwater sediment and an oligotrophic freshwater sediment, were exposed to 1 mg/g of either AgNO 3 , uncoated AgNPs (35-nm and 75-nm), or polyvinylpyrrolidone coated AgNPs (PVP-AgNPs) (30-50 nm) for 45 days. High-throughput sequencing of 16S ribosomal ribonucleic acid (16S rRNA) genes using the Illumina MiSeq platform was conducted to evaluate the effects of Ag addition on bacterial community composition. Moreover, sediment microbial biomass and activity were assessed by counting cultivable bacterial number and determining enzyme activities. During the 45-day exposure, compared with no amendment control, some treatments had resulted in significant changes and alterations of sediment biomass or bacterial enzyme activities shortly. While the microbial components at phylum level were rarely affected by AgNPs addition, and as confirmed by the statistical analysis with two-factor analysis of similarities (ANOSIM), there were no significant differences on bacterial community structure across the amended treatments. Redundancy analysis further demonstrated that chemical parameters acid-volatile sulfide (AVS) and simultaneously extracted silver (SE-Ag) in sediment significantly structured the overall bacterial community in sediments spiked with various silver species. In summary, these findings suggested that the ecotoxicity of AgNPs may be attenuated by the transformation under complex environmental conditions and the self-adaption of sediment microbial communities. Copyright © 2016 Elsevier Ltd. All rights reserved.

Spectroscopic interaction study of human serum albumin and human hemoglobin with Mersilea quadrifolia leaves extract mediated silver nanoparticles having antibacterial and anticancer activity

NASA Astrophysics Data System (ADS)

Maji, Anukul; Beg, Maidul; Mandal, Amit Kumar; Das, Somnath; Jha, Pradeep K.; Kumar, Anoop; Sarwar, Shamila; Hossain, Maidul; Chakrabarti, Pinak

2017-08-01

This study looks into a safe, proficient and low-cost way for the preparation of novel silver nanoparticles by using 5% aqueous leaves extract of a medicinal plant, Marsilea quadrifolia (family: Marsileaceae) without using any external reducing and stabilizing agents. The synthesized AgNPs showed maximum UV-Vis absorbance at 435 nm due to surface plasmon resonance (SPR). The average diameter (∼22.5 nm) of AgNPs was measured from TEM analysis and was also supported by FE-SEM. The existence of a silver signal in EDX spectra supported the AgNPs formation and negative zeta potential value (-18.7 mV) which suggested its stability. FT-IR spectroscopic analysis showed that the functional groups like sbnd Osbnd H, sbnd Nsbnd H and sbnd Cdbnd O were responsible for the synthesis of AgNPs. The antibacterial activity of the AgNPs was tested against E. coli ATCC 25922. The anticancer potential of AgNPs was also assessed using two different cell lines, such as MCF-7 and HeLa. The interaction study of AgNPs with human serum albumin (HSA) and human hemoglobin (Hb) was performed by means of UV-Vis, fluorescence spectroscopy, Circular dichroism (CD) and zeta potential measurement. More negative zeta potential values of AgNPs-HSA/Hb (-21.1/-19.5 mV) complexes than AgNPs (-18.7 mV) indicated corresponding stability of bio-conjugates. The basic structure of HSA/Hb remained unchanged and its secondary structure was slightly changed upon interaction with the AgNPs concluded from Circular dichroism. So, it can be predicted that this AgNPs may be applied in the medical field.

Two Types of 2D Layered Iodoargentates Based on Trimeric [Ag3I7] Secondary Building Units and Hexameric [Ag6I12] Ternary Building Units: Syntheses, Crystal Structures, and Efficient Visible Light Responding Photocatalytic Properties.

PubMed

Lei, Xiao-Wu; Yue, Cheng-Yang; Zhao, Jian-Qiang; Han, Yong-Fang; Yang, Jiang-Tao; Meng, Rong-Rong; Gao, Chuan-Sheng; Ding, Hao; Wang, Chun-Yan; Chen, Wan-Dong; Hong, Mao-Chun

2015-11-16

With mixed transition-metal-complex, alkali-metal, or organic cations as structure-directing agents, a series of novel two-dimensional (2D) layered inorganic-organic hybrid iodoargentates, namely, Kx[TM(2,2-bipy)3]2Ag6I11 (TM = Mn (1), Fe (2), Co (3), Ni (4), Zn (5); x = 0.89-1) and [(Ni(2,2-bipy)3][H-2,2-bipy]Ag3I6 (6), have been solvothermally synthesized and structurally characterized. All the title compounds feature 2D microporous layers composed by [Ag3I7] secondary building units based on AgI4 tetrahedra. Differently, the [Ag3I7] trimers are directly interconnected via corner-sharing to form the 2D [Ag6I11](5-) layer in compounds 1-5, whereas two neighboring [Ag3I7] trimers are initially condensed into a hexameric [Ag6I12] ternary building unit as a new node, which further self-assembles, leading to the 2D [Ag6I10](4-) layer in compound 6. The UV-vis diffuse-reflectance measurements reveal that all the compounds possess proper semiconductor behaviors with tunable band gaps of 1.66-2.75 eV, which lead to highly efficient photocatalytic degradation activities over organic pollutants under visible light irradiation compared to that of N-dotted P25. Interestingly, all the samples feature distinct photodegradative speeds at the same reaction conditions, and compound 1 features the highest photocatalytic activity among the title phases. The luminescence properties, band structures, and thermal stabilities were also studied.

A chemical bath deposition route to facet-controlled Ag{sub 3}PO{sub 4} thin films with improved visible light photocatalytic activity

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

Gunjakar, Jayavant L.; Jo, Yun Kyung; Kim, In Young

A facile, economic, and reproducible chemical bath deposition (CBD) method is developed for the fabrication of facet-controlled Ag{sub 3}PO{sub 4} thin films with enhanced visible light photocatalytic activity. The fine-control of bath temperature, precursor, complexing agent, substrate, and solution pH is fairly crucial in preparing the facet-selective thin film of Ag{sub 3}PO{sub 4} nanocrystal. The change of precursor from silver nitrate to silver acetate makes possible the tailoring of the crystal shape of Ag{sub 3}PO{sub 4} from cube to rhombic dodecahedron and also the bandgap tuning of the deposited films. The control of [Ag{sup +}]/[phosphate] ratio enables to maximize themore » loading amount of Ag{sub 3}PO{sub 4} crystals per the unit area of the deposited film. All the fabricated Ag{sub 3}PO{sub 4} thin films show high photocatalytic activity for visible light-induced degradation of organic molecules, which can be optimized by tailoring the crystal shape of the deposited crystals. This CBD method is also useful in preparing the facet-controlled hybrid film of Ag{sub 3}PO{sub 4}–ZnO photocatalyst. The present study clearly demonstrates the usefulness of the present CBD method for fabricating facet-controlled thin films of metal oxosalt and its nanohybrid. - Highlights: • The crystal facet of Ag{sub 3}PO{sub 4} films can be tuned by chemical bath deposition. • The crystal shape of Ag{sub 3}PO{sub 4} is tailorable from cube to rhombic dodecahedron. • Facet-tuned Ag{sub 3}PO{sub 4} film shows enhanced visible light photocatalyst activity.« less

Effect of media composition on bioavailability and toxicity of silver and silver nanoparticles in fish intestinal cells (RTgutGC).

PubMed

Minghetti, Matteo; Schirmer, Kristin

2016-12-01

To understand conditions affecting bioavailability and toxicity of citrate-coated silver nanoparticles (cit-AgNP) and dissolved silver at the luminal enterocyte interface, we exposed rainbow trout (Oncorhynchus mykiss) gut cells (RTgutGC) in media of contrasting composition: two amino acid-containing media, one of which was supplemented with proteins, as can be expected during digestion; and two protein and amino acid-free media contrasting low and high chloride content, as can be expected in the lumen of fish adapting to freshwater or seawater, respectively. Dose-response curves were generated measuring cell metabolic activity, membrane and lysosome integrity over a period of 72 hours. Then, nontoxic doses were applied and total silver accumulation, metallothionein and glutathione reductase mRNA levels were determined. The presence of proteins stabilized cit-AgNP keeping them in suspension. Conversely, in protein-free media, cit-AgNP agglomerated and settled, resulting in higher cellular accumulation of silver and toxicity. Chloride concentrations in exposure media modulated the toxicity of AgNO 3 but not of cit-AgNP. Moreover, while amino acid-containing media are protective against AgNO 3 , likely due to the formation of thiolate complexes, they are only partially protective against cit-AgNP. Viability assays indicated that lysosomes are targets of cit-AgNP, supporting the hypothesis that cit-AgNP exert toxicity intracellularly. Metallothionein, a sensor of metal bioavailability, was induced by cit-AgNP in high chloride medium but not in low chloride medium, indicating that chloride might have a role in mobilizing silver from intercellular vesicles. Overall, this study shows that AgNP bioavailability and toxicity in the intestine is linked to its luminal content.

Hepatitis B virus surface antigen and anti-hepatitis C virus rapid tests underestimate hepatitis prevalence among HIV-infected patients.

PubMed

Hønge, Bl; Jespersen, S; Medina, C; Té, Ds; da Silva, Zj; Ostergaard, L; Laursen, Al; Wejse, C; Krarup, H; Erikstrup, C

2014-10-01

In the case of coinfection with HIV and hepatitis B virus (HBV) and/or hepatitis C virus (HCV), hepatic disease progression is often accelerated, with higher rates of liver cirrhosis and liver-related mortality. We aimed to evaluate the performance of the rapid tests used routinely to detect HBV surface antigen (HBsAg) and anti-HCV among HIV-infected patients in Guinea-Bissau. Blood samples from HIV-infected patients in Guinea-Bissau were stored after testing for HBsAg and anti-HCV with rapid tests. Samples were subsequently re-tested for HBsAg and anti-HCV in Denmark. Two rapid tests were used in Guinea-Bissau: HBsAg Strip Ref 2034 (VEDA.LAB, Alençon, France; sensitivity 62.3%; specificity 99.2%) and HEPA-SCAN (Bhat Bio-Tech, Bangalore, India; sensitivity 57.1%; specificity 99.7%). In the two tests the ability to obtain the correct outcome depended on the antigen and antibody concentrations, respectively. Sex, age, CD4 cell count and antiretroviral therapy status did not differ between false negative and true positive samples in either of the tests. The study is limited by a low number of anti-HCV positive samples. New diagnostic rapid tests should always be evaluated in the setting in which they will be used before implementation. © 2014 British HIV Association.

Effect of protein tyrosine kinase inhibitors on the current through the Ca(V)3.1 channel.

PubMed

Kurejová, Martina; Lacinová, L'ubica

2006-02-01

In the present study, we have investigated the effects of protein tyrosine kinase (PTK) inhibitors on the Ca(V)3.1 calcium channel stably transfected in HEK293 cells using the whole-cell configuration of the patch-clamp technique. We have tested two different tyrosine kinase inhibitors, genistein and tyrphostin AG213, and their inactive analogs, genistin and tyrphostin AG9. Bath application of genistein, but not genistin, decreased the T-type calcium current amplitude in a concentration-dependent manner with an IC(50) of 24.7+/-2.0 microM. This effect of genistein was accompanied by deceleration of channel activation and acceleration of channel inactivation. Intracellular application of neither genistein nor genistin had a significant effect on the calcium current. Extracellular application of 50 microM tyrphostin AG213 and its inactive analogue, tyrphostin AG9, did not affect the current through the Ca(V)3.1 channel. The effect of genistein on the channel was also not affected by the presence of catalytically active PTK, p60(c-src) inside the cell. We have concluded that genistein directly inhibited the channel. This mechanism does not involve a PTK-dependent pathway. The alteration of the channel kinetics by genistein suggests an interaction with the voltage sensor of the channel together with the channel pore occlusion.

A comparative study about electronic structures at rubrene/Ag and Ag/rubrene interfaces

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

Sinha, Sumona, E-mail: sumona.net.09@gmail.com; Mukherjee, M.

The contact between the electrode and the organic semiconductor is one of the most crucial factors in determining the organic device performance. The development and production technology of different organic devices require the understanding of different types of metal/organic semiconducting thin film interfaces. Comparisons about the electronic structures at Rubrene/Ag and Ag/Rubrene interfaces have been studied using photoemission spectroscopy. The Ag on rubrene interfaces is found to show more interesting and complex natures than its counterpart. The vacuum level (VL) was shifted about 0.51 eV from push back effect for deposition of 5 Å rubrene onto Ag film whereas themore » electronic features of silver was only suppressed and no energy shift was resulted. While the deposition of 5 Å Ag onto rubrene film leads to the diffusion of the Ag atoms, as a cluster with quantum size effect, inside the film. Angle dependent XPS measurement indicates that diffused metal clusters were present at entire probed depth of the film. Moreover these clusters dope the uppermost surface of the rubrene film which consequences a shift of the electronic states of thick organic film towards higher binding energy. The VL was found to shift about 0.31 eV toward higher binding energy whereas the shift was around 0.21 eV for the electronic states of rubrene layer.« less

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

Sergienko, V. S., E-mail: sergienko@igic.ras.ru; Martsinko, E. E.; Seifullina, I. I.

The synthesis and X-ray diffraction study of compound ([Ag{sub 2}Ge(HCit){sub 2}(H{sub 2}O){sub 2}] ∙ 2H{sub 2}O){sub n}, where H{sub 4}Cit is the citric acid, are performed. In the polymeric structure, the HCit{sup 3–} ligand fulfils the tetradentate chelate–μ{sub 4}-bridging (3Ag, Ge) function (tridentate with respect to Ge and Ag atoms). The Ge atom is octahedrally coordinated by six O atoms of two HCit{sup 3–}ligands. The coordination polyhedron of the Ag atom is an irregular five-vertex polyhedron [four O atoms of four HCit{sup 3–} ligands and the O(H{sub 2}O) atom]. An extended system of O–H···O hydrogen bonds connects complex molecules intomore » a supramolecular 3D-framework.« less

Rapid chromatographic separation of dissoluble Ag(I) and silver-containing nanoparticles of 1-100 nanometer in antibacterial products and environmental waters.

PubMed

Zhou, Xiao-Xia; Liu, Rui; Liu, Jing-Fu

2014-12-16

Sensitive and rapid methods for speciation analysis of nanoparticulate Ag (NAg) and Ag(I) in complex matrices are urgently needed for understanding the environmental effects and biological toxicity of silver nanoparticles (AgNPs). Herein we report the development of a universal liquid chromatography (LC) method for rapid and high resolution separation of dissoluble Ag(I) from nanoparticles covering the entire range of 1-100 nm in 5 min. By using a 500 Å poresize amino column, and an aqueous mobile phase containing 0.1% (v/v) FL-70 (a surfactant) and 2 mM Na2S2O3 at a flow rate of 0.7 mL/min, all the nanoparticles of various species such as Ag and Ag2S were eluted in one fraction, while dissoluble Ag(I) was eluted as a baseline separated peak. The dissoluble Ag(I) was quantified by the online coupled ICP-MS with a detection limit of 0.019 μg/L. The NAg was quantified by subtracting the dissoluble Ag(I) from the total Ag content, which was determined by ICP-MS after digestion of the sample without LC separation. While the addition of FL-70 and Na2S2O3 into the mobile phase is essential to elute NAg and Ag(I) from the column, the use of 500 Å poresize column is the key to baseline separation of Ag(I) from ∼ 1 nm AgNPs. The feasibility of the proposed method was demonstrated in speciation analysis of dissoluble Ag(I) and NAg in antibacterial products and environmental waters, with very good chromatographic repeatability (relative standard deviations) in both peak area (<2%) and retention time (<0.6%), excellent spiked recoveries in the range of 84.7-102.7% for Ag(I) and 81.3-106.3% for NAg. Our work offers a novel approach to rapid and baseline separation of dissoluble metal ions from their nanoparticulate counterparts covering the whole range of 1-100 nm.

Attenuation of Microbial Stress Due to Nano-Ag and Nano-TiO2 Interactions under Dark Conditions.

PubMed

Wilke, Carolyn M; Tong, Tiezheng; Gaillard, Jean-François; Gray, Kimberly A

2016-10-04

Engineered nanomaterials (ENMs) are incorporated into thousands of commercial products, and their release into environmental systems creates complex mixtures with unknown toxicological outcomes. To explore this scenario, we probe the chemical and toxicological interactions of nanosilver (n-Ag) and nanotitania (n-TiO 2 ) in Lake Michigan water, a natural aqueous medium, under dark conditions. We find that the presence of n-Ag induces a stress response in Escherichia coli, as indicated by a decrease in ATP production observed at low concentrations (in the μg L -1 range), with levels that are environmentally relevant. However, when n-Ag and n-TiO 2 are present together in a mixture, n-TiO 2 attenuates the toxicity of n-Ag at and below 20 μg L -1 by adsorbing Ag + (aq) . We observe, however, that toxic stress cannot be explained by dissolved silver concentrations alone and, therefore, must also depend on silver associated with the nanoscale fraction. Although the attenuating effect of n-TiO 2 on n-Ag's toxicity is limited, this study emphasizes the importance of probing the toxicity of ENM mixtures under environmental conditions to assess how chemical interactions between nanoparticles change the toxicological effects of single ENMs in unexpected ways.

Synthesis, characterization, optical and antimicrobial studies of polyvinyl alcohol-silver nanocomposites

NASA Astrophysics Data System (ADS)

Mahmoud, K. H.

2015-03-01

Silver nanoparticles (Ag NPs) were synthesized by chemical reduction of silver salt (AgNO3) through sodium borohydride. The characteristic surface plasmon resonance band located at around 400 nm in the UV-Visible absorption spectrum confirmed the formation of Ag nanoparticles. Polyvinyl alcohol-silver (PVA-Ag) nanocomposite films were prepared by the casting technique. The morphology and interaction of PVA with Ag NPs were examined by transmission electron microscopy and FTIR spectroscopy. Optical studies show that PVA exhibited indirect allowed optical transition with optical energy gap of 4.8 eV, which reduced to 4.45 eV under addition of Ag NPs. Optical parameters such as refractive index, complex dielectric constant and their dispersions have been analyzed using Wemple and DiDomenco model. Color properties of the nanocomposites are discussed in the framework of CIE L∗u∗v∗ color space. The antimicrobial activity of the nanocomposite samples was tested against Gram positive bacteria (Staphylococcus aureus NCTC 7447 &Bacillus subtillis NCIB 3610), Gram negative bacteria (Escherichia coli, NTC10416 &Pseudomonas aeruginosa NCIB 9016) and fungi (Aspergillus niger Ferm - BAM C-21) using the agar diffusion technique. The antimicrobial study showed that PVA has moderate antibacterial activity against B. subtillis and the 0.04 wt% Ag NPs composite sample effect was strong against S. aureus.

Calix[4]arene-phosphine dimers: precursors of flexible metallo-capsules and self-compacting molecules.

PubMed

Sameni, Soheila; Jeunesse, Catherine; Matt, Dominique; Toupet, Loïc

2009-10-12

The first diphosphines based on a double calixarene, namely 1,4 (or 1,3)-bis-(5-diphenylphosphino-25,26,27,28-tetrapropoxycalix[4]aren-17-yl)benzene (L(2), L(3)) were each prepared in four steps starting from 5,17-dibromo-25,26,27,28-tetrapropoxycalix[4]arene. Upon reaction of L(2) with [Au(tht)(thf)]BF(4), (tht = C(4)H(8)S) a rigid metallo-capsule was quantitatively formed, which adopts an oblique form owing to the distinct nature of the spacers linking the two calixarene half-spheres. In the solid state, the 1,4-substituted phenylene linker is turned towards the gold ion, suggesting the existence of weak bonding interactions between two aromatic CH protons of this ring and the metal centre (AuH =2.67 A). In contrast to this gold complex, the related silver complex shows dynamic behaviour in solution, the exchange between two enantiomeric oblique forms being facilitated by the greater stereochemical flexibility of Ag(I) vs. Au(I). A heteronuclear (109)Ag{(1)H} HMQC experiment established strong correlations between the CH protons of the phenylene linker and the (109)Ag ion. Dynamic behaviour similar to that observed for the silver complex was further observed in trans-[PtCl(2)L(2)], a chelate complex that could be obtained quantitatively from L(2) and [PtCl(2)(PhCN)(2)]. The intended formation of a chelate complex leading to a capsule with an endo-oriented metal centre was achieved by reacting L(3) with [Pd(allyl)(thf)(2)]BF(4). The complex thus formed constitutes the first organometallic transition metal complex embedded in a cavity with large portals. Binding of [RuCl(2)(p-cymene)] to L(2) and L(3) resulted in self-compacting bimetallic complexes in which each calixarene basket entraps a Ru(p-cymene) unit, thereby forming molecules occupying a minimal volume.

Complex supramolecular interfacial tessellation through convergent multi-step reaction of a dissymmetric simple organic precursor

NASA Astrophysics Data System (ADS)

Zhang, Yi-Qi; Paszkiewicz, Mateusz; Du, Ping; Zhang, Liding; Lin, Tao; Chen, Zhi; Klyatskaya, Svetlana; Ruben, Mario; Seitsonen, Ari P.; Barth, Johannes V.; Klappenberger, Florian

2018-03-01

Interfacial supramolecular self-assembly represents a powerful tool for constructing regular and quasicrystalline materials. In particular, complex two-dimensional molecular tessellations, such as semi-regular Archimedean tilings with regular polygons, promise unique properties related to their nontrivial structures. However, their formation is challenging, because current methods are largely limited to the direct assembly of precursors, that is, where structure formation relies on molecular interactions without using chemical transformations. Here, we have chosen ethynyl-iodophenanthrene (which features dissymmetry in both geometry and reactivity) as a single starting precursor to generate the rare semi-regular (3.4.6.4) Archimedean tiling with long-range order on an atomically flat substrate through a multi-step reaction. Intriguingly, the individual chemical transformations converge to form a symmetric alkynyl-Ag-alkynyl complex as the new tecton in high yields. Using a combination of microscopy and X-ray spectroscopy tools, as well as computational modelling, we show that in situ generated catalytic Ag complexes mediate the tecton conversion.

Self-referential and social cognition in a case of autism and agenesis of the corpus callosum

PubMed Central

2012-01-01

Background While models of autism spectrum conditions (ASC) are emerging at the genetic level of analysis, clear models at higher levels of analysis, such as neuroanatomy, are lacking. Here we examine agenesis of the corpus callosum (AgCC) as a model at the level of neuroanatomy that may be relevant for understanding self-referential and social-cognitive difficulties in ASC. Methods We examined performance on a wide array of tests in self-referential and social-cognitive domains in a patient with both AgCC and a diagnosis of ASC. Tests included a depth-of-processing memory paradigm with self-referential and social-cognitive manipulations, self-report measures of self-consciousness, alexithymia, and empathy, as well as performance measures of first-person pronoun usage and mentalizing ability. The performance of the AgCC patient was compared to a group of individuals with ASC but without AgCC and with neurotypical controls. These comparison groups come from a prior study where group differences were apparent across many measures. We used bootstrapping to assess whether the AgCC patient exhibited scores that were within or outside the 95% bias-corrected and accelerated bootstrap confidence intervals observed in both comparison groups. Results Within the depth-of-processing memory paradigm, the AgCC patient showed decreased memory sensitivity that was more extreme than both comparison groups across all conditions. The patient’s most pronounced difficulty on this task emerged in the social-cognitive domain related to information-processing about other people. The patient was similar to the ASC group in benefiting less from self-referential processing compared to the control group. Across a variety of other self-referential (i.e. alexithymia, private self-consciousness) and social-cognitive measures (i.e. self-reported imaginative and perspective-taking subscales of empathy, mentalizing), the AgCC patient also showed more extreme scores than those observed for both of the comparison groups. However, the AgCC patient scored within the range observed in the comparison groups on measures of first-person pronoun usage and self-reported affective empathy subscales. Conclusions We conclude that AgCC co-occurring with a diagnosis of ASC may be a relevant model at the level of neuroanatomy for understanding mechanisms involved in self-referential and high-level social-cognitive difficulties in ASC. PMID:23171505

Quantum computational complexity, Einstein's equations and accelerated expansion of the Universe

NASA Astrophysics Data System (ADS)

Ge, Xian-Hui; Wang, Bin

2018-02-01

We study the relation between quantum computational complexity and general relativity. The quantum computational complexity is proposed to be quantified by the shortest length of geodesic quantum curves. We examine the complexity/volume duality in a geodesic causal ball in the framework of Fermi normal coordinates and derive the full non-linear Einstein equation. Using insights from the complexity/action duality, we argue that the accelerated expansion of the universe could be driven by the quantum complexity and free from coincidence and fine-tunning problems.

A new μ3-oxo-centered tri-nuclear carboxyl bridged iron (III) complex with thio-methyl groups in the periphery: Structural, spectroscopic and electrochemical studies

NASA Astrophysics Data System (ADS)

Lu, Maofeng; Chen, Tingting; Wang, Miao; Jiang, Guomin; Lu, Tianhong; Jiang, Guoqing; Du, Jiangyan

2014-02-01

A tri-nuclear iron (III) complex [Fe3(μ3-O)(O2CC6H4SCH3)6(Py)3]FeCl4 has been synthesized and characterized by X-ray crystallography, Surface enhanced Raman Scattering (SERS), Fourier Transform Infra Red (FT-IR), Ultraviolet-Visible (UV-Vis) spectroscopy and Thermogravimetric analysis (TGA)/Differential scanning calorimetry (DSC). The functionalized thio-methyl groups around the periphery of the complex 1 may provide binding sites to the surface of some specific materials, such as noble metals. The Ag sols and complex 1-Ag sol had been characterized by SERS and UV-Vis spectroscopy. The complex 1 were also self-assembled on gold electrode by AuS bond, exhibiting an irreversible process at E1/2 = 0.967 V (ΔE = 0.525 V). Meanwhile the Raman spectra were compared with FT-IR, and the results indicated that the strong Raman lines either correspond to weak Infrared absorptions or are absent in the Infrared spectra.

STEM-EELS analysis of multipole surface plasmon modes in symmetry-broken AuAg nanowire dimers

NASA Astrophysics Data System (ADS)

Schubert, Ina; Sigle, Wilfried; van Aken, Peter A.; Trautmann, Christina; Toimil-Molares, Maria Eugenia

2015-03-01

Surface plasmon coupling in nanowires separated by small gaps generates high field enhancements at the position of the gap and is thus of great interest for sensing applications. It is known that the nanowire dimensions and in particular the symmetry of the structures has strong influence on the plasmonic properties of the dimer structure. Here, we report on multipole surface plasmon coupling in symmetry-broken AuAg nanowire dimers. Our dimers, consisting of two nanowires with different lengths and separated by gaps of only 10 to 30 nm, were synthesized by pulsed electrochemical deposition in ion track-etched polymer templates. Electron energy-loss spectroscopy in scanning transmission electron microscopy allows us to resolve up to nine multipole order surface plasmon modes of these dimers spectrally separated from each other. The spectra evidence plasmon coupling between resonances of different multipole order, resulting in the generation of additional plasmonic modes. Since such complex structures require elaborated synthesis techniques, dimer structures with complex composition, morphology and shape are created. We demonstrate that finite element simulations on pure Au dimers can predict the generated resonances in the fabricated structures. The excellent agreement of our experiment on AuAg dimers with finite integration simulations using CST microwave studio manifests great potential to design complex structures for sensing applications.

Syntheses, spectroscopic properties and molecular structure of silver phytate complexes - IR, UV-VIS studies and DFT calculations

NASA Astrophysics Data System (ADS)

Zając, A.; Dymińska, L.; Lorenc, J.; Ptak, M.; Hanuza, J.

2018-03-01

Silver phytate IP6, IP6Ag, IP6Ag2 and IP6Ag3 complexes in the solid state have been synthesized changing the phosphate to metal mole ratio. The obtained products have been characterized by means of chemical and spectroscopic studies. Attenuated total reflection Fourier transform infrared technique and Raman microscope were used in the measurements. These results were discussed in terms of DFT (Density Functional Theory) quantum chemical calculations using the B3LYP/6-31G(d,p) approach. The molecular structures of these compounds have been proposed on the basis of group theory and geometry optimization taking into account the shape and the number of the observed bands corresponding to the stretching and bending vibrations of the phosphate group and metal-oxygen polyhedron. The role of inter- and intra-hydrogen bonds in stabilization of the structure has been discussed. It was found that three types of hydrogen bonds appear in the studied compounds: terminal, and those engaged in the inter- and intra-molecular interactions. The Fermi resonance as a result of the strong intra-molecular Osbnd H⋯O hydrogen bonds was discovered. Electron absorption spectra have been measured to characterize the electron properties of the studied complexes and their local symmetry.

Broadband Energy Harvester Using Non-linear Polymer Spring and Electromagnetic/Triboelectric Hybrid Mechanism

NASA Astrophysics Data System (ADS)

Gupta, Rahul Kumar; Shi, Qiongfeng; Dhakar, Lokesh; Wang, Tao; Heng, Chun Huat; Lee, Chengkuo

2017-01-01

Over the years, several approaches have been devised to widen the operating bandwidth, but most of them can only be triggered at high accelerations. In this work, we investigate a broadband energy harvester based on combination of non-linear stiffening effect and multimodal energy harvesting to obtain high bandwidth over wide range of accelerations (0.1 g-2.0 g). In order to achieve broadband behavior, a polymer based spring exhibiting multimodal energy harvesting is used. Besides, non-linear stiffening effect is introduced by using mechanical stoppers. At low accelerations (<0.5 g), the nearby mode frequencies of polymer spring contribute to broadening characteristics, while proof mass engages with mechanical stoppers to introduce broadening by non-linear stiffening at higher accelerations. The electromagnetic mechanism is employed in this design to enhance its output at low accelerations when triboelectric output is negligible. Our device displays bandwidth of 40 Hz even at low acceleration of 0.1 g and it is increased up to 68 Hz at 2 g. When non-linear stiffening is used along with multimodal energy-harvesting, the obtained bandwidth increases from 23 Hz to 68 Hz with percentage increment of 295% at 1.8 g. Further, we have demonstrated the triboelectric output measured as acceleration sensing signals in terms of voltage and current sensitivity of 4.7 Vg-1 and 19.7 nAg-1, respectively.

Feasibility study of a cyclotron complex for hadron therapy

NASA Astrophysics Data System (ADS)

Smirnov, V.; Vorozhtsov, S.

2018-04-01

An accelerator complex for hadron therapy based on a chain of cyclotrons is under development at JINR (Dubna, Russia), and the corresponding conceptual design is under preparation. The complex mainly consists of two superconducting cyclotrons. The first accelerator is a compact cyclotron used as an injector to the main accelerator, which is a six-fold separated sector machine. The facility is intended for generation of protons and carbon beams. The H2+ and 12C6+ ions from the corresponding ECR ion sources are accelerated in the injector-cyclotron up to the output energy of 70 MeV/u. Then, the H2+ ions are extracted from the injector by a stripping foil, and the resulting proton beam with the energy of 70 MeV is used for medical purposes. After acceleration in the main cyclotron, the carbon beam can be either used directly for therapy or introduced to the main cyclotron for obtaining the final energy of 400 MeV/u. The basic requirements to the project are the following: compliance to medical requirements, compact size, feasible design, and high reliability of all systems of the complex. The advantages of the dual cyclotron design can help reaching these goals. The initial calculations show that this design is technically feasible with acceptable beam dynamics. The accelerator complex with a relatively compact size can be a good solution for medical applications. The basic parameters of the facility and detailed investigation of the magnetic system and beam dynamics are described.

Characterisation of the Native Lipid Moiety of Echinococcus granulosus Antigen B

PubMed Central

Obal, Gonzalo; Ramos, Ana Lía; Silva, Valeria; Lima, Analía; Batthyany, Carlos; Bessio, María Inés; Ferreira, Fernando; Salinas, Gustavo; Ferreira, Ana María

2012-01-01

Antigen B (EgAgB) is the most abundant and immunogenic antigen produced by the larval stage (metacestode) of Echinococcus granulosus. It is a lipoprotein, the structure and function of which have not been completely elucidated. EgAgB apolipoprotein components have been well characterised; they share homology with a group of hydrophobic ligand binding proteins (HLBPs) present exclusively in cestode organisms, and consist of different isoforms of 8-kDa proteins encoded by a polymorphic multigene family comprising five subfamilies (EgAgB1 to EgAgB5). In vitro studies have shown that EgAgB apolipoproteins are capable of binding fatty acids. However, the identity of the native lipid components of EgAgB remains unknown. The present work was aimed at characterising the lipid ligands bound to EgAgB in vivo. EgAgB was purified to homogeneity from hydatid cyst fluid and its lipid fraction was extracted using chloroform∶methanol mixtures. This fraction constituted approximately 40–50% of EgAgB total mass. High-performance thin layer chromatography revealed that the native lipid moiety of EgAgB consists of a variety of neutral (mainly triacylglycerides, sterols and sterol esters) and polar (mainly phosphatidylcholine) lipids. Gas-liquid chromatography analysis showed that 16∶0, 18∶0 and 18∶1(n-9) are the most abundant fatty acids in EgAgB. Furthermore, size exclusion chromatography coupled to light scattering demonstrated that EgAgB comprises a population of particles heterogeneous in size, with an average molecular mass of 229 kDa. Our results provide the first direct evidence of the nature of the hydrophobic ligands bound to EgAgB in vivo and indicate that the structure and composition of EgAgB lipoprotein particles are more complex than previously thought, resembling high density plasma lipoproteins. Results are discussed considering what is known on lipid metabolism in cestodes, and taken into account the Echinococcus spp. genomic information regarding both lipid metabolism and the EgAgB gene family. PMID:22616019

Silver Clusters in Zeolites: From Self-Assembly to Ground-Breaking Luminescent Properties.

PubMed

Coutiño-Gonzalez, Eduardo; Baekelant, Wouter; Steele, Julian A; Kim, Cheol Woong; Roeffaers, Maarten B J; Hofkens, Johan

2017-09-19

Interest for functional silver clusters (Ag-CLs) has rapidly grown over years due to large advances in the field of nanoscale fabrication and materials science. The continuous development of strategies to fabricate small-scale silver clusters, together with their interesting physicochemical properties (molecule-like discrete energy levels, for example), make them very attractive for a wide variety of applied research fields, from biotechnology and the environmental sciences to fundamental chemistry and physics. Apart from useful catalytic properties, silver clusters (Ag n , n < 10) were recently shown to also exhibit exceptional optical properties. The optical properties and performance of Ag-CLs offer strong potential for their integration into appealing micro(nano)-optoelectronic devices. To date, however, the rational design and directed synthesis of Ag-CLs with specific functionalities has remained elusive. The inability for rational design stems mainly from a lack of understanding of their novel atomic-scale phenomena. This is because accurately studying silver cluster systems at such a scale is hindered by the perturbations introduced during exposure to various experimental probes. For instance, silver possesses a strong tendency to cluster and form ever-larger Ag aggregates while probed with high-energy electron beams and X-ray irradiation. As well, there exists a need to provide a stabilizing environment for which Ag n δ+ clusters can persist, setting up a complex interacting guest-host system, as isolated silver clusters are confined within a suitable hosting medium. Fundamental research into Ag n δ+ formation mechanisms and their important optical properties is paramount to establishing truly informed synthesis protocols. Over recent years, we have developed several protocols for the ship-in-a-bottle synthesis of highly luminescent Ag-CLs within the microporous interiors of zeolite frameworks. This approach has yielded materials displaying a wide variety of optical properties, offering a spectrum of possible applications, from nano(micro)photonic devices to smart luminescent labels and sensors. The versatility of the Ag-zeolite multicomponent system is directly related to the intrinsic and complex tunability of the system as a whole. There are several key zeolite parameters that confer properties to the clusters, namely, the framework Si/Al ratio, choice of counterbalancing ions, silver loading, and zeolite topology, and cannot be overlooked. This Account is intended to shed light on the current state-of-the-art of luminescent Ag-CLs confined in zeolitic matrices, emphasizing the use of combinatorial approaches to overcome problems associated with the correct characterization and correlation of their structural, electronic, and photoluminescence properties, all to establish the important design principles for developing functional silver-zeolite-based materials. Additionally, examples of emerging applications and future perspectives for functional luminescent Ag-zeolite materials are addressed in this Account.

Determination of cosmogenic Ca-41 in a meteorite with tandem accelerator mass spectrometry

NASA Astrophysics Data System (ADS)

Kubik, P. W.; Elmore, D.; Conard, N. J.; Nishiizumi, K.; Arnold, J. R.

1986-02-01

The first use of tandem accelerator mass spectrometry (TAMS) to measure the content of Ca-41 in a natural sample, the iron Bogou meteorite, is reported. Ca in the samples was extracted by hydroxide precipitation and purified by means of a caution exchange resin (AG 50W-X8). After adding 4 percent ammonium oxide, the precipitate was ignited to CaO in a quartz vial at about 1100 C. The Ca-41/Ca ratios were determined following acceleration by alternate measurements of the Ca-40 beam current in an image Faraday cup. Ca-41 particles were also measured using a gas counter. The measured Ca-41/Ca ratio was 3.8 + or -0.6 x 10 to the 12th, which corresponds to a Ca-41 activity of 6.9 + or -1.1 d.p.m. per kg. Calculation of the half-life of Ca-41 in the Bogou meteorite yielded an age of 103,000 years.

Biochemical changes in cyanobacteria during the synthesis of silver nanoparticles.

PubMed

Cepoi, L; Rudi, L; Chiriac, T; Valuta, A; Zinicovscaia, I; Duca, Gh; Kirkesali, E; Frontasyeva, M; Culicov, O; Pavlov, S; Bobrikov, I

2015-01-01

The methods of synthesis of silver (Ag) nanoparticles by the cyanobacteria Spirulina platensis and Nostoc linckia were studied. A complex of biochemical, spectral, and analytical methods was used to characterize biomass and to assess changes in the main components of biomass (proteins, lipids, carbohydrates, and phycobilin) during nanoparticle formation. The size and shape of Ag nanoparticles in the biomass of both types of cyanobacteria were determined. Neutron activation analysis was used to study the accumulation dynamics of the Ag quantity. The analytical results suggest that the major reduction of Ag concentration in solutions and the increase in biomass occur within the first 24 h of experiments. While in this time interval minor changes in the N. linckia and S. platensis biomass took place, a significant reduction of the levels of proteins, carbohydrates, and phycobiliproteins in both cultures and of lipids in S. platensis was observed after 48 h. At the same time, the antiradical activity of the biomass decreased. The obtained results show the necessity of determining the optimal conditions of the interaction between the biomass and the solution containing Ag ions that would allow nanoparticle formation without biomass degradation at the time of Ag nanoparticle formation by the studied cyanobacteria.

In Situ Analysis of a Silver Nanoparticle-Precipitating Shewanella Biofilm by Surface Enhanced Confocal Raman Microscopy

PubMed Central

Schkolnik, Gal; Schmidt, Matthias; Mazza, Marco G.; Harnisch, Falk; Musat, Niculina

2015-01-01

Shewanella oneidensis MR-1 is an electroactive bacterium, capable of reducing extracellular insoluble electron acceptors, making it important for both nutrient cycling in nature and microbial electrochemical technologies, such as microbial fuel cells and microbial electrosynthesis. When allowed to anaerobically colonize an Ag/AgCl solid interface, S. oneidensis has precipitated silver nanoparticles (AgNp), thus providing the means for a surface enhanced confocal Raman microscopy (SECRaM) investigation of its biofilm. The result is the in-situ chemical mapping of the biofilm as it developed over time, where the distribution of cytochromes, reduced and oxidized flavins, polysaccharides and phosphate in the undisturbed biofilm is monitored. Utilizing AgNp bio-produced by the bacteria colonizing the Ag/AgCl interface, we could perform SECRaM while avoiding the use of a patterned or roughened support or the introduction of noble metal salts and reducing agents. This new method will allow a spatially and temporally resolved chemical investigation not only of Shewanella biofilms at an insoluble electron acceptor, but also of other noble metal nanoparticle-precipitating bacteria in laboratory cultures or in complex microbial communities in their natural habitats. PMID:26709923

One-step, room temperature, colorimetric melamine sensing using an in-situ formation of silver nanoparticles through modified Tollens process

NASA Astrophysics Data System (ADS)

Wang, Huiying; Chen, Dinglong; Yu, Longquan; Chang, Ming; Ci, Lijie

2015-02-01

We have developed a rapid, sensitive, one-step, and selective colorimetric detection method for melamine (MEL) in milk powder based upon an in-situ formation of silver nanoparticles (AgNPs) through modified Tollens process at room temperature. The triazine ring N atoms of MEL molecule were strategically designed to complex the Ag+ through electron donor-acceptor interaction. During the AgNPs formation procedure, the MEL molecule, which has been covalently bonded with the Ag+ ions, was adsorbed to the surface of as-prepared AgNPs, resulting in the aggregation of the adjacent AgNPs with detectable decreases of absorption signal. The concentration of MEL can be determined with the naked eye or a UV-vis spectrometer at which the yellow-to-brown color change associated with aggregate enhancement takes place. This method enables rapid (less than 30 min) and sensitive (limit of detection, LOD, 10 nM) detection, and it was also able to discriminate MEL from sixteen other milk relevant coexisting compounds. This assay does not utilize organic cosolvents, enzymatic reactions, light-sensitive dye molecules, lengthy protocols, or sophisticated instrumentation thereby overcoming some of the limitations of conventional methods.

A novel glucose biosensor platform based on Ag@AuNPs modified graphene oxide nanocomposite and SERS application.

PubMed

Gupta, Vinod Kumar; Atar, Necip; Yola, Mehmet Lütfi; Eryılmaz, Merve; Torul, Hilal; Tamer, Uğur; Boyacı, Ismail Hakkı; Ustündağ, Zafer

2013-09-15

This study represents a novel template demonstration of a glucose biosensor based on mercaptophenyl boronic acid (MBA) terminated Ag@AuNPs/graphene oxide (Ag@AuNPs-GO) nanomaterials. The nanocomposites were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) method. The TEM image shows that Ag@AuNPs in the nanocomposite is in the range of diameters of 10-20 nm. The nanocomposite was used for the determination of glucose through the complexation between boronic acid and diol groups of glucose. Thus, a novel glucose biosensor was further fabricated by immobilizing glucose oxidase (GOD) into MBA terminated Ag@AuNPs-GO nanocomposite film (MBA-Ag@AuNPs-GO). The linearity range of glucose was obtained as 2-6mM with detection limit of 0.33 mM. The developed biosensor was also applied successfully for the determination of glucose in blood samples. The concentration value of glucose in blood samples was calculated to be 1.97±0.002 mM from measurements repeated for six times. Copyright © 2013 Elsevier Inc. All rights reserved.

Triazole-functionalized N-heterocyclic carbene complexes of palladium and platinum and efficient aqueous Suzuki-Miyaura coupling reaction.

PubMed

Gu, Shaojin; Xu, Hui; Zhang, Na; Chen, Wanzhi

2010-07-05

Imidazolium salts bearing triazole groups are synthesized via a copper catalyzed click reaction, and the silver, palladium, and platinum complexes of their N-heterocyclic carbenes are studied. [Ag(4)(L1)(4)](PF(6))(4), [Pd(L1)Cl](PF(6)), [Pt(L1)Cl](PF(6)) (L1=3-((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)-1-(pyrimidin-2-yl)-1H-imidazolylidene), [Pd(2)(L2)(2)Cl(2)](PF(6))(2), and [Pd(L2)(2)](PF(6))(2) (L2=1-butyl-3-((1-(pyridin-2-yl)-1H-1,2,3-triazol-4-yl)methyl)imidazolylidene) have been synthesized and fully characterized by NMR, elemental analysis, and X-ray crystallography. The silver complex [Ag(4)(L1)(4)](PF(6))(4) consists of a Ag(4) zigzag chain. The complexes [Pd(L1)Cl](PF(6)) and [Pt(L1)Cl](PF(6)), containing a nonsymmetrical NCN' pincer ligand, are square planar with a chloride trans to the carbene donor. [Pd(2)(L2)(2)Cl(2)](PF(6))(2) consists of two palladium centers with CN(2)Cl coordination mode, whereas the palladium in [Pd(L2)(2)](PF(6))(2) is surrounded by two carbene and two triazole groups with two uncoordinated pyridines. The palladium compounds are highly active for Suzuki-Miyaura cross coupling reactions of aryl bromides and 1,1-dibromo-1-alkenes in neat water under an air atmosphere.

Toward a mechanistic understanding of the damage evolution of SnAgCu solder joints in accelerated thermal cycling test

NASA Astrophysics Data System (ADS)

Mahin Shirazi, Sam

Accelerated thermal cycling (ATC) tests are the most commonly used tests for the thermo-mechanical performance assessment of microelectronics assemblies. Currently used reliability models have failed to incorporate the microstructural dependency of lead free solder joint behavior and its microstructure evolution during cycling. Thus, it is essential to have a mechanistic understanding of the effect of cycling parameters on damage evolution and failure of lead free solder joints in ATC. Recrystallization has been identified as the damage rate controlling mechanism in ATC. Usually it takes 1/3 of life for completion of recrystallization regardless of cycling parameters. Thus, the life of the solder joints can be predicted by estimating global recrystallization. The objective of the first part of the study was to examine whether the damage scenario applies in service is the same as the harsh thermal cycling tests (i.e. 0/100 °C and -40/125 °C) commonly used in industry. Microstructure analysis results on a variety of lead free solder SnAgCu assemblies subjected to the both harsh (0/100 °C) and mild (20/80 °C) ATC confirmed similar failure mechanism under the both testing conditions. Sn grain morphology (interlaced versus beach ball) has a significant effect on the thermo-mechanical performance (and thus the model) of the lead free solder joints. The longer thermal cycling lifetime observed in the interlaced solder joints subjected to the ATC compared to the beach ball structure was correlated to the different initial microstructure and the microstructure evolution during cycling. For the modeling proposes, the present study was focused on Sn-Ag-Cu solder joints with either a single Sn grain or beach ball structure. Microstructural analysis results of the simulated thermal cycling experiment revealed that, the life can be approximated as determined by the accumulation of a certain amount of work during the high temperature dwells. Finally the effect of precipitates spacing on acceleration factor was investigated. Results indicated that a smaller initial precipitate spacing would tend to result in a longer life in mild thermal cycling/service (where there is lower stresses). Accordingly, it is essential to incorporate the dependence of damage rate (i.e. recrystallization) on precipitate coarsening in any predictions.

Interplay between quantum confinement and surface effects in thickness selective stability of thin Ag and Eu films

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

Liu, Xiaojie; Wang, Cai -Zhuang

Using first-principles calculations, we show that both face-centered cubic (fcc) Ag (1 1 0) ultrathin films and body-centered cubic (bcc) Eu(1 1 0) ultrathin films exhibit thickness selective stability. Furthermore, the origin of such thickness selection is different. While the thickness selective stability in fcc Ag(1 1 0) films is mainly due to the well-known quantum well states ascribed to the quantum confinement effects in free-electron-like metal films, the thickness selection in bcc Eu(1 1 0) films is more complex and also strongly correlated with the occupation of the surface and surface resonance states.

Interplay between quantum confinement and surface effects in thickness selective stability of thin Ag and Eu films

DOE PAGES

Liu, Xiaojie; Wang, Cai -Zhuang

2017-04-03

Using first-principles calculations, we show that both face-centered cubic (fcc) Ag (1 1 0) ultrathin films and body-centered cubic (bcc) Eu(1 1 0) ultrathin films exhibit thickness selective stability. Furthermore, the origin of such thickness selection is different. While the thickness selective stability in fcc Ag(1 1 0) films is mainly due to the well-known quantum well states ascribed to the quantum confinement effects in free-electron-like metal films, the thickness selection in bcc Eu(1 1 0) films is more complex and also strongly correlated with the occupation of the surface and surface resonance states.

Ameliorating Effects of Green Synthesized Silver Nanoparticles on Glycated End Product Induced Reactive Oxygen Species Production and Cellular Toxicity in Osteogenic Saos-2 Cells.

PubMed

Ashe, Sarbani; Nayak, Debasis; Kumari, Manisha; Nayak, Bismita

2016-11-09

Advanced glycation end-products (AGEs) that result from nonenzymatic glycation are one of the major factors involved in diabetes and its secondary complications and diseases. This necessitates our urge to discover new compounds that may be used as potential AGEs inhibitors without affecting the normal structure and function of biomolecules. In the present study, we investigated the inhibitory effects of AgNP (silver nanoparticles) on AGEs formation as well as their inhibitory effects on glycation mediated cell toxicity via reactive oxygen species (ROS) production and DNA damage. The excitation-emission fluorescence spectroscopy was employed to investigate the interaction of AgNP during glycation. The values of conditional stability constant (log K a = 4.44) derived from the Stern-Volmer equation indicate that AgNP have strong binding capacity for glycated protein. UV-vis, fluorescence, and Fourier transform infrared spectral data reveal complexation of AgNP with glycated bovine serum albumin, which significantly inhibits AGEs formation in a concentration-dependent manner. Cytotoxic evaluations suggest that simultaneous administration of AgNP and glycated product reduces cell death (42.82% ± 3.54) as compared to the glycated product alone. Similarly, ROS production in AgNP treated cells is significantly less compared to only glycated product treated cells. Although DNA damage studies show DNA damage in both GP and GP-AgNP treated cells, fluorescence activated cell sorting analysis demonstrates that glycated products induce cell death by necrosis, while AgNP cause cell death via apoptotic pathways. AgNP have a positive effect on restoring native protein structure deduced from spectral studies, and hence, inferences can be drawn that AgNP have ameliorating effects on glycated induced cytotoxicity observed in osteogenic Saos-2 cells.

Frequency of hepatitis B surface antigen variants (HBsAg) in hepatitis B virus genotype B and C infected East- and Southeast Asian patients: Detection by the Elecsys® HBsAg II assay.

PubMed

Kim, Hyon Suk; Chen, Xinyue; Xu, Min; Yan, Cunling; Liu, Yali; Deng, Haohui; Hoang, Bui Huu; Thuy, Pham Thi Thu; Wang, Terry; Yan, Yiwen; Zeng, Zhen; Gencay, Mikael; Westergaard, Gaston; Pabinger, Stephan; Kriegner, Albert; Nauck, Markus; Seffner, Anja; Gohl, Peter; Hübner, Kirsten; Kaminski, Wolfgang E

2018-06-01

To avoid false negative results, hepatitis B surface antigen (HBsAg) assays need to detect samples with mutations in the immunodominant 'a' determinant region, which vary by ethnographic region. We evaluated the prevalence and type of HBsAg mutations in a hepatitis B virus (HBV)-infected East- and Southeast Asian population, and the diagnostic performance of the Elecsys ® HBsAg II Qualitative assay. We analyzed 898 samples from patients with HBV infection from four sites (China [Beijing and Guangzhou], Korea and Vietnam). HBsAg mutations were detected and sequenced using highly sensitive ultra-deep sequencing and compared between the first (amino acids 124-137) and second (amino acids 139-147) loops of the 'a' determinant region using the Elecsys ® HBsAg II Qualitative assay. Overall, 237 distinct amino acid mutations in the major hydrophilic region were identified; mutations were present in 660 of 898 HBV-infected patient samples (73.5%). Within the pool of 237 distinct mutations, the majority of the amino acid mutations were found in HBV genotype C (64.8%). We identified 25 previously unknown distinct mutations, mostly prevalent in genotype C-infected Korean patients (n = 18) followed by Chinese (n = 12) patients. All 898 samples were correctly identified by the Elecsys ® HBsAg II Qualitative assay. We observed 237 distinct (including 25 novel) mutations, demonstrating the complexity of HBsAg variants in HBV-infected East- and Southeast Asian patients. The Elecsys ® HBsAg II Qualitative assay can reliably detect HBV-positive samples and is suitable for routine diagnostic use in East and Southeast Asia. Copyright © 2018 Roche Diagnostics International Ltd. Published by Elsevier B.V. All rights reserved.

The growth of intermetallic compounds at Sn-Ag-Cu solder/Cu and Sn-Ag-Cu solder/Ni interfaces and the associated evolution of the solder microstructure

NASA Astrophysics Data System (ADS)

Zribi, A.; Clark, A.; Zavalij, L.; Borgesen, P.; Cotts, E. J.

2001-09-01

The evolution of intermetallics at and near SnAgCu/Cu and SnAgCu/Ni interfaces was examined, and compared to the behavior, near PbSn/metal and Sn/metal interfaces. Two different solder compositions were considered, Sn93.6Ag4.7Cu1.7 and Sn95.5Ag3.5Cu1.0 (Sn91.8Ag5.1 Cu3.1 and Sn94.35Ag3.8Cu1.85 in atomic percent). In both cases, phase formation and growth at interfaces with Cu were very similar to those commonly observed for eutectic SnPb solder. However, the evolution of intermetallics at SnAgCu/Ni interfaces proved much more complex. The presence of the Cu in the solder dramatically altered the phase selectivity at the solder/Ni interface and affected the growth kinetics of intermetallics. As long as sufficient Cu was available, it would combine with Ni and Sn to form (Cu,Ni)6)Sn5 which grew instead of the Ni3Sn4 usually observed in PbSn/Ni and Sn/Ni diffusion couples. This growing phase would, however, eventually consume essentially all of the available Cu in the solder. Because the mechanical properties of Sn-Ag-Cu alloys, depend upon the Cu content, this consumption can be expected to alter the mechanical properties of these Pb-free solderjoints. After depletion of the Cu from the solder, further annealing then gradually transformed the (Cu,Ni)6Sn5 phase into a (Ni,Cu)3Sn4 phase.

Surface-enhanced Raman scattering from metal and transition metal nano-caped arrays

NASA Astrophysics Data System (ADS)

Sun, Huanhuan; Gao, Renxian; Zhu, Aonan; Hua, Zhong; Chen, Lei; Wang, Yaxin; Zhang, Yongjun

2018-03-01

The metal and transition metal cap-shaped arrays on polystyrene colloidal particle (PSCP) templates were fabricated to study the surface-enhanced Raman scattering (SERS) effect. We obtained the Ag and Fe complex film by a co-sputtering deposition method. The size of the deposited Fe particle was changed by the sputtering power. We also study the SERS enhancement mechanism by decorating the PATP probe molecule on the different films. The SERS signals increased firstly, and then decreased as the size of Fe particles grows gradually. The finite-difference time domain (FDTD) simulation and experimental Raman results manifest that SERS enhancement was mainly attributed to surface plasma resonance (SPR) between Ag and Ag nanoparticles. The SERS signals of PATP molecule were enhanced to reach a lowest detectable concentration of 10-8 mol/L. The research demonstrates that the SERS substrates with Ag-Fe cap-shaped arrays have a high sensitivity.

Ag Nanoparticles-enhanced Fluorescence of Terbium-Deferasirox Complexes for the Highly Sensitive Determination of Deferasirox.

PubMed

Abolhasani, Jafar; Naderali, Roza; Hassanzadeh, Javad

2016-01-01

We describe the effect of different sized gold and silver nanoparticles on the terbium sensitized fluorescence of deferasirox. It is indicated that silver nanostructures, especially 18 nm Ag nanoparticles (AgNPs), have a remarkable amplifying effect compared to Au nanoparticles. Based on this observation, a highly sensitive and selective method was developed for the determination of deferasirox. Effects of various parameters like AgNPs and Tb(3+) concentration and pH of media were investigated. Under the optimal conditions, a calibration curve was plotted as the fluorescence intensities versus the concentration of deferasirox in the range of 0.1 to 200 nmol L(-1), and detection limit of 0.03 nmol L(-1) was obtained. The method has good linearity, recovery, reproducibility and sensitivity, and was satisfactorily applied for the determination of deferasirox in urine and pharmaceutical samples.

Imaging charge transfer in a cation-π system: velocity-map imaging of Ag(+)(benzene) photodissociation.

PubMed

Maner, Jonathon A; Mauney, Daniel T; Duncan, Michael A

2015-11-19

Ag(+)(benzene) complexes are generated in the gas phase by laser vaporization and mass selected in a time-of-flight spectrometer. UV laser excitation at either 355 or 266 nm results in dissociative charge transfer (DCT), leading to neutral silver atom and benzene cation products. Kinetic energy release in translationally hot benzene cations is detected using a new instrument designed for photofragment imaging of mass-selected ions. Velocity-map imaging and slice imaging techniques are employed. In addition to the expected translational energy release, DCT of Ag(+)(benzene) produces a distribution of internally hot benzene cations. Compared with experiments at 355 nm, 266 nm excitation produces only slightly higher translational excitation and a much greater fraction of internally hot benzene ions. The maximum kinetic energy release in the photodissociation sets an upper limit on the Ag(+)(benzene) dissociation energy of 32.8 (+1.4/-1.5) kcal/mol.

In vivo quantification of amygdala subnuclei using 4.7 T fast spin echo imaging.

PubMed

Aghamohammadi-Sereshki, Arash; Huang, Yushan; Olsen, Fraser; Malykhin, Nikolai V

2018-04-15

The amygdala (AG) is an almond-shaped heterogeneous structure located in the medial temporal lobe. The majority of previous structural Magnetic Resonance Imaging (MRI) volumetric methods for AG measurement have so far only been able to examine this region as a whole. In order to understand the role of the AG in different neuropsychiatric disorders, it is necessary to understand the functional role of its subnuclei. The main goal of the present study was to develop a reliable volumetric method to delineate major AG subnuclei groups using ultra-high resolution high field MRI. 38 healthy volunteers (15 males and 23 females, 21-60 years of age) without any history of medical or neuropsychiatric disorders were recruited for this study. Structural MRI datasets were acquired at 4.7 T Varian Inova MRI system using a fast spin echo (FSE) sequence. The AG was manually segmented into its five major anatomical subdivisions: lateral (La), basal (B), accessory basal (AB) nuclei, and cortical (Co) and centromedial (CeM) groups. Inter-(intra-) rater reliability of our novel volumetric method was assessed using intra-class correlation coefficient (ICC) and Dice's Kappa. Our results suggest that reliable measurements of the AG subnuclei can be obtained by image analysts with experience in AG anatomy. We provided a step-by-step segmentation protocol and reported absolute and relative volumes for the AG subnuclei. Our results showed that the basolateral (BLA) complex occupies seventy-eight percent of the total AG volume, while CeM and Co groups occupy twenty-two percent of the total AG volume. Finally, we observed no hemispheric effects and no gender differences in the total AG volume and the volumes of its subnuclei. Future applications of this method will help to understand the selective vulnerability of the AG subnuclei in neurological and psychiatric disorders. Copyright © 2017 Elsevier Inc. All rights reserved.

Measurement of Charged Particle Interactions in Spacecraft and Planetary Habitat Shielding Materials

NASA Technical Reports Server (NTRS)

Zeitlin, Cary J.; Heilbronn, Lawrence H.; Miller, Jack; Wilson, John W.; Singleterry, Robert C., Jr.

2003-01-01

Accurate models of health risks to astronauts on long-duration missions outside the geomagnetosphere will require a full understanding of the radiation environment inside a spacecraft or planetary habitat. This in turn requires detailed knowledge of the flux of incident particles and their propagation through matter, including the nuclear interactions of heavy ions that are a part of the Galactic Cosmic Radiation (GCR). The most important ions are likely to be iron, silicon, oxygen, and carbon. Transport of heavy ions through complex shielding materials including self-shielding of tissue modifies the radiation field at points of interest (e.g., at the blood-forming organs). The incident flux is changed by two types of interactions: (1) ionization energy loss, which results in reduced particle velocity and higher LET (Linear Energy Transfer); and (2) nuclear interactions that fragment the incident nuclei into less massive ions. Ionization energy loss is well understood, nuclear interactions less so. Thus studies of nuclear fragmentation at GCR-like energies are needed to fill the large gaps that currently exist in the database. These can be done at only a few accelerator facilities where appropriate beams are available. Here we report results from experiments performed at the Brookhaven National Laboratory s Alternating Gradient Synchrotron (AGS) and the Heavy Ion Medical Accelerator in Chiba, Japan (HIMAC). Recent efforts have focused on extracting charge-changing and fragment production cross sections from silicon beams at 400, 600, and 1200 MeV/nucleon. Some energy dependence is observed in the fragment production cross sections, and as in other data sets the production of fragments with even charge numbers is enhanced relative to those with odd charge numbers. These data are compared to the NASA-LaRC model NUCFRG2. The charge-changing cross section data are compared to recent calculations using an improved model due to Tripathi, which accurately predicts the observed (slight) energy dependence. An additional set of data will be presented from an analysis of shielding material performance in the 1 GeV/nucleon iron beam at the AGS. A wide variety of candidate materials for spacecraft construction, as well as elemental targets, have been placed in this beam and their effects on transmitted dose and dose equivalent measured. The results support a prediction by J. Wilson et al. that hydrogen-loaded materials give the greatest dose reduction per unit mass.

Fermilab | Tritium at Fermilab | Frequently asked questions

Science.gov Websites

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Colorimetric detection of ammonia using smartphones based on localized surface plasmon resonance of silver nanoparticles.

PubMed

Amirjani, Amirmostafa; Fatmehsari, Davoud Haghshenas

2018-01-01

In this work, a rapid and straightforward method was developed for colorimetric determination of ammonia using smartphones. The mechanisms is based on the manipulation of the surface plasmon band of silver nanoparticles (AgNPs) via the formation of Ag (NH 3 ) 2 + complex. This complex decreases the amount of AgNPs in the solution and consequently, the color intensity of the colloidal system decreases. Not only the variation in color intensity of the solution can be tracked by a UV-vis spectrophotometer, but also a smartphone can be employed to monitor the color intensity variation by RGB analysis. Ammonia, in the concentration range of 10-1000mgL -1 , was successfully measured spectrophotometrically (UV-vis spectrophotometer) and colorimetrically (RGB measurement) with the detection limit of 180 and 200mgL -1 , respectively. Linear relationships were also developed for both methods. Also, the response time of the developed colorimetric sensor was around 20s. Both of the colorimetric and spectrophotometric methods showed a reliable performance for determination of ammonia in the real samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Surface-confined Ullmann coupling of thiophene substituted porphyrins

NASA Astrophysics Data System (ADS)

Beggan, J. P.; Boyle, N. M.; Pryce, M. T.; Cafolla, A. A.

2015-09-01

The covalent coupling of (5,10,15,20-tetrabromothien-2-ylporphyrinato)zinc(II) (TBrThP) molecules on the Ag(111) surface has been investigated under ultra-high-vacuum conditions, using scanning tunnelling microscopy and x-ray photoelectron spectroscopy. The findings provide atomic-level insight into surface-confined Ullmann coupling of thiophene substituted porphyrins, analyzing the progression of organometallic intermediate to final coupled state. Adsorption of the TBrThP molecules on the Ag(111) surface at room temperature is found to result in the reductive dehalogenation of the bromothienyl substituents and the subsequent formation of single strand and crosslinked coordination networks. The coordinated substrate atoms bridge the proximal thienyl groups of the organometallic intermediate, while the cleaved bromine atoms are bound on the adjacent Ag(111) surface. The intermediate complex displays a thermal lability at ˜423 K that results in the dissociation of the proximal thienyl groups with the concomitant loss of the surface bound bromine. At the thermally induced dissociation of the intermediate complex the resultant thienylporphyrin derivatives covalently couple, leading to the formation of a polymeric network of thiophene linked and meso-meso fused porphyrins.

The Vip3Ag4 Insecticidal Protoxin from Bacillus thuringiensis Adopts A Tetrameric Configuration That Is Maintained on Proteolysis

PubMed Central

Palma, Leopoldo; Scott, David J.; Harris, Gemma; Din, Salah-Ud; Williams, Thomas L.; Roberts, Oliver J.; Young, Mark T.; Caballero, Primitivo; Berry, Colin

2017-01-01

The Vip3 proteins produced during vegetative growth by strains of the bacterium Bacillus thuringiensis show insecticidal activity against lepidopteran insects with a mechanism of action that may involve pore formation and apoptosis. These proteins are promising supplements to our arsenal of insecticidal proteins, but the molecular details of their activity are not understood. As a first step in the structural characterisation of these proteins, we have analysed their secondary structure and resolved the surface topology of a tetrameric complex of the Vip3Ag4 protein by transmission electron microscopy. Sites sensitive to proteolysis by trypsin are identified and the trypsin-cleaved protein appears to retain a similar structure as an octomeric complex comprising four copies each of the ~65 kDa and ~21 kDa products of proteolysis. This processed form of the toxin may represent the active toxin. The quality and monodispersity of the protein produced in this study make Vip3Ag4 a candidate for more detailed structural analysis using cryo-electron microscopy. PMID:28505109

Earthquake response of storey building in Jakarta using accelerographs data analysis

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

Julius, Admiral Musa, E-mail: admiralmusajulius@yahoo.com; Jakarta Geophysics Observatory, Indonesia Agency of Meteorology Climatology and Geophysics; Sunardi, Bambang, E-mail: b.sunardi@gmail.com

As seismotectonic, the Jakarta city will be greatly affected by the earthquake which originated from the subduction zone of the Sunda Strait and south of Java. Some occurrences of earthquakes in these location are often perceived by the occupants in the upper floors of multi-storey buildings in Jakarta but was not perceived by the occupants on the ground floor. The case shows the difference in ground-motion parameters on each floor height. The analysis of the earthquake data recorded by accelerographs on different floors need to be done to know the differences in ground-motion parameters. Data used in this research ismore » accelerograph data installed on several floors in the main building of Meteorology Climatology and Geophysics Agency with a case study of Kebumen earthquake on January 25{sup th} 2014. Parameters analyzed include the Peak Ground Acceleration (PGA), Peak Ground Displacement (PGD), Peak Spectral Acceleration (PSA), Amplification (Ag), and the Effective Duration of earthquake (t{sub e}). Research stages include accelerographs data acquisition in three (3) different floors, conversion and data partition for each component, conversion to units of acceleration, determination of PGA, PGD, PSA, Ag and t{sub e} as well as data analysis. The study shows the value of PGA on the ground floor, 7{sup th} floor and 15{sup th} floors, respectively are 0.016 g, 0.053 g and 0.116 g. PGD on the ground floor, 7{sup th} floor and 15{sup th} floor respectively are 2.15 cm, 2.98 cm and 4.92 cm. PSA on the ground floor, 7{sup th} floor and 15{sup th} floor respectively are 0.067 g, 0.308 g and 0.836 g. Amplification of the peak acceleration value on the ground floor, 7{sup th} floor and 15{sup th} floor to the surface rock are 4.37, 6.07 and 7.30. Effective duration of the earthquake on the ground floor, 7{sup th} floor and 15{sup th} floor respectively are 222.28 s, 202.28 s and 91.58 s. In general, with increasing floor of the building, the value of the peak ground acceleration, peak ground displacement, peak spectral acceleration and amplification growing, contrary to the value of the effective duration of earthquake decreases. The difference in this parameter is strongly influenced by local soil conditions and building construction.« less

Visual Identification of Light-Driven Breakage of the Silver-Dithiocarbamate Bond by Single Plasmonic Nanoprobes

PubMed Central

Gao, Peng Fei; Yuan, Bin Fang; Gao, Ming Xuan; Li, Rong Sheng; Ma, Jun; Zou, Hong Yan; Li, Yuan Fang; Li, Ming; Huang, Cheng Zhi

2015-01-01

Insight into the nature of metal-sulfur bond, a meaningful one in life science, interface chemistry and organometallic chemistry, is interesting but challenging. By utilizing the localized surface plasmon resonance properties of silver nanoparticles, herein we visually identified the photosensitivity of silver-dithiocarbamate (Ag-DTC) bond by using dark field microscopic imaging (iDFM) technique at single nanoparticle level. It was found that the breakage of Ag-DTC bond could be accelerated effectively by light irradiation, followed by a pH-dependent horizontal or vertical degradation of the DTC molecules, in which an indispensable preoxidation process of the silver was at first disclosed. These findings suggest a visualization strategy at single plasmonic nanoparticle level which can be excellently applied to explore new stimulus-triggered reactions, and might also open a new way to understand traditional organic reaction mechanisms. PMID:26493773

Electromigration induced high fraction of compound formation in SnAgCu flip chip solder joints with copper column

NASA Astrophysics Data System (ADS)

Xu, Luhua; Han, Jung-Kyu; Liang, Jarrett Jun; Tu, K. N.; Lai, Yi-Shao

2008-06-01

To overcome the effect of current crowding on electromigration-induced pancake-type void formation in flip chip solder joints, two types of Cu column in 90μm flip chip SnAgCu solder joints have been studied. They were (1) the solder contacts the Cu column at bottom and side walls and (2) the solder wets only the bottom surface of the copper column. With a current density of 1.6×104A/cm2 at 135°C, no failure was detected after 1290h. However, the resistance increased by about 10% due to the formation of a large fraction of intermetallic compounds. We found that electromigration has accelerated the consumption rate of copper column and converted almost the entire solder joint into intermetallic compound. Mechanically, drop impact test indicates a brittle fracture failure in the intermetallic. The electromigration critical product for the intermetallic is discussed.

Prospects for the study of the properties of dense nuclear matter at the NICA heavy-ion complex at JINR (Dubna)

NASA Astrophysics Data System (ADS)

Kolesnikov, V. I.

2017-06-01

The NICA (Nuclotron-based Ion Collider fAcility) project is aimed in the construction at JINR (Dubna) a modern accelerator complex equipped with three detectors: the MultiPurpose Detector (MPD) and the Spin Physics Detector (SPD) at the NICA collider, as well as a fixed target experiment BM&N which will be use extracted beams from the Nuclotron accelerator. In this report, an overview of the main physics objectives of the NICA heavy-ion program will be given and the recent progress in the NICA construction (both accelerator complex and detectors) will be described.

Neutral Guest Capture via Lewis Acid/Base Molecular Square Receptors. X-ray Crystal Structure of {Cyclobis[(cis-(dppp)Pt(4-ethynylpyridyl)(2))(cis- (PEt(3))(2)Pt)]Ag(2)}(+6)(phenazine)- ((-)OSO(2)CF(3))(6).

PubMed

Whiteford, Jeffery A.; Stang, Peter J.; Huang, Songping D.

1998-10-19

Interaction of {cyclobis[(cis-(dppp)Pt(4-ethynylpyridyl)(2))(cis-(L)M)]Ag(2)}(+6)((-)OSO(2)CF(3))(6), where M = Pt(II) or Pd(II) and L = dppp or 2PEt(3), with pyridine, pyrazine, phenazine, or 4,4'-dipyridyl ketone results in coordination Lewis acid/base host-guest assemblies via the "pi-tweezer effect" and mono or bis neutral guest coordination. All host-guest complexes are air stable microcrystalline solids with decomposition points greater than 170 degrees C. The homometallic Pt(II) receptors are more stable than the heteroaromatic Pt(II)-Pd(II) receptors toward heteratom-containing aromatic guests. The X-ray crystal structure of the host-guest complex {cyclobis[(cis-(dppp)Pt(4-ethynylpyridyl)(2))(cis-(PEt(3))(2)Pt)]Ag(2)}(+6)(phenazine)((-)OSO(2)CF(3))(6) is reported. The crystals with the empirical formula C(62)H(68)AgF(9)N(3)O(9)P(4)Pt(2)S(3) are triclinic P&onemacr; with a = 12.3919(8) Å, b = 17.160(1) Å, c = 18.932(1) Å, alpha = 90.892(1) degrees, beta = 97.127(1) degrees, gamma = 89.969(1) degrees, and Z = 2.

Multifunctional silver nanocluster-hybrid oligonucleotide vehicle for cell imaging and microRNA-targeted gene silencing.

PubMed

Chen, Hau-Yun; Albert, Karunya; Wen, Cheng-Che; Hsieh, Pei-Ying; Chen, Sih-Yu; Huang, Nei-Chung; Lo, Shen-Chuan; Chen, Jen-Kun; Hsu, Hsin-Yun

2017-04-01

Novel therapeutics is urgently needed to prevent cancer-related deaths. MicroRNAs that act as tumor suppressors have been recognized as a next-generation tumor therapy, and the restoration of tumor-suppressive microRNAs using microRNA replacements or mimics may be a less toxic, more effective strategy due to fewer off-target effects. Here, we designed the novel multifunctional oligonucleotide nanocarrier complex composed of a tumor-targeting aptamer sequence specific to mucin 1 (MUC1), poly-cytosine region for fluorescent silver nanocluster (AgNC) synthesis, and complimentary sequence for microRNA miR-34a loading. MiR-34a was employed because of its therapeutic effect of inhibiting oncogene expression and inducing apoptosis in carcinomas. By monitoring the intrinsic fluorescence of AgNC, it was clearly shown that the constructed complex (MUC1-AgNC m -miR-34a) enters MCF-7 cells. To evaluate the efficacy of this nanocarrier for microRNA delivery, we investigated the gene and protein expression levels of downstream miR-34a targets (BCL-2, CDK6, and CCND1) by quantitative PCR and western blotting, respectively, and the results indicated their effective inhibition by miR-34a. This novel multifunctional AgNC-based nanocarrier can aid in improving the efficacy of breast cancer theranostics. Copyright © 2017 Elsevier B.V. All rights reserved.

High purity silver microcrystals recovered from silver wastes by eco-friendly process using hydrogen peroxide.

PubMed

Gatemala, Harnchana; Ekgasit, Sanong; Wongravee, Kanet

2017-07-01

A simple, rapid, and environmentally friendly process using hydrogen peroxide, was developed for recovering high purity silver directly from industry and laboratory wastes. Silver ammine complex, [Ag(NH 3 ) 2 ] + Cl - , derived from AgCl were generated and then directly reduced using H 2 O 2 to reliably turn into high purity microcrystalline silver (99.99%) examined by EDS and XRD. Morphology of the recovered silver microcrystals could be selectively tuned by an addition of poly(vinyl pyrrolidone). The main parameters in the recovering process including pH, concentration of Ag + and the mole ratio of H 2 O 2 :Ag + were carefully optimized though the central composite design (CCD). The optimized condition was employed for a trial recovery of 50 L silver ammine complex prepared from a collection of silver-wastes during 3-year research on industrial nanoparticle production. The recovered silver microcrystals >700 g could be recovered with 91.27%. The remaining solution after filtering of the recovered silver microcrystals can be used repeatedly (at least 8 cycles) without losing recovery efficiency. Matrix interferences including Pb 2+ and Cl - play a minimal role in our silver recovery process. Furthermore, the direct usage of the recovered silver microcrystals was demonstrated by using as a raw material of silver clay for creating a set of wearable silver jewelries. Copyright © 2017 Elsevier Ltd. All rights reserved.

Anopheles gambiae Purine Nucleoside Phosphorylase: Catalysis, Structure, and Inhibition

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

Taylor,E.; Rinaldo-Matthis, A.; Li, L.

The purine salvage pathway of Anopheles gambiae, a mosquito that transmits malaria, has been identified in genome searches on the basis of sequence homology with characterized enzymes. Purine nucleoside phosphorylase (PNP) is a target for the development of therapeutic agents in humans and purine auxotrophs, including malarial parasites. The PNP from Anopheles gambiae (AgPNP) was expressed in Escherichia coli and compared to the PNPs from Homo sapiens (HsPNP) and Plasmodium falciparum (PfPNP). AgPNP has kcat values of 54 and 41 s-1 for 2'-deoxyinosine and inosine, its preferred substrates, and 1.0 s-1 for guanosine. However, the chemical step is fast formore » AgPNP at 226 s-1 for guanosine in pre-steady-state studies. 5'-Deaza-1'-aza-2'-deoxy-1'-(9-methylene)-Immucillin-H (DADMe-ImmH) is a transition-state mimic for a 2'-deoxyinosine ribocation with a fully dissociated N-ribosidic bond and is a slow-onset, tight-binding inhibitor with a dissociation constant of 3.5 pM. This is the tightest-binding inhibitor known for any PNP, with a remarkable Km/Ki* of 5.4 x 107, and is consistent with enzymatic transition state predictions of enhanced transition-state analogue binding in enzymes with enhanced catalytic efficiency. Deoxyguanosine is a weaker substrate than deoxyinosine, and DADMe-Immucillin-G is less tightly bound than DADMe-ImmH, with a dissociation constant of 23 pM for AgPNP as compared to 7 pM for HsPNP. The crystal structure of AgPNP was determined in complex with DADMe-ImmH and phosphate to a resolution of 2.2 Angstroms to reveal the differences in substrate and inhibitor specificity. The distance from the N1' cation to the phosphate O4 anion is shorter in the AgPNP{center_dot}DADMe-ImmH{center_dot}PO4 complex than in HsPNP{center_dot}DADMe-ImmH{center_dot}SO4, offering one explanation for the stronger inhibitory effect of DADMe-ImmH for AgPNP.« less

SERS-Based Flavonoid Detection Using Ethylenediamine-β-Cyclodextrin as a Capturing Ligand

PubMed Central

Choi, Jae Min; Hahm, Eunil; Park, Kyeonghui; Jeong, Daham; Rho, Won-Yeop; Kim, Jaehi; Jeong, Dae Hong; Lee, Yoon-Sik; Jhang, Sung Ho; Chung, Hyun Jong; Cho, Eunae; Yu, Jae-Hyuk; Jun, Bong-Hyun; Jung, Seunho

2017-01-01

Ethylenediamine-modified β-cyclodextrin (Et-β-CD) was immobilized on aggregated silver nanoparticle (NP)-embedded silica NPs (SiO2@Ag@Et-β-CD NPs) for the effective detection of flavonoids. Silica NPs were used as the template for embedding silver NPs to create hot spots and enhance surface-enhanced Raman scattering (SERS) signals. Et-β-CD was immobilized on Ag NPs to capture flavonoids via host-guest inclusion complex formation, as indicated by enhanced ultraviolet absorption spectra. The resulting SiO2@Ag@Et-β-CD NPs were used as the SERS substrate for detecting flavonoids, such as hesperetin, naringenin, quercetin, and luteolin. In particular, luteolin was detected more strongly in the linear range 10−7 to 10−3 M than various organic molecules, namely ethylene glycol, β-estradiol, isopropyl alcohol, naphthalene, and toluene. In addition, the SERS signal for luteolin captured by the SiO2@Ag@Et-β-CD NPs remained even after repeated washing. These results indicated that the SiO2@Ag@Et-β-CD NPs can be used as a rapid, sensitive, and selective sensor for flavonoids. PMID:28336842

Cyclo[n]pyrroles: Size and Site Specific Binding to G-Quadruplexes

PubMed Central

Baker, Erin Shammel; Lee, Jeong T.

2014-01-01

Inhibiting the enzyme telomerase by stabilizing the G-quadruplex has potential in anticancer drug design. Diprotonated cyclo[n]pyrroles represent a set of expanded porphyrin analogues with structures similar to telomestatin, a natural product known to bind to and stabilize G-quadruplexes. As a first step towards testing whether cyclo[n]pyrroles display a similar function, a series of diprotonated cyclo[n]pyrroles (where n = 6, 7 and 8) was each added to the human telomere repeat sequence d(T2AG3)4 and examined with mass spectrometry, ion mobility and molecular dynamics calculations. Nano-ESI-MS indicated that the smaller the cyclo[n]pyrrole, the stronger it binds to the telomeric sequence. It was also found that cyclo[6]pyrrole bound to d(T2AG3)4 better than octaethylporphyrin, a finding rationalized by cyclo[6]pyrrole having a +2 charge, while octaethylporphyrin bears no charge. Ion mobility measurements were used to measure the collision cross section of each d(T2AG3)4/cyclo[n]pyrrole complex. Only one peak was observed in the arrival time distributions for all complexes and the experimental cross sections indicated that only structures with d(T2AG3)4 in an antiparallel G-quadruplex arrangement and each cyclo[n]pyrrole externally stacked below the G-quartets occur under these experimental conditions. When the cyclo[n]pyrroles were intercalated or nonspecifically bound to the quadruplex or if different conformations than antiparallel were considered for d(T2AG3)4, the theoretical cross sections did not match experiment. On this basis, it is inferred that 1) external stacking represents the dominant binding mode for the interaction of cyclo[n]pyrroles with d(T2AG3)4 and 2) the overall size and charge of the cyclo[n]pyrroles play important roles in defining the binding strength. PMID:16492050

Efficient interfacial charge transfer through plasmon sensitized Ag@Bi2O3 hierarchical photoanodes for photoelectrocatalytic degradation of chlorinated phenols.

PubMed

Eswar, Neerugatti KrishnaRao; Adhikari, Sangeeta; Ramamurthy, Praveen C; Madras, Giridhar

2018-01-31

The present work demonstrates an extremely proficient and robust study of efficient interfacial charge transfer through plasmonic Ag decorated Bi 2 O 3 hierarchical photoanodes for the photoelectrochemical treatment of chlorinated phenols. Unique 2D flake-like Bi 2 O 3 hierarchical nanostructures were grown onto a fluorine-doped tin oxide (FTO) substrate by a simple chemical bath deposition method using triethanolamine as complexing agent. The formation of Bi 2 O 3 on FTO was governed by the decomposition of a nucleated bismuth-hydroxyl complex (Bi 2 O 1-x (OH) x ) and modification to the electrode was carried out by the deposition of Ag via a chemical reduction method using hydrazine hydrate. Both the fabricated electrodes were well characterized for their photo- and electro-optical properties. Efficient charge separation was observed due to the surface plasmon resonance phenomenon of silver nanoparticles with the favorable intrinsic properties of Bi 2 O 3 under application of a small electric bias of 1 V preventing the recombination of charge carriers and thereby increasing the rate of photoelectrocatalytic degradation of the chlorinated phenols. PEC degradation using the Ag@Bi 2 O 3 photoelectrode followed the trend 4-CP < 2,4-DCP < 2,4,6-TCP < P-CP due to efficient attack at the chlorinated positions by reactive oxygen species with increasing chlorine substitution and also due to the absence of an expected chain reaction of the generated chlorine radicals (Cl˙) during the PEC reaction. The PEC activity of Ag@Bi 2 O 3 was 1.5 times higher than a Bi 2 O 3 nanoflake electrode for 4-CP over 2 h. The fabricated Ag@Bi 2 O 3 proved to be an efficient photoelectrode with synergistic solar-induced photoactivity. A detailed mechanistic study in the presence of scavengers suggests degradation by produced hydroxyl radical species. Thus, physical insights into the degradation of chlorinated phenols were obtained.

Adsorption, vibration and diffusion of oxygen on Ag(110)

NASA Astrophysics Data System (ADS)

Rawal, Takat; Hong, Sampyo; Pulkkinen, Aki; Alatalo, Matti; Rahman, Talat

2015-03-01

We have performed density functional theory calculations for the adsorption, vibration and diffusion of oxygen on Ag(110). At low coverage, O2 adsorbs at the four-fold hollow (FFH) with the molecular axis aligned along the [ 1 1 0 ] direction. The dissociation of O2 is easier along the [001] direction than along the [ 1 1 0 ] direction. For O2 species in FFH aligned along the [001] the O-O intra-molecular stretching mode is coupled with the substrate vibration and thus its dissociation can be induced by surface phonon. In addition, O diffusion barrier from FFH to next FFH along the [ 1 1 0 ] is small (0.07 eV only) but is by far larger (0.4 eV) along [001]. On the other hand, O species in the short-bride (SB) site prefers to diffuse along the [001] (to FFH) rather than along the [ 1 1 0 ] direction (to next SB). Finally, the preference of atomic oxygen to form O-Ag-O complex on Ag(110) is responsible for disordering of the surface by means of substantial lateral and vertical displacements of Ag atoms in the topmost layer. In fact, such disordering phase of Ag(110) may act as a precursor of the reconstructed phase of Ag(110). Work supported in part by NSF under Grant CHE-1310327.

Baseline characteristics of HIV & hepatitis B virus (HIV/HBV) co-infected patients from Kolkata, India

PubMed Central

Sarkar, Jayeeta; Saha, Debraj; Bandyopadhyay, Bhaswati; Saha, Bibhuti; Kedia, Deepika; Guha Mazumder, D.N.; Chakravarty, Runu; Guha, Subhasish Kamal

2016-01-01

Background & objectives: Hepatitis B virus (HBV) and HIV co-infection has variable prevalence worldwide. In comparison to HBV mono-infection, the course of chronic HBV infection is accelerated in HIV/HBV co-infected patients. The present study was carried out to analyse the baseline characteristics (clinical, biochemical, serological and virological) of treatment naïve HIV/HBV co-infected and HIV mono-infected patients. Methods: Between July 2011 and January 2013, a total number of 1331 HIV-seropositive treatment naïve individuals, enrolled in the ART Centre of Calcutta School of Tropical Medicine, Kolkata, India, were screened for hepatitis B surface antigen (HBsAg). A total of 1253 HIV mono-infected and 78 HIV/HBV co-infected patients were characterized. The co-infected patients were evaluated for HBeAg and anti-HBe antibody by ELISA. HIV RNA was quantified for all co-infected patients. HBV DNA was detected and quantified by real time-PCR amplification followed by HBV genotype determination. Results: HIV/HBV co-infected patients had proportionately more advanced HIV disease (WHO clinical stage 3 and 4) than HIV mono-infected individuals (37.1 vs. 19.9%). The co-infected patients had significantly higher serum bilirubin, alanine aminotransferase (ALT), alkaline phosphatase and ALT/platelet ratio index (APRI). CD4 count was non-significantly lower in co-infected patients. Majority (61.5%) were HBeAg positive with higher HIV RNA (P<0.05), HBV DNA (P<0.001) and APRI (P<0.05) compared to those who were HBeAg negative. HBV/D was the predominant genotype (73.2%) and D2 (43.7%) was the commonest subgenotype. Interpretation & conclusions: HIV/HBV co-infected patients had significantly higher serum bilirubin, ALT, alkaline phosphatase and lower platelet count. HBeAg positive co-infected patients had higher HIV RNA and HBV DNA compared to HBeAg negative co-infected patients. Prior to initiation of antiretroviral treatment (ART) all patients should be screened for HBsAg to initiate appropriate ART regimen. PMID:27488008

Halide addition/abstraction in phosphido derivatives: isolation of the thallium and silver intermediates.

PubMed

Forniés, Juan; Fortuño, Consuelo; Ibáñez, Susana; Martín, Antonio

2008-07-07

Reaction of unsaturated (44e (-) skeleton) [PdPt 2(mu-PPh 2) 2(mu-P 2Ph 4)(R F) 4] 4 with Br (-) produces the saturated (48e (-) skeleton) complex [NBu 4][(R F) 2Pt(mu-PPh 2)(mu-Br)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 5 without any M-M' bond. Attempts to eliminate Br (-) of 5 with Ag (+) in CH 2Cl 2 as a solvent gives a mixture of [(R F) 2Pt (III)(mu-PPh 2) 2Pt (III)(R F) 2] and some other unidentified products as a consequence of oxidation and partial fragmentation. However, when the reaction of 5 with Ag (+) is carried out in CH 3CN, no oxidation is observed but the elimination of Br (-) and the formation of [(R F) 2(CH 3CN)Pt(mu-PPh 2)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 6 (46e (-) skeleton), a complex with a Pt-Pd bond, takes place. It is noteworthy that the reaction of 5 with TlPF 6 in CH 2Cl 2 does not precipitate TlBr but forms the adduct [(R F) 2PtTl(mu-PPh 2)(mu-Br)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 7 with a Pt-Tl bond. Likewise, 5 reacts with [AgOClO 3(PPh 3)] in CH 2Cl 2 forming the adduct [AgPdPt 2(mu-Br)(mu-PPh 2) 2(mu-Ph 2P-PPh 2)(R F) 4(PPh 3)] 8, which contains a Pt-Ag bond. Both adducts are unstable in a CH 3CN solution, precipitating TlBr or AgBr and yielding the unsaturated 6. The treatment of [NBu 4] 2[(R F) 2Pt(mu-PPh 2) 2Pd(mu-PPh 2) 2Pt(R F) 2] in CH 3CN with I 2 (1:1 molar ratio) at 233 K yields a mixture of 4 and 6, which after recrystallization from CH 2Cl 2 is totally converted in 4. If the reaction with I 2 is carried out at room temperature, a mixture of the isomers [NBu 4][(R F) 2Pt(mu-PPh 2)(mu-I)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 9 and [NBu 4][(R F)(PPh 2R F)Pt(mu-PPh 2)(mu-I)Pd(mu-PPh 2) 2Pt(R F) 2] 10 are obtained. The structures of the complexes have been established on the bases of NMR data, and the X-ray structures of 5- 8 have been studied. The relationship between the different complexes has been studied.

Heterobimetallic Silver-Iron Complexes Involving Fe(CO)5 Ligands.

PubMed

Wang, Guocang; Ceylan, Yavuz S; Cundari, Thomas R; Dias, H V Rasika

2017-10-11

Iron(0) pentacarbonyl is an organometallic compound with a long history. It undergoes carbonyl displacement chemistry with various donors (L), leading to molecules of the type Fe(CO) x (L) 5-x . The work reported here illustrates that Fe(CO) 5 can also act as a ligand. The reaction between Fe(CO) 5 with the silver salts AgSbF 6 and Ag[B{3,5-(CF 3 ) 2 C 6 H 3 } 4 ] under appropriate conditions resulted in the formation of [(μ-H 2 O)AgFe(CO) 5 ] 2 [SbF 6 ] 2 and [B{3,5-(CF 3 ) 2 C 6 H 3 } 4 ]AgFe(CO) 5 , respectively, featuring heterobimetallic {Ag-Fe(CO) 5 } + fragments. The treatment of [B{3,5-(CF 3 ) 2 C 6 H 3 } 4 ]AgFe(CO) 5 with 4,4'-dimethyl-2,2'-bipyridine (Me 2 Bipy) and Fe(CO) 5 afforded a heterobimetallic [(Me 2 Bipy)AgFe(CO) 5 ][B{3,5-(CF 3 ) 2 C 6 H 3 } 4 ] species with a Ag-Fe(CO) 5 bond and a heterotrimetallic [{Fe(CO) 5 } 2 (μ-Ag)][B{3,5-(CF 3 ) 2 C 6 H 3 } 4 ] with a (CO) 5 Fe-Ag-Fe(CO) 5 core, respectively, illustrating that it is possible to manipulate the coordination sphere at silver while keeping the Ag-Fe bond intact. The chemistry of [B{3,5-(CF 3 ) 2 C 6 H 3 } 4 ]AgFe(CO) 5 with Et 2 O and PMes 3 (Mes = 2,4,6-trimethylphenyl) has also been investigated, which led to [(Et 2 O) 3 Ag][B{3,5-(CF 3 ) 2 C 6 H 3 } 4 ] and [(Mes 3 P) 2 Ag][B{3,5-(CF 3 ) 2 C 6 H 3 } 4 ] with the displacement of the Fe(CO) 5 ligand. X-ray structural and spectroscopic data of new molecules as well as results of computational analyses are presented. The Fe-Ag bond distances of these metal-only Lewis pairs range from 2.5833(4) to 2.6219(5) Å. These Ag-Fe bonds are of primarily an ionic/electrostatic nature with a modest amount of charge transfer between Ag + and Fe(CO) 5 . The ν̅(CO) bands of the molecules with Ag-Fe(CO) 5 bonds show a notable blue shift relative to those observed for free Fe(CO) 5 , indicating a significant reduction in Fe→CO back-bonding upon its coordination to silver(I).

Experimental and Modeling Study on Detachment of Silver Nanoparticles in Saturated Granular Media

NASA Astrophysics Data System (ADS)

Kim, I.; Jeon, C. H.; Lawler, D. F.

2017-12-01

The detachment of citrate-capped silver nanoparticles (AgNPs) previously captured in a column packed with 350-μm glass beads was investigated either by increasing the hydrodynamic force (filtration velocity) or by reducing electrosteric attraction. Overall, the physical enforcement showed negligible (0.4 0.7%) release of attached AgNPs while the chemically-driven force resulted in the noticeable release up to 25.5% of attached AgNPs. Among the chemical parameters tested in this study, Na ionic strength reduction clearly demonstrated the reversible deposition in the secondary energy minimum of classical DLVO theory, yielding the most significant release of the attached AgNPs. The immediate and transient AgNP release after the ionic strength reduction further corroborated the weak deposition. However, an insignificant release was observed with Ca ionic strength reduction due to the strong Ca-citrate complexation and the subsequent deposition in the primary energy minimum; calculations indicated that the depth of the secondary energy minimum was only 1/10 that of the Na ion case. The natural organic matter (NOM) coating on both AgNPs and granular media resulted in approximately 6.1% greater AgNP release compared to the case without NOM coating, indicating additional weak deposition due to the reduced steric attraction between AgNPs and granular media. A modified filtration model in agreement with the experimental data provided the estimated detachment coefficient as a transient AgNP releasing capacity independent of the amount of attached AgNPs. The marginal difference between the detachment coefficients from Na ionic strength reduction and NOM coating indicates the release potential by NOM coating was possibly underestimated in the experimental study due to a lesser amount of the initially attached AgNPs. The findings provide insights into chemical factors on possible reentrainment behavior of the engineered nanoparticles in soil and groundwater contamination.

Genome Sequencing and Comparative Genomics of the Broad Host-Range Pathogen Rhizoctonia solani AG8

PubMed Central

Hane, James K.; Anderson, Jonathan P.; Williams, Angela H.; Sperschneider, Jana; Singh, Karam B.

2014-01-01

Rhizoctonia solani is a soil-borne basidiomycete fungus with a necrotrophic lifestyle which is classified into fourteen reproductively incompatible anastomosis groups (AGs). One of these, AG8, is a devastating pathogen causing bare patch of cereals, brassicas and legumes. R. solani is a multinucleate heterokaryon containing significant heterozygosity within a single cell. This complexity posed significant challenges for the assembly of its genome. We present a high quality genome assembly of R. solani AG8 and a manually curated set of 13,964 genes supported by RNA-seq. The AG8 genome assembly used novel methods to produce a haploid representation of its heterokaryotic state. The whole-genomes of AG8, the rice pathogen AG1-IA and the potato pathogen AG3 were observed to be syntenic and co-linear. Genes and functions putatively relevant to pathogenicity were highlighted by comparing AG8 to known pathogenicity genes, orthology databases spanning 197 phytopathogenic taxa and AG1-IA. We also observed SNP-level “hypermutation” of CpG dinucleotides to TpG between AG8 nuclei, with similarities to repeat-induced point mutation (RIP). Interestingly, gene-coding regions were widely affected along with repetitive DNA, which has not been previously observed for RIP in mononuclear fungi of the Pezizomycotina. The rate of heterozygous SNP mutations within this single isolate of AG8 was observed to be higher than SNP mutation rates observed across populations of most fungal species compared. Comparative analyses were combined to predict biological processes relevant to AG8 and 308 proteins with effector-like characteristics, forming a valuable resource for further study of this pathosystem. Predicted effector-like proteins had elevated levels of non-synonymous point mutations relative to synonymous mutations (dN/dS), suggesting that they may be under diversifying selection pressures. In addition, the distant relationship to sequenced necrotrophs of the Ascomycota suggests the R. solani genome sequence may prove to be a useful resource in future comparative analysis of plant pathogens. PMID:24810276

Silver-mordenite for radiologic gas capture from complex streams. Dual catalytic CH 3I decomposition and I confinement

DOE PAGES

Nenoff, Tina M.; Rodriguez, Mark A.; Soelberg, Nick R.; ...

2014-05-09

The selective capture of radiological iodine ( 129I) is a persistent concern for safe nuclear energy. In these nuclear fuel reprocessing scenarios, the gas streams to be treated are extremely complex, containing several distinct iodine-containing molecules amongst a large variety of other species. Silver-containing mordenite (MOR) is a longstanding benchmark for radioiodine capture, reacting with molecular iodine (I 2) to form AgI. However the mechanisms for organoiodine capture is not well understood. Here we investigate the capture of methyl iodide from complex mixed gas streams by combining chemical analysis of the effluent gas stream with in depth characterization of themore » recovered sorbent. Tools applied include infrared spectroscopy, thermogravimetric analysis with mass spectrometry, micro X-ray fluorescence, powder X-ray diffraction analysis, and pair distribution function analysis. Moreover, the MOR zeolite catalyzes decomposition of the methyl iodide through formation of surface methoxy species (SMS), which subsequently reacts with water in the mixed gas stream to form methanol, and with methanol to form dimethyl ether, which are both detected downstream in the effluent. The liberated iodine reacts with Ag in the MOR pore to the form subnanometer AgI clusters, smaller than the MOR pores, suggesting that the iodine is both physically and chemically confined within the zeolite.« less

Silver-bearing minerals in the Xinhua hydrothermal vein-type Pb-Zn deposit, South China

NASA Astrophysics Data System (ADS)

Wang, Minfang; Zhang, Xubo; Guo, Xiaonan; Pi, Daohui; Yang, Meijun

2018-02-01

Electron probe microanalysis (EPMA) results are reported for newly identified silver-bearing minerals from the Xinhua deposit, Yunkaidashan area, South China. The Xinhua deposit is a hydrothermal vein-type Pb-Zn deposit and is hosted in the Pubei Complex, which consists of a cordierite-biotite granite with a U-Pb zircon age of 244.3 ± 1.8-251.9 ± 2.2 Ma. The mineralization process is subdivided into four mineralization stages, characterized by the following mineral associations: mineralization stage I with quartz, pyrite, and sphalerite; mineralization stage II with siderite, galena, and tetrahedrite; mineralization stage III with quartz and galena; and mineralization stage IV with quartz, calcite, and baryte. Tetrahedrite series minerals, such as freibergite, argentotetrahedrite, and tennantite are the main Ag-bearing minerals in the Xinhua deposit. The greatest concentration of silver occurs in phases from mineralization stage II. Microscopic observations reveal close relationship between galena and tetrahedrite series minerals that mostly occur as irregular inclusions within galena. The negative correlation between Cu and Ag in the lattices of tetrahedrite series minerals suggests that Cu sites are occupied by Ag atoms. Zn substitution for Fe in argentotetrahedrite and Cd substitution for Pb in tetrahedrite are also observed. Micro-thermometric data reveal that both homogenization temperatures and calculated salinities of hydrothermal fluids decrease progressively from the early to the later mineralization stages. The metal ions, such as Ag+, Cu+, Pb2+, and Zn2+, are transported as chlorine complex ions in the early mineralization stage and as bisulfide complex ions in the late mineralization stage, caused by changes in oxygen fugacity, temperature, and pH of the hydrothermal fluids. Because of the varying solubility of different metal ions, Pb2+, Zn2+, and Cu2+ ions are initially precipitated as galena, sphalerite, and chalcopyrite, respectively. With decreasing temperature of the fluids, Pb2+ ions are incorporated along with Cu+, Sb3+, and As3+ ions into sulfosalt minerals, and Ag+ ions are coprecipitated with Cu+, Sb3+, and As3+ ions forming tetrahedrite series minerals or replacing earlier sulfides and sulfosalts.

Sjögren's syndome and extragonadal sex steroid formation: a clue to a better disease control?

PubMed

Konttinen, Y T; Stegajev, V; Al-Samadi, A; Porola, P; Hietanen, J; Ainola, M

2015-01-01

Sjögren's syndrome (SS) is an autoimmune disease characterized by lymphoplasmacytoid focal adenitis leading to mucosal dryness, with 9:1 female dominance and peak incidence at menopause. Due to autoimmune adenitis it can be speculated that the normal epithelial cell renewal has failed, possibly as a result of local intracrine failure to process dehydroepiandrosterone (DHEA) to dihydrotestosterone (DHT). Local intracrine/-cellular DHT deficiency seems to predispose to SS if estrogens are low, in menopausal women and in men. This intracrine failure could be the initial noxious stimulus, factor X, initiating the development of SS. Abnormal release and presentation of exocrine gland-derived antigens (Ag-epitopes), in a complex with major histocompatibility complex class II (MHC II), by migratory dendritic cells (DC) activates T-cells in the regional lymph nodes. B-cells with the same specificity capture and present self-Ag to Th-cells which provide T-cell help. B-cells transform to plasma cells and start to produce autoantibodies (Ab) against these T-cell-dependent Ag. Ab against SS-A/Ro and SS-B/La ribonucleoproteins occur only in HLA-DQw2.1/DQw6 heterozygous individuals, but hY-RNA and RNA polymerase III transcripts in these Ag may in all SS patients stimulate toll-like receptors (TLR) 7 and 9 of the plasmacytoid DCs, because IFN-α and IFN-signature are produced. CD8+αEβ7+cytotoxic T-cells activated via cross-presentation recirculate to attack intracrine-deficient, apoptotic epithelial cells expressing self-Ag on their surface. Exocrine glands fall into the sphere of mucosal/gut-associated lymphatic tissue. This together with immune complexes spreads the immunological memory/aggression to extra-glandular sites explaining the systemic nature of the syndrome. Secondary SS could be explained by disturbed lymphocyte recirculation. There is no conclusive evidence that SS in those few men affected is more severe than in women, suggesting that sex steroid endo-/intracrinology has its major impact on the target tissue, not on immune modulation. This article is part of a Special Issue entitled 'Essential role of DHEA'. Copyright © 2014 Elsevier Ltd. All rights reserved.

Low temperature-induced DNA hypermethylation attenuates expression of RhAG, an AGAMOUS homolog, and increases petal number in rose (Rosa hybrida).

PubMed

Ma, Nan; Chen, Wen; Fan, Tiangang; Tian, Yaran; Zhang, Shuai; Zeng, Daxing; Li, Yonghong

2015-10-05

Flower development is central to angiosperm reproduction and is regulated by a broad range of endogenous and exogenous stimuli. It has been well documented that ambient temperature plays a key role in controlling flowering time; however, the mechanisms by which temperature regulates floral organ differentiation remain largely unknown. In this study, we show that low temperature treatment significantly increases petal number in rose (Rosa hybrida) through the promotion of stamen petaloidy. Quantitative RT-PCR analysis revealed that the expression pattern of RhAG, a rose homolog of the Arabidopsis thaliana AGAMOUS C-function gene, is associated with low temperature regulated flower development. Silencing of RhAG mimicked the impact of low temperature treatments on petal development by significantly increasing petal number through an increased production of petaloid stamens. In situ hybridization studies further revealed that low temperature restricts its spatial expression area. Analysis of DNA methylation level showed that low temperature treatment enhances the methylation level of the RhAG promoter, and a specific promoter region that was hypermethylated at CHH loci under low temperature conditions, was identified by bisulfite sequencing. This suggests that epigenetic DNA methylation contributes to the ambient temperature modulation of RhAG expression. Our results provide highlights in the role of RhAG gene in petal number determination and add a new layer of complexity in the regulation of floral organ development. We propose that RhAG plays an essential role in rose flower patterning by regulating petal development, and that low temperatures increase petal number, at least in part, by suppressing RhAG expression via enhancing DNA CHH hypermethylation of the RhAG promoter.

Development of a new colorimetric assay for detection of bisphenol-A in aqueous media using green synthesized silver chloride nanoparticles: experimental and theoretical study.

PubMed

Khalililaghab, Shiva; Momeni, Safieh; Farrokhnia, Maryam; Nabipour, Iraj; Karimi, Sadegh

2017-04-01

In the present study, a cost-effective, green and simple synthesis method was applied for preparation of stable silver chloride nanoparticles (AgCl-NPs). The method was done by forming AgCl-NPs from Ag + ions using aqueous extract of brown algae (Sargassum boveanum) obtained from the Persian Gulf Sea. This extract served as capping agent during the formation of AgCl-NPs. Creation of AgCl-NPs was confirmed by UV-visible spectroscopy, powder X-ray diffraction, energy-dispersive X-ray spectroscopy, and high-resolution transmission electron microscopy, while the morphology and size analyses were characterized using high-resolution transmission electron microscopy and dynamic light scattering. After optimization of some experimental conditions, particularly pH, a simple and facile system was developed for the naked-eye detection of bisphenol-A. Moreover, a theoretical study of AgCl interaction with bisphenol-A was performed at the density functional level of theory in both gas and solvent phases. Theoretical results showed that electrostatic and van der Waal interactions play important roles in complexation of bisphenol-A with AgCl-NPs, which can lead to aggregation of the as-prepared AgCl-NPs and results in color change from specific yellow to dark purple, where a new aggregation band induced at 542 nm appears. The absorbance at 542 nm was found to be linearly dependent on the bisphenol-A concentration in the range of 1 × 10 -6 -1 × 10 -4  M, with limit of detection of 45 nM. In conclusion, obtained results from the present study can open up an innovative application of the green synthesis of AgCl-NPs using brown algae extract as colorimetric sensors.

A direct solid sampling analysis method for the detection of silver nanoparticles in biological matrices.

PubMed

Feichtmeier, Nadine S; Ruchter, Nadine; Zimmermann, Sonja; Sures, Bernd; Leopold, Kerstin

2016-01-01

Engineered silver nanoparticles (AgNPs) are implemented in food contact materials due to their powerful antimicrobial properties and so may enter the human food chain. Hence, it is desirable to develop easy, sensitive and fast analytical screening methods for the determination of AgNPs in complex biological matrices. This study describes such a method using solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry (GFAAS). A recently reported novel evaluation strategy uses the atomization delay of the respective GFAAS signal as significant indicator for AgNPs and thereby allows discrimination of AgNPs from ionic silver (Ag(+)) in the samples without elaborate sample pre-treatment. This approach was further developed and applied to a variety of biological samples. Its suitability was approved by investigation of eight different food samples (parsley, apple, pepper, cheese, onion, pasta, maize meal and wheat flour) spiked with ionic silver or AgNPs. Furthermore, the migration of AgNPs from silver-impregnated polypropylene food storage boxes to fresh pepper was observed and a mussel sample obtained from a laboratory exposure study with silver was investigated. The differences in the atomization delays (Δt(ad)) between silver ions and 20-nm AgNPs vary in a range from -2.01 ± 1.38 s for maize meal to +2.06 ± 1.08 s for mussel tissue. However, the differences were significant in all investigated matrices and so indicative of the presence/absence of AgNPs. Moreover, investigation of model matrices (cellulose, gelatine and water) gives the first indication of matrix-dependent trends. Reproducibility and homogeneity tests confirm the applicability of the method.

Improvement of gas-adsorption performances of Ag-functionalized monolayer MoS2 surfaces: A first-principles study

NASA Astrophysics Data System (ADS)

Song, Jian; Lou, Huan

2018-05-01

Investigations of the adsorptions of representative gases (NO2, NH3, H2S, SO2, CO, and HCHO) on different Ag-functionalized monolayer MoS2 surfaces were performed by first principles methods. The adsorption configurations, adsorption energies, electronic structure properties, and charge transfer were calculated, and the results show that the adsorption activities to gases of monolayer MoS2 are dramatically enhanced by the Ag-modification. The Ag-modified perfect MoS2 (Ag-P) and MoS2 with S-vacancy (Ag-Vs) substrates exhibit a more superior adsorption activity to NO2 than other gases, which is consistent with the experimental reports. The charge transfer processes of different molecules adsorbed on different surfaces exhibit various characteristics, with potential benefits to gas selectivity. For instance, the NO2 and SO2 obtain more electrons from both Ag-P and Ag-Vs substrates but the NH3 and H2S donate more electrons to materials than others. In addition, the CO and HCHO possess totally opposite charge transfer directs on both substrates, respectively. The BS and PDOS calculations show that semiconductor types of gas/Ag-MoS2 systems are more determined by the metal-functionalization of material, and the directs and numbers of charge transfer process between gases and adsorbents can cause the increase or decline of material resistance theoretically, which is helpful to gas detection and distinction. The further analysis indicates suitable co-operation between the gain-lost electron ability of gas and metallicity of featuring metal might adjust the resistivity of complex and contribute to new thought for metal-functionalization. Our works provide new valuable ideas and theoretical foundation for the potential improvement of MoS2-based gas sensor performances, such as sensitivity and selectivity.

Soft chemical synthesis of Ag{sub 3}SbS{sub 3} with efficient and recyclable visible light photocatalytic properties

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

Gusain, Meenakshi; Rawat, Pooja; Nagarajan, Rajamani, E-mail: rnagarajan@chemistry.du.ac.in

2014-12-15

Highlights: • Highly crystalline Ag{sub 3}SbS{sub 3} synthesized using soft chemical approach. • First time report of photocatalytic activity of Ag{sub 3}SbS{sub 3}. • Ag{sub 3}SbS{sub 3} degraded the harmful organic dyes rapidly under visible radiation. • Pseudo first order kinetics have been followed in these sets of reactions. • Up to 90% of Methylene Blue degraded even after 4th cycle of catalyst reuse. • Structure of catalyst is intact after reuse. • As the catalyst is heavy, its separation after use is quite simple. - Abstract: Application of Ag{sub 3}SbS{sub 3}, obtained by soft chemical approach involving rapid reactionmore » of air stable metal–thiourea complexes in ethylene glycol medium, as visible light photocatalyst for the degradation of dye solutions was investigated. Ag{sub 3}SbS{sub 3} was confirmed by high resolution powder X-ray diffraction pattern and its no defined morphology was present in SEM images. From UV–vis spectroscopy measurements, optical band gap of 1.77 eV was deduced for Ag{sub 3}SbS{sub 3}. Rapid degradation kinetics and recyclability was exhibited by Ag{sub 3}SbS{sub 3} towards Methylene Blue, Methyl Orange, Malachite Green, and Rhodamine 6G dye solutions under visible radiation. All these processes followed pseudo first order kinetics. High surface area (6.39 m{sup 2}/g), with mesopores (3.81 nm), arising from solvent mediated synthesis of Ag{sub 3}SbS{sub 3} has been correlated to its catalytic activity.« less

Magnified fluorescence detection of silver(I) ion in aqueous solutions by using nano-graphite-DNA hybrid and DNase I.

PubMed

Wei, Yin; Li, Bianmiao; Wang, Xu; Duan, Yixiang

2014-08-15

This paper describes a novel approach utilizing nano-graphite-DNA hybrid and DNase I for the amplified detection of silver(I) ion in aqueous solutions for the first time. Nano-graphite can effectively quench the fluorescence of dye-labeled cytosine-rich single-stranded DNA due to its strong π-π stacking interactions; however, in the presence of Ag(+), C-Ag(+)-C coordination induces the probe to fold into a hairpin structure, which does not adsorb on the surface of nano-graphite and thus retains the dye fluorescence. Meanwhile, the hairpin structure can be cleaved by DNase I, and in such case Ag(+) is delivered from the complex. The released Ag(+) then binds other dye-labeled single-stranded DNA on the nano-graphite surface, and touches off another target recycling, resulting in the successive release of dye-labeled single-stranded DNA from the nano-graphite, which leads to significant amplification of the signal. The present magnification sensing system exhibits high sensitivity toward Ag(+) with a limit of detection of 0.3nM (S/N=3), which is much lower than the standard for Ag(+) in drinking water recommended by the Environmental Protection Agency (EPA). The selectivity of the sensor for Ag(+) against other biologically and environmentally related metal ions is outstanding due to the high specificity of C-Ag(+)-C formation. Moreover, the sensing system is used for the determination of Ag(+) in river water samples with satisfying results. The proposed assay is simple, cost-effective, and might open the door for the development of new assays for other metal ions or biomolecules. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Yang, Sangmo; Paranthaman, Mariappan Parans; Noh, Tae Won

The voltage spectroscopies in scanning probe microscopy (SPM) techniques are widely used to investigate the electrochemical processes in nanoscale volumes, which are important for current key applications, such as batteries, fuel cells, catalysts, and memristors. The spectroscopic measurements are commonly performed on a grid of multiple points to yield spatially resolved maps of reversible and irreversible electrochemical functionalities. Hence, the spacing between measurement points is an important parameter to be considered, especially for irreversible electrochemical processes. Here, we report nonlocal electrochemical dynamics in chains of Ag particles fabricated by the SPM tip on a silver ion solid electrolyte. When themore » grid spacing is small compared with the size of the formed Ag particles, anomalous chains of unequally sized particles with double periodicity evolve. This behavior is ascribed to a proximity effect during the tip-induced electrochemical process, specifically, size-dependent silver particle growth following the contact between the particles. In addition, fractal shape evolution of the formed Ag structures indicates that the growth-limiting process changes from Ag +/Ag redox reaction to Ag +-ion diffusion with the increase in the applied voltage and pulse duration. Our study shows that characteristic shapes of the electrochemical products are good indicators for determining the underlying growth-limiting process, and emergence of complex phenomena during spectroscopic mapping of electrochemical functionalities.« less

One-step synthesis and characterization of polyaniline nanofiber/silver nanoparticle composite networks as antibacterial agents.

PubMed

Poyraz, Selcuk; Cerkez, Idris; Huang, Tung Shi; Liu, Zhen; Kang, Litao; Luo, Jujie; Zhang, Xinyu

2014-11-26

Through a facile and effective seeding polymerization reaction via a one-step redox/complexation process, which took place in aqueous medium at ambient temperature, silver nanoparticles (Ag NPs) embedded polyaniline nanofiber (PANI NF) networks were synthesized as antibacterial agents. During the reaction, not only NF morphology formation of the resulting conducting polymers (CPs) but also amplification of the aqueous silver nitrate (AgNO3) solutions' oxidative potentials were managed by vanadium pentoxide (V2O5) sol-gel nanofibers, which acted as well-known nanofibrous seeding agents and the auxiliary oxidative agent at the same time. The PANI/Ag nanocomposites were proven to exhibit excellent antibacterial property against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus. Antibacterial property performance and average life span of the nanocomposite network were optimized through the homogeneous distribution/embedment of Ag NPs within one-dimensional (1-D) PANI NF matrix. The antibacterial efficacy tests and nanocomposite material characterization results further indicated that the sole components of PANI/Ag have a synergistic effect to each other in terms of antibacterial property. Thus, this well-known catalytic seeding approach via a one-step oxidative polymerization reaction can be considered as a general methodology and a substantial fabrication tool to synthesize Ag NP decorated nanofibrillar PANI networks as advanced antibacterial agents.

Separation and preconcentration of Ag(I) in aqueous samples by flotation as an ion-associate using iodide and ferroin followed the determination by flame atomic absorption spectrometry.

PubMed

Hosseini, Mohammad Saeid; Hashemi-Moghaddam, Hamid; Kardan-Moghaddam, Gholamreza

2007-01-01

A simple method for separation/preconcentration and determination of Ag(I) in aqueous samples is described. The method is based on formation of an ion-associate between Ag(I)-iodide complex and ferroin, which can be floated at the interface of the aqueous/n-heptane phases. The flotation process was carried out using 500-ml aliquot of the aqueous solution and the floated layer was dissolved in 5 ml of 1 M HNO3 containing methanol (50% v/v) as the solvent. The Ag(I) content was then determined by flame atomic absorption spectrometry (FAAS). The method so could be considered as an enrichment process, was achieved to a quantitative feature, when the pH of the solution was adjusted to 4 and the concentrations of iodide and ferroin were about 3.2 x 10(-4) M and 6.25 x 10(-5) M, respectively. The LOD and RSD (n = 7) were obtained 1.0 x 10(-8) M and 2.4%, respectively. It was found that a large number of cations and anions even at high considerably foreign ion/Ag(I) ratios were not interfered. The method was applied satisfactorily to recovery of Ag(I) from different aqueous samples.